Rocketdyne-Hydrogen Peroxide Handbook

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AFRPL-TR-67-144

HYDROGEN PEROXIDE HANDBOOK

00

00 By

Chemical and Material Sciences DepartmentResearch Division

Rocketdyne, a Division of North American Aviation, Inc.Canoga Park, California

Technical Report AFRPL-TR-67-144

July 1967

This document is subject to special export controls and each transmittalW WA AMIA~UV~ UUR~W i~ AurLR ~ twAUinI Mlay heB macip. nnfiV Witfl fliflli

approval to AFRPL(RPPR/STINFO), Edwards, California 93523.

Air Force Rocket Propulsion Laboratory [ A;UG 29 1967"Research and Technology Division •U-L D

- Edwards Air Force Base, California ULAir Force Systems Commandna

United States Air Force

AFMP-TR-67-1'44

UYEV•OGEN PULOXIDE HANDBOOK

By

Chemical and Material Sciences DepartmentResearch Division

Rocketdyne, a Division of North American Aviation, Inc.Canoga Park, California

July 1967

this document is subject to special export controls and cach transmittalto foreign governments or foreign nationals may be made only with priorr - to Edw ,--=-,MA

Air Foroe Rocket Propulsion LaboratoryResearch and Technology Division

Edwards Air Force Base, CaliforniaAir Force Systems Com ond

United States Air Force

FOEWOR1D

This handbook is submitted as the final report under

Rocketdyne G.O. 7108 in compliance with Contract

AF040(b -11397, Part I, Para. B.1, and line items

2 and 3 of DD 1I23. The effort under this contract

was sponsored by the Air Force Rocket Propulsion

Laboratory, Research and Techltology Division, Air

Force Systems Command, USAF, Edwards, California,

with l/Lt. Ralph Fargnoli acting as the Air Force

Project Officer.

This program was conducted by the Propellant Tech-

nology function of the Rocketdyne Research Division,

with Dr. E. F. C. Cain serving as Program Manager

and Mr. M. T. Constantine serving as Responsible

Project Scientist. Technical personnel who contrib-

uted to the compilation and analysis of the data and

information in this handbook include M. M. Williams

and K. J. Youei.

This handbook has been assigned the Rocketdyne iden-

tification number R-6931.

This report has been reviewed a..d is approved.

W. H. EBELKE, Colonel, USAFChief, Propellant Division

Ii

ADJSTHACT

This handbook in a compilation of the engineering

properties and handling characteristics of propellant-

grade hydrogen peroxide. The handbouli includes data

and information on hydrogen peroxide phiysicochemical

properties, production, storability, materials com-

patibility, materials treatment and passivation,

facilities and equipjdent, disposol, transportation,,

safety, and decomposition.

i i i/i v

ACGNOWLWQUtMT

This handbook iucludP2 data and information generated through experimentaland analytical studies conducted at many differpnt organizations. Althoughevery effort has been made to reference these studies, a great number ofindividuals responsible for these data have been neglected. These indi-vidual contributions as well as the contributions of the industry and govern-ment organizations are gratefully acknowledged.

Apj'reciution is also gratefully extended to the various organizations whoresponded tC a request for data and information during an industry survey.These organizations (with the responding individual noted) are as follows:

Aerojet-General Corporation, Azusa, California (S. D. Rosenberg)Aerojet-General Corporation, Sacramento, California (Robert J. Kuntz)Air Reduction Company, Inc., Murray Hill, New Jersey (Walter B. Hoen)Explosives Research and Development Establishment,

Waltham Abbey, England (A. L. Lovecy)General Electric Company, Philadelphia, Pennsylvania (Arnold V. Cohen)Hughes Aircraft Company, El Segundo, California (M. E. Ellion)Jet Propulsion Laboratory, Pasadena, California (D. D. Evans)Walter Kidde and Co., Inc.,Belleville, New Jersey (John C. Scheider)Laporte Chemicals, Ltd., Luton, England (H. L. Hlulland)The Marquardt Corporation, Van Nuys, California (R. Carl Stechman)Penasalt Chemicals Corporation, Los Angeles, California (J. C. Neighbors)Pesco Products, Bedford, Ohio (F. G. Johnston)Pratt and Whitney Aircraft, West Pals Beach, Florida (Hark H. Young)Rocket Propulsion Establishment, Westcott, England (J. D. Lewis)Southwest Research Institute, San Antonio, Texas (Herbert I. Hoffman)TRW Incorporated, Redondo Beach, California (Glen W. Howell)U.S. Army Missile Coinand, Redstone Arsenal, Alabama (Walter W. Wharton)

V

In addition, a special acknowledgemcnt is due the folloving organizatioza'

(and the noted pereonnel) for providing technical conisultation duriugy the

industry survey:

bell Aerotystews

h1. iluebusch, A. Bottara, J. L. lispisa, S. Lung, W. lReinhalrt, It. Spereazza

E. I. dulloait dc Newours & Co.

J. H. Snyder, V. J. Reilly, T. D. Canby, F. Ii. Lindberg, J. C. Schwenberg-'r,

A. D. Stafford, J. E. Williams

F.M.C. Cori'oi-ati on

J. McCormick, C. Rawleigh, L. i)il'we, L. Dierdorfl

LTV Astronautics Division

U. H. Robinson, A. B. Featherstona

Picatinny Arvitl I

W. Buckley

Shell Chemical COmIMI!Y

G. J. Moore, R. It. Rcnshaw, W. !1. Wulf

Shell IkDelo,!ment Comlmny

I!. J. Iauqgartlnelr, G. C. Hood, J. H. Monger, .1. Toombm

ihiokol Chemical Corporation - Reaction Motors Division

HI. A. Kock, F. Hoffman, C. Diaick, W. Fis!igrund, P. Gwoidy, A. Lur

U.S. ,iaval Ordnance Test Station

D. Couci

vi

CONTLNT8

Foreword .:. .. ... i i

Abstract . . . . . . ... . ..

Acknowledgzient . . ..

Section 1; Introduction . . . . . . . . . . . 1

1.1 General . . . . . . . . . . . . 11.2 Handbook Format . . . . . . . . . . . ..

1.3 Rleferences . . . . . . . . . . 6

Section 2: Physico-Chemical Properties . .3

2.1 General Description ......... .......... * . . 13

2.2 Physical Properties . ............ .. . 14

2.3 Chemical Properties ......... ............ 34

2.4 Solubility and Miscibility ....... ... ........... 35

2.5 Gelation ................. ............ .. 37

2.6 Heat Transfer Properties . . . ........... 37

2.7 Ignition Characteristics ...... ........... . 39

2.8 References ............. ............... 44

Section I, Production ............ ............. . 135

3.1 M4anulacturing Techniques ...... .... ........... 135

3.2 Current Production . . . ........... .. 140

3.3 Propellant Specification ............ . .142

3.4 Chemical Analysis ............ ............... 144

3.5 References ............. ................ 150

Section 4: Storage and ltandling . ........ 154

4a.1 Storability ...... ................ 154

4.2 Materials of Construction 4 .............. 169

4.3 Materials Treatment and Passivaticn . . ...... 208

4.4 Facilities and Equipment . . . .. 227

4.5 Decontamination aad Disposal . . . 262

4.6 References . . . ............ . 0 264

Section 5: Transportation . . . . . .... ..... 371

5.1 Chipping Containers and Vehicles . . ....... 371

5.2 Shipping Regulations ........ 374

5.3 Operation and Maintenance of Equipment . . . . . . . 375

vii

5.4 . .fe .enccu . ... . . . . .*30

Section 6: Safety . . . . . . . . . . . .. . 38L1

6.1 Hazard . . . . . . . . . . .. 381

6.2 Hazard Prevention a 395

6.3 Hazard Control .... . . . . . . . 398

6.4 Nr-rsounel Protection .. . . . . . . . 400

6.5 Referencos . .. .. . . . . . . . 405

Section 7: Decomposltlon . 4a17

7.1 Dccomposition echanism . . . . . . . . . . . 417

7.2 Controlled Decosmposltion ................ 422

7.3 References .............. . . ............ . 434

Section 8: Bibliography ............ . ........ ... 437

8.1 General References . . . . . . . . . . . . . . 4

8.2 Physical Properties .................. 439

8.3 Structue.. ... . . .......... . ........... ... 446

8.4 Solubility .......... . . . .... ........ .... 447

8.5 HaudJing and Storage ............. .......... . 44

8.6 Materials Compatibility ....... . . ........ .. 452

8.7 Transportation ............... . . ..........- 454

8.8 Safety . .................. ... .. ... .. . . .454

8.9 Dccomposition . . .... . ... .......... . 459

vI L

ULUJSTIATlO.NS

2.1. Concentration sad Apparent Molecalar Weight of

Aqueous kTdrogeu Peroxide Solutions . . ... 90

9.2. reeaing Points of 1Hydo;en Peroxide-Water SolutioA . 91

Aw.2.2. remeing Points of E,-drogeu Peroxide-W&ter Solutions 92

2.). Critical Temerature, Critical Fressure, and loiliug

Point of Prop. llwt-.Grade ky.drogeu Peroxide-

Water Solutions . . . . . . . . . . 0 * 93

2.4. Density of Projellant-Urade k•drogeu ]Peroxide-

Water Solutions ..... .. . . .9

"2.4o. Density of Propellant-Grade fEydrogen Peroxide-

Water Solutions . ......... 95

2.5. Coefficients (Cubical) of Thermal Expaasiou for

Propellant-Grade Aydrogeu Peroxide-Water Solutions 96

2.5a. Coefficients (Cubical) of Thermal Expansion for

Propellant-Grade HWdrugen Peroxide-Water Sulutios- 97

2.6. Adiabatic Comprossibility of Propellant-Grade

Hydrogen Peroxide-Water Solutions .... ........ 98

2.6L. Adiabatic Compressibility of Propellant-Grade

,Adrogeu Peroxide-Water Solutonus . . . . 99

2.7 Vapor Preasure of Propallaut-(1rade Eydrugen

Pmrnxid-MWater •olutiona ......- -. 1z00

2.7.. Vapor Paessure of Prppellaat-GOrde Hlydrogen

Peroxido-Water Solutious .. .. ........ . . 101

2.8 Vapor Composition Over Eydrouin Peroxide-

Water Solutions . .......... ... .............. 102

2.9 Vapor'-Liquid Equilibrium 2or the Lydrogen PJeroxi(-

Water byatm ............. . . . .. 103

2.10. Activity Coefficients for Hydrogen Peroxide-

Water Solutiou. ..... ........... 10t

2.11 Surface Tension of Mydrzgen Perozid.-Water Solutions . 105

2.1La. Surface Tension of Hydrogen Peroxide-Water Solutions . 106

2.12 Bets of Formation of Propellaut-Grade Hydrogen

teroxide-Mater Solutions . ..* .a. .0 a 1 . 107

ix

2.12s. Beat& of Formation of Props Il.at-Grade WI~drone-

Peroxide-Water Solutions . . . . . .. 0.

2.13 B" s of Formntiou of Fropellat-Grad. Hydrogeu

Peroxide-41ater Solutions at 25 C a . . * . . . 109

2.13•. Boats of Forution of Propellaut-Grade Hydrogen

Perox4de-NJater Solutions at 77 r . . . . . . . 310

2.14. Baots of Ysporization of Hydrogeu Peroxide-

Vats 8olutions . . * . . .. . . . .. . 111

2.14s. Beats of Vcporiuation of H~ydrogeu Peroxide-

Water Solution 1 .. . . . . ..... 112

2.15. Beats of Mixing of Hydrogen Peroxide-Water Solutions . 113

2.15s. Boats of Mixing of Aydrogen Peroxide-Water bolutions . 114.

2.16. Ematm of Deomposition of Propell"nt-Grade Hydrogen

Feroxide-Watea Solutions at 25 C .... ... ........ 115

2.16a. Boats of Decomposition of Propellant-Grade Lkdrogeu

Peruxide-Woater Solutions at 77 F . .... . . 116

2.17. beat Campactios of Propellant-Grade Elydrogeu

Peroxide-Water Solutions ........ .......... . 117

2.17a. Beat Capacitiea of Propellazt-Grade Hydrogeu

Peroxidi-Water Solutions .......... .......... 118

2.18. Viscosity of Liquid Itydrogen Peroxide-Water Solutions . 119

2.18a. Viscosity of Liquid flydrogen Peroxide--ater Solutions . * 120

2.19. Viscumities of 98 w/o Hydroaeu Peroxide, 70 w/o

rkvdrozen Peroxide,- and W-.,- ...................... ... .

2.19a. Viocomitito of 98 w/o Hydrogeu Peiroxide, 70 W/o

*ydrogen Peroxide, and Water ..... ......... .. 122

2.20. Viscosity of Hydrogen Peroxide and Water Vapor . . . . 12.3

2.21. Thermal Conductivity of 98.2 w/o Hydrogen Peroxide . * 42(.

2,22. Velocity of Bound in Propellant-Grade kdrogeu

,roxide-Uater Solutions ..... .......... 12

2.22s. Velocity of Sound in Propellant-Grade B3-drogeu

Peroxide-Water Solutions . . . . . . . . . . 26

2.23. Dielectric Constant of Propellant-Grade fydrogon

Peroxide-Water Solutions .............. .327

2.23s. Dielectric Constant of Fropellan"t-Grde HLydrogen

Peroxide-Water Solutions .... ....... . . 12

2.24. Heat Flux From a 34*7 Stainless-Steel Surface to 90 W/o

Hydrogen Peroxide as a Function of Surface Temperature . 129

2.25. Typical Curve of Heat 7lux vs Inside Wall Temperature

(98 w/o Hydrogen Peroxide 1-1/2 Inches Upstream From

Exit of Heated Section) . . . ............. 130

2.26. Correlation of heat Transfer Coefficients of 98 W/o

Rydrogen Peroxide With Dittus-Boelter Equation ..... 131

2.27. Correlation of Heat Transfer Coefficients of 98 w/o

Hydrogen Peroxide With Colburn Equation .. ....... . 132

2.28. Correlation of Heat Transfer Coefficients of 98 W/o

Hydrogen Peroxide With Sieder-Tate Equation . . . . .. 133

4.1. Stability of Hydrogen Peroxide as a Function

of Concentration ............. ............... 360

4.2. Typical Decomposition Rates for Various Hydrogen

Peroxide Samples at 32 F ........... . . 361

4.3. Results of Sealed Storage Tests With Unstabilized

90 w/o and 98 w/o 1%0 2......... ............. 362

4.4. Heterogeneous Decomposition of 90 w/o Hydrogen

Peroxide at Various Temperatures .. ........ . 363

4.5. Decomposition Rates of 90 Weight Percent Hydrogen

Peroxide-Water Solutions an a Function of

Surface-to-Volume Ratio ........ . . . . 364

4.6. Results of Sealed Storage Tests at 72 F With Unstabilized

98 Weight Percent H202 in Bli iders Treated by

Various Techniques . . .365

4.7. Effect of Surface to Voltme Ratio on the Decomposition Rate

of 99+ Weight Percetrt Hydrogen Peroxide During Storage. . 366

4.8. Effect of Stabilization of 98 Weight Percent H202 a a

Function of Temperature . . . . ............. 367

4.9. Effect of Stabilization of 90 w/o B2 02 as a Function of

Stabilizer Concentration at 212 F ... . ....... . 368

4.10 Volume of OXygen Liberated per Year From the Decomposition

of Hydrogen Peroxide at a Rate of 0.1 Percent AOL/Year . . 369

4.11. Pressure Increase in a Sealed ConiAiner Resulti4g From

Hydrogen Peroxide Decomposition at a Rate of

O.1 Percent ............. 370

2i

6.. Ignition Delay of hydrogen Peroxide With Filt .. . . 413

6.2. Ignition Limits of Hydrogen Peroxide Vapor . . . . . 41

6.3. Liquid Comnpouitions Which Result in Ignitable Vapor

Concentrations . . . * .. . . . . . 4 115

6.1t. Hydrogen Peroxide Vapor Explosive I16zard Region . . . 4*16

Xii

TABLES

1.1. Pysical Constants . . 7 .

1.2. Conversion Factors ......... . .. 8

1.3. Temperature Conversion . . . . . . . . . .. 11

2.1. Physical Properties of Hydrogen Peroxide at 25 C .... 54

2.2. Calculated Saturation Pressure, Activity Coefficients, and

Vapor Compositions for Hydrogen Peroxide-Water Solutions

at High Temperatures and Pressures . . . ..... 572.3. Solid- and Liquid-Phase Thermodynamic Properties of

100 w/o 1202 . . . . . .... ......... . . . 59

2.4. Solid- and Liquid-Phase Thermodynamic Properties of

94 v/o H202 Solutions ........ . . . . . . . 61


95 w/o "202 Solutions . . . . . . . . . . . . . 63


90 v/o H202 Solutions . . . . . . . . . . . . 65

2.7. Solid- and Liquid-Phase Thermodynamic P.operties of

75 v/o H2 02 Solutions .................. . . 67


70 w/o H202 Solutions .... .......... . . . 69

2.9. Vapor-Phase Thermodyuamic Properties of 100 w/o %202 . . 71

2.10. Vapor-Phase Thermodynamic Properties of 98 w/o H20 2

Solutions . . . . . . . . . . . . 72

Souton M. U -- --- e .oe w of ^5 .. .72.12. Vapo-Phaseo Thermodyna r . . r"i r of 90 - / U

Solutions . . . . . .. . . . . . . .... 73

2.12. Vapor-Phase Thermodynamic Properties of 90 w/o H202Solutions . . . . . . . . . . . . . . . . 74

2.13. Vapor-Phase Thermodynamic Properties ofT70 w/o H202Solutions .... . . . . . . . . . . . . 75

2.14. Vapor-Phase Thermodynamic Properties of 70 w/o %020

S...Solutions . ....... . • 76

2.15. Refractive Index (Sodium D-Line) of Propellant-Grade

%0 2 -H2 0 Solutions at 25 C .... . .. 77

2.16. Verdet Constant of Hydrogen Peroxide-Water

Solutions At 10 C .. • 79

Xiii,

2.17. Miscellaneous Molecular and Electromagnetic Properties

of Hydrogen Peroxide . . . 80

2.18. Structure and Structural Parameters of lHydrogen

Peroxide . . . . ................ . 81

2.19. Reactions of Hydrogen Peroxide ......... .......... 82

3.1. Summary of Military Specifications Used in• the

Procurerent of Hydrogen Peroxide ..... ........ 152

3.2. Comparison of Typical Analyses for Propellant-Grade 90 w/o

Hydrogen Peroxide From Three Different Commercial

Manufacturers ............ ... ............... 1-3

4.1. Storage Stability of Hlydrogen Peroxide . . . . . .. 272

',4.2. A comparison of the Rate of Decomposition of 90 w/o

HydrPgen Peroxide Manufactured in 1947, 1953, and 1965 . 273

S.3. Criteria for Classifications of Materials and Hydrogen

Peroxide Service on the Basis of Laboratory Tests . . 271,

.4. Compatibility of Hydrogen Peroxide With Aluminum Alloys . 276

;4,05. Compatibility of Hydrogen Peroxide With Stainless

Steel Alloys ................ ........ ...... 280

4.6. Compatibility of Hydrogen Peroxide With Pure Metals . . . 285

4.7. Compatibility of Hydrogen Peroxide With Metal Alloys . . 287

4.8. Compatibility of ly-drogen Peroxide With Polyethylene

and Halogenated Polyethylene ... .......... . 292

11.9. Compatibility of Hydrogen Peroxide With Polyvinylehoride

and Co-Polymers . . . . . . . . . ... . 298

4.,,0. 'V,,,..],•,,•.,,..jV ity &&,• . V.fuw.I, zeroxslde 'VV"IthI Siliconte

Rubber Compounds . ................ . .3004.11. Cohpatibility of Hydrogen Peroxide With General

Rubbers and Plastics . . . . . . . . 302

4.12. Compatibility of Hydrogen Peroxide With Laminates,

Diaphragms, and Adhesives . ..........

4.13. Compatibility of kLvdrogen Peroxide With Porous Materials. . 305

4.14. Compatibility of Hya.-ogen Peroxide With Lubricants . N)6

4.14a. Compatibility of 90 w/o Hydrogen Peroxide With

Potential Lubricants ... . . . . . .312

4.15. Recommended Joint Sealinig Compounds for Use With 90 and

98-Percent Hydrogen Peroxide . . . 3 . . . . . 316

xiv

4.16. Compatibility of Hydrogeu Peroxide With Ceramics,

Refractories, and Miscellaneous Materials . # . . * 318

4.17. Results of Evaluation of Protective Coatings for 90 w/o

Hydrogen Peroxide Service . . . . . . . . . .. 320

4.18. Evaluation of Clothing Materials for Contact With

90 w/o Hydrogen Peroxide . . . .. .......... 324

4.18a. Clothing Materials not Suitable for Use When Handlirig

90 w/o Hydrogen Peroxide ... ....... . .. 325

4.19. Compatibility of Various Metals With 98 w/o lydrogen

Peroxide at High Temperatures .. ....... .. 326

4.20. Compatibility of 90-Percent Hydrogen Peroxide With 1060

and 1100 Aluminum Alloys ... ... . ... 328

4.21. Compatibility of 90 w/o Hydrogen Peroxide With

6061-T6 Aluminum Sheet ............ 329


304 Stainless Steel .................... . 334


316L Stainless Steel ..... ............ 335


321 Stainless Steel .. ...... .... 337


Selected Stainless Sho Alloy . . . . . . 342


Viconen 85 Elastomer . . . . . ..... 3

4.27. Compatibility of 90 W/o Hydrogen Peroxide With

Silastic 9711 Elastomer Sheet ......... 345


Selected Viton Elastomeric Materials . . ... . . 348

4.29. Compatibility of 90 v/o Hydrogen Peroxide With

Selected Plastics . . . . . . .. . . . 349

4.30., Compatibility of 90 v/o Hydrogen Peroxide With

Selected Composite Materials . . . ..... 351

4.31. Heterogeneous Decomposition Rate of Hydrogen Peroxide

as a Function of Surface Preparation ... .. . 353

4.310. Procedures Used for Surface Preparation in Table 4.31 357

4.32. Comparison of the Various Miethods of Tank Temperature

Measuremnt in Order of Increasing Cost . . . .. . 359

6.1. 90- to 100-Percent Hydrogen Peroxide Thermal

.,nsitivity Data ..... . . •. 0.. 4 405xv

8WTIk l 1: rINTRODUCTIOIN

1.1 GOIGAL

The discovery of hydrogen peroxide was reported to the Paris

Academy of Sciences in July 1818 by Louis-Jacques Thenard and

was initially described as oxidized water. The discovery was a

result of government-subsidized research on the preparation of

woltaic cells. Thenard, in working with alkaline earth oxides,

discovered that the reaction of barium peroxide with cold nitric

acid resulted in the formation of "oxygenated water." Thenard

then conducted a fairly extensive study of hydrogen peroxide,

which included catalytic decomposition studies, density determi-

nations, neasurements of the volume of oxygen released, etc.

Ble noted extensive supercooling and the inability to achieve

appreciable concentration increases with crystallization tech-

niques. Thenard also reported that vacuum distillation could

"continue to complete dryness in the reservoir without appreciable

decoaposition, although the determination of normal boiling points

waLs impossible because of decomposition of the hydrogen peroxide.

His work led to the publication of several papers, which are

extensively summarized in Ref. 1.1.

A" uin work, Thenard ciie. reaction! with soae 1%1 elements,oxides, salts, acids, and bases with frequent notations of

decomposition of the hydrogen peroxide. These decomposition

reactions were sometimes accompanied with the note that "in these

decompositions, chemical action is evidently missing; it is neces-

sary then, to attribute these actions to a physical cause; but the

actions are dependent on neither heat nor light, whence it follows

that they are probably due to electricity" (Ref. 1.1). These

"unexplained" reactions were later recognized by Berselius (Ref.

1.2) in 1336 in the first notation of catalysts and catalytic

activity.

Although Thenard's only noted uses for hydrogen peroxide were in

removing sulfide deposits on oil paintings and as a skin irritant

for medicinal purposes, hydrogen peroxide and its aqueous solu-

tions have found a number of commercial applications since its

discovery. The primary bulk of this commercial use is limited to

bydrcgen peroxide grades of less than 52 percent EO2 by weight;

these "industrial grades" havt been used for many years in tex-

tile and pulp bleaching, synthesis of chenical derivatives, the

aanufactuxe of foam rubber, the oxidation of dyes, the purifica-

tion of metal salt solutions, the treatment o! metal surfaces, etc.

The requirement for higher concentrations and their subsequent

commercial development was based primarily on the establishment

of hydrogen peroxide as a source of energy.

_Wdrogen peroxide (in a 60 w/o aqueous solution) was first uti-

lized as an energy source for underwater propulsion in Germany in

1934; this w-ork led to its subsequent application (in higher con-

.,centrations) during World War II for auxiliary propulsion and gas

generation concepts in aircraft and rockets. Its use in these

areas reculted from its thermally or catal)tically initiated exo-

therniic decomposition (with substantial beat release) to yield

a gaseous mixture of oxygen and superheated steam. Although its

advantages as a monopropellant include a 4i7 w/o available oxygen

and nontoxic exhaust gases, the initial areas of application for

hydrogen pieroxide were limited because of its questionable stor'-

age stability.

The use of hydrogen peroxide has been expanded with ifprovements

in its stability, through stabilization additives and increased

purification. Currently, hydrogen peroxide is the primary mono-

propellant used for underwater propulsion, aerospace propulsion,

and auxiliary power concepts. •ydrogen peroxide/water solutions

can now be stored for extended periods without significant

decw~ooition (i.e., decamposition rates of < 0.1 percent/year

2

are readily attainable). Reaction control systems using hydro-

gen peroxide have already demonstrated space storability in excess

of 2 years (with an estimated storability of 5 years).

The use of hydrogen peroxide as a monopropellant in the aerospace

industry has been widespread in the areas of station maintenance,

space maneuvering, thrust vector control, power generation, etc.

So.me examples of systems which have used or are presently utiliz-

ing hydrogen peroxide include the V-2 (gas generator), Redstone

(gas generator), Mercury Spacecraft (reaction control system),

Scout (reaction control system--2nd and 3rd stages), Little Joe II

(reaction control system), Burner II (reaction control system),

SATAR (reaction control system), ASSLE (reaction control system),

122Y (attitude control system), Lunar Landing Simulator (main

propulsion and attitude control systems), Astronaut Maneuvering

Unit (main propulsion), SYNCOG (reaction control system), COKSAT

(reaction control system), HS-303A "Blue Bird" (reaction control

syetem), ATS (reaction control system), Personnel Rocket Belt,

and X-15 (gas generator, reaction control, and auxiliary power

systems). Although the use of hydrogen peroxide in operational

bipropellant systems has been limited thus far to extremely high-

performance aircraft rockets, hydrogen peroxide is potentially

applicable to a variety of liquid bipropellant and hybrid propel-

lant systeLs.

This widespread application potential of hydrogen peroxide has

led to the requirement for a comprehensive and definitive compil-

ation of physical, chemical, and handling properties of this

important oxidizer. As a result of this interest, this handbook

represents a curreat summary of the engineering properties of

propellant-grade hydro#o* paroxide. Propela!&t-grade hydrogen

peroxide is dofiaea in this report as high-purity Wy~rogen

peroxide/vater soluti~no in which the hydrogta peroxide conen-

tratica is • 70 perceat by .Tight. WIi'hii this copc.liýtration

range of interest, solutions containing 70, 75, 90, 95, 98, and 100

percent by weight hydrogen peroxide have been designated as con-

centrations of special interest.

1.2 EIANPOOK IMKAT

The material contained in this handbook has been organized into

sections. These are:

Section 1: Introduction

Section 2: Physico-Chemical Properties

Section 3: Production

Section 4: Storagc and Hlandling

Section 5: Transportation

Section 6: Safety

Section 7: Decomposition, Stabilization, and Catalysts

Section e: Bibliography

Each section is subdivi4Pd further to permit the user of this

handbook to obtain specific information expeditiously. The

materiil is arranged in ouch a manner as to permit convenient

updatz... or various secLionsi as dala are geuzrated from addi-

tional studies in these areas.

-T. •he interest of each individtuwl user may be limited to specific

A - aspects of the subject material; hov,'cver, it is recanmended that

persounel involved in 1102 handling be thoroughly fiuuiliar with

S... of' the engineering propertieH contained in this report.

S° •Although everv effort has been made to provide presently avail-

* :•' 'ble inforciatign on 1L20 2 in wifficient detail for most of the

So., tejitial •sers of the hai~dbookh size limitations of the hand-

book obviously preclude inclusion of every conceivable detail,

=&

Thus, for those users who desire additional details on specific

Items, 'Pousultatiou of the many referenced publications is

: re comk~uude'•,

Wherever a serien of rcports or ippers has betin utilized to report

the progress in a particular study, the data and information ref-

erenced are from final repor ts, whenever applicable. This was

done to eliminate confusion in efforts whecre progress reports

included incopq)lete experimentation and/or analysis of the data.

In those efforts where a final report has not been issued or

does not contain sufficient detail of the itesm, the e.a* were

taken from the latest progress report giotainiug the pertinent

results.

The tables figures, and references noted in each section are con-

tained in that section for convenience. Each table, figure, and

reference Pumber is preceded by the section number (i.e., Table 1.3

to the third table in Section 1, etc.).

Because the major portion of this handbook is related to areas

of #4ngineering interest, all of the data ar presented iii eagi-

noering terminology (i.e., English units). However, as a con-

wenience to al, of1 the users, data in certain sections (notably,

the physical properties section) of the handbook are presented

In both motric a-U4 L4iish units. Where data are presentel iu

both units, tho attendant discussion indicates the units of the

referenced work.

.AA a further convenience to the user, physical constants and

conversion factors are presented in Tables 1.1 througI' 1.3 to

enable the user to convert the values to his particular needs.

Also, because these constants are presputed to the known dsgree

of significance, they can bo roauded to fit particular needs.

1.3 wli"~CkES

1.1 8Ikumb, 'W. C., C. N. 8.tterf iold,, suid I. L. Weutvorthe

&ldrogfui Peroxide, A.C.S. Moaiograjoh 128, Ikiubold Puil~ishinA

Curporatioai, New York, New York, 1955.

1.2 berzelius, J. 4., Jahresbex-. Chew.,.IjI, 237 (1836,), fsve

seate in Mf. kA..

7 '

TABLE I.I

FIMiXICAt C QdSW4TS

Vail Remarks Va lue

Standard gravitatioual 32.1740 ft/oec2accelcration 900.665 co/sec

I ato Standard atmosphere l,013#250 d4-nes/sq cm

I M lBA 6taudard mi,llimcter 1g I'333.2237 d,,nea/eq c%

I cal •Thcraochenical caloric 4.184C abs joules41.2929 10.0020 cu

I cal (I T.) International Stream 1.O00Ci54 thermoches-Tables calorie ical c€Aories

"T0 C Ice Point, 491.6880 10.018 R273.160 ±0.010 1

S)P-O (iT)0 Prer :,tr.-Volume product 22,414.6 10.4 cu co-o CC for .ide..- &no at 0 C ata/g mole

2271.16 iO.04 abejoules/g mole

f tMlar.,;i ru..aut p.31439 0.0003 absjoules/K-g mole

1.96719 ±0.00013 calfK-g mole

82.0567 ±0.004 cu cs--ast -g mole

59.4'7 cU ft-ata 1A-lb- -mole I0.7, cu.'€- Alal-ib

' " sole

1 Btu 1055.040 abs joulce252.161 thermochemical

calories251.996 I. T. calories

I in. United states unit 2.54000.50 cm

I ft United States unit 30.800610 ca

I lb Avoirdupois 453.5924277 a

I Sol United States unit 0.133680555 cu ft3785.4349 cu c..

)let*: Compilad by Rossini, F. D. St J., A, ican Petroleum Institute_geirarch Proect 44, U.S. Department oa Coerce, Watl. Dii.

Standards, Circular 461, U.S. Government Printing Of ice,Washiogtou, D. C., 1947.

7

CONVERSION FACT(IOS

Temperature

C + 273.16 K

F + 459.69- R

(c x 1.8) + 32 - F

(F - 32)/1.8 - C

K(1.8) - R

Pressure

atm x 14.69618 - psi

, Hg x 0.00131579 = atr

Mw Hg x 0.019337 - psi

g/sq cm x 0.00096784 - at.

g/sq cm x 0.0142234 = psi

bars x 0.98692 = atm

bare x 14.504 = psi

megabaryes x 1 - bars

W _as

grams (mass) x 0.002204622 - pounds (mass)

Length

centimeters x 0.393700 = inches

centimeters x 0.032808 - feet

Area

* square centimetors x 0.15590 - square inches

square centimeters x 0.0010764 - square feet

square feet x 1a4 square inches

8

TAJBIZ 1.2

(Concluded)

Viscosity

centipoises x 0.672 x 10O3 . lb./ft-sec

centistokes x 1.076 x 10-5 sq ft/eec

(kinematic viscosity) x(density) -(absolute) viscosity

Thermal Conductivi&

(cal/cu-sec-Gc) x 241.8588 -Btu/ft-.hr-F'

Velocity of Sound

(un/eec) x 3.28083 -ft/sec

Compressibility

(sq cm/dyne) x 1.01325 x 106 - at.1

(sq cm/dyie) x 6,8947 z~, =1Pal

k9

TA.BZ -1.2

(Coutinued)

Volume

cubic centimeters x 0.061023 cubic inches

cubic centimeters x 3.531445 •10-5 -mcubic feet

cubic Inches (U.S.) x 5.78704 x 10- cubic feet

Time

seconds/60 -' linutes

seconds/3600 - hours

seconds/86,IO0 - days

Force

dynes x 0.00101972 - grams (force)grams (force) x 0.0022046 2 - pound. (force)

Density and Specific Volume

(g/cu cm) x 62.43 - lb/cu ft

(cu cm/g) x 0.016018 - cu ft/lb

Surface Tension

(dynes/cm) x 6.8523 x 10-5 . lbf/ft

Thermodynamic Proper ties

(cal/g mole) x 1.8 - Btu/lb sole

(Cal/g mole- 4 x 1 - Btu/lb mole - R(Btu/lb mole)/mol. wt - Btu/lb

(Btu/lb mole- Rl/mI -a = - ,/lb-R

(Cal/g) x 1.8- Btu/lb

10

TABLE 1 .3

TIf • AUk1 tE CONVIMION

-49t. 0 0 1..0 50 t. 305 300 t. 1.90 w0 oco I00 3000 1. t19 1) . woo)4

C V C t C 9 -VC- T C V V

- mu --A" -17.3 oj 32.0 10.0 322.0 100*12 260 50 9356 IOUQ 0 043 316 1900 2712

-466 -4) .47.2 1 353.5 10.6 it 123.5 43 110 2)0 S"6 330 930 -A) 3010 1250 4) V,133,0 27W0411W *4449 -16.7 2] 35 6 11.3 12 123.6 %9 12" 2458 271 320 960 'A9 10231 351. W7 1120 2764157 -430 -31.1 3 37.4 11.7 9) 127.1. % 130 26k 177 530 9% l56 1. 03(2 3 6 53 1140 271,P

-51 -420 -15.6 .4 3912 12.1 329.2 10 1%0 251 252 %4 3001 "o4) 19" 11) 1.0 goo.

.41. .410 -33.0 5 41..0 12.4551 131.0 ".' 130 102 98 $5) 023 1 ¶456 t(0150 192 51.) 0 3 150 2W22-140 -400 -14.1. 1. 42.8 13). 9* IN2.@ 713 b 314120 29) 5W1.3040 713 1064W 391.0 5491%064 25140-234. -19W -0-9 7 4%.b 31).9 37 134.b 77 370 330 299 570 10)58 377 33rG17 39) 014 51.370 2"")-229 -140 -13.3 5 Io.k 4 9 1. 14,1 O5 16.1 35b ) 1% 0404 1076 W02 IooUj ,7 5N64) 3)500 2576-23) -170 -32.45 4 .6.2 31.0 "9 138.2 50 139 I7A 110 390 109 300 !-0I~ k 899 5 16390 2091.-410 -you6 -32.2 30 541.0 315.1. 60 140.0 93~ 2Q04)592 336 60)0 1112 4,0) 3300 0012 :471 34,434 2912

4312 -350 -331 3 1. 5 313. b16.3 1. 1%1.8 "9 210 41.0 121 6130 330 W99 3330 2010 .17 3610 29104801, -¶40 -31.1 30 33.6 36.7 b: 31%3.6 3120 2k2 1.41 317 624) 31%8 604 112o) 20)40 Pw0 31.2 291.

401 -330 .10.6 13 53.41. 7. 6 1.) 3.1. 01 220 %244 132 630 31111 630 3310 2064, OFF l360 29t4.

2.1340 .ttt,

-1"9 432 -130.0 14 37.2 17.5 64 Ik..2 330 18,6 3)0 610 1154 64 31.0 MOM W5 o 3602w-39 -130 -91A. 31 59.0 13.3 65 349.0 116 210 161 11. 6)0 1202 W13 1130 21 59 1630 3002

3.1 2 3:. -1-4 -300 -. 59 31 64. 13.9' 1. .1 2 0 152 11.9 660 1220 627 3360 920. 904 1 3660 )10•.67i3 5.41 -179 -294 -5.3) 37 2,. 39A 67 3i.6 27 260 500 154 670 12384 6)w 370 21)8 90 31.70 303,

2.22 1. 7. :,, -17, 4-7.75 IF 6%,1. 20.0 61.5 34.1. 3) 210 51635 60 6804 125b 635 3350 231.-, 931. 31,0 30565.705 3 9.1.)3 1 0.0 -31" -27) -4)9 - 7'. 19 16.1.2 0.6 b9 I3b.I 115 220 536 690 .274 1.3 3390 2371 921 690 1v713-14i 7 3'6 927 17 3924.41 5 3,:6 -31.5 -270 -454 - 6.67 20 65.0 23.3 70 355.0 3M 290 554 717 740- 1292 61.9 3200 2192 974))30925.001 9 36.2 - 1 .0 -41. - 6.3 11 2 1.9.A 23.7 71 159.8 1.9 N0 572 377 730 1)10 b54 3230 2230 9)2 3170 330

30 1.0 -17 4,50 -418 - 3.3b J2I 71.6 22.2 71 361.6 154 330 94 3342 720 13)2 660 3290 228 91s 3720 3120

3151 An43 -400 - 5.00 2) 73.1. 92.5 7) 16,.360 13201 600 303 730 13316 6(4. 13)0 2246 91.)37,10 31.%b-01.6 4)0 -34U - 4.4- 24 7-.2 2).) 741. 63.2 316 330 62b 19) 7%0 1)61. 673 32.0 24 919 37.0 31(1

-340 -220 -164 - Y"0952 77. 0 23.9 75 367.0 171 340 641. 3"' 750 IM 677 1250 12202 9)4 37150 3382-134 -230 -416 - 3.33 26 7".5 24.A 76 360A.04I 3 5710 662 404 7M 3400u 6W 12640 5300 9V-0 1760 3201)-329 -400 -m2 - 2.75 27 50. 6 25.0 77 17ft? 3)4. 36f) 600 1.10 770) 3435 6534 1270 2318 966 1774) 32318-320-1-3 -1" 30 - 2.0 24 2 .g4 33.1 75 172.4 158 370 60 1.1 750 31. 493 32310 336 971 13740 1923,4-10 -100 -82 - .1.67 29 .0 .3 2(,179 374.2 13) W 736b1.23 7) 31.54 69 3294 23)% 9',7 3790 1251

-112 -370 -274 -31.113"056.0 3b. 750 176."9990 7341.2P. 50031.72 704 310 0172 95233404)3272-307 -360 -M3 0.56 313 67.5 7.2 I 1 377.8 O01 4-00 7532 1.5U 130 31.9 730 3310 2190 955 3530 329-101 -1" -" a 32 5"9 7.0 52 179.6 3RIO430 770 453 820 3505 7(6 31 2G1.O "9 320 )300

- 95.6 -31.5 AM2 0.51. 33 91.1. U3. 33 3531.4 836 46" 75S 41.) 030 1356 721 13)30 0426 999 3530 1)31- 90.0 -130 -200 3.33 ¶4 93.3 53.98 51 3.8 523 40 0 19 54 1341 727 31%0 541. 3504 3 3111- "4.4 -130 -134 3.67 " .9 •.0 9.4 5" 35.0 327 41.0 524 1 M 3 7W2 130 *162 34)30 o 3062

- 79?-310 -366 2.32 36 96.5 0.0 36 3346.5 212 4" S4.240 660 OW 350 7V15 360 OW1.5 016 3540 )300- 73.5 -351 -146 8.75 37 95. W0.6 a7 365.6 232 44 560 466 570 15" 7431.3)70 2495 3023 157) 3395- 67.41 - "0 -130 3.3532 P 310.4- )33 (51. N 5" f4, 170 07" 471 NO 16316 74-9 13)0 25316 315 3540 IO 43A6- 62.v2-so -112 1.59 19 35.5 31.759 1".2. 949 We0096 1.77 "9a 3143 7.0 3590 8534 303s 3o90%345

-596.7 -70 - 94 4.4'A 1.0 304.6 U2.2 90 396.0 25 4" 90 1, 4W2 900 31.52 764 3400 2)52 1035 3900 3452

- 5I• . - to - 76 5.00 431 130.5 V2. 91 1".0 W3 90 3470 76 311 "70 104) 1930 31470--15.6 -5 -X1 -5.96 1. 307.6 33.3 " 2 197.6 49) 90 163 771 3420 53 1%9 3920- 10.0 - 1.0 - 40 6.13 4) 109.4 13.9 93 39.1 1.o930 370. 7 4340 2606 01 19") !306-3% ,-530 -32 6.67- ' 1137.1C 34.494 203.2 50 "017347523440 M4 100 19%0 3524-a.9 -,0 -1. 7.32 45 11.6 35.0 9 01.0 310 9503762730 964 3066 130 5542-23. -310 341 7.75 66 1134.5 •, "3.6 96 3s04.3 6 9" 1760 79)34 6010 073 3960 3535-17.6 0 32 0.33 47 316.6 76.3 97 1.6 522 970 1778 " 31.,70 3673 307 3570 3537

-. 39 42 117. 56.7 " W.4 W27 0 176 5ON 3400 6 1062 310 3396-. 1.4 49 320.3 -7.1 " .•0. 933 9. 1014 5 3 1." 9714 2731. 0 1"30 56361

10.50 -0 331.0 37.5 306 1132.0 5 vI 3N 03"0 03a "

11/12

SECTION 2: MN[SICO-VJIkICAL PWOPLU1TI

2.1 GD4E AL DElCRIPIION

Hydrogen peroxide is a chemical compound with the empirical formula

•20V Because of the compound's complete miscibility with water

above 32 Fs hydrogen peroxide is commercially available in aqueous

solutions at concentrations to -98 percent by weight 1202.

Propellant-grade hydrogen peroxide has generally been limited to

aqueous solutions 2 70 w/o B2 02 with regulation of the concentra-

tions and impurity levels of the more frequently applied propellant

grades by government procurement specifications.

Rydrogen peroxide and its aqueous solutions are water-like in

appearance in both the liquid and solid states. Although hydrogen

peroxide is generally considered odorless, the odor of high vapor

concentrations has been described as sweet and comparable to the

odor of weak concentrations of ozone and the halogens. Aqueous

hydrogen peroxide solutions are more dense, slightly more viscous,

and have higher boiling and lower freezing points than water.

Although hydrogen peroxide solutions are normally insensitive to

shock and impact and are nonflammable, they are active oxidizing

materials and can decompose exothermally to yield water and oxygen.

Because of their strong oxidizing nature and the liberation of

oxygen and heat during their decomposition, propellant-grade

solutions can initiate the vigorous combustion of many common

organic materials such as clothing, wood, wastes, etc. In the

absence of contamination, propellant-grade hydrogen peroxide

solutions are relatively stable (nominal decomposition rates are

0.1 percent per year) over ambient temperature ranges. However,

in the presence of higher temperatures and/or various contaminants

-'(including many inorganic materials), the decomposition rate is

13

drastically increased. Rapid decomposition ctu occur in situations

where extreme temperature levels and/or mass contamination are

present. As the decomposition rate increases, the attendant heat

release causes additional decomposition; this bootstrap effect

can lead to a runaway reaction.

Hydrogen peroxide is normally stored, shipped, and handled as a

liquid under its own vapor pressure with provisions for relief of

pressure buildup. When stored and/or transferred in clean, pass-

ivated, compatible systems by properly educated and trained person-

nel, hydrogen peroxide does not present a serious storage or

handling problem.

2.2 HMYSICAL PR0PkRTIES

A majority of the physical properties of propellant-grade solutions

of hydrogen peroxide have been experimentally characterized (or ana-

lytically extrapolated) with a reasonable degree of accuracy over

ambient temperature ranges. However, because of the i..creasing

decomposition rates of these propellant solutions with increase

in temperature, very few measurements have been conducted above

200 F. In addition, the accuracy of data is questionable in

temperature ranges where decomposition rates are relatively high.

This is evident in the discontinuity of some of the data at the

higher temperature ranges.

It should also be noted that the data reported for "pure" (or

100 W'/o) 11202 is questionable since there is some doubt as to the

existence of 11.0. concentrations above 99.7 to 99.8 v/o. Some of

the data reported for 100 w/o 1It0d were obtained by extrapolation

22of property data of IL20 2 solutions of low er concentration, wbile

other experimental Aneasurements reported on "100 w/o" It 02 ind.•-

cated propellant assays of "99+ percent," "99 ±0.5 percent," etc.

Even for most of those studies which report the HL,)0 concentrations,

161

the methods of determining these concentrations are not reported

or are based on an assumption e: purity related to the purifica-

tion technique.

--.Although it is suspected (because of discontinuities in the data)

.-,that many of the measurements on the "100 w/o" 1120 represent, in

reality, measurements on 20 2 of lower concentrations, p operties

are reported for 100 w/o ll.00 wherever an extrapolation (from

lower concentrations) seems reasonable. This characterizaLion is

of academic interest only because - 98 w/o H202 is the highest

concentration presently available commercially. Future aerospace

industry utilization of higher concentrations appears unlikely

because of practical and economical considerations.

Nominal values for physical property data that are recommended as

the most representative of the existing data are summarized for

the "100", 98, 95, 90, 75, and 70 w/o hydrogen peroxide grades

in Table 2.1. All of the data presented are diiect expcr;mei-.tal

determinations or are derived from curve-fits of the experimental

data, except for those data referenced with an asterisk; the data

referenced with an asterisk were a result of calculations made

during the referenced work and based on standard analytical cor-

relations and physical relationships. The absence of data on a

particular property is denoted by blank spaces in the tables.

Properties sor which property-temperature relationships have

been eatablished are noted in Table 2.1 with a figure or another

table number; the corresponding property-temperature relationships

are shown in Fig. 2.1 through 2.23aand Tables 2.2 through 2.17.

'The graphical illustrations represent either curve-fits of the best

available experimental data or analytical estimations of the

property; curve-fits of experimental data are noted with a solid

line, while a dashed line designates calculated data*. Equations

15

resulting from computer curve-fits of some of the data are

presented in attendant discussions.

The origin of the selected data is referenced in each table

and figure. A brief discussio. ;! the available data for

each property is presented in the following paragraphs.

2.2.1 General Identificatio

The physical classification3 under general identification

are those prolprties that are used to identify hydrogen

peroxide and its physical state.

2.2.1.1 Molecular Weight. The molecular weight of hydrogen peroxide

was experimentally determined by freezing point depression

(Ref. 2.1 and 2.2) and vapor density (Ref. 2.3) measurements.

The results of these studies are comparable to the value of

34.016 calculated from the International Atomic Weights.

The mole percent and apliarent molecular weight as a function

of weight pericent 11-0- for various aqueoun solutions of H0.v aS

shown iii Fig. 2.1, were calculated from the molecular weights

of 120 and 1202 based on the International Atomic Weights.

2.2.1.2 Freezing Point. The determination of freezing and melting

points of H20 2 -1 2 0 solutions is relatively difficult because

of the large degree of supercooling possible with these solu-

tiona. In addition, phase equilibrium measurements (Ref. 2.2)

have indicated that solid solutions are not formed in the

solidification of concentrated (greater than 65 w/o %202)

aqueous solutions of 1102; instead, the solid consists of

crystals of 1202 with occluded mother liquid. Thus, the

range of temperatures over which the material melts or freezes

is a function of the crystallization pattern of the P-202.

16

The freezing poirnt of "100 percent" 1t202 hau been reported as

-0..61 c (31.17 F), -0.43 C (31.23 '),and -0.41 C (31.26 F)

in Ref. 2.2, 2.4, and 2.5, respectively. Based on a reported

sample purity of 99.97 w/o Y202, the freezing point deter-

tination of Ref. 2.4 was selected as representative of 100

percent I2L2*. Meusurements of the freezing points of aqueous

solutions of ,1120 (Ref. 2.2) indicate eutectics at 45.2 w/o

11,02 and -52.4 C (-62.3 F), and at 60.2 w/o 11202 and -56.5 C

(-69.7 F). The results of these measurements, which are

graphically illustrated in Fig. 2.2 and 2.2a, represent the

temperatures at which 20 to 30 percent of thM liquid had

solidified. Experimental melting point otudies (Ref. 2.6),

based on observation of the temperature at which melting was

complete, resulted in slightly higher melting temperatures for

concentrations above 60 w/o ' 2 02 .

A variety of experimental studies have produced no signifi-

cantly effective freezing point depreasants for propellant-

grade L2 02 solutions. These studies, described in detail in

Ref. 2.3 and 2.6 through 2.9, have shown that many additives

will form, unstable or shock-sensitive mixtures with 1.02.

2.2.1.3 Triple Point. The triple point of 99.97 m/o H2 02 was estimated

am 272.74 K (-0.42 C or 31.24 F) from experimental heat of

fusion studies (Ref. 2.5). Although no vapor pressure

measurements have been made on solid H202, the vapor pres-

sure at the triple point has been calculated (Ref. 2.10) as

0.26 ma 1g (0.005 psia).

2.2.I.� �Normal Boiling -Point. The normal boiling points of propellant-

grade V202 solutions have not been experimentally determined

by conventional means since these points are in a tewperature

region where thermal decomposition of the %2 02 .is significant.

The normal boiling pints listed in Table 2.1 and Fig. 2.3

17

for prolellant-grade I.202-1•LO solutions represent extrapola-

tions of the vopor presoure data of Section 2.2.2.4 to 1

atmosphere of pressure. Other references (i.e., Ref. 2.11

and 2.12) give very similar boiling polats even though these

toeperatures were calculated from extrapolations of different

individual sets of vapor pressure data. The correlation of

these individual sets of data, which rebults in the newly

calculatLd normal boiling points, is discussed in Section

2.2.2..4.

2.2.1.5 Critical Properties. There has been no experimental deter-

imiuations of critical properties of H202 mince the compound

undergoes extensive decomposition before the critical tempera-

ture is achieved. However, because thim prorerty ia of academic

interest, the critical teanpcruture has been estimated by"assuming that the critical temperatur-o/boiling point ratio

of U202 is equal to that of water. Based on this technique,

a critical temperature (To) of 458.8 C (857.8 F) has been

rJeported for 100 w/o 11202 (Ref. 2.11); another Tc value of

457 C (855 1') for 100 w/o IL02. which was alluded to in

Itef. 2.12, was reported in Ref. 2.10. Using a vapor pres-

sure equation established in Ref. 2,12, the critical pressure,

Pc was calculated (Ref. 2.10) as 214 atmospheres (314.0 psia)

at the latter T

Using the estimated boiling point given in Table 2.1 and

correlation technique described above, a T. of 733 1K (460 C,

860 F) is recommended for 100 w/o K12 02 . An estimation

technique suggested in Ref. 2.12 (Pc/Tc is equivalent for

both "202 and IV12) resulted in a calculated and recommended

P of 247 atmospheres (3630 pain) for 100 w/o L202 using the

Te value of 733 K. Pseudocritical constants were calculated

for the propellant-gradc H202-IO solutions through the use

of Kay's method (Ref. 2.13); the results of these calcula-tions are shown in Table 2.1 and in Fig. 2.3.

18

2.2.2 Ihase Pr-operties

Those properties of hydrogen peroxide,whlch are associated with

one particular phase (either solid, liquid, or gas) have been

grouped as phase properties.

2.2.2.1 Density. A density of 1.70 ga/cc (106.76 lb/cu ft) was

computed for solid 100-percent H202 from X-ray diffruction

measureents (Ref. 2.14) at -20 C (_4 F). Density measure-

wents on 1V02-120 solutions during cooling and freezing

(Ref. 2.15) indicated that true solid solutions of H20Oand

1,20 were not formed; this was later verified in Rlef. 2.2.

Since the occlusion of the mother liquor occurred in freezing,

the measured densities were a function of the freezing

technique. however, it was noted (Ref. 2.15) that solutions

containing < 45 If/o 1202 expand during freezirg and solutions

> 65 w/o IV22 conraUct during freezing.

Expcrimental determinations of the liquid densities of various'..202-120 solutions were reported as a function of composition

in Ref. 2.6 (at 0 and 18 C), Ref. 2.15 (at 0 C), Ref. 2.16 (at

20 c), a"d Ref. 2.17 (at 0, 10, 25, 50, and 96 C). In addition,

experimental studies have determined the density of 90 w/o 1102

from 76 to 193 C (Ref. 2.18), and the density of 98 w/o 1,202

from 27 to 105 C (Ref. 2.19). The data frtm these six studies

were simultaneously curve fitted by a least-squares computer pro-

gram, a"d the following equation was found to adequately (actual

deviation for each experimental point was < 0.0022 gi/cc) describe

the data from 0 to 193 C (32 to 379 F) over a concentration range

of 60 to 1O0 W/o o202.

19

10(~' c -100479 +. 2.455 x 10-31 + 1.7831 x lO-W-6.76 ~

10- T(C)-2.4 X 1o-7I 2(-3.9 x l0-6T(,)

where W is weight percent U1 02 .

Converting to English units, this equation becomes:

P(lb/cu ft) m 66.166 +1.577 X 10-w + 1.112 x 10 -

2.31 10- 2 T -4.7 10- -1.638 X aO-N F)

The curves described by these equations are graphically illus-

trated for propellantý-grade lt202 solutions in Fig. 2.4 and

2.4a, respectively.

Experimental vapor density measurements (Ref. 2.3) at 92

C (165.6 F) showthat " 202 is not associated in the vapor

stat.c., If it is assumed that uo decomposition occurs, the

vupor ,ensity may be calculated through use of the perfect

gas law.

2.2.2.2 Coefficient of Thermal ltIansion. Using the curve fits of the

density data, the coefficients (cubical) of theiua! expansion

were calculated for propellant-grade I02-H1O solutions from

0 to 100 C (32 to 212 F) through the following relationship.

20

Curve fits of these calculations are presented in Fig. 2.5and 2.5a.

2.2.2.3 'Compressibility. The aidiabatic compressibilitiew of 1202

solutions were calculated (Ref. 2.16) from experimental density

and sonic velocity data covering a temperature range of 3.5

* -•to 33.5 C (38.3 to 92.3 F) and a concentration range of 0 to93.A m/o (9 to 96.5 w/o). These data were used to plot the

adiabatic compressibilities of propellant-grade H202 solutione

shown in Fig. 2.6 and 2°6a.

Although no experimental data have been reported on the isother-

nml compressibility of 11202, the adiabatic compressibility,

density, and heat capacity data were used to calculate (Rtef.2.16)

an isothermal compressibility of 26.514 x 10-12 cm2 /dyne

(26.865 x 10 - atm-1P 18.281 x 10-5 psia-1) for 100 w/o IR02

at 20 C (68 F).

2.2.2.!4 Vapor Pressure. The vapor pressure data resulting from four

different experimental measurements (Ref. 2.11, 2.12, 2.20,

and 2.21) on various aqueous solutions Cf "202 over temperature

ranges of 0 to 90 C (32 to 194 F) have been correlated. Using

a least squares curve-fit computer program, these data were

curve-fitted with the following equations (in the metric

Sys tem:

100 w/o PlO2 log P(m ) 8.92536-2482" 60- 5:T(K) T(K)

W8 w/o H20 log P(Mm HI 7.89728-1797.84 -134089T(K) T(K)2

21

, 95 wto "" log P(m ,a) -7.68235- 16 47.17 12S665W J... .~ ("g) •(K) T(K)

• .... "" • 2 og '(n fi) 7 729 -1606.47 =

w/o (H 0 0 7.67297 - ~ 176T(K) T(K)

75 w/o H ,) log P 7 3910886 _ 185863

ST(K) T(K)2

2.o W/o 120.2 Log P( 7.42560 - 135.O 18179

2(K) T (K)2

Converting these equations to English uniis resulted in the

following:

100 w/o 2%0 log 4468.68 79947

_______ 7.21175-T2lg _ T(R) T(R )2

98 0/0 1120 log 6(p.ia) 6.18367 3236.11 - 434448

T()(R)

95 w/o 10 100,l Pa 5.96874 2964.91 _ 501115g ( : a T ) 29- •o lo Pi-)T(R) T(R)

90 W/o H 0 log Pp - 5.95936 2891.65 510504

S(R) T(u)

75 w/o 11tt0 log P(psia) 5.67747 - 60() 2" (R) T(a1)

70 w•o log P(psia) 5.71199 2 L7.38 589026h0(R) T9R)2

The equations are illustrated graphically ini Fig. 2.7 and 2.7a,

where the data are extrapolated to temperatures above 90 C

(194 F) by assuming a linear relationship between the tempera-

tures for which 11202 solutions and water have the same vapor

pressures. These extrapolations were used to determine the

pseudo-boiling points (the temperatures where the pressures are

equivalent to 760 mm Hg) of the propellant-grade H1202 mixtures.

2.2.2.5 Vapor-Liquid Equilibrium. Vapor-liquid equilibrium compositions

of H2 02 -1120 solutions were determined experimentally in two dif-

ferent studies (Ref. 2.12 and 2.21). Although comparable, there

are slight differences in the data at some of the temperatures.

The data of Ref. 2.12 were used in Ref. 2.22 to plot vapor com-

position and vapor-liquid equilibrium, and to calculate and

plot activity coefficients for the system. These plots arc

shown in Fig. 2.8 through 2.10.

Calculations (Ref. 2.23) of saturation prensure, activity coef-

ficients, and.vapor compositions have been made for three dif-

ferent R202-H20 solutions (90, 81.5, and 65.4 w/o) at high

temperatures and pressures. The computation of these data,

which are shown in Table 2.2, are described in detail in Ref.

2.23. Although these computations were based on assumptions

of H202 critical constants that are different (critical tempera-

ture a 457 C., criti"al pree-Wire m21r% at+-espheret,,' +hk_ .'l~--... . ) * J

recommended in this handbook, corrections to Table 2.2 are slight.

2.2.2.6 Surface Tension. The surface tensions of H2 0 2-I12 0 solutions

have been experimentally determined (Ref. 2.24) as a function

of composition at 0 C (32 F) and 20 C (68 F). Graphical repre-

Fentations of the data are shown in Fig. 2.11 and 2.11a.

2.2.3 T~hermodynamic Properties

The H202 properties which define energy changes in the physical

transitions through the various solid, liquid, and gas states,

as well as in chemical changes, hove been listed under thermo-

dynamic properties.

2.2.3.1 Heat of Fopmation. The heats of formation (AYF) of propellant-

grade 1202 solutions were calculated in this study from heat of

dissociation data given In Ref. 2.25. Heat of fusion, heat of

vaporization, heat of mixing, and heat capacity data used to

characterize the heat of formation over & range of temperatures,

phases, and concentrations are given in subsequent sections.

Data for the aqueous solutions are presented as heats of forma-

tion of ti' solution (which includes the heat of formation con-

tributions of both H 0 and and the heat of mixing).2 H 1202, n h et fmxn)

The AHF data for the liquid and solid phases of propellant-

ghade H202 solutions are given in Tablcs 2.3 through 2.8 and

Fig. 2.12 and 2.12%. Figures 2.13 and 2.13a illustrate the

AHF of the liquid at 25 C (77 Fý as a function of composition.

The heats of formation of the vapor of propellant-grade H2 0 2-H2 0

solutions are given in Tables 2.9 through 2.14.

2.2.3.2 Heat of Fusion. The heats of fusion of propellant-grade H2 0 2

solutions were taken from the experimental studies of Ref. 2.2;

these data are shown in Tables 2.3 through 2,8 as the change in

enthalpy at the freezing point.

2.2.3.3 Heat of Vaporization. The experimental data, of Ref. 2.26 were

used to plot the heats of vaporization of H2 0 2-H 20 solutions

as a function of temperature; curve-fits of the data at 0, 25,

1,5, and 60 C (32, 77, 11%, and 140 F) are shown in. Fig. 2.14

24

and 2.14a. Heats of vaporization of propellant-grade H202

solutions at other temperatures can be obtained by computing

the difference in the heats of formtiou of the liquid (Tables

2.3 through 2.8) and vapor (Tables 2.9 through 2.14) phases of

the V 02,-H20 solutions at the corresponding temperatures and

11.0 conceptrations.

2.2.3.4. Heat of Sublimation. The heat of sublimation of 100 w/o H2 02

has been calculated (Ref. 2.10) from the heats of fusion and

vaporization as 457.8 cal/gm (824 Btu/lb).

2.2.3.5 Heat of Mixing. Graphical representations of the heats of mix-

ingof propellant-grade H20 2-H20 solutions, shown in Fig. 2.15

and 2.15a, were plotted from smoothed data given in Ref. 2.26.

AThese data represent experimental data of the referenced work,

previous experimental studies (Ref. 2.25), and their extrapola-

tion to higher temperatures for comparison with the experimental

data of Ref. 2.12. Excellent agreement is noted between the

data of Ref. 2.26 and Ref. 2.12 except in the 20 to 30 w/o

11202 concentration range.

2.2.3.6 Heat of Decomposition. The heats of decomposition, graphically

, epresented in Fig. 2.16 and 2.16a, were converted from smoothed

data from the experimental studies of Rqf. 2.25. The figur&s

illustrate the heats of dtcompasition of propellant-grade

H O -HO solutijns, wxiildecoaposition to either'liquid water

or, waer. vapor. ' K.::'

2.2.3.7 Heat Capacity. ' &The-hýt capacitieseof, solid and liquid- propellant-

grade H202-lH20 soluUoiiiasre' ahowjijn 'Tales 2.8 through 2.13

and in Fig. 2-17 and. I.t7a" from 0 to WOD o to 720 R). 'T.

p p. ..23

heat capacities of solid 11202 were taken from the data ofRef. 2.5. Since solid solutions of 11202 and 1100 are not formed

in the concentration region of interest, the heat capacities of

the'solid phases of propellant-grade H202-1120 solutions were

assumed to be the sum of the individual heat capacity contri-

butigns of solid 1120 and solid H202'

The liquid heat capacities were curve-fitted from the experi-

mental data of Ref. 2.25 and 2,26; these studies indicated that

the change in heat capacity of an H202-H20 solution of constant

composition over the indicated temperature range was of the order

of the accuracy of the experimental data. Experimental measure-

ments of liquid heat capacity were not conducted below 0 C

(32 F); therefore, the heat capacity was estimated in this re-

gion u3ing the heat capacity of supercooled H 0 and the extra-2

; ,polated heat capacity contribution of the 02.

During experimental heat transfer studies at: relatively high

temperatures (Ref. 2.18), the heat capacities of 90 w/o H2 02

were indirectly determined from heat transfer data over a tem-

perature range of 240 to 380 F. An equation was de'veloped forthe data which indicated an increasing deviation of the experi-

mental data from the curve fit of the data with increasing

temperature. The differences in these data from extrapolations

of the data presented in Fig. 2.17 and 2.17a, which are '0.0l

Btu/lb-F (cal/gm-C), ere assumed to be theresult of H2 0 de-

composition in the experimental study.

The heat capacities of the vapor phase of propellant-grade H2 02

solutions are given in Tables 2.9 through 2.14. The origin of

these data `is discussed in Section 2.2.3.9.

,0 2.2.3.8 Enthropy and Enthalpy. The entropy and enthalpy of the solid

and, liquid phases of propellant-grade H 0 solutions were cal-22

culated from the other thermodynamic functions given in Tables 2.3

10

2j

through 2.8. The basis for the vapor-phate entropy and entbalpy

data on propellant-grade H202 solutions, given in Tables 2.9

through 2,14 is discussed in 8ection 2.2.3.9.

2.2.3.9 Vapor-Phase Thermodjsnaic Properties. The thermodynamic proper-

ties of hydrogen peroxide vapor were calculated (Ref. 2.27) from

structural data. These data, which replaced earlier reported

data (Ref. 2.28), were based on new spectroscopic measurements

(Ref. 2.29) and new calorimetric data (Ref. 2.5 and 2.25). The

primary difference in the presently accepted values and those

reported earlier are in the internal rotation values.

The structural values used by Ref. 2.27 in the computation of

the vapor-phase thermodynamic properties, given in Tables 2.9

through 2.14, are:

r O-H - 0.965A U1 -3610 cm-1

r 0-0 - 1.49A U2 u135 0 cmu

f 0011 - 100 degrees 13 - 880 em-I

-lV = 95 degrees u 4 - 520 cm

IA n 2.785 x 10-40gm-cm2 U 5 m3610 ia-1

IB a 34.0 x 10 -0 gm-cm2 %6 -1266 cm-1

T .-c -- A40 2Ac - 33. AV gu m -M! 2

IRed - 0.696 .x 10-40 ao-cm2

2.2.1. Transport.]Properties

All properties of propellant-grade solut-.ons of V202 that in-

volve the transfer of mass or energy at I.he molecular level

aro presented in the following paragraphL•

27

2.2.4.1 Viscosity. Experimental determinations of the viscosity of

liquid H2 0 2 -YI0 solutions ranging in composition from 0 to

100 w/o !102, have been reported in Ref. 2.6 (0 and 18 C),

Ref. 2.24 (0 and 20 C), and Ref. 2.22 (0, 25, and 50 C). Curve-

fits of these data at 0, 20, 25, and 50 C (32, 68, 77, and 122 F)

are graphically illustrated as a function of w/o 1YO2 (from 50

to 100 w/o) in Fig. 2.18 and 2.18a. In addition, viscosity

measurements have been conducted on 98 w/o YlO 2 (Ref. 2.19) from

20 to 85 C (68 to 185 F) and on 90 w/o 11202 (Ref. 2.18) from

77 to 325 F (25 to 162.8 C). The data for 98 and 70 w/o 1'2

from the various sources has been plotted as a function of tem-

perature and compared to the viscosity of water in Fig. 2.19

and 2.19a.

The viscosity of the vapor phase of H202-I20 solutions at 1

atmosphere has been calculated (from experimentally determined

data) as reported in Ref. 2.30. An equation (Ref. 2.30) repre-

"senting these data from 100 to 300 C (212 to 540 F) with an

estimated precision of ±2 percent is given as:

$A (micropoises) - 134 + 0.35 [T W - 100] -14 Y

where

Y = mole fraction iiV 2 in vapor

This equation, comparing the vapor viscosity of water with 100

w/o H202, is graphically represented in Fig. 2.20.

2.2.4.2 Thermal Conductivity. Experimental measurements of the thermal

conductivity of H202-H20 solutions have been limited to leter-

minations (Ref. 2.22) on 98.2 w/o H1202 at 0 C (32 F) and 25 C

(77 F) and on 50 w/o 1Y02 at 25 C; resulting thermal conductiv-

ities were 0.321. 0.339, aud 0.347 Btu/hr-ft-F, respectively.

'2

Using the two experimcntal data points, the thermal conductivity

of 98.2 w/o H202 was extrapolated to the critical point (Ref.

2.31). This extrapolation, shown in Fig. 2.21, used I,20 a

reference substance and assumed no deromposition and a thermal

conductivity of 0.100 Btu/hr-ft-F at the critical point.

Experimental heat transfer studies (Ref. 2.19) indicated that

the estimated thermal conductivities reported in Ref. 2.31 agree

reasonably well with those calculated from the experimental heat

transfer data.

2.2.4.3 Coefficient of Diffusion. The experimental determination of the

diffusion coefficient of liquid 1202 into water has beer reported

(Ref. 2.32) for 0.17 w/o H2102 from 0 to 40 C (32 to 104 F) and

for 0.019, 1.44, and 7.92 w/o 11202 at 20 C (68 F). At 20 C

(68 F), the diffusion coefficients were <1.2 cm2/day for the

concentrations studied.

The diffupion coefficient of H202 vapor into air was experi-

mentally determined (Ref. 2.33) in a vertical tube as 0.188

cm2 /sec at 60 C (140 F) and 1-atmosphere pressure. This can

be compared to a diffusion coefficient of 0.320 cm2 /sec reported

(Ref. 2.34) for water vapor under identical conditions,

2.2.4.4 Sonic Velocity. The velocity of sound was experimentally

mea.ured (Ref. 2.16) in H202-H20 solutions from 3.'r to

33.5 C (38.3 to 92.3 F). These data are plotted for

propellant-grade 11202 solutions in Fig. 2.22 and 2.22a.

2.2.5 Electromagnetic Properties

The electrical, magnetic, and electromagnetic (optical) proper-

ties of H202 have been grouped as electromagnetic properties.

29

These properties generally are related to the electronic

structure of the atoms ia contrast to the transport properties

which involve only molecular movement.

2.2..5.1 Index of Refraction. The refractive indexes of 12024120 solu-

tions were experimentally determined (lRcf. 2.15) using the sodiuw

D line. The data for propellant-grade IO2 -11,0 solutions are

presented in Table 2.15 at 25 C (77 F) with a temperature cor-

rection guide.

2.2.5.2 Dipole Moment. Calculated dipole moments of 11202 were reported-18 .0

as 2.22 Debye (or 2.22 x 10- esu-cm) and 2.05 Debye in Ref.

2.35 and 2.36, respectively. In addition, a value of 2.26 Debye

was estimated (Ref. 2.37) from the Stark effect, and a value

of 2.13 Debye was determined (Ref. 2.38) foor 1k202 in dioxane.

The latter value was selected as the representative dipole

moment for !t202.

2.2,5.3 Dielectric Constant. Figures 2.23 and 2.23a show the dielectric

constants of propellant-grade It202-1120 solutions as a function

of temperature. These data were interpolated from the experi-

mental studies reported in Ref. 2.39, in which the dielectric

constskzts were determined as a iunction of composition at con-

stant temperatures from -40 to 30 C (-40 to 86 F). because

of the supercooling of the !1202-4120 solutions, measurements

were obtained on the liquid below the freezing point. The data

from the measurements on 100 w/o It202 were curve-fitted from

-60 to 30 C (-76 to 86 F) to the following equation (Ref. 2.40):

C - 84.2 - o.b2 T(C) + o.0o32T (C) 2

30

2.2,.5. Electrical Conductivity. The conductivity of "pure" 12% has

been reported by several investigators with values ranging from

2 to 0.39 micromhos (microolus-I ). Experimental studies (Ref.

2.41) of the (.inductivity of unstabilized i1,02 were coiducted as

a possible means of determining its purity. The results of this

study are summarized as follows:

1. Fractional crystallization reduced the conductivity of

commercial 90 W/o 1"02 (11.5 microolums- at 25 C) to

approximately one-half (5.0 microohms at 25 C) of

its initial value, while increasing its concentration

to 98.tw/o 1120

2. Distillation of the crystallized 11,0, reduced its

specific conductance to --Q microlhos. This value com-

pared with that reported in earlier studies (Ref. 2.42).

3. A second distillation of the crystallized and once-

distilled H202 reduced its specific conductance to

1.2 micromhos; this value was still greater than that

reported in Ref. 2.43 and 2.44.

4. The specific conductance of both 98 w/o 1202 and de-

ionized water increased on storage in contact with

Pyrex glass. A conclusion of these studies indicated

that only a rough correlation between low electrical

conductivity and high stah•bi ty wAs found (or th-•t

electrical conductivity per se is not a reliable in-

dicator of stability).

The electrical conductivity of both water and hydrogen peroxide

is increased by the addition of one to the other.

2.2.5.5 Magnetic-Optic Rotation (Verdet Constant). Although not op-

tically active, 1202, when placed in a magnetic field, will

31

-L .polarized light. This is expressed as:

C " k tH

whlere

Ot - degie.. of rotation

S- path length

ii - field strength

k - Verdet constantV

The Verdet constant, ku, as reported in Ref. 2.15 at 10 C (50 F),

is shown for various "202-H,20 solutions in Table 2.16.

2.2,5.b Magnetic Susceptibility. Hydrogen peroixide is diamagnetic.

The magnetic suaceptibility of liquid 1202 has been summarized

in Ref. 2.10.

Values of -).73 X 10-6 cgs-emu/cc at 10 C, -0.50 x 10-6 cgs-emu/g,

-17 x 10-6 cgs-emu/g mol, and 0.9999909 are reported for the

volume susceptibility (K), mass susceptibility (x ), molar sus-

ceptibility (Xm), and permoability (P), respectively. In addi-

Lion, at, equuuLion~ux, ~ ia "ri j aawo e. .aj 1 a-.

solutions at 10 C (50 F) is given as:

X 10 6 -0.720 * 0,218wg

wiscre

w- weight fraction H2 0 2

The susceptibility of the solid becomes more poiitive upon

freezing, while the susceptibility of the vapor is a#sumed to

be the same as the liquid.

sam a ,,q ,. ...

2.2.5.7 Other Molecular and Electromagnetic Properties. A number of

miscellaneous molecular and electromagnetic properties have

been summarized for H202 in Table 2.17. The origin of these

data is referenced in the table.

2.2.6 Structure and SpectrA

The equilibrium geometry of hydrogen peroxide was established

by an electron diffraction study (Ref. 2.48). This was sup-

ported by an X-ray study (Ref. 2.14) with limited least-squares

data reduction, an infrared study (Ref. 2.49 and 2.50), and a

microwave study (Ref. 2.37 and 2.51). The results of these

studies are summarized in Table 2.18. The infrared study may

be regarded as definitive, although the structure of the solid,

as determined by X-ray, may be appreciably different from the

gas phase. The X-ray study may be questioned, however, because

the data analysis used visual intensity estimation and primitive

nuirerical machines. The rotational constants measured in the infra--1-1 -1red are A' - 10.356 cm-1 B' = 0.8656 cm , C' - 0.8270 cm

Dj 4•.5 n 10-6 cm , DK K 7.5 x 10-4 cm- , and DJK - -2 x 10-5J--1

cm Dipole moments of 3.15 ±0.05 D and 3.24 ±0.05 D were

measured (Ref. 2.51) for each of the two potential minims. A

far infrared study (Ref. 2.50) showed the angle T has two

equilibrium values (with the lowest at 111.5 degrees ±0.5) and

determined an accurate hindered-rotation potential function.

The best geometric parameters are those underlined in Table 2.18.

Hydrogen peroxide forms tetragonal crystals, space group

D4 - P4 12 1, upon freezing (Ref. 2.14). There are four molecules

in the unit cell of dimensions a - 4.061 and c = 8.001 The

crystal structure has been comfpletely determined, and the vol-

ume of the unit cell is 131-9A3 (Ref. 2,14). This gives a crystal

density of 1.70 &M/cc.

33

Hydrogen peroxide is the simplest molecule having an internal

rotation motion, and, therefore, has hod fairly extens.ve study

'with respect to absorption spectra. Hindered internal rotib-

tion effects are observed in all regiuns of the spectrum.

Extensive studies have been conducted on the vapor, the crystal-

line solid, and dilute solutions. Less work has been spent

on the concentrated liquid 6olutions, because of decompooition

effects and t02 diffic"lty in fiuding suitable window materials.

Since the 6pectrum as a whole is very complicated, it is con-

sidered beyond the scope of this handbook; thus, references to

H2 02 spectrum characterization are provided as a guide for

interested ind-viduals.

The infrared absorption by 1202 is not very useful for chemical

analysis because the spectrum is quite similar to that of water

and since suitable window materials are not widely available.

Ultraviolet absorption by K202 is quite sti'ong, and (although

Beer's law does not hold strictly) if the solution is clear and

transparent to ultraviolet, direct spectrophotometry measure-

ments are suitable for analysis of dilute solutions. The

ultraviolet spectrum of concentrated hydrogen peroxide has

been reported for 50 and 90 w/o solutions in Ref. 2.39, and

for 55 and 99 w/o hydrogen peroxide solutions in Ref. 2.24.

The infrared absorption spectrum of H102 has been reported in

Rei. 2.50, 2.52, and 2.53. The Raman spectrum of concentrated

hydrogen peroxide (99+ percent) is probably covered best in

Ref. 2.39.

S2 3 C_•fICAL PROPERTIES

Hydrogen peroxide is a strong oxidizing agent in either acid

or alkaline solutions; however, with a very strong oxidizing

agent such as MnO, it will also behave as a reducing agent.

Hydrogen ion concentration (pH), tCe presence and nature of

catalysts, and temperature are important controlling parameters

in hydrogen peroxide reactions. By proper choice of reaction

conditions, it is possible to modify the oxidizing action of

concentrated hydrogen peroxide solutions. As an oxidizing agent,

hydrogen peroxide has the distinct advantage of producing only

water as a by-product. Hydrogen peroxide also forms simple

addition complexes, forming compounds similar to hydrates. These

compounds are normally called hydroperoxidates. These are gen-

erally accepted as hydrogen-bonded compounds, which are analogous

to anion water compounds. Hydroperoxidates are readily formed

with highly electronegative atoms such as nitrogen, oxygen, and

fluorine. Amino groups form stronger bonds with peroxide than

carboxyl or hydroxyl groups.

Compilations of typical hydrogen per,,xide reactions have been

reported in Ref. 2.10 and 2.55. These compilations were com-

bined and are presented in Table 2.19 along with references

to the original work.

2.4 SOLUBILITY AND MISCIBILIT11

Because of hydrigen peroxide's chemical and thermodynamic

activity (as noted in Section 2.3), precautions should be ob-

served when considering solutions of H202 with various organic

and inorganic compounds. Although violent reactions upon mix-

ing are the exception, such reactiors have beei, observed. Ma.y

H202 solutions may be fairly stable whern undisturbed but are

subject to violent detonation under certain conditions. The

addition of any materzal which may be oxidized or reduced should

be suspect, particularly as the relative concentrations approach

stoichiometric proportions. For theae reasons, it is suggested

that appropriate references be consulted in detail to define the

35

chemical nature of the proposed solution as well as the solu-

bility of the solute before solutions of H2 0 2 with other mater-

ials are attempted.

The solubility and miscibility of hydrogen peroxide and its

aqueous solutions with a number of organic and inorganic com-

pounds are referenced in detail in Ref. 2.10. In general, con-

centrated H 202 solutions a•'e completely miscible with most or-

ganic liquids (including ethanol, isopropanol, acetone, ethyl

cellosolve, pyridine, etc.) that are miscible with water in

all proportions. In addition, hydrogen peroxide is more mis-

cible than water in a number of organic materials, such as

methyl methacrylate, dimethyl and diethyl phthalate, ethyl

acetate, and aniline. Compounds with which hydrogen peroxide

is nearly immiscible include petroleum ether, toluene, styrene,

carbon tetrachloride, chloroform, kerosene, fuel oil, and

gasoline.

Hydrogen peroxide and its aqueous solutions also possess, in

general, solvent or solute relAtionships thet are similar to

water. The results of several experiments show that sodium

fluoride, potassium nitrate, various potassium or sodium phus-

phates, potassium chloride, aad sodium or potassium sulfate are

more soluble in H1202 than in water. Sodium nitrate, sodium

chloride, silver nitrate, lead nitrate, and lithium nitrate

and sulfate are less soluble in H202 than in water. Chlorine

and iodine are only slightly soluble in anhydrous H2 02

in consideration of the m-ate rai n-oIpAi. I•t.es of various

lubricants with H2202, the solubilities of several organic com-

pounds in propellant-grade H 202 are discussed in Table k.14a,

Section 4

36

2.5 GELATION

Results of gel studies on hydrogen peroxide are given in detail

in Ref. 2.99 and 2.100.

2.6 HEAT TRANSFER PR0PERTIES

Since heat transfer involves a combination of phase, thermo-

dynamic, and transport properties, as well as some consideration

of chemical kiaetics, this section on heat transfer propertieshas been included as part of the physico-chcmical properties.

This section is designed as a reference guide and summary of

the various experimental heat transfer studies that have been

conducted on propellant-grade hydrogen peroxide solutions.

Experimental heat transfer studies on 90 w/o H1202 solutions

(reported in Ref. 2.101) indicated that a high flux heat transfer,

usually associated with boiling, was obtained from a 347 stainless-

steel surface to liquid 90 w/o H1202 as a result of the H2 02 de-

composition mechanism. This decomposition,' which simulates

boiling by the liberation of gas bubbles at the heat transfer

surface, is accelerated with temperature increate of the sur-

face. Figure 2.24 illustrates the magnitude of this effect, as

well as the lesser effect of pressure and liquid temperature,

in terms of heat flux. Because of these effects, the study

showed that the temperature difference between the surface and

liquid was not significant.

An extension of these studies to high fluid velocities and

moderately high temperature differences was reported in Ref.

2.102. At high flowrates and high Reynolds numbers (where

decomposition is limited by the short liquid residence time),

the resultant heat transfer data agreed with that expected for

37

"7 forced convective heat transfer. It was found that heat fluxes

its high as 11.75 Btu/sq in.-sec (at liquid velocities of - 80

ft/sec) could be obtained with 90 w/o 11202 without complication

by decomposition of the hydrogen peroxide. A least-squares fit

of the heat transfer data obtained on 90 w/o 11202 resulted in

the following expression:

(N )f - 0.0287 (N~ 0e'f0(Nr) 1/3

The standurd deviation of the experimental data from this equa-

tion was 10.2 percent.

Heat transfer studies in the forced convective region of both

90 w/o and 98 w/o H202 were reported in Ref. 2.103. Peak heat

fiutes of 7.80 Btu/sq in.-sec were measured for 90 w/o H1202

at fluid velocities of 41.3 ft/sec. The results ottained for

peak heat flux of 98 w/o H202 at the conditions investigated

are sbown in Fig. 2.25. The correlation of the dat& cn 98 w/o

H202 with the Dittus-Boelter, Colburn, and Sieder-Tate equa-

tions (Fig. 2.26 through 2.28, respectively) indicated better

agreement of the data with the Dittus-Bcelter relationship.

It has been suggested, however, that somc: of the apparently

low heat transfer coefficients, indicated by the correlations

of Fig. 2.26 through 2.28, may be due to slight scaling (oxida-

tion) of heat transfer surfacea.

A current study on the use of 98 w/- hydrogen peroxide for re-venerativelv cooled rocket chgs '"a6 reported eeng ----- --

that during 18 experimental tests (with fluid velocities from

25 to 198 ft/sec, pressures from 2000 to 4700 paia, and feed

"temperatures from 60 to 240 F), heat fluxes uý, to 48.2 Btu/sq

in.-sec were achlieved. It was found that the heat flux at

"burnout (under the conditions tested) was directly proportional

38

to the fluid velocity by the relationship: heat flux -

0.21 x velocity. These results indicated good correlation Gf

heat ilux and fluid velocity with the studies of Ref. 2.102 and

2.103. During these tests, no appreciable difference in heat

transfer could be associated with feed temperature, and no

detectable decomposition was evident. Four similar tests with

90 w/o hydrogen peroxide indicated no discernible differences

from the results of the 98 w/'o hydrogen peroxide tests. As in

the studies of Ref. 2.103, the Dittus-Boelter correlation wab

found to represent the data more closely than either the Colburn

or Sieder-Tate relationships.

The results of all of these studies have shown that hydrogen

peroxide has eoolast properties comparable to those of water.

Of course, the difficulty in its use a3 a regenerative coolant

lies in the limited stability of the 11202 at higher temperatures.

As a result, various bulk liquid temperature limits have been

suggested and established in the use of H202 as a regenerative

coolant. These limits range from established (Ref. 2.105) maxi-

mum allowable temperatures of 225 F (with a 105 F rise over

inlet temperature) to suggested operating limits (Ref. 2.106)

of 250 F (with red line conditions at 275 F). More detailed

analysis of minimum safe design criteria of H202 regenerative-

cooling systems, based on the assailable data from various sources,

is presented in terms of ultimate heat flux and fluid velocity

in Ref. 2.107. Additional analysis of transient heat transfer

for an H 202 regeneritively cooled engine modal are given in

Ref. 2.108.

2.7 IGNITION CKLRACTERISTICS

Although ignition characteristics are system-related parameters,

they are also a direct indication of chemical reactivity and/or

stability. As such, these characteristics have been included

as a part of the Physico-Chemical Properties Section of this

39

handbook. Hlowevcr, because a detailed characterizatior of

these parameters would involve a discussion of system design

variables (such as configuration, intended use environment,

operating sequence, etc.) that are beyond the intended scope

of this handbook, this review of hydrogen peroxide ignition

characteristics is limited to a general and brief summary and

reference guide to various ignition studies previously con-

ducted. In addition, this summary is limited further by the

security classification of many of these studies as opposed

to the unclassified nature of this handbook. For the purpose

of clarity, the characterization of hydrogen peroxide ignition

is 'presented in terms of its two primary application areas:

monopropellant systems and bipropellant systems.

2.7.1 Monopropellant Systems

Studies of the controlled decomposition process, that .,haracterize

hydrogen peroxide's use as a monopropellant, are given ii

Section 7.2. As a result of these studies, which are detailed

and referenced in Section 7.2,the initiation period for hydrogen

peroxide decomposition in a monopropellant cha.iber are fairly

well-defined for all propellant-grade concentrations. As ex-

pected, all the studies demonstrate the effect of i.any variables,

such as the initiating source and type (catalyst or thermal bed),

injection -technique, chamber configuration, hydrogen peroxide

concentration$ hydrogen peroxide inlet temperature, initial

chamber temperature, exit pressuje, etc., on the start tr.ansient.

(The start transient is defined in these efforts as the time

period from injection of hydrogen peroxide into the decomposition

chamber to the achievement of 90-percent of the operating

chamber pressure.)

In general, the start transient for a hydrogen peroxide catalytic

monopropellant decomposition chamber normally ranges fromi 50

to 15C ms. This start transient is typical of all of the

4o

catalysts used in the decomposition of hydrogen peroxide

concentrations ranging from 76 w/o (Ref. 2.109) to 98 w/o

(Ref. 2.18, 2.110 and 2.111).

The greatest effect on this typical rtkrt transient is causedby variation in the hydrogen peroi•ide and/or catalyst bedtemperature. Laboratory studic6 (Ref. 2.41) have demonstratedthe lach of reaction between solid or super-cooled hydrogen

peroxide and a typical catalytic material, while studies with act-

ual engine catalyst beds (Itef. 2.110) have shown limited initia-tion of decomposition and excessive start transient periodswhen the temperature approaches the propellant's freezing point.Ilowever, the low temperature start characteristica of variouscatalyst beds have been improved through special design of thecatalyst chtaber and special treatmont of the catalyst bed(Ref. 2.18, 2.110, and 2.111). Conversely, an increase in propel-lant or caitalyst bed tempera ure (such as experienced in pulsingor other heat feedback operations) has resulted in start transientsas low as 10 ms (Ref. 2.18, 2.104, 2.109, 2.110, and 2.111).

Although exit pressure has a slight effect on the start tra.'sient,this effect is usually within the ranges noted above and con-trolled by the temperature effects. 0f course the start trtkn-sients are affected by the catalyst life and generally are thebest indication of the decline in catalytic effectiveness.

The start transients in a hydrogc-xa peroxide thermal docomposi-tion chamber are entirely related to the tech"ique rnd con-figuration employed. Since this concept depends on the initialheating of a thermal pack (see Section 7.2.2) prior to injectionof the hydrogen peroxide, the start transient of the main hydrogenperorxide stream should approach the hot bed start transients(- 10 me) noted above. However, studies with botl, 90 w./o( .ef. 2.18) and 98 w/o (Ref. 2.113) have indicate.d that ade-quate heating of the thermal pack may require periods ranging

500 mw to several minutes depending on the technique employed.

Ibpergolic slugs of Ihydrazine containing mixed cyanide salts

(Ref. 2.18) have produced initial start transients (i.e., the

period measured from injection of the hypergol) of 10 to 20 me,

but this technique required 300 ms hydrogen peroxide leads and

500 ma hypergol injection periods.

2.7.2 biipropellant Systte•e

Although some studies have indicated that 90 w/o and 98 w/o

hydrogen peroxide solutions are hypergolic (i.e., ignites

without producing damaging overpressures to the system) Ifihl

the hydrazine and 50 w/o N211 4•-50 w/o (CII 3 )2 2N fuels (Ief. 2.111),

other studies (RIef. 2.18) have indicated that the hypergolicity

of' 90 w/o hydrogen perioxide with both hydrazine mid (CII 3)qN21I 0

is questionable. Ignition delays (e.g., the time period from

injection of the second propellant into the combustion chamber

to 90 percent of the designed chamber pressure) of - 5 to 25 ws

2ere reported for 2[ 2 0N2l 4A systems in Ref. 2.111; however,

large overpressures (e.g., the peak pressure to chamber pressure

ratio) and erratic chamber pressure fluctuations were demon-

strated in these systems. In the studies reported in Ref. 2.18,

which d,'monstrated ignition delays for this system of 10 to

109 mB (with average delays of 35 to 52 ms recorded for various

mixture ratios), it was concluded that hypergolicity was marginal

and unreliable.

As a result of these mid similar studies of other hydrogen

peroxide bipropellant systems, including the H2202/C11 N2113

(Ref. 2.111) and U)02/BJ19 (Ref. 2.113) systems, it is con-

eluded that the hypergolicity of hydrogen peroxide with various

fuels is, at best, marginal. For this reason many hydrogen

peroxide bipropellant systems utilize hydrogen peroxide de-

composition gases (resulting from injection of the hydrogen

42

peroxide in a catalyst chamber upstream of the main combustion

chamber) as the ignition source. Through the use of this con-

cept, succesaful system ignition haa been demonstrated with

various liquid (including those noted above, as well as with

JP-5 in the AR-2 system), solid (Ref. 2,11) and heterogeneous

(Ref. 2.104) fuels. Ignition delays between the hot decomposi-

tion gases mid the fuels are minimal (5 to 10 ms), althiugh the

system design controls the overall start transient period (i~e.,

from injection of the hydrogen peroxide into the catalyst chamber

to the achievement of main chamber combu tion). Manty system

designs employ only a small "pilot light" catalyst chamber with

subsequent main stream liquid injection (which bypasses the

catalyst chamber), while other systems utilize prior decomposi-

tion of all of the hydrogen peroxide throughout the operation

of the bipropellant system.

The use of hypergols in the ignition of hydrogen peroxide-

oxidized bipropellant systems has been studied (Ref. 2.18)

with the hydrazine, (C11 3 )2N212 (UDMI), and JP-5 fuels. In

these studies, which were designed to demonstrate the feasibility

of direct liquid inj2ction of 90-percent hydrogen peroxide into

bipropellant chambers, relatively smooth and rapid igni-ýion was

achieved with all three fuels using nitrogen tetroxide as the

hyjergol for the first two tuels and aluminum triethyl with

the J.atter fuel. In addition, the use of mixed cyanide salts

as an ignition aid to the 1lV2/IN 21A system is noted in Ref. 2.18.

43

2.8 iUa'U"CJI

2.1 Giguere, 1'. A. and 0. HMass, "Solid Solutions of Hydrogen Peroxide

and Wtex , " Can. J. Rx., 18B, 66-73, (1940).

2.2 Foley, W. T. and 1. A. Giiguere, "bydrogen Peroxide and Its Analogues.

I1. Phaise Equilibrium in the System Hydrogen Peroxide-hWater, Can.

J. Chem., 29, 123-32 (1951).

2.3 Matheson, G. L. and 0. Mauss, "Properties of Pure Hydrogen Peroxide.

Vl.,"J. Am. Chem. Soc., :L, 671-87 (1929).

2.4 Socco, E. A., Ph.D. Thesis, Laval University, Quebec, Canada, 1953.

2.5 Giguere, P. A., I. D. Li", J. S. Dugdale, and J. A. Morrison,

"Hydrogen Peroxide- the Low-Temmerature Bleat Capacity of the Solid

and Third-Law LEtropy," Can. J. Chiem. 32, 117-28 (1954).

2.0 Haass, 0. and IV. I1. hatcher, "Properties of Pure hydrogen Peroxide.

III," J. Am. Chem. Soc. , 44, 2172--80 (1922).

2.7 QFR-LU-15 and 19, Flreezir Point, Depressants for I &J,1"1C Corpora-

tion, Buffalo, New York, CcitraAt 110a(s) 53-10341-c, 1963.

S2.8 RU-E2, Development of Freezing Point Depressants for 90% llydrogen

Peroxide, INMC Coiporation, Buffalo, New York, Contract NOa(s)-52-

779-c, 1954.

2.9 111-78, Part I, Final Report, Low Freezing llydrogen Peroxide-Based

Propellants and Oxidants, FMC Corporation, Buffalo, New York,

Contract NOa(s)-53-103'i-e.

2.10 Schumb, W. C. , C. N. Satterfield, and It. L. 1Wentworth, lydrogeni

Peroxide, A.C.S. Monograph 128, lReinhold iPub1i -hir-g Corp'ratioe" ,

New York, New York, 1955.

2.11 Maass, 0. and P. G. Iliebert, "The Properties of Pure ltydrogen

Peroxide. V. Vapor Pressure," J. Am. Clihem. Soc., (_., 2693-2700

(192,).

1

2N12 Scatc hard , i. , G. M. liavantigh, and L. 11. 'Ti chi)or, " Vajlm -Li qtd d

lKlu Ilbri mu. VI. llydroreix Peruxidd-Water Nix , J. Antes. Chem.

Soc._, 71, 3715-20 (195'-').

2.13 Kay, W. 13. , "D)ensity of Hydrocarbon Gases and Vapors at High Tempera-

ture and Pressure," Industrial and Elginaering Chemistry, =28, 10 1h

(1936).

2.14 Abruhwanw, S. C., It. L. Collin, and W. N. Lipscomb, "The Crystal

Structure of Hydrogen Peroxide," Acta Cryst. , L, 15-20 (1951).

2.15 Giguere, P. A. an1 Pierre Geoff'i on, ':Changes of Densi ty of Hydrogen

Peroxide Solutions on tooling and Freezing," Can. J. Research, 28D,

599-607 (1930).

2.16 Paljousek, D. , "lntermolecular Interaction in Liquids. I. Adiabatic

Compressibility and Structure in the System Hydrogen Peroxide- L•er,"

Chem. list, 519, 1781-b (1957).

2.17 Ea~ton, H. 1". , A. G. Mitchell, and W. F. K. Wynne-Jones, "Beha¢i or

of Mixtures of Hydrogen Peroxide and Water. I. Determination of the

Densities of Mixtures of Hydrogen Peroxide and Water," Trans.

Faraday Soc. , _48, 796-801 (1952).2. 18 R-2094i, Suutnry I )ort, Itemorchx Program on 11.0 Itocketdyne, a

Division of Northl, Aniir- can Aviation, -Ic., Cao... P'ark, CaUifornia,

1 Mbarch 1960, CONFID'l)U'I'1AL. 4

2.19 ANUI'L-TR-66-6, Final leport, Advanced Propellant Staged Combustion

Feasibility Program, Phase I, Part 2, Aerojet-General Corporation,

Sacramento, California, Aqpril 1966, CONFIDEWrlAL.

2.20 Egerton, A. C., W. bute, and G. J. Rinkoff, "Some Properties of

Organic Peroxides," Discussions.FpA rady Society, 1951 (10),

278-82 (1951).

2.21 Giguere, P. A. and 0. Maass, "Vapor Pressures and Boiling Points

of Binary Mixtures of Hydrogen Peroxide and Water," Can. J. tesearch,

18B, 181-93 (19•,0).

45

2.'22 bulletin No. 07, lb"iyrozzc9 Peroxide J)hysical Pioi~ertius Dataibook,

F'MC Corporation, Buffalo, Nov York, 1953.

2.23 290-63, !Iydroueni lPeroxide DeIkcomposition. I, Shell Developmonl

C 'oiany, Hlaeryvi 1 le, Ca li fornia, January 1961j.

2. 2. Phibbs, M. K. and 1. A. (iiguere, "Hlydrogena Pe'roxide and Its Anlalogues.

I. Density, leflrac'tive Index, Viscosity, and Surface Teision of

D)cuteriumn Peroxide-Deuterium Oxide Solutionts," Can. J. Chlm., 2:,

173-31 (195).

2.25 Giguere, P. A. , D. (i. Moriamette, A. W. Ohnos, and 0. Knop, "Hlydrogen

Peroxide and Its Atialoguges. VII," Can. J. Chem. , 22, 8014 (1955).

"2.26 Giguere, P. A. and J. L. Carmichael , "Heat Capacities for tile Water-

1202 Sypite.m letween 25 and 60'," J. Chem. ln DAta, 7, 1t. 1,

526-7 (196:2).

2.1' • iguere, 1'. A. mnd I. 1). Liu, "Iteconunrended Values for the Therwody-

numic Plopertiem of Hiydrxogen and lDeutcritun Peroxides ," J. Am. Chem.Soc_. , 77, 0,77-9) (1955).

2.28 Giguere, 1'. A., "The Thermodynamic Iuuicctiomos o; llydrogen Peroxide,"

, Call, J. .Ites. , '-) Is=.= ), 18 - 91 (19w 0)

)~.09 Giguere, 1'. A. and Osias Bain, "Force Constants in Hydrogen andDeuter'i a 'er'oxidem , --1 J.)f' .h s Ae .,ýl 1 -

2.30 Satterti,-IJ, C;. N. , It. L,. Wlentworlh0, and s. T'. Deuletrilidem, "Visc:onity

of Vapor' Mixtures of' Hydrogcen JPtroxi do and hsater, " J. Arm. Chem. Soc.

2.31 Private coumunmication, L,. It. D~ier-doa'f, FMHC Coriporatioll, toM. T. CotnuIaittire, IRocketdyne, December 1960.

32 Stern, K. (. , Bericht., 60, 54'7 (1933), us given by ]tef. 2.22.

2.33 McM-uxtrie, It. L. and I'. G. Keyes, J. Am. Chow. Soc., 70, 3755 (191.8),

us given by Ref. 2.22.

2.31, Montgomer'y, It. B., J. -eteorclogy, L_, 193 (19117), It given by

lief. 2.2:2.

46

2.39 J.tkar, 8. K. K., "lipole HoJ•wutm of V'olyatowic Muleculue," N4ture,

._.2., 316-17 (19••1').

2.36 Amako, Y. and 1'. A. Giguicx, "Cialculation of thie 11,04 Holeculu by

the IAAO-HO-SCI" Method," Cun. J. Chem., 1hO, 765-7/1 (1962).

2.37 Maissey, J. T. and I). It. Bianco, "lhe Mic(owlave Spectrum of Hydrogen

Peroxide," J. Chew. Phy". 2, .il12-4 (1954)

"2.38 Linton, C. 1. and 0. Mutian, "The Electric Hoiment of Hydrogen Peroxide,"

Can. J. JResearch, I, 81-5 (1932).

2.39 Gross, PChM. , Jr.nud It. C. Taylor, "The Dielectric Conztaitv of

Water, hlydrogen Peroxide, and Hydrogen Peroxide-Wavt'or Mixt'areu"

J. Am. Che-. See., 7•2, 2075-80 (1950).

2.40 Talut-Erben, "Tihe ielectric Conotant of Pure Hlydrogen Peroxide aU

a 'unction of Temperature," Bull. Soc. Chim. Fraule, 1ý2, 176 (1952).)

2.ItI A}UP'L-TI--66-13, Final ltelort Itedearch on the Stabi lity of Ifigh Strength

10,00 E. I. dul'out de Nemourts and Company, Lic. , Wi hini ngton, N laware,Conti-act AIF04(611)-I0216, Hatch 1966.

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B!Dielecteio Coxietanta, Itefractive Indicen and Ionizing Power of

Hiydrogen Peroxide and ito Aquecum Solution,," J.. Am. Chew. 8oc., 1

1,89-99 (1930).

2.043 Schumb, W. U., "The Stability of Concentrated Hydrogen Peroxide

Solutions," Ind. Er%. Chem., 1,1, 992 (1949).

2.44J Roth, E. M., dr-V and E. S. : hanley, "Stability of Pure UydrogenPeroxide," Ind. Eng. Chem., 45, 2343-9 (1953).

2.45 Giguere, P. A. and 11. Feeny, Can. J. Item., 21__A, 69 (1943)), as given

by Ref. 2.22.

2.46 Savithri, K. and S. It. Rao, "Hagnetic Suusceptibility of Some Peroxide#,",

Proc. Indian Acad. Sci., 6Aj, 221-30 (191,1).

2.47 Gray, F. W. and J. Farquharmon, "Diamtgnetiom and Submolecular:-Structure,," Phl u. (7), 1-0, 191-216 (1930).

"47

2. 485 Giguere , 1'. A. utid V. V. Sclifiownke, "Aii EU ct .rosi-IDi f~ractti ol ltudy

of 11,A), witd Hydi'uzzin," J. Am. Chumi. Soc.., U, 210215-9 (19113).I

!2. t4 ) Itoding~toii, It. L. 1, . Bi. Olison, and 11. C. CrossM, "Hlydroge~n P'eroxi de,

Itil zred Spect rwu iond the lzitevuil, Itotati ol Przob lem," J. Chem. J'IiyI.

1(-, 1311-26 (19w2).

2.50 Illujt , Rt. If. , It. A. 14vauch~k, C. W,' Peters'M, wald K. Tý liecit, "nteoruuul-

Itotutiozu in Hlydrogen Peroxide: the Jur-lzuivured Spectri-i-i aiud tile

IX, etuzi anti on of the Ili Aide ii jig J'ol'euti it I, J. Chema. I' ,s 42 (W)

2.51 Masseuy, J. 1'. iand It. IV, Hurt, "J1,3fuut of ui high ci-li4Urrieri onj the

Mi ca'oviuvus SPectruw of Htydrogen Peroxide," J. Cheri. JIy.,~ 4

2 ,521 Giguere , 11. A. and C. Chipadovii, "Trhe Far Isif'rared Spectra of' 11,), 0Witd D,,0 2 in the Solid Staten," Si'ectrochaimicca Actt, 121 1131 -1137

(1900).

M ~ i I lot. ,? It L. a .I 1. Hotnig "Igafruried SIpectrutii of Crx'Ntzl line I. j a*w10.." . ale, Pnadu.. 2i 0 *(1aa9o S

2. Ta Calculated, thius study.

4) . "u ~ I1~J w * 5A"% l 1111d1 1" F . Gr tfn al -I I IIfIII ý i t )IIa -q

l'uroxide--.Piyaicuad and Chemical Propertic-;," baid. Eaaiij. Chema. , 2

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1 "49

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J. C11w.1. Sue. , I1/,, 11 , 1o (1918).2.7 o1, I. Jrichts, 22, 13U7 (1906)).

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2.85 Hal1perinz, J. anid If, Taube, 4L. Am. Ch~ew. 60c., 7-, 380 (1952);8-: Wite f.~ia i*nd HI. V. A. Iiriscov, ' . Aw. Chezu. Svc.~ ,7, 496)

(1951); 11. W. Albu and H1. D. vou Schpweinitz, Bvricbte, 6.-, 729(1935); 6. Glumbtune uud A. Ilichding, Electrolytic Oxidationi and&-ducti-oi, P. 257, New York, D. Van Numtrund Co., Inc., 1936);

It. Willutaittur, Jkriebte, ý6, 18331 (1903); N. Tarugi anid G. Vituli,Guai W1. tu1., 22, 1, 418' (1909); K. Sundyed and J. B. Ilolte,Kj.Noreliý Videmokab., Seltskubid. Furb., 11, 189 (1938) (Pub. 1939);

50

E. Abel, Huo b. j, 1239 (19O7); E. Ab.l, Mouutsh., 2.., 8'1.•i ~ ~~(1913); E. Abel, 18 J__roie.l, 705 (1912); E;. Abel, Mountsl.,

8,, 798 (1950); Y. Usucma mad T. Okui&•, J. Chem. buc. JAIA, ltu'e

Che-. ••ct., aj, 48 (1950).

2.86 i,,big, 1., B.r.ht., j., 2743 (1885).

2.87 osueuniii, It. , It. W. Neptwie, and Bi. W. Alleu, United btUte# Patelnt

2,61U,791 (4 Novewibel 1952).

2.88 Gilbe'tsoi, L. 1. uiid G. B. King, lUorgatlic byntheses, Vol. III,

p. 137, Mc~ruw-l• 11 Book Co., New York, •93U; J. Am. Chem. So'.,58, 180(n~)

2.b9 Thon•aen, Atj. PhYs. , (2), 1 94, l9' (1874•); 8. lluoeelkog, Sveu4-.

b'arm. Tidi., ;a, 149 (1921); 11. Lido antd G. Yt.huoyniu, ci•e•tce,

Itepts. Reevurch hnsts. , Toboku UWivereity, ber. A, , a449 (1950).

2.90 Schluck, G., MonuLtb.•., J, 489 (1916).

2.91 Iligginmon, W. C. L., D. Sutton, and 1'. Wright, J. Chem. Suoc., _Z,

1380 (1953).9- Julu-, K. J., LIAL' 1&L. Get. Sci., Puit 111, 1'. 170 (1948).

2.93 Klyachko, Y. A. and L. 1. J•ulhLchwiovu, Dokludy Ak~ud. Nauk. S.S.S.I.,,823 (1947); Chem. Zeatr. (ltumpiau Zone U4.), 1948, i1, 555.

2.94 Nee,, I., P. B. Ilkport 74717 (fralnew 199-205). 4

2.95 Oddo, B. and It. Binaghi, Gazz. chii. itul., ý_, II, 313 (1921);

B. Oddo and It. Binughi, Atti. IR. Acad. Lincei htowa (5), 31, 39 42.96 Greeuspwi, F. P. Lud. iagl. Chew., 22, 847-.8 (1947), uas given by

lef. 2.55.

2.97 D'Aus, J. aud A. K"eip, Berivhitv, 46, 113640 (1915), 't given by

JIf. 2.55.

2.98 boeveken, J. and M. L. Von Konigsfeldt, Itec. tav. chimi., 24,

313-1 (1935), an given by Ref. 2.55.

2.99 rTD-TDR-63-1002, TP 206, Pesigzn Criteria for Advanced Prop ellant§ystems, Texaco Experimeut, Iucorporated, fichmomd, Virginiu,

June 06(3.K 51

2. 100 LILILO5-20, -No#ifaig Gertuzi Vyl c4iei&J)al~ne~ of Ligiiid

t'roz elLWufjl, T'eclujidyuti, Incorpuzruted, West Chevster, Villinsylvuliiu,

April 1965, CoutI4ct. 1)A-30-034.-ANC-OI53Z, CON1kZFl'1FA.L.

2.101l SLunburn, C. E~. , Ii. J. Dhuumgttrtner, G. C. Rouod, aind J. M. MongLer,I 'I~"ecoulpovitioal fleut TrusisfIer to Liquid 9U% itydrugeii P'eroxide,"

Presented art the 0th N~itional lktt Tr'unkiJer Cunfrlenez, A. LChl.L. -

A.b.M.oEs , Bioston, Marssa~chusetts, Augutit 1903, A.1.Ch.E. Prept-lin{ 21U.

2.1U2. bauburn, C. E. , 11. J. iltiwugurtner, G. U. Ilood, utrid J. M. MongerI

"Co nvective' leut T'iunafer to Liquid 9U% Ikydroui~en Perokide at H~ig~h

fiuta "Ilux," P'resenrted ut thre 0tb Nationul lleat Trunsier Couleijueric,

A~lCh..-AS.ML. Boiston, Muosschusette, August 1903, A.1.C1.U.

1'repxi-ut 21.

2. 103 btudlev done by J'rutt and Whitneuy, as reported by James McCuruii ch,

Alydro-gea Peroxide IRucket Narrwul, I"MC Corpurutioni, b~uffalo, New Yorh,

2. l0'i ýAG42 10785-03, kullrterb- R~eport. Advanced J'ryupeIlinit 6tiLdg(-

ComubustLion leasi biIi ty I'ro&gtwin, Acerojc t-4iencriAl Corporati on,

Sacramczrto, cul ifornIiu, Jiuw 1900, Cunltrct, t. j`'. (ol i) -1745 42. 105 ?mvrINtv comwznicati on, Y. Iiofiwwzl, VC Corporation, to

2.106 Privatc comwmuleai~utl, 0. Wc~ortuich, INC Corpur-Utiuri, to '

M. T. Conlbtalutjrw, flcktUCVdy'II.4

,.107 Vani flull, N. t. aud D). C. R~ouser, "Ultiwtite lheat Flux Lintist of

Storarble J'ropeIloirtb," Acroje t-Gvnerul Cw-poruti on, 8ucraineit',,

Calilorniu, us presented to the CI'IA 8th Liquid Propulsion 5ym-w

posium, Cleveland, Ohio, November 196Ui, C0NF1DMIlAL.

2. 108 AI§-'J-,-23 jec jul Rteport, Advanced Pi'olpe laut Stuged-

CobmiuFaibltPorm Acroje t-Geiel-Ul Corporati on,

Sucrumento, (All iforzui, August 1966, Conitract AV'0'i(to1) -10785,ICONFI D)MIA'Lb

5.2

2. 109 11-2985, Ifrds-tv iCutaI' t bmuewtJrirt,'nIt;~x

2 .11 &i~UL-1t-47)i0 1'etvgt oncui~- 11Ut IJt'ornw~i-diiea Ditti slJ Oft

North Al u viv-it~w A ivliii Iii(e~ ., (lOrjljNOii, Utdion, rintt '! 0. 91

NCIR JVJ'0(st MLLPCIl I407, GOn ti'U(w t A04(6H i) -iI 1208, (JONFI"IWI'J.AL.

2 .111 Muc;ormiicl , J. ,W dytutt'i I'eroid' occ ItyA t ýWiugtI, M~C ColpI' t ion

Lbuffult, Nvw Yurlh, 190'.5

2.1 uzxiaA I.,"hrwul Decompositi on Studies~ of '4H~ lO

Unpimb1iliged Witaa (u10 -1 ) , llckvtdyuc', a 1)i'i ami o of North

.Awurcitan Avitittion , hinc. Ctuiunuj Ptah, Cal .1 1'ruit, 19 Mukrcl 1 958

.13AYli'C-Tlt-(0U-b, L~vietIPi fft~c'of 13I ~lUP

,jy-bin&gtio on Dit tU ound Thrust liuchet LuLiEt , Air Furce Fl igit,

Tes~t Cutnter, Ldwards Air Force Ibubc, Ctklifornitk, Huy 1960,

CONFI.DINT Il 1 .

2.114~ AN'U'L-TH-65--'2JU, Yi 1 lijoxtý lcvt'Io rnwnt oý 'ilit Metil

lb-driqc 1i1y-jr~id Sysa _(16 Nuvemiut'wbc 141 ~t)'irmurli 10i Atiiqad 1905i!3

lloclit~dynt., u 1)ivi~idoi of North Awericuzi Aviution, inc ., Cwiugu

1Parl, Cul i or~iia, 1)vcep'tber 1 905, Coutruc t AJNJ4 (Li) -907u,

CONFIDENTIAL .A

44

53

TADLL 2!.1

PHYSiCAL PIWJI2GI I 01,' HYD1kUWLN PtOXI1)L AT

Uai t. 00 i'.oant Ave(I YN po~ 9) rmeat %0v

~mIa dea tl&1lj" rssoatulo taeo Ptaae17doewISV~

Freaming Voint vF -'i.5 .1.14. 8U-.1Ife

monal boiling Po.Ant C I10' 17 ~

1 g. ait '. n

o"Bgi . b'u t17 t4 C1.7 t &iqtlai properties's.1.3L 9. .~. t.

ateatr ii uf e a h1.d. Me eit .XL .Cai

sold aSt. jet puke1

U 1-7 a t)-v LU.ba atU~a1 ~ 1b 0a1'a1' I

Thrataal alaxu 7al .b a 10- 4.t0 aI LO 4a k. 15 at 1 1 t! 1!,ao a~.I! dln./u 4bI 01 t t .~ ttc tM .7 t ~ 911 tU)C~ ( tW

Adabti 4t&Iatem lo s*- .4 o ~ vA1 .4 o, 165.1.1 1.w .- ~ ,9,1- t

poln9.6", o- tso 3.40 .lo wI

TABLE 2.1(Continued)

Units 100 Perceut 0 Percent 8202 95 Percent 202

Property Metric Englieh Hetric TU1TnIiW Hetric--' -w--T "-- weir[ C 4li-r

Thermodynamic Properties

Soats of

Formation cal/g Stu/ib -1320 -2376 -1369 -2464 -1'4-4 -4601

Fusion cal/g Btu/lb 8b 115 87 157 85 153

Vaporisation cal/S Dtu/ib 364 651..5 368 661.5 376 677

Sublimation cal/& Btu/lb 457.8 8241

mixing cal/g (solutiou) Dtu/lb (solution) 0 0 1.0 1.8 2.4 %.2

Decomposition cal/g Btu/lb See Fig. 2.16 andI

Heat Capacity

Solid cal/g-C Stu/lb-4' 0.461 at 0.461 at C.461 at 0.461 at 0..14 at 0.41. atinstini point melting point melting point melting poiut melting peint melting pot

Liquid cal/g-C Btu/lb-4' 0.62 0.626 0.03 0.633 0.645 0.(A5

Gas

C cal/g-C Btu/lb-F 0.303 0.30 0.306 0.300 0.310 0.310

Entop cal/gi-4 Iitu/'lb-F

Enropy Cal/Ig- C Btu/b-* see Section 2."

Enthalpy cal/s Btu/lb Be* Section 2.2

Transport Properties

Viscosity 075a1

Liquid Contipoises lb/ft-sec 1.153 0.770 x 1u- 1.158 0.772 x 10- 1.160 0.775 a 10

Gas Centipoises lb/ft-eec 1.91 10- 1.283 x 10-5

Th•rmal Conductivity 03

Liquid cal/cm-eec-C Btu/ft-bhr4 1.40 10 0.4

Gas cal/ca-eec-C Btu/ft-hr-I

Coefficient of cm /eec in.2/8ecDiffusion

Sonic Velocity

Liquid %/soc ft/eec 1781.0 5843 1774.6 5821 1767.0 5791

Gas m/esec ft/sec

TABLE 2.1

(Continued)

"95 Per nt % 02ce0 P e c t UO2 75 Percent i0 o 70 Perceat . 0.2 Fi gure a .taer efie- metc -- L Metric Englihe Metric Englieh Metric Elish Table Number Number

-1445 -a6o1 -1571 -2828 -1%6 -3503 -3070 -372o T2.3-- 2.14, 2.35, 2.4

F2.12 - 2.1 385 153 62 148 77 138 72 129 T2.3- 2.e 2.9376 677 369 700 427 768 438 789 T2.3 - 2.14 2.26

F2.14, F2.14 22.10O

2.4 4.2 4.3 7.6 8.15 14.65 9.0 16.01i F2.15, 12.15. 2.2bsee Fig. 2.1o and 2.16&

F2.16, 12.16s 2.25

at 0.414 at 0.414 at 0.417 at 0.417 at 0.377 at 0.377 at 0.415 at 0.415 at T2.3-2.8 2.5jg point melting point melting point melting point melting point melting point melting point melting point valting point 12.17, 72.1760.645 0.645 0.663 0.663 0.720 0.720 0.738 0.738 T2.3-2.0 2.18, 2.25, 2.26

F2.17, •2.17&

0.310 0.310 0.317 0.317 0.338 0,338 0.346 0.346 T2.9 -T2., 1 2.-27

oee Sectien 2.2.3.6 T2.3 -T2.14 2.54$ee Section 2.2.3.6 T2.3 -T2.14 2.54

10-3 . 0.77 a 10-3 1.150 0.777 x 10-3 1 106 1.123 0.738 a 10- f2.18, t2.18& 2.6, 2.22, 2.24

1. Iw.0.,5 x 1010.69210,3 3 n2i,, nag12.19, 12.19.

12.20 2.30

F2.21 2.31

1767.0 579%s 1758.3 5745 1706.9 5598 1690.3 533 F2.22, F2.22a 2.16

TABLE 2.1

(Cor.c luded)

100 Percent %0 W Percent %02 Percent %%3

Prjierty watis 4~ l lb Nitria Ift1ish mitric S~imaeb ketric MaSllek

sl.et,.madmtie rpit

Ledesa iS 3.ruaties (Goidle 3-Li..)

IUqe.1 1.4067 1.4049

vielestrie Cpteat 70.5 71.6

Electrical Cmd"itivity me-lu 1 SeSet.

J 91~i"l~ip~lt se T _______________________

madmtis Pooribilty 0" 3 0 a

to C 14

rBLE 2.1

'oucluded)

Pormet X0, 90 percest U202 75 Percent 82270 PercentU~ %0p

INetri. Z;Sg1Lsk Metric Yatlish metric Lftlish Metri Eqilb table biumer Nu~or

1.543 .~a4 LaltT2.15 2.15

73.0 75.0 76.6 79-1 f-2.15 2.)9

i~~2e1 Rmie 2,%3 I.

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lpoo'l~ ~ ~ ~ !rd .03 Va k )

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6-4 t3 4. .44 44ow)~ Ow~' - N-

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70

TABIJ 2.9

VAPO1t-PWIiE THMIOMUNAMIC PMOPJLUHLE OF

100 w/o "2%

Heat Capacity Ethtropy, Eutbalpy Heat ofTemperature cal/tapac-y Ca/o-k (T - H298) Formation

K R (Btu/lb-R) (Btu/Ib-R) cal/gm Btu/Ib cal/pa Btu/Ib

0 0 0 0 -76.26 -137.27 -912.08 -1641.74

100 180 0.235 1.310 -52.86 -95.15 -931.45 -1676.61200 360 0.259 1.479 -25.78 -46.40 -942.56 -1696.61298 536.4 0.303 1.636 0.0 0 -956.38 -1721.48300 540 0.304 1.638 0.56 1.01 -956.86 -1722.35400 720 0.340 1.743 32.81 59.06 -965.61 -1738.10500 900 0.369 1.810 68.35 123.03 -972.11 -.1749.80600 1080 0.391 1.879 106.4.6 191.63 -976.81 1758.26700 1260 0.407 1.941 146.41 263.54 -980.34 -1764.61800 1440 0.420 1.996 187.83 338.09 -983.13 -1769.43900 1620 0.432 2.o46 230.47 414.85 -985.37 -1773.67

1000 1800 0.441 2.092 270.15 486.27 -987.13 -1776.831100 1980 0.451 2.135 318.78 573.80 -988.48 -1779.261200 2160 0.459 2.175 364.27 655.69 -989.54 -1781.171300 2340 0.466 2.211 410.42 738.76 -990.31 -1782.56

i4.00 ' 2521 ' 0.474 ' 2.206 457.55 823.59 -990.87 -1783.571500 2700 0.480 2.279 505.18 909.32 -991.31 -1784.36

*Refer to Section 2.2.3

71

TABLE: 2.10

VLJ"M-MIiE THiM0POh&1IC iOPERTIES (IF

98 w/o U-2.02 bOWATIWQ1S

Enthalpy

Teuperature Heat C- city Entrupy ("1 11298) Yeat of FormationSca I/g-I ca A/ -.,kK a (Btu/I-4) Btu/Ib-4R2 cal/gm Btu/Ib cal,/gm Btut/Ib

0 0 0 0 -77.36 -139.25 -957.2 -1723.0

100 180 0.239 1.32 -53.55 -96.39 -976.6 -1757.9

200 360 0.262 1.49 -26.13 -471.03 -987.6 -1777.7

298 536.4 0. 306 1.65 0.0 0 -1001.4 -1802.5

300 540 0.307 1.65 0.56 1.01 -1001.9 -1803.4

4W0 720 0.342 1.74 33.07 59.53 -1010.7 -1819.3

500 900 0.370 1.83 68.82 123.88 -1017.3 -1831.1

600 1081 0.39) 1.90 107.11 192.80 -1022.2 -140.0

700 1260 0.409 1.96 147.25 265.05 -1025.9 -18'6.6

800 1440 0.422 2.01 188.84 339.91 -1028.8 -1851.8

900 1620 o.434 2.06 231.67 417.01 -1031.2 -1856.2

1000 1800 0.443 2.11 271.64 488.95 -1033.2 -1859.8

1100 1980 0.453 2.15 320.41 576.74 -1034.6 -1862.3

1200 2160 0.461 2.19 366.13 659.03 -1035.8 -1864.4

1300 2340 0.469 2.23 412.53 742.55 -1036.7 -1866.1

1400 2520 0.477 2.25 449.55 80N.19 -1037.4 -1867.3

*Refer to Section 2.2.3

72

11515 2. 11

YAPCa-IKA THIMVY?4AMIC rMOPFTIBS W

Dthu IpyHeat cpaity Eitro,,y (ca _ IL)

a (Btu/lb-41) (Btu/lb-Ii) cal/gm Dtu/Ib cal/gm Btu/1bTTeapersture B sCaa city c&lropy (" - 298eat of Furm mt~iu

0 0 0 0 -79.0 -142.2 -1024.9 -1644.8

100 1IO 0.245 1.345 -55.1 -99.2 -1044.2 -1879.6

200 360 0.268 1.52 -2t,.7 -48.1 -1055.2 -1899.4

298 536. 0.310 1.68 0.0 0 -1068.9 -1924,.0

300 540 0.311 1.68 0.6 1.1 -1069.4 -1924.9

400 720 0.346 1.75 33.5 60.3 -1078.4 -1941.1

500 900 0.374 1.80 69.5 125.1 -1085.2 -1953.4

600 1080 0.395 1.86 108.1 194.6 -1090ý3 -1962.5

700 1250 0.411 1.92 148.5 267.3 -1"%.2 -1969.6

800 1440 0.425 2.05 190.4 342.7 -1097.4 -1975.3

900 1620 0.437 2.09 233.5 420.3 -1100.0 -1980.0

a in ( a nI 8;DL I . I I- fýl 10 80. I I. -n - I ta.-. IL'v FJU all ..6IUU YA7 v ).9 d,9 . - . -L7044.v

1100 1980 0.457 2.18 322.8 581.0 -1103.9 -1987.0

1200 2160 0.465 2.22 3W8.9 664.0 -1105.2 -1989.4

1300 2340 0.472 2.26 415.6 748.1 -1106.3 -1991.3

11,00 2520 0.481 2.32 463.5 834.3 -1107.0 -1992.6

Afer to Section 2.2.3

TAB1 2.1L2

'90 W/o Mo2 0,LWTI1WW

Te Ileat Capacity, Lutropy, 1 ,(Ii 8 Blout of-- cul/gm-e Val/gm4w. '1"298' FJox mati:.;;

IL II (tu/lb-4L) (Btu/1b41R) Ca]/gni Btw'lb vua/gm - Btu,/lb

0 0 0 0.0 -.81.76 -147.17 -1137.8 -2048.0

100 180 0.256 1.38 -56.34 -40U.41 -1157.0 -2082.6

200 360 0.277 1.56 -'27.55 - 49-59 -1167.9 -2102.2

298 536.4 0.317 1.72 0.0 0 -1181.5 -2126.7300 540 0.318 1.72 0.58 1.04 -1182.0 -2127.6

'dO0 720 0.351 1.81 34.1l k 1.i U -1191.2 -2144 .2500 900 0.379 1.90 70.69 127.24 -1198.3 -2156.9

600 1080 0.400 1.96 jo9.73 197.51 -1203.8 -2166.8700 1260 0.416 2.03 151.53 272.7 5 -1208.1 -2174.6

800 1440 0.429 2.09 192.91 347.24 -1211.7 -2181.1

900 1620 0.4 A42 2.15 236.50 4-25.70 -12141.7 -2186.5

1000 1800 0.452 2.19 277.59 499.66 -1217. 2 -2191.0110 1980 0. 42 2.23 326.92 588.46 -1219.2 -21911.6

1200 2160 0.471 2.27 373-57 1672.43 -1I'0.9 -2197.6• 1, ,I.. 0.479 2.31 2.0.97' 757.75, -122o.

1400 2520 0.488 2.39 469.42 8a4.96 -1223.3 1-2201.9

fefer to Section 2.2.3

7'

MIE 2.13

VALJ%4'HUIIBE T In(O Lh.C PM0PMI~i Of

75 wr/o N0 2 BOIUr1OMB*

buthu4p'hetoBout, Capacity, Euatrop~y, (]UT4L28 Rout of

Tempera..ure o apaci-y cIt/o1-y, Formatiozi- - AI/gw-4 (Cul/gm-s

- - - -

.. (Btu/lb-it) (Btu/lb-lt) cal/gm Btu/ib cal/gm Btu/Ib

0 0 0 0 -90.02 -162.04 -1476.4 -2657.5

100 180 0.287 0.98 -4)1.57 -110.83 -1493.5 -2691.9

200 360 0.305 1.64 -30.21 -51.138 -1505.8 -2710.4

298 536.4 0.338 1.80 0.0 0 -1519.2 -273 4. 6

300 540 0.339 1.80 0.62 1.12 -1519.6 -2735.3

400 720 0.368 1.90 36.06 64.91 -1529.5 -2753.1

500 900 0.393 1.99 74.21 133.38 -1537.7 -2767.9

600 1080 0.413 2.06 114.64 206.35 -1544.2 -2779.6

700 1260 0.429 2.13 156.83 282.29 -1549.8 -2789.6

8oo 1440 0.443 2.19 200,52 360.94 -1554.6 -2798.3

900 1620 0.456 2.24 245.55 441.99 -1558.8 -2805.6

3000 1800 0.ý-47 2.29 288.76, 519.77 -1562.4 -2812.3

1100 1980 0.479 2.33 339.13 610.43 -1565.4 -2817.7

L200 2160 0,IA89 2.37 387.53 697.55 -1566.0 -2822.-4-1. . .. . .

1YJuu 25Ydu 1. 496 2. 41 O6.81 7b6.26 -1570.2 -082b.-4

1400 12520 0.508 2.58 487.2- 877.03 -1572.0 2829-61500 2700

•t¢efr to Sectime 2.2.3

75

TABLE 2.14

VAPOR-PIIASE THERMODYNAMIC PROPERTIES OF

70 w/o H202 SOLUTIONS*

Erithalp� !Heat ofTemperture lHeat Capacity, Entropy, (IT-J1298) Formation

Scal/gm-K cal/gm-K - -rmation

K R (Bl u/lb-R) (Btu/lb-R) cal/gm Btu/lb cal/gm Btu/lb

0 0 0 0 -92.8 -167.0 -1589.2 -2860.6

100 180 0.297 1.52 -63.3 -113.9 -1608.3 -2894.9200 360 0.314 1.75 -31.1 -56.0 -1618.5 -2913.3298 536.4 0.346 1.89 0.0 0 -1631,8 -2937.2

300 540 0.3416 1.90 0.63 1.13 -1632.2 -2938.0

400 720 0.374 1.99 36.7 66.1 -1642.3 -2956.1

500 900 0.398 2.09 75./1 135.7 -1650.8 -2971.4600 1080 0.418 2.16 116.2 209.2 -1657.8 -2984.0700 1260 0.434 2.23 158.9 286.0 -1663.8 -2994.8

800 1440 0.448 2.28 203.1 365.6 -1668.9 -3004.0900 1620 0.461 2.34 248.6 447.5 -1673.4 -3012.1

1000 1800 0.473 2.39 292.5 526.5 -1677.4 -3019.31100 1980 0.485 2.40 343.2 617.8 -1680.8 -3025.41200 2160 0.495 2.50 392.2 706.0 -1683.7 -3030.71300 2340 0.505 2.52 442.1 795.8 -1686.1 -3035.0

L1400 2520 0.515 2.71 493.2 887.6 -1688.2 -3038.8

*Refer to Seatioii 2.2.3

76

TABLE 2.15

1maXwI InnE (soDUM D-LINE) O. PROPELLANT-GRDE 2-

SOLUTIONS AT 25 C*

"l2 02 2 0.3, 0.2, 0.4, 0.6, 0.8,

w/o percent percent percent percent percent

66 1.3782 1.3784 1.3785 1.3787 I1.3788

67 790 792 793 796 796

68 798 800 801 803 804

60 806 808 809 811 812

70 1.3814 1.3816 1.3817 1.3819 1.3820

71 822 824 825 827 828

72 830 832 833 835 836

73 838 840 841 843 84t1

74 846 848 849 851 852

75 851, 856 857 859 860

76 862 864 865 867 868

77 870. 872 873 .875 876

78 878 880 881 883 884

79 886 888 889 891 892

80 1.3894 1.3896 1.3897 1.3899 1.3901

81 903 904 906 C908 909

82 911 913 915 916 918

83 920 921 923 925 927

84 928 930 932 933 935

85 937 939 940 942 91,4

86 945 947 949 950 952

87 94 _ _ 91 s7 959961

88 962 964 966 968 96989 971 973 974 976 978

*Retor to Section 2.2.5.1

NOTE: Temperature correction is -0.34 x 10-1/C from 15 to 25 C.

77

TABLE 2.15

(Concluded)

11202' 0.3t 0.2, 0.0, 0.6, 0.8,w/o percent percent percent perce*ut percent

90 1.3880 1.3981 1.3983 1.3985 1.3986

91 988 990 992 993 995

92 997 999 1.1*000 1.4*002 1.1*004

93 1.1*006 1.I*097 009 O11 113

91* 014 016 018 020 02195 023 025 027 028 030

96 032 0314 035 037 039

97 0*1 042 04* 046 048

98 049 051 053 055 05699 058 060 062 063 065

100 1.4*067

78

TABLE 2.16

VUUEr COhSTANT OF HYDROGEN Pfl0GIDE-.ATU

'SOLUTIONS AT 10 C*

-ky, .in/gauss-cm x 103Ht202 l _. 1

W/o 5893 A 5780A 5461A 4358A

100 11.48 11.90 13.52 22.65

96 11.60 12.03 13.64 22.70

78.5 11.98 12.,,5 14.07 23.45

62.0 12.30 12.80 14.-43 24.11

50.9 12.53 12.98 14.60 24.22

38.1 12.69 13.15 14.86 24.47

18.1 12.91 13.38 15.13 25.00

0 13.09 13.64 15.40 25.21

*Refer tc Section 2.2.5.5

79

TABLE 2,17

MiS •OhICUIAR AM) k E TRWAGNETIC PRMOJiTIEB

W1 HYDROGEN PZ3WUDZ

Property Value Temperature Reference

Specific Refraction 0.1705 cl/gw 25 C 2.15

Molar l"fraction 5.801 cm3 /mole 25 C 2.15

Polarizability 2.30 x 10 c.34.le 25 C 2A3

Molar Dispersion 1.3576 cm3/mole -- 2.45

Dispersion Constant 8.479 x 1030 sec- 2 2.45

Characteristic Frequency 2.979 x 1 ec 2.45

Molecular Radius 1.32 A - 2.45

Molecular Susceptibility -21.0 ±. 25 C 2.46

Molecular Diamagnetism 16.73 ±0.20 25 C 2.17

so

VA N 2.18

STUCI AND 8TZUC kL PAMktrE

OF EXPROEN PSUALIDE

ISStructure

Structural Parameters

So9(ooH), 7 (HOOK),R((ý-ajA_______ degrees dere

Electron Diffraction 1.4*7

Crystal Iiffraction 1.49 97

Far Infrared 1.475 ±0.004 0.950 ±O.005 9 12 (119.8 ±3)

Microwave 111.5

81

TANA 2.19

MCTI 1O8 Or RUUBOGEN PlUXIDE

Reference

INOiQA.NIC CWMUNXIH

AS 4- 1202 acid S dissolves (Ag) 2.56

PIAI(H 2.10

Al + %02 ... 3 2.10

As03-3 + H 2 02 PlAsA01O,- 2.17

AsO 3P)3 + H202 O.YB0 2.57

Au + U202 sdissolves 2.58

alkaline_Oxid' A gold + N202 a - reduction 2.58

B (colloidal) + 1202 H 3BO3 2.59

115(01)2 + 11202 O-B&02 + H120 2.10

Bi0.., + H,. 3 Bt..nOL 2.60

Bi(N03 ) 3 + H1202 alkaline, Ii(OR)3 2.61

BrO3-1 + 11202 -' Br-1 + Br 2 2.10

CN-I +202 PC0 + CNO-1 2.62H202 3

(• - + H202 PNH3 -- 022-- -N03 -1 2.63

82

4

TABLE 2.19

(Continued)

nimcGAac cCu•OUNM (coat.)

C l2 + %202 - -'Cl-I 2.64

-1 alkaline orCO + N02 neutral no reaction 2.63

CI0-1 + H202 acid #-CI2 + C1O2 2.65

DI•b4 + H202 *no reaction 2.10

10ocd + 1202 0-c i- 1 2.64

Co + H202 bdissolves 2.66

Co + V202 alkalines Co(HO) 3 2.10

Cr + Y2 02 P dlow solution 2.10

CrO3 + Y2 gCr+3 2.67

Cu + 1202 acid * dissolves 2.68

CuO + Y1202 S CuO2 + H120 2.69

CuO2 + 1202 -"WCuO + B120 + 02 2.69

Fe + %102 e+•F e+ 2.10

Fe(CN) 6 -4 + H202 a-cid Fe(CN) 6 -3 2.70

83

TANX 2.19

(Continued)

R1efereace

IN(tA~NIC COMPOUNDS (cont.)

Fe(CN) 6 -3 + 11202 alkaline Fe(CN) 6 - 2.70

Rg + H202 -'-aci_' dismo lves 2.10

+ alkaline- oxides of mercury 2.101l + H202, -Ircury

12 + 1202 .- 1 lJ4l 1 0 1 2.71

HI + 11o2 0-12 4 120 2.10

Li+1 + 20

2 k -Li 2 02 2.10

Ng + H2(12 1g(o.M I)2 2.10

moo 4-1 + H202 acid 0Mu+2 ' H20 + 02 2.10

on04-1 + H202 alkaline -HU02 2.10

MOS 2 + 11202 ,--S04_-2 2.10

Ni 4H HCl or 0d l 2.1022 H 2 SO -4

H+

NiSO 4 - H0 no reaction 2.72

NAI4 + H202 - various products depending upon conditions 2.73

HONHl2 + B2 02 - WNO0 2.74

84

TABLE 2.19

(Continued)

Reference

INOWAKIC COMPOUNDS (cont.)

NO 2-1 + it202 . -NO• 31 2.75

NO3- + 1202 - - no reaction 2.10

03 + 1202 *-U2o f 02 2.76

P 11202 P pit3 4 li 3 PO 4 2.77

Po5, 5+ 1202 + 1120 H3p' 5 2.78

P•-3 + 1202 O- no reaction 2.10

P•-3 + H202D- own__-3 2.79l+

Pb + "20 2 H - dissolves 2.80

Pb 4 1202 alkaline, s PbO 2 2.80

Po + 1202 *, dissolves 2.81

,n .ýan

Pt + 1202 no reaction & &I

S * 1202 6no reaction 2.10

N2s (aq.) •+ 102 acid 2.83

S= (sq.) + H202 alkaline so4-2 2.8

X2S + 1202 ' = 4-2 S plus various products depending upon 2.84

metal

85

TABLE 2.19

(Continued

Reference

l4oaIc cCr0.mP .& (cont.)

O-2 : - 2 0b- 2 2.85

Sb 4 1t202 - -- no reaction 2.10

Sb s antimoniate 2.86b2S3 11 202

Sc + •5e2 2.87

Se 22 H •2 Sl2 SeO2 2.10

YI2Se + N202 . rapidly attacked 2.10

SeO 3-2 " _t202 S SeO -2 2.88

Sn +2 Sn+0 2.89

snO2 4 H,202 -*no reaction 2.10

Te + "2 0 2 s ki 6Te06 2.90

Ti+3 1 H202 01_ TiO3

Ti02 4 2 *202 0Ti(O 2 4 2.92

TI + B202 . TIOH 2.10

TI0 2 + 1202 23TI203 2.10

_____ 0 2.10W + H202-

96

uTWA 2.19

(Continued)

RWference

1WORA.NIC COUULMX (cunt.)

ZL 4 %202 a- EnO 2.10

a Ika l ine d.Zn • M2 02 mlcoholiEdasidve. 2.93

Zr + %2 02 --$no reaction 2.94

tr(SO4) 2 + ! 2 02 -ono reaction 2.94

f3•,LIC CmeOPDWS

Alkanes:

Saturtec paraff ins + 2 with and without reaction 2.55Y2 catalysts

y0 ith and withoutCyclic Alkan + %0 2 catalysts v-.O reaction 2.55

Grignerd reagent (H"g) + %202 i-alcohol 2.95

Alkimes:

= !W4+ . - - -4 h--4

" "V2 catalysts 2.55

fl '+ %% j0 j~' RISH' --.O B 2.10,N ' 2.55glycol

87

TA13LE 2.19

(Continued)

Reference

ORGANIC COMPOUNDS (cont.)

Alcohols:

cold wito reactionROil + HO0 noctls-°rato 2.55H202 noe catalyst~

RCH20 + H202 Fe 3 g RCOOH , C02 2.55

Carbuxylic Acids:

1% H 2SO 10001+1RCOOH + H202 RC000H + H20 2.55

peroxy acid

Aldehydes,:

ECHO + H202 80 C --RCOOH 2.55

H+

Aromatics:

Benzene or toluene + 202 no catalys rcS--no reaction 2.10

Fe++ catalyst2Benzene + .2-2 Al strips -phenal

1-naphthol + "202 RCOOO, -o-carborycinnamic acid 2.96,

(in acetic 2.98

acid)

Hydrazobenzene + H202 22-23C 0azobenzene 2.55

1% H280 4Azobenmene + H 0 --- 000H - azoxybenzene 2.55

2 2 RC00001(in acetic

acid)

TABLE 2.19

(Concluded)

Refcrence

OWANIC COMPOUNDS (cont.)Aromatics:

Aniline + u2 C2 2 2 2 3C aniline black products 2.55

Aniline + H02 22-23C; oxidant nitrobenzene + 2.96(in acetic added to water slurry- azoxybenzene

acid) of aniline containingNa bicarbonate

Benzaldehyde + H 0 2benzoic acid 2.972 2 1ý H 2so~ b4 ziai

(in acetic RCOOOHacid)

RCOOOH ~nhaunn

Anthracene + H2 0 2 O anthraquinone 2.96

(in aceticacid)

Primary Amines:

RNH2 + H2 02 vigorous decomposition of peroxide; 2.552 22ection;,. ;difficult. to control; no

products isolated

Secondary Amines:

(R)2 NIX + H202 -" (R) 2NOH 2.55

hydroxylamine

Tertiary Amines:

(R)3N + H202 IbmR 3N0 2.55

amineoxide

89

100

j t14f I1m

90 APPAREN MOLECULAR WEIGHTS FRO4

A' 111i 11 1, 1

70 tO0WEIGHT ~~ PREtill0

9011

0T-0

1 4 Cilit-.4

11MIN11"I13 14 MttC

OD/

IM it 11

Sn

VIM :1 WINMI t 1M 0

4,++4.. *i44- ý4)

_4414

ME0. ~ ~ ~ ~ ~ ~ ~ K ............ ...

a -4)

044

911

I-AM11111111 HM Mj113

411111TS"IT it 'd iHIPth 11,0

1 11 [111t ItIM"' lit ql lifii'lali

fl~ ifilfiff li11 tI I 10 1 il 1 11 1-14 In,1444444,11111

11 H I ilt 119 "fllil'til ItIUJ~it'l Jil 11-1

1 tj i I

W i 01 liltif 14

I, !JV 4 1'011HI T114U

Ta fltt~fll, ift ll, lilit-

111i IH I I I ilt

1 111 IM t 411 111HIII fi 11 mvm Z- AM 11-1!i,14:1 11R0

ý4,'10

"410 1 1 " IT

MR- H. 1911"A1111

lffý*,~: 1`4 1911f B l 1114 A 'I-1 t W IA0e4 tI lilt

H I~ I?* :J 0

IffllfT11111 Tf M .;i 11P3111Ifl VI HMdK31 llf~ifli

f92-

450

hoi

04 10i 40~

Ii li I

it w

0-CRITICAL TEMPERATURE CRITICAL TEMPERATURE

ihi

T16

IM N% , qj ill 1 40J I.-

SOIMIN PONTA

hi IT

WEIGHTICA PERENTH 2 0

Fiure23 rtclTmeaue rtia rse n oln onof PrplatG4 efyrgnPrxd-ae ouin

C93

0

02QN ASH I

0i~"4,

NH;, it H if H11

OM

T All K H N !H1111

. . .. . .. .i jr

ft (u

It,-

-fit

......... N ,f +

1 fit

ftC.

1 1 If iTH -

o- 00I

IN

4p

CL

RI~~ ~ 4IdHIMi V'AIISNJQIH I

950

8.4 14!oi . ~

Cl)

z 10

w S.0

-IH

ill1 5, :1 ,1, w iy 11~:~ < ' !Wi

7.4zW

70 809 w

w 7.6

z

0 4.8 4110T ill, i.; ¶

Ow I fl T 1

14 If ii, Jliiwo P -vt" flti j

r24 VII ~ _ r'itz I I' i

4i ; ITT ~

I iHýjililIlftl.. IfIs- 71 FIto4 0 .0 20 1 41400i,4

WEIGHT PERCET H~

Fiur 1.a oefcets(uial fTera xaninfr rplan-rdN yrgz Peoit-ae Sidution

IL I97

I I I4 1 i

CUV IIT Ir IT "'IS O I E 2. !I

lit

2.~. ~ j4*ilk

if~p No .9

W4GH PEREN I ,O .

Figure 2.6. Aiabt, Copesiilt ofiriel't:rdtitoenPrxdeWtrSouin

I98tlk 1

if~ ~ tl It- 4

II

04I

t i i

4: ~ ~ I ' 1 TJ*',,oT

41 hk-t]f II il 411

1 14.4t

70" ii100111 t !~~~~~ qE(~1 tECNTH

Figure~~~~~~~~~~~~!t 866.Aiba4FCqesiiiyo roeLzVGad LdoePeuztD~a~ 4oltiikl

* ~ ~~ ~ L41, I'% * . .

1000- -- ----------------Soo

It600

...... ........-

Z= Z L

:Z 7Z __7

200.___

EXTRAPOLATED DATA100 (ASSUMING NO DECOMPO ITIONN

t _t a I I 4ý I 1 4 :-t t -- A

so

E 60E

if-2-f- 100 W/O 2ýO

UF 40 98 W/o

5-_ -.--==F-:- = - -

w =--e m.0 90 W/oac ------ _T10L. 20 70

Ix 70 W/O __t___0

> io

0ý

4 t 4 4

CURVE FIT OF DATA FROMR E F. 2,11, 2.12, 2.20 AND 2.21

20 40 60 00 100 120 140

TEMPERATURE, C

Figure 2.7. Vapcr Pressure of Propellant-Grade HydrogenPeroxide-Water Solutions

100

20.0-----------------

----------------------

10.0 IT

8.0

T AA= -7 7

6.0

T-14.0 ------

fil

T_ EXTRAPOLA J DATA__E_ --ý--t(ASSUMING NO DECOMPOSilook)

_j j2.0-.

_j__H

- f-I -1, -4+ -

44-

1.0

100 Wo HRot 7 :T0.8

w 90 W/o J,' 4 114' 10.6 - -------- ... 1!44ýfl95 W/o

OL4 iA -i L4

90 W,10L. T

A 73 W/o

40.2>

7P 4- f- t-4- t t-+4-121T 4 ±±=H

1:1- _LATý7 ý1

0.1

CO)LO B ........... ..........U

a0e

CURVE FIT OF DATA FROM REF.2.11, 2.12,2.20, AND 2.21

OL04

-4-4-4- Fý+_

. ....... .... .Q02z:: ------- 7::::::: z

CLO I

40 60 So 100 120 140 160 180 200 220 240 260 280 300 320

TEMPERATURE, F

Figure 2.79. Vapor Pres-jure of Propellant-GradeHydrogen Peroxide-Water Solutions

101

11 Hi : tl ! I M 111

1il 000 Iso

I70 IlIil i 1 I1

60i Ii. V!l 1 1

c 0 4jS1ý

T4~ v ~ ~ 1<

0 O a 0 4 060 a0 60 v tO

(Re 2 .22) lIl

510

lid I

I.0ltt 1

30z8FfoT0......

60C( 4 ) -;

-

-- I

0

0.6 0. M10

U. ~yse (Ref 2.22)i,441f

0 103

I t

0 .2 4-

DON~~ DAT OFRF.2

z 0. 0 ow04l.-08,.

T104

J -1__ _ _ _ _ _

.. . . .. .... .

W..

63 ....

Ht4I F.

CURVE FITS OF DATA

62

e I0 408 0 0S 9 0

50'so

.. 7~ -rl-

- CURVE FITS FROM DATA ,

OF REF2.24 AA~~

- L- ;

- ITIT 1 lT75-1

L 4t j.!' IHl 4

;7I -T ... .......

( 5.4 IT:

500

307 40i 50 507 8 0WEGH PEREN I It

Fiur 5.3 la Surac Tenio of J4doc eoieWae ouin

IT 68F

-J30

DAABSDO NEAT DISSOCIATIONJDAT

ffiiiIitHI-ILIUDH~a 2 'oIýýIIII 1 11

U1 II-li

-I(=

ItIi-1107

.t ... ..

a17 v it IN--- 41 t0110

-43700

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i HI

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70 /oHe00

IITERTURE, R

Figure! .7a Heat WOf Hoato o0Poplat-rd

10

2000

T 1

100

1500N BASEDl O! HETOF'SSCATO

70 80 90ý 100 l lWEIGT PECENTHZO

Fiur Ii.111. Iat oI FrainfPopllan-rd I

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Tw I

BASMED ON HEAT OF DISSOCIATION I I -lý

-2600 ;l ~tDATA (REF 2.25a) 0 :~j~

1111L" lit

W EIGHT PERCENT, HZOZ

Figure 2.138. Heats of Formation of Propellant-Grade Hydrogen

Peroxide-water solutions at 77 F4

110

Go6001Z

.....300..

if1

40

3000MT

I1I

0 4400 I

H- li

1100 *

1000 1 ' 4j

7 I t

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IIT

F-7

CURVE FIT FROM DATA OF REF 2.26 oi 1:

00 204 08 O

WEIGHT PERCENT H 02Figure 2.14&a. Heats of Vaporization of Hydrogen Peroxide-

Water Solutions

112

1002 I [0l

o [0.0 7

z I fMI-0

S6.0 251

HIT 14 i5 . 0 C I i~ T

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117

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TEMPERATURE, C

Figurec 2.19. Visusoitiee of 98 W/o Bydr-ogenL Peroxide,70 w/o flydrogon Peroxide, und Wuter

1221

-1-' -

-,

,I , a ý

'.3 - -- -- I - ' 1 01'4f

- -- -, -- -I11 -Jiv l l

1.0 - ~ - -

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CURVE FITS OF DATA FIROREF 26, 219, 2.22, AND 224 i

0.5

0.4 202-

0.3

TEMPERTURE, 2

112

1. 4 1 If71.3 1 t

--.2 7-7- - ý- - '

1.0 t :ili

0.9~ -7 !:ý0.. .. w 4 . , __ __ ., l

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0L.5 1 IL J~ .!L

0.44.4 HI

__ 72W62o 2022

0.2 -r

4I1

+i HI 'it

20 40 60 70 100 120 140 160 180 200 220 240 260

TEMPERATURE, F

Figure 2.19a. Vibcosities of 98 w/o H~ydrogen Peroxide,70 w/o Hyýdrogen Peroxide, and Water

122

T.M.

Ifl Will -till I Ilif HIf T. cr

A IWjI t J.

W: a- W

r .1 e ON l- - 1114011M, 'T-

IN 'thimfilof I ::t 11 ...tititlMý- I lHiff I:MAI

It at M M

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LiTT ---

------ MW OR --- f- t

TT"T5E0 1:1

crw T:

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TT T 1-If OD

ýTRMM I ...... ......Mm 4 flumil: F ITTP

X1

.':! 8TM, 7714A

.......... M .Cývf+ 4+ ++ f It lif-- w - . .1 N

M a Tlý T.:7

I f X IX XXT:: : T: VIM .- MMlim -T Tý 1, T: ý x4' HIM

M ý M-x t: It XT T".

-aýMLL

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MlOdOUDIN "AIISOOSIA

123

t ------U4ýiiflj ..................

4X

fpjlul ti

Q36 tt-tEl. I St lmmý tQ.rat Al.

14t! t" t-t i i f-t4 +

034I + , Hi t 4-ý --fffj+

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TTr-M00 aw ',T4W44jT:RM J+H4 W 4

4 41 -V

TT R44MA VX 0.327w

OL310 100 200 300 400 GDO

TEMPERATURE, F

Figure 2.21. Therual Conductivity of 98.2 w/ok-drogen Peroxide (Ref. 2.31)

124

1820

- Hi 'I ILI*

4!4'ui'TrJ1

1680 tL it

1205

6000 if~T

it' 1 i

5900,

70 60 F 0 10

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U. 126

ill0

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41,4

u- t

ITi1 TT

ivy1.4

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in

if 54

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it

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1124

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o SYSTEM PRESSURE ,-50W PSIA, FEED AT AMBIENT TEMPERATURE

L SYSTEM PRESSURE" 500 PSIA, FEED AT Av200 F

. SYSTEM PRESSURE-"14.7 PSIA; FEED AT AMBIENT TEMPERATURE

(G/P) = LIQUID FLOW (GAL/MIN)PRESSURE (PSIA)

A A

0- O (GGP /P11/2 0. 25

00,

00

0, 0' (G./P20.0

0

REPRINTED FROM

REF. 2.1011 _ 1 1

o • .L . _, .... .... _ _ _ _

1.0 1.1 1.2 1.3 1.4 1.5 1.6 1.7

1000/SURFACE TEMPERATURE, R"

Figure 2.24. Heat Flux From a 347 Stainless-SteelSurface to 90 w/o Hydrogen Peroxideas a Function of Surface Temperature

129

N-I-I--- n -i -

-- a -• -n, -_ - - - -

4. - -r-

SI0 .-.. .....---

4p4 _ _ _ _ _ _-.

- • p -- - - -

0 0 _ _ _ _P-_7_ _0 _ _ _ __A

fOf

- { Q/A(014, 15.4 BriSEC IN2'-

-,,- ,- . ... .. a-

S-,

Rteprinted from Ref. 2.103

_ _ _ _ _ I 3000Inside Wall Temperature, F

Figure 2.25.Typical Curve of Heat Flux va Inside Wall Temperature(98 w/o Hydrogen Peroxide 1-1/2 Inchie UpstreamFrom Exit of Hleated Section)

130

.- .DITTUS-'BOLL~TR EQUATION /0

NU, 023 R4 4, PR 10 0120

-

*0v

C-4 NUb% NUSSELT NUMBER>40 - Rb= REYNOLDS NUMBER

PRb PRANDTL NUMBER

NOTE: SUBSCRIPT b DENOTES20 .PROPERTIES BASED ON FLUID

BULK TEMPERATURE

I .I I I I I R~eprinted f ram Ref. !2.101

10 L1L 1 1 1 1 11I ý--.kmow

Figure 2.26.Correlation of Beat Transfer Coefficient. of 9t3 W/oIiydrelcu Peroxide With Dittus-iloeltcr l4uation(Convectir* Region)

600

400 COLBURN EOU/TI0N400 Nut .3 Ref Prf Vl - - -

0

200 - - -- - &

.100 -----

60 n Nur. NUSSELTNUM

" ", 0 Ref : REYNOLDS NUMBER

Prf : PRANDTL NUMB"R"

40

SUBSCRIPT f DENOTES20 PROPERTIES BASED ON----

ARITHMETIC MEAN FILMTEMPERATURE Reprinted from Ref. 2.1013

12. 4 6 8 105 20 40 60Ref

Figure 2.27.Correlatio- of Beat Transfer Coefficients of 98 w/ohlydrogen Peroxide Wit~h Colburn Equation(Convective Region)

132

60-000- - - -"-- , , - - -

IOO SEE-T- -EA Io N -4- --- - --

9 - -.- -

tt

.-rbi. -. m u - -

zI

c'J NubaNUSSELT NUMBER0 R~b zREYNOLDS NUMBER--;

/LzFLUID VISCOSITY

_____ 00 SUBSCRIPT b DENOTES0PROPERTIES BASED ON E

FLL 1 3 IK EMERATURE

SUBSCRIPT w DENOTESReprinted from Ref. 2.1(-U PROPERTIES BASED ON

JAL EMPERTUIE I

K RiWO I I% I

Figure 2.28. Correlation of Heat Transfer Coefficients of 98 w/oHydrogen Peroxide With Sieder-Tate Equation

* (Convective Region)

• , //y"

* O••-S O.-----ATO• _ -,

SECTION 3: PROWCTYON

3.1 MANUFACTURING TECRNIQUES

3.1.1 Preparation

The early laboratory preparation of hydrogen peroxide was based

on the technique that Thenard used during the initial preparation

of hydrogen peroxide. In this technique, barium nitrate, puri-

fied by recrystallization, was decomposed by heating in air in a

porcelain retort. The resulting oxide was further oxidized by

heating in a stream of oxygen to a dull red heat. The barium

peroxide which formed was then dampened, ground, and dissolved

in hydrochloric acid (nitric acid was used in Thenard's initial

experiments). A slight excess of sulfuric acid was then added

to precipitate barium sulfate and regenerate hydrochloric acid.

The procedure of barium peroxide solution and sulfate precipita-

tion was repeated several times in the stme solution to increase

the peroxide concentration (concentrations of up to 33 percent

by weight hydrogen peroxide could be achieved in this manner).

The concentrated solution containing water, hydrogen peroxide,

and hydrochloric acid, along with accumulated impurities, vas

copled with ice and saturated with barium peroxide; iron and

manganese impurities in the solution were then precipitated out

as phosphates. The hydrochloric acid was rczoved by the addition

of silver sulfate and the sulfate ion was removed by the subse-

quent addition of barium oxide. Further concentration was accom-

plished by vacuum distillation until "no further density increase

occurs." Thenard reported that 100 w/o hydrogen peroxide (on

the basis of density data and the measurement of the volume of

oxygen released) could be obtained by this technique.

131

The first record of comoercial production of hydrogen peroxide

appeared in the 1865 to 1875 period. The first comercia, pro-

duction in the United States was by the Oakland Chemical Company,

Brooklyn, New York, in 1881. Laporte Chemicals Ltd. established

a factory in Yorkshire, England in 1888. With the exception of

substitution of fluorosilicic acid for the hydrochloric acid,

Thenard's process was used essentially unchanged for the manu-

factureof hydrogen peroxide until nearly 1900. The formation of

hydrogen peroxide in the electrolysis of sulfuric acid was first

reported in 1853; later developments made the manufacture of

hydrogen peroxide by an electrolytic process possible in 1908.

By 1939, only 10 percent of the world's production was by the

barium peroxide process.

Currently, hydrogen peroaide is commercially manufactured either

by an electrolytic (inorganic)method or one of two organic proc-

esses. The electrolytic process (Ret. 3.1) involves the electro-

chemical formation of either peroxydisulfuric acid or ptroxydi-

sulfates (from an ammonium bisulfate solution), their subsequent

hydrolysis, and separation of hydrogen peroxide by distillation.

The basic equations for these reactions may be suumarized as

follows:

2NiHS0.4 -electrolysis b (NuI) 2 s 2 8 + 2

(NH 4 )2S208 hydrolysis • 2NHJ4HS0/ + H202

Although sulfuric acid may be used as the starting material, the

ammonium bisulfate process is cheaper and has a higher cell

efficiency.

The electrolysis is carried out in stoneware tanks with platinum

electrodes; conversion of bisulfate to the persulfate trakes place

at the anode. After hydrolysis of the peroulfate (with steam)

in an evaporator, the resulting dilute aqueous solution of 1202

is separated from the bisulfate and further distilled in a

136

stoneware distillatiou column. The resulting solution is approx-

imately 30 w/o O2 . Both the cathode liquor (after purification)

and the bisulfate from the evaporator (and separator) are recycled

bak to the cells.

One of the organic processes used commercially for the manufacture

of hydrogen peroxide involves the catalytic reduction of a substi-

tuted anthraquinone and subsequent oxidation back to the quinone

structure with the production of H2 02 (Ref. 3.2). Although the

process may vary slightly among the several comercial manufac-

turers who use it, the basic reactions can be summarized as

follows:

0 /H 0

CatalysI Air (or 2 H

where R may be ethyl, t-butyl, etc.

The reduction of the substituted anthraquinone with hydrogen is

accomplished from room temperature to 40 C or more aud at 1 to 3

atmospheres of pressure in the presence of a Raney nickel, nickel,

palladium, or platinum catalyst. The catalyst is separated from

the hydroquinoue solution and recycled to the hydrogenator. After

oxidation of the hydroquinone by either air or oxygen, the result-

ing quinone solution containing 0.5 to I w/o B202 in extracted

with water at 25 to 40 C. The aqueous solution of hydrogen peroz-

ide (-- 15 to 35 w/o %0 2 ) is cleaned of organic contamination and

vacuum distilled to ~- 70 W/o U2 02 . The organic phase from the

extractor ie tvaporated from entrained water, partially dried,

cleaned of %02 (by a decomposition catalyst), and recycled as

tb* work solution t% the hydrogenator.

137

The second organic process used in the present comercial manu-

facture of hydrogen peroxide is based on the oxidation of pro-

pane or a propane derivative (such as isopropyl alcohol).

Although the actual details of hydrogen peroxide manufacture by

these processes are not defined, the basic reactions of the pro-

pane oxidation are postulated as follows (Ref. 3-.3):

C3% 02 -C3H7*

C9 17 • + 02 -O'C39 7 00- --- poxygenated species

C9 .7 . + 02 - 3H6 + HO2 .

C3..L. + H__4PCR + CII

H02 . + C3% 8 -C 9 "7-* + H2 02

As noted, the side products in this reaction series are a variety

of oxygenate4 organic species, propylene, methane, and ethylene.

The oxidation of isopropyl aicvhol may occur as follows (Ref. 3.3):

(c 3 )2•CoH + 02 -- (C- 3 )2 co + Y2

It is reported that the latter reaction can be conducted in

either the liquid or vapor phases. Hydrogen peroxide concentra-

tions of 15 to 17 w/o o202 and 25 to 30 w/o B202 are obtained

from the propane and isopropyl alcohol oxidations, respectively.

3.1.2 Concentration

In most applications outside the propulsion field, only dilute

solutions of hydrogen peroxide are required and the product grades

normally obtained from the conventional cosmercial processes are

adequate. To meet the demands of propellant-grade hydrogen per-

oxide, additional concentration is required. Although hydrogen

138

peroxide is normally concentrated commercially by fractional dis-

tillation to concentrations 1 90 w/o 1202, other concentration

procedures, such as fractional crystallization combined with vacuum

distillation, have been frequently used for small-scale purifica-

tion. The concentration of the 9G w/o H'202 solutions to - 98 w/o

202 is presently being accomplished commercially (Ref. 3.4) by

fractional crystallization. This crystallization process also

removes most of the impurities.

The high volatility of water with respect to hydrogen peroxide

mmkes it relatively easy to concentrate peroxide by simple dis-

tillation procedures; however, there are several disadvantages

to this technique. Concentration of the nonvolatile impurities,

which occurs in the hydrogen peroxide during disatillation,

decreases the stability of the product. In addition, the rate

of decomposition increases with temperature rise (2.3 times for

each 10 C rise in temperature). Finally, hydrogen peroxide vapors

which are in excess of 26 M/o 1202 are explosive.

3.1.3 Purification

For some purposes, a relatively high impurity and stabilizer con-

tent may be innocuous and a lower stability acceptable; however,

for most propellant applications it is essential that the impuri-

ties be removed or kept to a minimum. This is particularly true

when concentrations of 80 w/o or more are desired. High purities

in the propellant-grade solutions are obtained by a multiple-stage

distillation process in which the hydrogen peroxide is completely

vaporized in the first stage, leaving only the nonvolatile impur-

ities. A vacuum distill2tion is usually performed (Ref. 3.3)

to keep the temperature (and subsequently, the decomposition)

to a minimum. This technique also decreases the potential

explosion hazard.

Theoretically, the removal of impurities by Jistillstion or frac-

tional crystallisation should be complots cept for impurity

pickup frog the apparatus itself in either the Cinal process

139

condenser or receiver. Elm or, because of the catalytic impur-

ities acquired during the handling and storage operations, a

stannate stabilizer is usually employed in small concentrations

to buffer the effects of these impurities. Hovever, the gradual

dropout of this stabilizer during storage results in additional

emphasis on the importance of impurity removal from hydrogen per-

oxide solutions.

Although ionic impurities may be removed by applying an electric

potential, the use of ion-exchange resins may prove to be a more

practical means of purification because this method could be

applied easily at the point of final use to remove contamination

acquired during transfer operations as well as residual manufac-

turing impurities. Extensive experimental studies in this area

(Ref. 3-.5) have indicated that staunic acid seems the most likely

choice for an ion-exchange media.

3.2 URRENT PRODUCTION

3.2.1 Availability

The principal European manufacturer of hydrogen peroxide is

Laporte Chemicals, Ltd. of Luton, Bedfordshire, England. Prin-

cipal U.S.A. manufacturers are Allied Chemical & Dye, Columbia

Southern Chemical Corporation, E. I. duPont de Nemours and Com-

pany, Inc., Food Machinery and Chemical Corporation (FMC), and

Shell Chemical Company. Of these U.S.A. manufacturers,

duPont (anthraquinone process), FIMC (electrolytic and anthra-

quinone processes), and Shell (oxidation of isopropyl alcohol)

are the major producers of propellant-grade (k 70 w/o 1202)

hydrogen peroxide. Allied Chemical, which presently produces

B202 grades to 70 w/o, has indicated a potential interest in

production of higher grades. Presently, FMIC is the only comer-

cial manufacturer of > 90 w/o NGC2 grades. Although hydrogen

peroxide concentrations of 99.7 to 99.8 w/o H202 have been pro-

duced commercially (Ref. 3.4 and 3.6), the economic- and

1.0

application-feasibility tradeoff will probably limit cowmrcial

manufacture to maximum concentrations, of 98 to 99 w/o K1,202.

The production of hydrogen peroxide was estimated (Ref. 3.7) to

be 55,000 short tons (as 100 w/!o 1L.202) for the year 1966. This

quantity, which includes all grades of hydrogen peroxide, repro-

seats an iucrease over the productions of 52,567, 45,519, and

39,085 short tuns which were quoted for the previous 3 years.

The present production capacities of the duPont (Memphis, Tenn.),

FMC (Buffalo, N.Y., Charleston, W. Va., and Vancouver, B.C.), and

Shell (Norco, La.) hydrogen peroxide plants have been quoted as

2.5 x 106 t x 1036, and > 5 x 106 pounds hydrogen peroxide (as

100 w/o 1202) per year, respectively.

1Wydrogen peroxide is available in various quantities up to tank

car sizes (4000-, 6000-, or 8000-gallon capacity). The use of

500- and l300-goilon capacity portable hydrogen peroxide tanks

that can be filled at the plant and used as storage vessels at

the user's site offers mauy advantages, particularly for remote,

owrseas, or temporary sites. Tank trucks vith capacities up to

4000 gallons are presently in service or available. finall quan-

titAi# are nur-hallV purchased in !CLgA!!on .

3.2.2 Cost

Because hydrogen peroxide sales are of a highly competitive nature,

the cost of propellant-grade hydrogen peroxide is flexible. The

grade (including concentration, purification, stabilization, etc.),

quantity, and present competition are all prime factors in the

determination of hydrogen peroxide cost. Thus, all individual

manufacturers should be contacted at the time of procurement to

determine the exact cost.

141

For the purpose of estimation, the citrrent price list (Ref. 3.6)

of IMC includes the following prices for three different grades

of hydrogen peroxide iu tank car quantities:

98 w/o 12 02 -40.60/lb

90 w/o H.o20-40.50/lb

70 v/o 11202-40.34/lb

The quoted list prices of the other manufacturers are similar

for the 90 and 70 w/o 1202 grades. However, the last Air Force

procurement (11 1907) of 90 w/no H202 was based on a cost of

00.23+ (tank car lots) to 40.3/lb (drum lots).

In the procurement of low concentrations of hydrogen peroxide

for initial system pasaivation, pond decontamination, or other

applications requiring limited stability, it has been recommended

by various manufacturers that higher couceutrations be purchased

and diluted on site; this technique effects some cost savings

in transportation (cost per pound of solution shipped as H202).

However, for the high-purity grades or grades requiring special

degrees of stabilization, product treatment should be limited to

that performed at the manufacturing site.

3.3 PROPEULANT SPECIFICATION

Currently, there are two government specifications for the pro-

curement of hydrogen peroxide. These are:

1. NIW-P-16005D, "Propellant, Ehydrogen Peroxide,"

(18 March 1965).

2. 1IL4-h22868 (Wep)-"Wydrogen Peroxide - Stabilized,

70% and 90% (for Torpedo Use)," (21 March 1961).

142

In edditioL. during the development snd utilization of the

Redstone Missile System, there wea a "purchase description"

document, A£RA-P)-4-763, dated 14 August 1958, which was issued

by the Army Ballistic Missile Agency for the purpose of procure-

ment of 102 used in this systam. Altuough no longer applicable,

this document controlled the previous procurement of 76 w/o "20 2 .

A comparison of the limits and analytical techniques used in these

specifications, which have been used in the procurement of 90 W/o

propellant-grade, 70 and 90 w/o torpedo-grade, end 76 w/o propellant-

grade hydrogen peroxide, respectively, is presented in Tabke 3.1.

It should be noted that many of the users of propellant-grade

hydrogen peroxide have compauy-procurement cnd use specifications

for hydrogen peroxide; however, because of the many variations,

these specifications are not discuased in this handbook.

The impurity limits established for torpedo-grade hydrogen peroxide

are based on stabilization -equirements for maximum storability with

respect to to pedo use; thus, the high concentrations of the phosphates,

tin, and nitrate ions are requir'sd. In the establishment of limits

for propellent-grade hydrogen peroxide, minimum stabilization require-

=.t _1-d be ,.t, but .I~ iia.awtic th ..ausa a-&_0^ 7I.yAU1uU

were strictly controlled. These impurities were identified during an

experimental stidy reported in Ref. 3.8. Phosphate, which acts as a

stabilizer by complexing the heavy metal ions which promote No02 decom-

position, is a severe catalyst poison; thus, its content in propellant-

grade 1202 is limited. Tin (as stannous chloride) is added to the

peroxide as a stabilizer to offset the effects of residual phosphate;

therefore, a minimum limit was established for tin. (The tin content

in 202 will gradually decline during storage due to drop-out from

the solution). The chloride and sulfate ions are limited because

they causo container corrosion (through solution of aluminuma).

Niitrate has been found to inhibit the eftects of chloride and sulfate,

and a lover level has been established for this ion to inhibit con-

%ainer corrosion. A1though cortoin carbonaceous mAterials are known

to be catalyst poisons, the effeot of carbon is not eotirplý deftiod.

This effect is discussed fvrthor in $ection 7.2.1.3.1.

143

All manufacturers of propellant-grade 90 w/o bydrogen peroxide

can pre'ostl~y meet the limits established in NIL-F-l60QI. This

is illustrated in Table 3.2 with typical analyses of products from

three different manufacturers, duPont, FNC, and Shell, compared to

the procurement specification requirements.

NOE: Although there arc some differ-ences in impurity types and levels inthe hydrogen peroxide produced by thevarious manufacturers, the limits cri-teria established by PUL-,P-l6OOD areadequate to govern the procurement andoperational quality of propulsion-grade90 w/o hydrogen peroxide. Further dis-cussion of this analysis is presented inSection 7.2.1.3.

Currently, there is no government procurement specification for

98 w/o hydrogen peroxide. ,jwever, the Air Force Rocket Propul-

sion Laboratory, which has been assigned primary responsibility

for DOD and NASA propellant specification coordination, has indi-

cated (Ref. 3.9) that a procurement specification for 98 w/o Vk02

will be released in 1967. Present plans are to revise MIL-P-

16005D to include the limitations for higher concentrations of

20 2O. The tentative limits on the 1202 assay of the higher con-

centration are 98 w/o minimum and 99 w/o maximum. In addition,

the revision will include some changes in the analytical tech-

niques recommended in the present specification. Au ludication

of these changes is given in the following discussion under

Chemical Analysis.

3." CHMICAL ANALYSIS

The currently reccended procedures and techniques for tht cow-

plete analysis of propellant-grade hydrogen peroxide are pre-

sented in the appropriate procurement specifications. The chem-

ical analysis of other propellaut grades, not included in the

present procurement specifications, can be conducted with similar

techniques. Chemical analysis teshniques for hydrogen peroxide

also are available from the hydrogen peroxide manufacturers

upon request.

1144

Necaua . the space limitations of this handbook and the ready

availability of the analytical procedures, they sw'. not repro-

duued ii this Landbook. Movever, in summ'Lion of th6 analytiLal

techniques recommended by NIL-P-lb0U5D, R2 02 ausay is determined

1by standard titration with ceric sulfate to a ferroin end point.

The Alt Cl, NM&, N03 , P0 and 80,1 ions are all determined spec-

trophotometrically, and tin is determined polarographicull.,.

Carboa content is determined by combusting the sample in a fur-

nace to change the carbon materials to C0 2 ; this is subsequently

determined by titration (Ref. 3.9). There are some differences

in the analytical techaiques recommended by NILJ-F-16005D arA

those recommended by the various manufacturers and v-sed in the

iridustry. The differences in these procedured, which are for

the most part minor, are summarized in the following paragraphs.

The Air Force Rocket Propulsion Laboratory has recognized these

differences and has indicated probable changes in the presently

recommended analy io.1 " chuiques during tke next revision of

the procurment specification.

3,4.1 IEý0 Assay

Although 4L.-P-16005D recumeatds determination of Y 02 assay by

ceric sulfate titration, a survey of the industry has indicated

that most laboratories prefer 202 assay determination by a per-

manganate titratioa because of the ease in identification of the

end point. However, all laboratories can perform the ceric sul-.

fate titration with equivalent accuracics.

3.4.2 Aluminum

In the spectrophotometric procedure specified in MIL-P-16005D

for determinaticn of the aluminum ion, an almIinon-&olatiL-

buffer solution is used for color formation. Tht duPont

(Bef. 3.10) and Shell (Ref- 3.11) procedures su1gest the use of

8-W4ydrogyquinoline and extraction with chloroform for

143

color forimtion. The FMC (Ref. 3.6a) procedure suggests that

the pcmple size be increased from 10 to 25 milliliters and that

the buffer solution, prepared by the specification method, may

be slightly less stable than the buffer solution preparation

detailed in the FMC procedure.

3.4a.3 Chloride

Shell (Bef. 3.12) suggests determination of the chloride ion by

measurement of turbidity with a colorimeter instead of the spec-

trophotometer specified in NIL-P-16005D. The FMC procedure(Ref. 3.6b) is a colorimetric method using mercuric thiocyanate

and ferric amonium sulfate.

3.4.4 Ammonium

In determination of the ammonium ion by spectrophotometry, duPont

(Ref. 3.10) separates the ammonia from the other contaminants by

distillation before color formation. The FMC (Ref. 3.6) and

Shell (Ref. 3.13) procedures essentially agree with MIL-P-16005Dexcept 1MC suggests that greater accuracy may be achieved by

increasing the sample size from 10 to 50 milliliters.

3.4.5 Nitrate

FMC (Ref. 3.6) reconmnends that the heating step with the phenol-

diswlfonic acid reagent, employed in the determination of the

nitrate ion, be increased to 15 minutes (from 5 minutes) to

ensure complete contact and nitration of the sample residue.

The Shell procedure (Ref. 3.14) utilizes t, larger sample size

and increases the heating time to 10 minutee.

146.

6 Phosphate

The duPont procedure for the determination of the phosphate ion is

essentially identical to I4L-P-16005D except that the ether extrac-

tion is omitted (Ref. 3.10). The Shell (Ref. 3.15) procedure also

omits the ether extraction and uses hydrazine instead of stannous

chloride to develop the molybdenum blue color. The FMC (Ref. 3.6c)procedure is somewhat different. FMC (Ref. 3.6) reports that

attempts to use this procedure (MIL-P-16005D) failed to give

valid or comparative results. Although only preliminary investi-gations have been conducted, studies indicate an error in pH

adjustment of the sample solution before extraction with ether.

It also appears that the stannous chloride reagent is too acid,

as the blue molybdate color is removed by this reagent. Three

reagents added to the sample solution (MBr, HCl, and ENO3 ), are

not added in the calibration curve procedure. Thus, the PO0

content of the sample could be enhanced by any P04 contained in

these reagents.

3.4.7 Sulfate

For the determination of sulfate, duPont (Ref. 3.10) recommends

the use of a preliminary perchloric acid oxidation to measure

total sulfur, instead of only sulfate sulfur. Shell (Ref. 3.16)

recommends precip'tution with barium chloride, stabilization of

the suspension by the addition of alcohol and glycerine, and

turbidity measurements with a photoelectric colorimeter. 1MC

(Ref. 3.6d) also suggests the use of a turbidimeter (rather than

the spectrophotometer), and a method which converts S0 to H2S

instead of a caustic addition with BaSO 4 precipitation.

.147

3.4.8 Tin

"Both duPont (Ref. 3.10) and FMC (Ref. 3.6.) suggest the use of

a polarographic method for determining tin in contrast to the

spectrophotometric technique recommended in HIL-P-16005D. Shell

(Ref. 3.17) uses a spectrophotometric technique which is differ-

ent from that in the MIL-P-16005D; the stannic ti.n in extracted

into an 8-bydrozyquivoline-chloroform solution at a p11 of 0.85,

and the tin in determined spectrophotometrically in the chloro-

form extract.

3.Ia.9 Carbon

DuPont (Ref. 3.10) suggests that measurement of change in con-

ductivity of the barium hydroxide scrubbing solution is a more

accurate technique for carbon determination than the titration

recommended in MIL-P-16005D. FMC (Ref. 3.6) suggests that the

M•L-P-1 600 V) procedure is (1) "ti-- consuming and hence expen-

sive to run, and (2) it requires rather elaborate combustion

equipment." Instead, FMC suggests the use of a procedure

(Ref. 3.6f) where the sample is decomposed by addition of silver

nitrate solution and the noncondensable vapors, from boiling of

the resulting solution, are passed through a combustion tube

packed with copper oxide at 750 C; the resulting gas is paosed

through a solution of barium hydroxide and potassium persulfate,

which is then titrated with standard HCl solution to determine

carbon. Shell (Ref. 3.18) uses a combuation technique to con-

vert the carbon to CO2 , which is determined in a gas chromato-

graphic column.

3.4.10 Residue

DuPont (Ref. 3.14 obtains residue by atmospheric pressure con-

centration rather than in a vacuum oven.

3.4.I1 particulate

The stringency of the particulate limit, 1 *&/liter, established

by NIa-P-16005D has been noted (Ref. 3.6) in comparison to that

established (10 m%/liter) for other propellants. In sdditiqnt

duPont (Ref. 3.10) prefers the use of a Teflon polytetrafluor-

ethylene filter instead of a polyethylene filter for reasons

of safety.

5.4.12 Stability

Host laboratories prefer gas collection techniques for deter-

mining stabl.lity in contrast to the weight loss technique recon-

mended in 1IIL-P-16005D.

3.5 �El�RW~tCES

3.1 __________, "Current Hydrogen Peroxide," Chen. g., 61,

304-307 (1954).

3.2 F.M.C. Corporation, New York, New York, "Hydrogen Peroxide,"

HLydrocarbon Processing, ý4, 225, (1965).

3.3 Schumb, W. C., C. N. Satterfield, and R. L. Wentworth,

Hydrogen Peroxide, A.C.S. Monograph 128, Reinhold Publishing

Corpiration, New York, New York, 1955.

3.4 Bloom, Ralph, Jr., and Norris J. Brunavold, "Anhydrous Hy-

drogen Peroxide as a Propellant," Chem. Eng. Prog., M, (11),

541-7 (1957).

3.5 Shell Development Company, Emeryville, California, Storable

Concentrated .Hydrogen Peroxide, Report No. AFRPL-TR-66-262,

Report period: June - August 1966, Contract AFO4(611)-l1416.

3.6 Private communication, J. C. McCormick, F.H.C. Corporation,U.€.rfa New York, to M. 1. Con taiJALe. Rouke'dye, Canoga&OV4.L aI A.,L AV p • JL A:% J 1 nJn% i L L'pesC n g

Park, California, December 1966.

3.6a Ref. 3.6, based on F.M.C. Analytical Procedure SC-55-11

(Rev. 0).

3.6b Ref. 3.6, based on F.M.C. Analytical Procedure SC-55-18

(Rev. 0).

3.6c Ref. 3.6, based on F.M.C. Analytical Procedure SC-55-21.

3.6d Ref. 3.6, based on F.M.C. Analytical Procedure SC-55-22B.

3.6e Ref. 3.6, based on F.M.C. Analytical Procedure SC-55-12.

3.6f Ref. 3.6, based on F.H.C. Analytical Procedure SC-55-5

(Rev. 0).

3.7 , Chemical and Engineering News, 5 September 1966.

150

3.8 Naval Research laboratory, Washiniton, D.C., The Role of

Inorganic Contaminants in the Catalytic Decomposition of

Hydrogen Peroxide, Report No. 5117, 15 April 1958.

3.9 Forbes, F. S., "Propellant Specification, Quality Control

Analysis," Presented at the Sixty-first National Meeting,

A.I.Ch.E., Houston, Texas, 19-23 February 1967.

3.10 Private communication, J.C. Snyder, duPont, Memphis, Ten-

nessee, to M. T. Constantine, Rockctdyne, Canoga Park,

California, 22 November 1966.

3.11 Shell Development Company, Emeryville, California, Shell

Analytical Methods for Hydrogen Peroxide, SNS 714/59, 1959.

3.12 Ref. 3.11, SNS 722/59, 1959.

3.13 Ref. 3.11, SMS 708/59, 1959.

3.14 Ref. 3.11, SMS 720/620 1962.

3.15 Ref. 3.11, SMS 712/59, 1959.

3.16 Ref. 3.11, SMS 725/59, 1959.

3.17 Ref. 3.11, NP-99/63, 1962.

3.18 Ref. 3.11, SMS 749/59 (Rev. 11/13/64), 1959.

SI ' .4 C4

k~4r PIN.

IH 0 0 0 U

N 16

U so- 40 w~ 40 go-

C4

qA40

-. U U 1 2

TABLE 3. 2

COMPARISON OF TIPICAL ANALYSES FOR PROPELLANT-G•l1E90 v/o UYOGEN PEROXIDE FROM TIME DUTUUW

COMERCI AL &A•UA(CTURERS

Military. Specification DuPont Shell FWC

Percent H202 90.0 to 91.0 90.7 90.7 90.8

Percent AOL 5.0 maximum 0.9 0.3 1.1

Carbon, nag/liter 200 maximum 11 150 pi1L*

Residuc, mg/liter 20 maximum 15 15 15

43-I, nag/liter 1.0 maximum 0.2 < 0.1 0.2

P04-3, mg/liter 0.2 maximum 0.1 0.04 0.07

NO 3, Iag/liter 3.0 to 5.0 3 3.6 3.5

s04 2, mg/liter 3.0 maximum 0.3 < 3.0 0.02

Sn, nag/liter 1.4 to 4.0 1.8 1.8 1.9

Nll., mag/liter 3.0 maximum 0_- < 3.0 0.031

Al, ng/liter 0.5 maximum 0.2 0.2 0.07

Insolubles, mg/liter 1.0 maximum <1.0 <1I0

*Below Detectable Limits

153/154k

SECTION 4: STORAGE AND HANDLING

1.1 STOHABILITY

41 .1 General

The storability (or storage stability) of hydrogen peroxide is

usually described in terms of decomposition rate and/or concentra-

tion change of the H20 2 over a period of time. Biause storability

is directly related to decomposition, it becomes a function of

the considerations involved in the decomposition mechanisms. In

a simplification of these mechanisms, which are described in

detail in Section 7, the basic factors controlling decomposition

rate in a storage system are 1202 concentra'iou; temperature;

impurity types and concentrations in the H202 t and the composition,

area, and condition of the surface in contact with the " 2 02 . Al-

though many of these factors are discussed in other sections of

this handbook as a result of studies of materials compatibility,

passivation techniques, decomposition mechanisms, etc., they are

interrelated and presented in this section in tmua of storability.

Until tho early 1960's, the generally accepted decomposiýion rate

A0L* of comercial, unstabilized, propellant-grade hydrogen peroxide

under normal storage conditions (e.g., in a 30-gallon storage drum

at an S/V of 0.38 in.- )was •-I percent/year at ambient temperatures

of 77 to 86 F (Ref. 4.1). This rate is theoretically equivalent to

a propellant-grade hydrogen peroxide concentration loss of

-0.5 w/o %02/year. Some examples of decomposition rates actually

experienced during drum storage (under field handling conditions) of

various types of hydrogen peroxide between 1945 and 1963 are shown

in Table 4.1 in terms of concentration changes and actual oxygen loss.

These results, which are essentially representative of propellant

manufactured before 1960 and of storage at the S/V (0.38 in.- )typically found in 30-gallon storage drums, were reported in Ref. 4.2.

*.AOL (active oxygen loss) is defined in Section 4.2.1.1.4.

There are somi discrepancies noted in Table 4.1 between the re-

ported oxygen losses and the 11202 concentration changes. It

would appear that if the magnitudes of the reported 1202 concen-

tration cha-ges were entirely attributable to 'V2Q2 decomposition,

the oxygen losses would be much higher. Althiough it is possible

that some of the H202 concentration change during the storage

period was due to moisture absorption from the air (during drum

"breathing"), the discrepancies do cause some doubt in the val-

idity of the oxygen losses reported. Because the technique for

determirw'tion of oxygen loss is not reported, and it is assumed

that such a measurement would be difficult under the uncontrolled

conditions of drum storage, the concentration change appears to

be the most indicative factor of decomposition rate during these

tests.

From the 11202 concentration changes reported in Table 4.1, the

decomposition rate of the unstabilized 90 w/o 1202 can be esti-

mated as approximately 1-percent AOL/year which corresponds to

that rate generally accepted by the industry during this period.

The data presented in the table also indicate smaller decomposi-

tion rates for both the 98 w/o 11909 propulsion grade and the

stabilized torpedo grades (90 and 70 w/o 1202) under essentially

the same storage conditions. These effects are discussed further in

Sections 4.1.3.2 and 4.1.3.5.

Recently, improvements have been reported in the storage stability

of hydrogen peroxide, particularly, in the 90 w/o grade. The

gross result of this improvement is illustrated in Table 4.2 with

data from studies conducted in 1947 (Ref. 4.3) and in 1965 (Ref.

4.1 and 4.4) or& 90 w/o 1202 and studies on 99+ w/o "202 in 1953

(Ref. 4-.5). In this table the rate of decomposition of the hy-

drogen peroxide has been reported as a function of temperature

'Pd as a function of contamination for the three different time

periods. Although the reasons for the improvement in hydrogen

peroxide stability are not defined in Table 4.2, the data are in-

dicative of the progress that has been made in the storability

of hydrogen peroxide.

•.1.2 Storability ImPvr9vement Studies

This reient increase in the storage stability of hydroten per-

oxide is a result of a combinatiot of factors including (1) in-

creased purity of the hydrogen perioxide, (2) better selectiou

of tha cuntainer materials, (3) improved surface treatment aud

passivation of the container, and (4) development of more effec-

tive stabilization techniques. A recent characterization of

these factors resulted from three primary studies directed at

the improvement of hydrogen peroxide storability. These studies,

which were conducted by duPont (Rof. 4.6), M (ef. 4.7), and

Shell (Ref. 4.1, 4.4 and 4.9), are summarized in the following

paragraphs.

DuPont (fief. 4.6) conducted studies on (1) the stability o! solid

and low-temperature (32 F) liquid hydrogen peroxide (90 to 100

W/o 11202) in Pyrex; (2) the effect of aluminum, Pyrex, polyethylmnt,

and fluorocarbon polymers on the stability of "202 in the 1.'2

to 158 temperature range; and (3) the reaotion mechanisms of hy-

drogen peroxide decomposition. As a result of this study, the

decomposition rate of high-purity or commercially stabilized hy-

drogen peroxide at -76 to 32 F was found to be less than 0.04,

percent per yesr in Pyrex. In addition, the decomposition rate

of 90 w/o 1202 in contact with a Teflon FEP fluorocarbon film

that had been mildly irradiated in air was less than one-third

of the rate involved in contact of the 90 W/o "202 with a passi-

vated aluminum surface and less than one -half the rate with

Pyrex.

Sealed storage studies of the commercial and propulsion grades

of 90 and 98 w/o H202 in TFE Teflon bladders (contained in mild

steel tanks) were conducted at 70 to 72 F (5 months), 120 F (7

days), and 165 F (72 hours) by FEW (Ref. 4.7). Although bleach-

ing and cracking of the bladders were experienced, the tests

demonstrated a reduction in "202 decomposition rates through

157

improved surface pretreatment and passivation techniques and use

of stabilizers. Extrapolations of the data indicated the oxygen

losses of 98 w/o %02 were less than 0.4 percent/year at 70 F in

the bladders. Compatibility screening studies indicated that

other bladder mterials such as NAA Vicone 185, duPont Viton B

(805)l and 3K Fluorel 2141 were superior to the TFE Teflon material.

In the study conducted by Shell (Ref. 4.1), experimental investi-

gations were directed into three major areas: (1) improvement

of "202 purity, (2) development of an improved liquid decomposi-

tion inhibition system, and (3) assessment of container materials

of construction for long-term storage. Storage decoqiosition

rates for 90 w/o H20, were reduced to 0.04 percent/year at ambient

tozkqrature as a resuilt, of B2 02 stabilization and careful selec-

tion and preparation of the storage container material (Pyrex).

It was also indicated that the use of other materials such as

ACLA•-33C and Kel-F plastics, 1260 aluminum, and electrolytic tin

plate (special preparation) in large storage tanks [minimum

surface-to-volume ratio (S/V)] could reduce overall decomposition

rates under normal storage conditions to 0.1 percent/Year. Var-

ious means of purification such as distillation, recrystalliza-

tion, and ion exchange on insoluble inorganic exchangers have

also been effective in reducing the decomposition rate; it was

also indicated that decomposition rates of 99 w/o 1202 were

slightly lower than those of 90 W/o V202 under the same environ-

Mental conditions (including the degree of contamiuntion).

Shell has continued the investigation of hydrogen peroxide pur-

ification and stabilization techniques and the passivatiou of

container materials to determine the feasibility of sealed htydro-

gen peroxide storage for periods of 5 years (Ref. 4.8 and 4.9).

In this study, which was scheduled to be concluded in January

1968, P-stannic acid was deternined to be, the most effective ion-

exchange purification medium for increasing the stability of

hydrogen peroxide ir, storage; decomposition rates of 90 w/o H202

treated with this technique were approximately one-third the

158

rates of untreated 90 w/o H202 after storage in aluminum for periods

of 1 year. It was also determined that the minimum decomposition

rate of hydrogen peroxide in contact with aluminum surfaces was

achieved vhen the aluminum was subjected to a caustic-nitric acid-

hot (212 F) 90 w/o H1202 pretreatment sequence prior to testing;

however, only minor changes in stability resulted from various

types of chemical pretreatment of stainless-steel surfaces (Tables

4.31 and 4.31a and Section '.2.2.12 The decomposition rate of

90 w/o H202 in contact with tin-plated (electroplated) aluminum

was greater than that observed with either the best tin surface

or the best passivated aluminum surface.

4.1.3 Factors Affecting Storability

As noted throughout the various stdies of storability, decomposi-

tion, passivation, materials compatibility, propellant purifica-

tion, etc., reported in various sections of this handbook, storage

stability of hydrogen peroxide is depeident on a variety of

factors. Because it is difficult, however, to separate the in-

fluence of each contributing factor under actual storage condi-

tions, many of these studies have been conducted under ideal or

isolated environments. Although, for this reason, the transla-

tion of the data from flese tests into gross storability in terms

of particular rates are difficult, the general degree of influence

can be fairly accurately predicted and established. Thus, the

general effect of factors such as concentration, purity, tempera-

ture, container material, container surface pretreatment, and

passivation, S/V container ratio, and propellant stabilization

system on storability are discussed briefly in the following

paragraphs.

4.1.3.1 Concentration. Under equivalent storage conditions, it has been

determicvt' that the storage stability of hydrogen peroxide is

increased with its concentration (Ref. 4.1 and 4.2). This is

159

* generally attributed to the decrease in impurities and ionization

with the loss in water content, and to the decrease in container

contact area with decrease in surface tension. This effect is

illustrated as a function of concentration from 90 to 98 w/o in

Fig. 4.1; comparisons of other decomposition rates between 90 and

98 w/o %202 are shown at two other conditions in Fig. 4.2 and 4.3.

4.1.3.2 Purification. As the various inorganic and organic contaminants

are removed from hydrogea peroxide-water solutions, storage sta-

bility will approach that of high concentration (98 w/o) hydrogen

peroxide; however, because of the various effects (described in

Section 4.1.3.1) resulting from water elimination, the 3torability

of the more aqueous solutions will never equal the stability of

98 w/o H202 assuming the same degree of impurities (Ref. 4.1).

Current studies (Ref. 4.8 and 4.9) have demonstrated that various

types of purification techniques will produce hydrogen peroxide

with homogeneous decomposition rates on the order of 0.03 to 0.07

percent AOL/year at 77 F.

4.1.3.3 Temperature. In general, the decomposition rate of hydrogen per-

oxide IAMO foun A t -increas 2.3 "iwes for efat10 C. (.O 1)rise in temperature; this effect is illustrated in Fig. 4.4 which

was reprinted from Ref. 4.1. Other data on this effect have been

reported in Ref. 4.5.

4.1.3.4 Container Surfaces. The ef ect of the storage contairer on the

storability of hydrogen peroxide is essentit.,ly a function of

the type of material, the surface treatment and passivation,

and the S/V of the material in contact with the liquid volume.

16o

4.1.3.4.1 Container Material. The effect of various materials in

contact with the hydrogen peroxide is described and compared

in the Materials Compatibility Section (Section 4.2.2). How-

ever, for comparison purposes, decomposition rates resulting

from the effect, of selected materials in combination with

other effects are shown in Fig. 4.4 (Ref. 4.1) and 4.5 (Ref.

4.1 and 4.10) for 90 w/o H202'

4,1.3.4.2 Surface Treatment and Passi-ation. Several studies (i.e.,

Ref. 4.1, 4.7 to 4.9, and 4.11 to 4.18) have established the

importance and effect of surface pretreatment and passivation

on the decomposition rate and the stability of hydrogen perox-

ide. Detailed data in this area are presented in Section

4.2.2.12 and Tables 4.21 through 4.31a as part of the Mater-

ials Compatibility Section. An example of 4he effect of sur-

face prctreatment in terms of storability of hydrogen peroxide

is shown in Fig. 4.6.

4.1.3.4.3 Surface to Volume Ratio. The effect of the storage con-

tainer surface on the decomposition rate of the hydrogen per-

oxide is usually illustrated in terms of S/V. This ratio is

generally defined as tha in-ersed surface area (that area in

contact with the liquid hydrogen peroxide)/liquid volume of

the hydrogen peroxide. The relationship between these two

factors has been found to be an effective means of expressing

the contribution of the heterogeneous decomposition rate of

the liquid to the overall decomposition rate of the hydrogen

peroxide.

In determination and comparison of the compatibility of various

materials, the S/V is usually kept constant. For most of thestudies illustrated in Section 4.2.2, a sample size of 1-1/2

by 1/2 by 1/16 inch has been iwmpraed in 75 milliliters of

hydrogen peroxide, thus establishing a S/V value of 0.38 in.2/in.3 (0.-38 in.- 1 ). This number generally corresponds to the

conditions found in the htorage of hydrogen peroxide in a

standard 30-gallon storage drum.

It is obvious that as the surface in contact with the liquid

is reduced (S/V o 0), the heterogeneous decomposition rate is

reduced. Thus hyCrogen peroxide stored in large storage tanks

should have a minimum decomposition rate, assuming the equiv-

alency of the other factors. This is illustrated in Fig. 4.5a

in which experimcatal studies (Ref. 4.1) were used to predict

the decomposition rates shown in the figure; as S/V is reduced,

the overall decomposition rate of the hydrogen peroxide ap-

proaches that of the homogeneous decomposition rate. Further,

it was indicated in this study that "decomposition rates of

the order 0.1 perceut AOL/year at ambient temperature appear

to be readily attainable by use of highest quality (90 w/o

"1202) stabilized with sodium stannate and stored in vessels

of low surface activity and low S/V ratio.

Other experimental studies (Ref. 4.5 and 4.10) of thi effect

of S/V on hydrogen peroxide storability are illustrated in

Fig. 4.5b, 4.5c, and 4.7. Figure 4.5a, 4.5b, and 4.5c also

indieato the Pffect of S/V as a function of different materials.

Figure 4.7 representswork (Ref. 4.5) that attempted to limit

the homogeneous decomposition rate through the use of high

purity (99+ w/o) hydrogen peroxide and limit the catalytic

effect of the container surface by using carefully pretreated

glass. It was concluded from the latter study that "the

whole inside surface of the container plays a part in the

decomposition, but per unit area the immersed surface is

more effective than the noninmersed surface."

t.1a3.5 Stabilization. The use of 'tabilizers to improve hydrogen

peroxide storage stability is essentially based on the premise,.,that they will inhibit decompositio4 .by "ontamination incurred

during storage and handling operations. .If the hydrogen

162

peroxide could be protected against contact with soluble and

insoluble contaminants, stabilization irould not be required. In

addition to the contamination of the hydrogen peroxide by the

system fabrication materials, Y202 contamination may result

from improper storage and/or handling systemcleaning and

passivation techniques. The incomplete removal of organic

solvents, acid,, detergents, chromic acid cleaning solutions,

etc., by inadequate rinsing or the use of rinse waters which

contain various impurities can readily cause contamination of

hydrogen peroxide by the storage or handling system. For

the preceding reasons, and because the normally manufactured

hydrogen peroxide does contain traces of impurities that will

cause R 202 decomposition, some degree of stabilization has

been effected in most of the conmercially manufactured hydro-

gen peroxide. The degree and type of stabilization has de-

pended on the planned une of the 1202.

There is no single stabilizing agent which may be designated

as the most effective or the most desirable. The selection of

a stabilizer must be made with regard to the conditions under

which the hydrogen peroxide ultimately is to be used, to thetyDe of £onttaminatinn like!- ton be encontr•redA and to s...h

considerations as the required storage period and the probable

prevailing temperature during that storage period. If the

storage period is to be relatively brief, an organic stabil-

izer may be satisfactory; however, over a long period of time,

slow oxidation my destroy the effectiveness of an organic

component. However, limitations may be placed upon the choice

of an inorganic stabilizer because of the quantity of undesir-

able residues which may remain after a large quantity of hy-

drogen peroxide has been decomposed. It is also appurentp

that a large proportion of stabilizer is unsatisfactory.

An extensivq number of i•abilizers, both inorganic and organic

have been tested (i.e., t4:,. 1 , 4.5, .:$, and 4.9) with both

dilute and coýcentrated zydirogen peroxide `"olutions. Among

163

these substances, the most notable success was obtained,

especially in the case of the highly concentrated hydrogen

peroxide solutions (Ief. 4.5),with sodium stannate or 8-

hydroxyquinoliae ("oxine") in the presence of a soluble pyro-

phosphate, or e phosphate-pyrophosphate mixture. A detailed

discussion of hydrogen peroxide stabilizers is presented in

Ref. 4.19 and 4.20.

Recently, the effect of the contaminants most commonly en-

countered in propellant-grade hydrogen peroxide on the stability

,of hydrogen peroxide was characterized (Ref. 4.21). Separate

90 w/o hydrogen peroxide solutions were contaminnted with var-

ious concentrations of selected ions (Cr+3 , Fe+ 3, Cu+ 2 , Ni+2,

PO -3, S0"42, NO3- 1 , CC 1-) to determine their influence upon

the stability of the hydrogen peroxide. Copper was found to

exhibit the greatest effect (toward decreasing the stability)

followed by iron, nickel, and chromium (Table 4.2). The anions

exhibited no detectable influence in the concentration ranges btudied

wten stability was measured by standard weight loss technique.

4.1.3.5.1 Stabilization Effects. The total effectiveness of hydro-

gen peroxide stabilization depends largely on the type and

quantity of stabilizer used, the initial H1202 conceptration

and purity, and the container material type and surface pre-

treatmetut. Recent studies by Shell (Ref.A4.5) on storage in

5-gallon drums has demonstrated that commercially available

90 w/o hydrogen peroxide can be stabilized and stored in prop-

erly prepared vesssls with a decomposition rate as low as 0.04

percent/year at ambient temperatures. The evolved gas at such

rates can be contained in the vessel with relatively low ullage

and at reasonable pressures for several years. The decomposi-

tion rate depends to an appreciable extent upon the container

material and the surface finish. Pyrex effects the lowest

decomposition rate. However, with the proper passivation and

surf~ace treatment, containers of ACLAR, Kel-F, 1260 aluminum

164

and electrolytic tin having low-6/V demonstrated decomposition

rates as low as 0.1 percent/year. The ra'aj predicted for

these materials as a function of S/V are shown in Fig. 4.Sa.

Other examples of the end results of stabilization are illus-

trated in Fig. 4.1, 4.8, and 4.9. Figure 4.1 (Ref. 4.2) com-

pares oxygen loss over a 24-hour period between commercially

stabilized and unstabilized hydrogen peroxide as a function

of concentration at 212 F. Figure 4.8 (Ref. 4.7) illustratea

the reduction in AOL by commercial stabilization of 98 w/o

hydrogen peroxide as a function of temperature. The effect of

stabilizer quantity is illustrated in Fig. 4.9 (Ref. 4.8); the

stabilizer used in this illustration was sodium stannate, which

was added in varying amounts to hydrogen peroxide obtained

from three different manufacturers.

4.1.3.5.2 Stabilization Reguirements. The requirement for hydrogen

peroxide stabilization is based on the end use to which the

hydrogen peroxide will be applied. Generally, stabilizers are

added to extend the storage life of the propellant, and as such,

would appear to be deeir-able for all, situntions. Hiowever,'

when the end use of the propellant depends on its decomposition

in a fixed catalyst bed chamber, the use of stabilization is

severely limited by the poisoning effect of the stabilizer on

the catalyst (Section 7). This is reflected in the two prim-

ary propellant specifications presently in use. The torpedo-

grade propellant specification, MIL-H-22868, -which requires

long-term sealod storage propellant not subject to decomposi-

tion in a fixed-bed catalyst, specifies a large amount'of

stabilizers. MIL-P-16005D, which is thb procuremenkt specifica-

tion for propulsion-grade hydrogen peroxide, limits the total

stabilizer content to a few mg/liter bet ause of the usual

application of this hydrogen peroxide giide in fixed catalyst

beds. Hydrogen peroxide used in the che ical pretreatment

and passivation of hydrogen peroxide sysyems is sometimes

165

(Ref. 4.2) heavily stabilized to provide enough ions to com-

plex all of the potential catalytic sites. Therefore, the

quantity and type of hydrogen peroxide stabilization is dictated

by the end use of the material.

Stabilization is usually effected by the hydrogen peroxide manu-

facturer as a condition of the procurement. The individual re-

quirements should be discussed with the manufacturer and his

assistance sought in determining the need for and type and

amount of stabilization required. All hydrogen peroxide manu-

facturers indicate that conventional stabilization should be

accomplished at the manufacturing site.

4.1.3.5.3 Emergency Stabilization. Stabilization of hydrogen per-

oxide at storage sites has been utilized under "emergency con-

ditions." The conditions, which necessitate this corrective

action, are usually associated with self-heating of hydrogen

peroxide storage systems due to excessive decomposition caused

by unanticipated contamination of the system. One source

(Ref. 4.22) has recommended such corrective action when the

temperature of the hydrogen peroxide (without external heating)

rises teo a level 20 F greater than that of the surround-ing.

The rate of temperature rise also determines the urgency of

the corrective measures. Another source (Ref. 4.3) considers

it desirable to maintain time-temperature records of all

storage units and recommends taking corrective action hdien the

bulk temperature achieves a 2 to 3 F increase in temperature

over the maximum ambient temperature. Corrective action is

also recommtnded if the rate of temperature increase is greater

than 0.5 F/hour. The more conservative methods limitations

of Ret. 4.3 should result in fewer "incidents" and provide

additional time to consider appropriate action.

In estimating the necessity of corrective action based on AOL,

Ref. 4.23 states that for a 30-gallon drum, a rate of more

than 2 percent AOL/year (or 0.0054 percent AOL/day) is abnormal;

166

for a 500-gallon tankt a rate greater than 1 percent AOL/year

or 0.0027 percent AOL/day is excessive and for flow systems a

decomp)osition rate of 0.05 percent AOL/hour is the maximum per-

missible rate concurrent with a temperature rise of approximately

5 F above ambient conditions.

In the early stages of storage system self-heating, temperature

rises may be counteracted by the use of water spray on the

storage container. If adequate pure water is available, if

.container free space is available, and if moderate dilution

is not critical to the end use, the most rapid cooling may be

achieved by the addition of water directly to the hydrogen

peroxide in the storage container. This cooling period allows

greater flexibility aDd additional time for analysis, procure-

went, or preparatiou of stabilizer, but does not eliminate the

need for further action.

When attempting to control a self-heating tank, a careful record

of the temperature vs time should be maintained to help evaluate

the effectiveness of the control technique. In projecting a

time-temperature curve from previous experience, several assump-

tions m-ust be made. Muoat of the approxiwations will overesti-

mate the hazard and underestimate the time before eruption

from the storage container. There are two major factors which

may result in decomposition rate accelerations with time: (1)

excessive temperature rise may result from the decomposition

of the stabilizer, and (2) decomposition at the container walls

may result in the formation of a gas blanket which prevents

adequate heat transfer through the container wall causing addi-

tional temperature increase of the solution and increased de-

composition. In the latter case, a temperature-indicating

device on the outside wall of the tank will not indicate the

temperature increase in the liquid but will indicate a lower

temperature. Because heat transfer under these conditions

may be somewhat erratic, this temperattare is a poor indication

of true liquid conditions.

167

The hNdrogeu perexide bulk temperature will lag changes in air

temperature depending on the container size. A large tank 'which

has been warmed during the day will require some time to cool

because of" the volume of solution. For a tank to be warumcr than

air temperature at night is normal and no cause for alarm. For

the tank temperature to be gradually increasing toward an in-

creased air temperature is normal. For the temperature of a

tank not exposed to direct rays of thie sun to be increasing

in temperature when the air temperature is decreasing is ab-

normal. For the tank temperature to be consistently higher

than ambient air temperature is not normal.

In making a decision to stabilize a "hot systemV' the advice

of the hydrogen peroxide manufacturer should be sought if at

all possible. If the conditions are so critical that this con-

tact cannot be accomplished, the guide of Paragraph 1.6.6 in

"The landling axid Storage of Liquid Propellants - Hydrogen

Peroxide" (Ref. 4.24) can be used:

1.6.6 l-hergency Stabilization: The decomposition of hy-drogen peroxide at an accelerating rate, as evidenced byincreasing gas evohi ti", J,_ and temperature may be broxh1

jl

under control by the following emergency stabilizationprocedure: add 1 pound of 85 percent phosphoric acid solu-tion (in water) for each 100 gallons of hydrogen peroxidesolution. Mixing is not necessary because the turbulencewill disperse the stabilizer. After being thus stabilizedand if the decomposition subsides, hydrogen peroxide maybe stored in aluminum containers until consumed or other-wise disposed of. This solution muxst not be used in appli-cations involving catalytic decomposition chambers, becausethe stabilizer will poison the catalyst.

4.1.•3.5.4 Effective Life of Stabilizers. Storage in metal containers

slowly destroys the stabilizing effect of stannate by precipa-

tation out of the solution. This normally takes approximately

4 months for aluminum containers; in Pyrex containers the

stabilizer is approximately 45 percent depleted in 4 months;

however, in polyethylene, no loss of stabilizer was detectable

(Ref. 4.20). The analysis of hydrogen peroxide solutions for

168

tin will also reveal varying concentrations depending upon

the age of the solution when tested. Comparison of analytical

reports from separate laboratories on the same solution must

allow for this variation.

Hydrogen peroxide used by the Germans during World liar II was

usu&lly 85 percent by %eight 11. 02 and was stabilized with 8-

hydroxyquinoline in the form of the pyrophosphate or mixed

with sodium pyrophosphate. This stabilizer slowly oxidized

and in approximately 6 months had effectively disappeared.

This organic stabilizer is normally considered superior to

stannate in protection against iron.

4.2 MATrIALS OF CONSTRUCTION

Initial selection of materials for application in hydrogen

peroxide storage and handling systems is based on a series of

materials compatibility tests. These tests may range from an

evaluation of a material sample under a set of general test

conditions to the definition of the specific limitations of

various pieces of hardware fabricated from a number of differ-

ent materials. Although the compatibility of materials with

a propellant is usually based primarily on the ability of the

material to withstand chemical attack by the propellant (as

expressed by corrosion rate), the emphasis in the evaluation

of materials compatibility with hydrogen peroxide is placed

on the effect of the material on hydrogen peroxide stability

(as expressed by decomposition rate). Because hydrogen per-

oxide decomposition is a function of several variables, includ-

ing material type, surface area, contamination, temperature,

etc., it is essential that the selection of a material repre-

sent an evaluation of all of these potential effects.

The available technology on materials compatibility testing

with hydrogen perGxide is sunnarized in this section. A

description of the comqatibility studies that have been conducted

169

and the criterin established by these results are used to pro-

vide a basis for the selection of materials of construction

for hydrsgen peroxide service. The final evaluation of a mate-

rial and its suitability for an application involving contact

with 11 00 2 is based on experience resulting from that applica-

tion. In general, the recommendations of materials classifi-

cation for 11V02 service contained herein are based on botli the

results of laboratory tests and on practical experience. In

a few instances, practical experience has revealed results

different from those of laboratory tests. Whenever this is

the case, the greater consideration has been given to practical

experience and conclusions are drawn accordingly. Criteria

established for laboratory tests are based as far as possible

on correlations with experience resulting from piacing the

materials in service.

NOTE: The user of this handbook should becautioned that the materials compatibilitydata presented herein should only serve asa b:,xis for selection of materials for hy-drogen peroxid? service. Careivl consider-ation should be given to the conditions oftesting; the use of the material under adifferent set of conditions may have anentirely different effect. Materiais whichare not suitable for use at high tempera-tures may be acceptable for uses at lowertemperatures. Different fabrication proce-dures and passivation techniques may resultin variation in compatibility clasnificat-tion. Even different lots of the same partsfabricated from "compatible" materials bythe same manufacturer using the same manu-facturing techniques have revealed variationsin compatibility. Thus, it must be emphasizedthat any material used in hydrogen peroxideservice be thoroughly tested and qualifiedunder the conditions of its intended usebefore it is placed in service.

4.2.1 C ompat ib iIi ty Studies

Compatibility studies that have been conducted with hydrogen

peroxide are described in terms of standard test procedures,

170

standard compatibility classification definitions, and standard

rating criteria. Although the illustrated procedursa and

classifications do not necessarily reflect the most desirable

methods for all purposes, they do represent the most typical

(as noted in Ref. 4.25) of the general tests, classifications,

and rating criteria presently employed.

4.2.1.1 Compatibility Test Procedure. The compatibility test procedure

normally consists of three basic tests. An initial screening

test is performed to eliminate all materials that cause gross

decomposition of the hydrogen peroxide. The compatibility of

the preselected materials with hydrogen peroxide is then de-

termined by measuring a rate of 11202 decomposition (as percent

AOL) during an immersion of the materials in hydrogen peroxide

(of a selected composition) for a stated temperature and time

interval. The final evaluation in the compatibility test

procedure is the determination of the stability of the hydro-

gen peroxide after contact with the material.

4.2.1.1.1 Screening. Prior to quantitative testing, a new or un-

tried material should be immersed (after chemical pretreatment)

in 75 milliliters of hydrogen peroxide in a passivated coutainer

at room temperature for 24 hours. Special attention should be

directed to possible violent decomposition, combustion, solu-

tion, dimensional dietor.tion, etc. iff no unusoual action occurs,

the sample should be subjected to a further Screening at 150 F

for 24 hours. If uo gross reaction occurs under these pre-

liminary conditions, the material is further tested using the

following technique.

4.2.1.1.2 Sample Size. In determinations of the cormpatibility of

solid materials, a sample strip, 3 by 1/2 by 1/16 inches, is

normally used for evaluation of both the liquid and vapor

phases. For those materials that will be used in a continuously

171

wetted condition, a sample strip, 1-1/2 by 1/2 by 1/16 inches,

is usually immersed in 75 milliliters of the hydrogen peroxide

solution. This test condition simulates an apparent sample sur-

face area of 1 sq in. per 42.8 milliliters of hydrogen peroxide

(which approximates the 0.33 in. 2/in .3 S/V of the wetted surface

of a standard drum containing 250 pounds of 11202). If it is

necessary to test a differently sized sample, retention of this

apparent S/V will aid in comparison of the results with those

of previous studies. In evaluating materials for specific

applications, the S/V of the application should be duplicated

if possible. In testing the compatibility of liquids with 110 2 ,a

5-milliliter sample size is normally used; evaluations of greases

are usually conducted with samples of 5-milliliter size which

have been smeared on the inside of the test flask. It is im-

portant to record and report surface area of the test sample

and the liquid volume of the H1202 used. Vapor space or ullage

should be minimized or held constant in comparison of different

materials.

4.2.1.1.3 Cleaning and Passivation of the Test Container and

Specimens. Prior to use, all glassware (the test container)

should be immersed in a 10-percent sodium hydroxide solution

for I hour at room temperature, rinsed with water, immersed ina 10-percent IINO solution (3-hour minimum), and finally rinsed

with dis+illed water. The use of chromic acid cleaning solutions

should be avoided, and passivttion with hot concentrated

(70+ percent) hydrogen peroxide is recommended,

Aluminum samples should be scrubbed with a warm detergent solu-

tion, immersed in 0.2b w/o (N/15) sodium hydroxide at room tem-

peruture for 15 to 20 minutes, wabhed, immersed in 45-percent

nitric acid for 45 minutes to 1 hour at room temperature, and

finally washed with distilled water. The samples should then

be pretreated with 35 w/o 11202 at 68 to 72 F for 8 to 24 hours.

172

Stainless-steel samples should be degreased by scrubbing with

trichloroethylene, rinsed with water, allowed to drip dry,

and immersed in 70-percent nitric acid for 4 to 5 hours at

room temperature. Then, the samples should be washed with

clean water, washed with distilled water, and finally pre-

treated with 35 w/o H202. In instances where the stainless-

steel specimens do not respond well to the preceding passiva-

tion technique (as noted by decomposition activity in the

35 w/o H2202), stainless-steel specimens may be passivated

by the following alternate procedure which has been utilized

successfully in the past:

1. Degrease by scrubbing with trichloroethylene and

allow to drip dry.

2. Immerse the specimen in 2-percent Na 2 Cr2 07 solution,

wash twice with H20, and immerse in a 20-percent 11N03

solution for 1/2 hour at 120 to 130 F. (This pro-

cedure has been questioned because contamination

with chromate ions is possible.)

3. Flush with potable water.

4. Flush with distilled water and pretreat with 35 w/o

112 02

In the case of rusted stainless-steel surfaces and stainleis-

steel welds, an acid pickling is required before satisfacthry

passivation can be achieved. Tle procedure for this treatment

is as follows:

1. Immerse in a 3-percent hydrofluoric acid-lO-percent

nitric acid solution for 30 minutes at 100 1, or 2

to 3 hours at 65 to 70 F.

2. Flush with rotable water and scrub with a stiff

brush to remove welding scale and rust.

173

3. Passivate by imzersion in 70-percent nitric acid

for 4 to 5 hours at room temperature, rinse with

clean potable rater, and finally rinse with dis-

tilled water. Expose the specimen to 35 w/o 11202

at 68 to 72 F for 8 to 24 hours.

Plastics and elastomer uimples sh_•uld be thoroughly scrubbed

in an 0.5-percent solution of a synthe:tic detergent, rinsed

with distilled water, and immersed in a 10-percent INO 3-water

solution at 68 to 72 F for 1 hour. The samples should then

be pretreated with 35 w/o N102.

During the final rinsing of all passivated specimens, the

samples should not be touched with bare fingers; at this

point only gloves or tongs should be used in sample handling.

It is usually convenient to wash sample strips on a Pyrex

funnel (as a handling medium), taking care to wash all areas.

The strip should be dried between two sheets of filter paper

at room temperature or in a 122 F oven and then placed in a

test flask which i~j immediately capped with aluminum foil to

eliminate possible contamination by dust, dirt, etc.

4.2.1.1.4 AOL Determination by WeiFdit Loss. The specimen, pre-

pared as described in the preceding paragraph, is placed in

a passivated 100-milliliter Kjeldahl flask that has been

rinsed with a small volume of hydrogen peroxide of the re-

quired strength. The flask is weighed to 0.01 gram and the

dosired quantity (usually 75 milliliters) of hydrogen peroxide

of the desired strength is added to the flanks. The flask

is reweighed and the initial weight of hydrogen peroxide

solution is recorded as the difference between these weights.

At conclusion o." the desired test, the flask and its contents

are renz'red from the constant-temperature bath, cooled to

room temperature and weighed. As a minimum requirement, these

tests should be conducted in duplicate.

174

The percent of active oxygen lost in calculated as follow.:

WI~WPercent Active Oxygen Loss 1 2 '7 x 100

wtere

W initial nct weight of hydrogen peroxide

W 2- final net weight of hydrogen peroxide

C = initial weight traction of hydrogen peroxide,1 (pecet concentration)

100

The results of some compatibility tests (Ref. 4.10 through

4.16 and 4.18) have been based on H 2 0 2concentration deter-

minations before and after the teats. During these tests the

active oxygen loss is determined by the expression

Percent AOL =(W 1 C1 - W2C2)x10

where

Wl, We., avi C 1 are as defined previously and C2 is the

f ine' concenitration of hydrogen peroxide.

NOTE: The term 0.47 in the first equationrepreaents the weight fraction of availableoxygen in 100 W/o H 20 2.

Qualitative observations are also recorded on sich effects

as discoloration of the hydrogen peroxide and apparent changes

in the physical properties of the test material. The latter

includes: (1) for metals--corrosion, staining, and any surface

change during or after testing; (2) for plastics and elastomera---

blistering, swelling, distortion, changes in flexibility,

175

color, transparency, tensile strength, and tear resistance;

and (3) for fabrics-changes in color, tensile strength,

burning, and tear resistance.

4.2.1.1.5 AOL DeterrainatioiL by Gas Evolution. During compatibility

tests where the AOL is small, probably the most accurate method

of measurement is by gas evolution. This technique, which is

described in detail in Ref. 4.26, involves the collection of

,he gas evolved during the test period in a small gas measuring

buret. The long neck on the special test flask nots as an air-

cooled condenser to reduce lose of the hydrogen peroxide vapor.

The neck is connected by means of small bore tubing to nozzles

submerged uncer a few centimeters of water in a trough. Burets

are inverted tver the nozzles to collect the gas. A multiple

arrangement of differently sized burets with appropriate valv-

ing is used to permit selection of the proper size and additional

volume without luss of any gas. The volume of gas collected is

converted to weight of oxygen evulved by use of the relationships

expressed in the perfect gas laws. The percent AOL is then com-

puted from the following expression:

Percent AOL - 100 x weight of oxygen evolved/O.47 x C1 x W1

where C1 and VJ, refer to the original concentration of hydrogen

peroxide in the test sample expressed as weight fraction and

W1 is the original weight of the test sample.

4.2.1.1.6 Stability Determination. The recommended procedure for

stability determinations on the resultant hydrogen peroxide

is the same as presented in the MIL-P-16005D procurement

specification (Ref. 4.27). The stability of the I[202, which

is obtained from the compatibility test flasks, is measured

by determining the active oxygen loss (by either weight loss

or gas evolution techniques) over a 24-hour period at 212 F.

176

In HIL-P-16005D the stability is expressed in percent AOL,

although most procedures essentially express stability as

(100-AOL) percent.

tI.2.l.l.7 Special Compatibility Test Methods. A suggested procedure

(Ref. 4.25) for determining the compatibility of protective

clothing is performed on 4 by It inch clean test samples of"as received" material. The 11202 is permitted to drop on the

cloth sample at a rate of 4 milliliters per minute for 1 1 hour.

Results are evaluated by visual observation of any changes in

the material during this period. To simulate"soiled cloth,"

a swatch of the material is soaked in a 0.005 N ItnO 4 solution

for 30 seconds and dried at 230 F for 1 hour. The test is

then performed with the procedure used with the "as received"

material.

Sealing compounds are tested (Ref. 4.25) initially for impact

sensitivity while iimersed in 1[202. Qualified (nonimpact

sensitive) materials are then applied to the male threads of

a plug and a nipple, which are assembled into a coupling and

tightened with a torque wrench (using a 1200 in. lb torque on

stainless-steel assemblies and a 600 in. lb torque on aluminum

aa 60CULI AtUj M. tti±L viU1'y ±g UL room temper~atiure lo ki -t Alours

to set the sealing compound, the assemblies are tested for

leakage by charging them with nitrogen and immersing them

in vater. A-maximum of 1200-psig nitrogen pressure is applied

to a stainless-steel assembly and 500-psig pressure is applied

to an aluminum assembly. The pressure at which leakage, if any,

occurs is noted. The torque required for disassembly should

be noted. The sealing compound may also be tested by coating

1-1/2 byl1/2 by 1/16 inch, clean, passivatod metal strips

of 1060 aluminum and 316 stainless steel on one side. After

drying at room temperature for 24 hours, the strips are suL-

jected to the normal strip compatibility test described in

Section 4.2.1.1

177

Protective coating materials are usually evaluated in accordance

with standard compatibility procedures. The coating i3 applied

according to the manufacturers' specifications to standard

test strips and is tested as generally described in Section

4.2.1.1. (It is important to differentiate between compat-

itiblity of the coating material and the effectiveness or

covering ability of the coating on the base metal) The percent

AOL is determined, and visual observations of any physical

changes in the coating are noted. Other varlations of this

coating test involve filling a coated steel cup with 11202,

inverting a second coated cup on top of the cup containing

the liquid, and maintaining two such sets at 86 and 150 F

for 1 year and 1 week, respectively. A final laboratory test

involves the half-filling of a coated 5-gallon container with

1202 and allowing the test container to stand at room tempera-

ture in the laboratory or in a controlled temperature room.

Containers with a 12-inch ID and 12 inches high with a 2-inch

vented opening in the top are recommended for a 12-month test

duration. Ifydrogen peroxide concentration is determined

initially and bimonthly thereafter for both the cup tests and

the container test. Prior inspection of the coating for

blisters or pinholes should be made before the tests are

initiated.

A method for determining the compatibility of bladder materials

has been suggested in Ref. 4.28. In this procedure, the bladder

is immersed in concentrated IINO3 for 10 days at the maximum

potential application temperature (110 F, Ref. 4.28). At the

conclusion of the immersion test, the bladder is removed and

the fIN03 id evaporated to dryness. The "residue" is treated

with the test 11202 at 140 F; acceptance of the bladder material

depends on the resultant noareaction between the "residues"

and the test 112 02

178

4.2.1.2 lHydrogen Peroxide Materials Compatibility Classifications.

The results of the various laboratory matcriuls compatibility

evaluations and of application experience have shown that

materials can be classified into various categories based

on their contemplated types of use in hydrogen peroxide service.

All materials need not, be suitable for indefinite storage

because in applications requiring only short-time contact with

11202, materials of a lesser degree of compatibility can be em-

ployed. To facilitate selection on this basis, materials have

been generally classified according to the types of applications

for which they are suited.

A system of four classes has generally been adopted (Ref. 4.25,

4.29, and 4.3) for materials for hydrogen peroxide service.

These classes are arbitrary bu' they do provide a standard

for rating materials compatibility %ith H202. These classes

are:

Class 1: Materials Satisfactory for Unrestricted Use with 11202.

Such service includes long-time contact with the 2 02.

Typical use is for storage containers.

Class 2: Materials Satisfactory for Repeated Short-Time Contact

with 11202. Such materials are used for transient con--

tact with the H1202 prior to storage of the H1202, or

limited contact with the H1202 prior to use. Such

contact is not to exceed 4 hours at 72 C (160 F)

or 1 week at 22 C (70 F). T~pical uses are for

valves and pumps in H202 transfer lines and feed

tanks.

Class 3: Materials Which Should be Used ONly for Short-Time Contact

with 1 02. These materials should be uscd only where

neither a Class 1 nor Class 2 material would suffice.

These materials can be used for repeated contact, but

a single use period should not exceed 1 minute at

179

160 F or 1 hour at 70 F. An example of a Class 3

application is materials for use in a flow system.

The hydrogen peroxide should be consumed iii the

application or disposed of after the test because

contamination of hydrogen peroxide solutions with

Class 3 material is usually sufficient to render it

unsuitable for storage. Many Class 3 materials in-

dicate satisfactory room temperature service; how-

ever, the material should be checked prior to use.

Class 4: Materials not Rtecommended for - Use with 1120). These

materials (1) cause excessive decomposition of 11201

even on short-time contact, (2) are attacked or de-

teriorate on contact, (3) yield corrosion or deteri-

oriation products which cause excessive decomposition

of 11202 on subsequent contact, or (4) form impact-

sensitive mixtures with concentrated 11202.

Other Classifications: Clothing materials are classified as"suitable" or "unsuitable". Within the classifica-

tion of "suitable," choices are made on the basis

of resistance of the material to deterioration in

contact with the 11202.

4t.2.1.3 Test Evaluation Criteria. An explanation of typical (Qef. 4.25)

criteria used to evaluate the materials compatibility tests

described in Section 4.2.1.1 (as well as results from appli-

cation experience), and to rate the results in the appropriate

classifications per Section 4.2.1.2 is illustrated in Table 4.3.

Because the illustrated classification system is general for

all types of materials of construction that may be used in

hydrogen peroxide storage and handling systems, and the class-

ification limits were selected arbitrarily, more precise

limits should be established for specific applications. The

application of the criteria of Table 4.3 to results from

180

compatibility tests are usually subjected to the followingmodifying considerations (Ref. 4.25):

1. If there in any doubt as to whether a material should

be in a given category, e.g., Class 1 or 2, the material

is placed in the lower category, e.g., No. 2.

2. If the results of practical experience are at variance

with the results of laboratory tests, then the greater

weight is given to the practical experience in selecting

the classification.

3. The main distinction between Class 2 and 3 is tilepossible effect on the stability of the I12 0. If

there is any doubt as to whether the stability might

be affected, the material is placed in Class 3. Slight

deterioration of the materials causing foreign matter

to enter the 11202 might cause decreased stability of

the I1 02.2 2

4. Numerical limits for the various classes are approximate.

Class I materials would fall within rather narrow liwits,

while Class 2 materials have much broader limits. In

general, the higher the active oxygen loss for a

particular material, the less reproducible are the

results.

The AOL reported during 11202 materials compatibility tests has

numerous meanings in the study of hydrogen peroxide solutions.

This report uses the expression "Active Oxygen Loss" (AOL) or

percent AOL as defined in the government procurement specifica-

tions for hydrogen peroxide; this definition may be simply ex-

plained by the following mathematical expression:

Percent AOL - 100 (H1202 viught loss during testing)/

initial H202 weight v 0.470

181

The weight loss is measured over a specific period of time

at a controlled (and known) temperature. The generally

accepted criteria for AOL vs acompatibility rating are pre-

sented in Table 4.3.

lHydrogen peroxide stability, which is usually reported as per-

cent stability, is the test used to determine the relative

homogeneous decomposition reaction rate of hydrogen peroxide

solutions. As applied in the materials compatibility tests,

it is e~sertially a measure of the degree of contamination

of the solution by the test material. This is determiaed by

essentially measuring the AOL of the 11202 during a 212 F ex-

posure for 24 hours. The stability is then expressed as

(100-AOL) percent.

Another rating criteria for 11202 materials compatibility is

that of impact sensitivity. Liquid and powdered materials,

including solids which might yield finely divided particles

in service such as a carbon bearing ring, -ust be evaluated

for possible sensitivity to inpact when in intimate contact

with hydrogen peroxide solutions. This impact sensitivity is

determined by subjecting varying proportions of the material

and 11202 to the impact of a weight dropped from a specified

height. Illustrations of some impact sensitivity results are

presented in Table 4.14; however, no weight-distance data

were reported for many of the positive results. Because there

are appreciable variations in impact results with various

machines, operators, and facilities, these data are not quan-

itative, but simply indicate that under some conditions

sensitive situations are possible with the noted materials.

In some impact test procedures, a small amount of wetting

agent is added to the 11202 to simulate the intimate contact

which might be created by mechanical load (such as might be

found in pump packings or bearings). This practice, however,

is not employed consistently. Any material which is impact

sensitive when in contact with 11202 in any proportion is

182

considered a Class 4 material. The criteria of impact sensi-

tivity of a material in contact with the 11 02 is the incidence

of any positive detonation on the basis of a minimum of 10

trials. A mixture which gives negative results during the

initial 10 valid tests is tentatively considered to be non-

impact sensitive unless later tests produce a positive result.

During tests of protective coating materials, special care is

necessary (and perhaps additional criteria are necessary) if

the test is to determine the compatibility of the coating

material and not its efficiciviy or covering power. Ideally,

coating materials should first be tested alone or as coatings

on known Class 1 base metals; after these tests are completed,

the materials should be tested as coatings on the particular

base metal contemplated for end use in the composite asseubly.

Criteria (Ref. 4.25, 4.29 used in expressing the results of

coating tests will depend on the type of service contemplated;

the coating must yield the class of compatibility required

for the application and must continue to tightly adhere to

the metal during the standard compatibility tests. Exact

ciritpria fnr the'4P cranfing tests have no bhean estahliahad;

but it is believed that the coating should show no blisters

or deterioration in contact with either the Hiquid phase or

vapor phase for a period of 1 year at 86 F or I week at 150 F

(or at the desired service temperature). Splash resistance

coatings to be used as protection for surfaces in V.02 installa-

tions should not react violently with the H1202 andashould

not blister during a period of 24 hours at room temperature.

Clothing materials are normally classified (Ref. 4.25) accord-

ing to recommendations for their use. Criteria for such

classification are as follows:

First Choice: The material does not burn on immersion or

during drip tests in the "as received" or "soiled"

1831

condition; the material fibers are not appreciably weak-

ened after immersion for 1 month in 11[02.

Second Choice: The material does not burn on immersion or

during drop tests in the "as received" stage; however,

the material may show some tendency toward burning in

the "soiled" state and its fibers may be significantly

weakened.

Not Suitable: The material either causes excessive decomposi-

tion of the 11202, burns, dissolves, and/or disintegrates

in either the "as received" or "soiled" state.

Selection of materials for use as joint sealing compounds with

iI202 is based primarily on the impact sensitivity of the com-

pound with the appropriate concentration of hydrogen peroxide.

The impact tests should show no positive results with a 3

kg-meter impact at room temperature. Decomposition of the

1i20 in contact with the compound is of secondary importance;

however, the compound must not act as a strong 112 0 decomposi-

tion catalyst and thl: compound should not be a Class 4 material.

These compounds should also show zero leakage during the tests

described in Section 4.2.1.1.7.

4.2.2 Materials Compatibil.it

A large number of laboratory hydrogen peroxide materials

compatibility tests and the expcrience provided by a number

of years of 11202 usage have resulted in a comprehensive know-

ledge of the effetts of certain materials on hydrogen peroxide.

These materials compatibility data are summarized in Tables

4.4 through 4.31a. Although the most extensive compilation

of materials compatibility data was taken from Ref. 4.25, the

most recent data are those of Ref. 4.10 through 4.18.

III general, the compatibility data reported in these tables

are tests for usage with 90 w/o 11,A0,; but it has been found

that materials suitable for >90 w/o 112 02 service are usually

suitable for use with lower concentrations. III a few in-

stances, materials that are unsuitable for > 90 w//o 112,0

service have been found suitable for service at lwer concen-

trations. However, it is uncertain as to whether materials

suitable for 90 w/o I202, service will be suitable for use in

higher concentrations. Thcrefore, some compatibility data have

been generated (Ref. 4.9, 4ý25, 4.29) on a selected number of

materials with 98 w/o h1202 and are presented in Tobles lt.Ii,

4.5, 4.8, 4.19, and 4.31.

The results presented in tlhese tables indicate that, in general,

the materials suitable for 90 w/o 11202 service are suitable for

98 w/o 11 2 0 serv;ce. Some plastics are attacked wore severely

by the more coucentrated 1,,)0,) solutions. With metals, 98 w/o

120 2 generally showed less active oxygen loss ihan did 90 w/o

if202. This apparent greater stability of 98 w/o hydrogen

peroxide in the presence of metals was found to result in in--

creased storage stability in the pure aluminum shipping drums....... .rc use for all hdvu'ugen peroxide shipents. The data

in Tables 4.4 through 4.18 are presented and classified accord-

ing to the criteria of Sction 4.2.1.2. Matcrials compatibility

presented in Tables 14a, and 4.19 through 4.31a are results of

studies conducted under special and specific conditions. These

results ure presented only in terms of measured values and no

attempt bas been made to classify the results to meet a specific

set of standards.

The results presented herein are based on the conditions noted.

Different conditions (i.e., temperatures, passivations, fabrica-

tion techniques, etc.) can result in significantly different

results. The data should be used as a basis for materials

eel-ction; however, all systems after construction or fabrica-

tion should be tested for compatibility prior to actual use.

185

The materials compatibility data presented in Tables 4.4

throulh i .1a31 are sumnarized with respect to various types

of materials in Sections 4.2.2.1 through 4.2.2.10, and various

controlling effects in Sections 4.2.2.11 through 14.2.2.111.

14.2.2.1 Aluminum and Aluminum Alloys. The results of a large number

of compatibility tests of aluminum alloys with 90 and 98 w/o

are summarized in Tables 4.4, 4.20, 4.21, and 4.31. These

resulte indicate that several aluminum alloys meet the stringent

requirements of Claus 1 materials. Of these, aluminum alloys

with low copper content suhi as l060, 1160, 1260, 5254, and

5652 have shown excellent service. Minimum corrosion has been

experienced with 1060 alloy, and this alloy is the one most

frequently used in storage containers. The higher strength

5254 and 5652 aluminum alloys have shown excellent service

in shipping drums, tank trucks, and tanki car fabrication

materials. The 5254 alloy, in various grades of temper, has

been used successfully in several missile applications.

Aluminum 10(,0 has been used extensively for standard piping

despite its low tensile strength and ultimate yield- Where,

pressures may be involved which are too great for standard

pipe, the use of schedule 90 pipe of 1060 aluminum is recom-

mended. Alternate choices of piping materiel are 5254 raid

5652 aluminum.

Other aluminum alloys with low copper content, such as 6061

and 6063, have shown Class 2 compatibility. The high strength

structural alloys such as 2014, 2017, and 2024 are unsuitable

for service with 11202 becauae of corrosion and a high rate of

decomposition of the 11202 in contact with them.

Aluminum casting alloys 43 and 356 have been employed success-

fully for pump and valve bodies for many years although some

corrosion generally does occur. The low copper casting alloy

186

D-356 has indicated Class 1 compatibility during laboratory

tests with 1100', mid satisfactory service experievee has re-

sulted with various i1202 concentrationm.

Some testing has been conducted on hard-coat aluminum. The

laboratory results from tests of 10-, 20-, mid 30-minute

penetration on aluminum alloy 6061 indicated Class 3 compat-

ibility with 11202. Use experienice is very limited, but it

way be desirable to apply tiara-coat aluminum in place of 300

serics stainless steel in equipment that is fabricated pre-

dominantly of aluminaw,. Experience is needed to determine

the resistance of hard-coat aluminum to corrosion in service

with intermittent wetting.

Host cases of aluminum corrosion in 12002 syqtems result in

localized pitting (cell effect) becaume of the presence of

foreign materials, and hydrated aluminum oxide formed during

wetting aid drying cycles. The presence of chloride ion in

hydrogen peroxide results in aluminum pitting; however, if

a 7:1 ratio of nitrate ion to chloride ion is present, almost

complete elimination of corrosive action is obtained (Ref.'.2). Th.erefore, teh nitrate ioa is added to 1i 0 to counter-

act the possibility of chloride damage to aluminum.

4.2.2.2 Stainless-Steel Alloys. The compatibility of stainless-steel

alloys with 90 and 98 w/o [12C is presented in Tables 4.5,

4.19, 4.22, 4.23, 4.24, 4.25, 4.31 and 4.3la. Although there

are no Class 1 stainless steels, several Class 2 stainless-

steel alloys are known. In general, the wrought or forged

AISI 300 series stainless-steel alloys with proper passivation

are euitable for Class 2 service with hydrogen peroxide. Cast

stainless steel is generally unsatisfactory for H1202 service

unless special casting techniquas are followed.

It has been reported that some folutAlaL of the tyjic 303 free

machining alloy are not suitablc fol use with 1I,0J.. Therefore,

prior to use of this alloy, it is suggested that 11 sample of

the lot to be used be evaluated for compatibility with the

pertinent IV, grade.

Cryogenically prestrained 301 acuinleus steel offers high

yield (200,O0U pai) strength and a 280,000 tensile strength.

The test data in Table 4.5 reveal that this treatenwt t resdUlts

in a materiol that hik a border)ine Class 1/Class 2 con pati-

bility uith 90 or 98 w/o If2O2 *

Lxp•rience with use of the wrought 300 series atvinjlc.u steoŽl

for 6c=Iesa tubing, seoreleas pipe, fabricated equimjuent for

piping systems, ajad welded tanks lhia been r_.-..isfactoir. The

use of 300 selics stainless steel ia recomended for. high-

pressure flow systems and applications wV:•re tle presece of

aluminum oxide, which is difficult to avoid in 12 0 handled

in tluminuzw, cannot be tolerated.

Usually hydrogen peroxide teat toaks have Lbeen fabricated

of 37 saLainlese steel which contains n•iobium (cý;Iumbium)

as a welding stabilizer. More th.fui 15 years of satisfactory

service have been aichieved ut f`MC witl, these tanks in the

handliug of 90 and 98 w/o 11902. Although 321 stainless steel

hiab been used in a'me systems, the ti.4anium welding stabilizers

have a slight catalytic effect upon the 11202. The eitra-low

carbon 304 stainless steel has been thown to be va excellont

H202 tank ~uterial. This matex-ial demonstrates good compat-

ibility with I1202 at room and elevated temperatures.

An extensie amount of testing has been conducted on

precipitation-hardening stainless-steel a1loys such as AM-350

trod 17-7 Hi alloys. The AM-350 material has given excellent

188

service in flight vehicles; however, the material hardness

wust be less thian 412 Ic (llockwelJ Hardness Scale C), or there

is an increase in !1 02 decompositioin said development of metal

rusting. The 7 P11 material has proved very successful

'With 7t w/o 11202 and moderately atsccessful with 90 w/o 11202;

however, a peCLial pa&&esivatioai treatment (itf. 1,.31) is re-

quired to achieve a Class 2 rating for this material. Surface

finishing of the sample with 120-grit abLasuije compound was

found to be effective in improving the compatibility of this

a llo)y.

The AISI 400 seriet stainless steels, whether aniealed or

in the heat-treated form, 40 to 58 Ic, will rust if the surface

finish is greater than 10 rms. This type of corrosion phenomenon

itndicates that it is necessary to examine samples froms comupat-

ibility tests after the actual test has been completed. It

is suggested that this examination should be made at 21.-hour

and 1-week inter-als of exposure to air after the sample ia

dried. It has been found that imuersion of a sample in dia-

tilled water for 24 hours following the compatibility test

will tend ti i.duce thi-'s_ type of stuir i 'L-ev I V-Urrom i on

In general, stainleao steels suitable for 112)02) service, i.e.,

AISI 300 series and precipitation-hardening alloys, are non-

magnetic or only weakly magnetic. Therefore, any metals that

are magnetic should be suspected of incompatibility with 11 0.

For exawple, iron, mild steel, and AISI 1.00 series stainless

steels are magnetic and are not suitable for 11,02 service.

Mny unknowI material that is magnetic is of questionable cow-

patibility with 11202 until completely tested.

It has been determined experimentally that, in general, the

snoother the material finish of 11202 system components, the

better the compatibility. Finishes should not exceed 32 rms,

189

and should be smoother if possible. This is especially im-

portamt Iin stainless-steel storage and hindling systems; airough spot in a tank, for example, will cause H)0 2 decýmpoa-

itlon. This condition can be avoided with propler deigvan and

system fabrication. In addition, it hlis been noted (tef. 4.32)

that stainiless-steel alloys require cleaning and repassivati oi

after extended service in l1202 t, limit, the gradual buildup

of decomposition activity.

4.2.2.3 P'ure Metals aid Other Metal Alloys. The compatibility of pure

metals and various other metal alloys with 90 w// hydrogen

peroxide is presented in Tables 4.6 and 4 .7,respectively.

Many metals other than tic al•'wiiajuw and stainless-steel alloys

have been evaluated, but few have been fotnd suitable for 11002

service. Silicon, tantalum, tin, and zirconiun are exceptions.

Of these, tin has been utilized to the greatest extent, i.e.,

for gaskets and an a solder for stainless steel.

Most other metallic elements exhibit catalytic actioii in con-

tact with I1000. This is especially true of silver, lead,

cobalt, and pl1atinum. Iron oxide causes rapid catalytic

decomposition of 11,)0,. Titaiiwtn and zinc are severely attacked

by the 11200.

A few alloys have shown suitability for Class 3 service end

might, vitlh other passivation techniques, be made suitable

for Clars 2 service; however, additional research would be re-

quirfd in this area. Unfortunately, none of the extreme hard-

ness metals tested have shown suitability for even Class 3

service, except thy 10 rms finish 440C stainless steel (5o to

58 11c) mid hard-bearing chrome plating (58 to 70 Itc).

190

4 .-. 2.. Illntics _and Itubber Compounds. An exeAlent summary of tile

results of compatibility tsts with vaiouts pitnitic and

rubber compoundn, preseanted in Tnbl is 4a.8 t(I!rough It.12 1ad

4. 2 through 4.30, was p~resented in lie '. 4.-.25, ilecatse plastics

and rubber compounds are oguan i ini ina ture, t he compatibility

with hydrogi'n peroxide varies coansiderably. INeve those tuatetiala

•ihich have shown excollea't compatibility with 90 wj/o 11i0r,

both in the laboratory wad in use, may be suslmect when new

coniditions arc met which have not ben encountered or simulated

prevIously . Conditions which may lead to reactioii between a

plastic materia aind II202 are extremely varied and di fficult

to predict or to evaluate in the laboratory. hlowever, the

following erie generalization must always be considered:

the c ombination of high-Ltren.tith hydroglci perovide, organic

materials, and heat itrout either an external source or from

112)0 deoomposition may lead to an explosive reilction.

The compatibili-ty of plastics oftev is not determined by the

chemical nature or compouitioo of the polymer itself Ilt is

determined by the impurities present in it Contaia,idatiot

of molding materials during handling aid storage with dirt.

dust, aid other organic materials as well as inclusion of

metal chips or granules can cause noticeable decomposition

reactions. A surface spec1 of foreign material originating

in the mold may initiate a reaction with hydrogen peroxide

with sufficient heat release to initiate reactioias with the

polymer. Laminated plastics or compression molded materials

vhich contain minute pores or air pockets may be incompatible

because of the accumulation of organic material in these voids.

This is usually the result of some cleaning or rinsing process

involving organic materials.

For these reasons, there may be differences in the compatibility

of plastics from different manufacturers nid even lot-to-lot

variations in a given pol)ymer material from the same majufactur'cr.

Lot-to-lot variations are usually much less noticeable than

191

differences caused by various prucossing and handling tech-

niques. Compatibility of plastic and other polymeric or

composite materials are therefore usually associated with it

mavtufactu-i-ei's3 name.

Cleani pulyethylene has been safely uti~ized during laboratory

wolt, and polyethylene has proved to be a satisfactory mate-

rial fur usv with 27.5 through 50 wio ||,04*. llowever,

polyethylene at ;ts melting temperature has ignited on coni-

tact with concentrated hydrogen peroxide and is therefore not

recommended for concentratioits in excess of 70 w/o L0o2.

Although no information has been obtaiticd, this possibility

should also be considered in the uve of other combustible

pol)shers for service at temperatures approaching their melt-

ing point or thermal decomposition temperature.

llighi-tempervture service materials such as Kel-t and Teflon

have not demonstrated any indication of reaction with hydrogen

pet-oxide ovor the entire concentraLion range at ambient temp-

erature conditions. These materials were also found to be

compatible 'With 90 w/o 11202 up to 270 F. There is no kn'own

relae... to avotid utainfit th(U-e IYIRtI 'rianlo !k o lh 11]0,- m0 ,lrvive

where the ll0(02 will remain below its nurmal atmospheric boil-

ist point. However, mixtures of these materials with other

materials must always be evaluated becauue reactions arc

varied and the compatibility of any added ingredient must

alway)' be considered. Glass-filled Teflon is acceptable,

carbon-filled Teflon may be acceptable, and asbestos-fillest-

Teflon is not acceptable. Kel-F, Aclar, and "virgin" Teflon

are the mast compatible plastic material, at high operating

temperatures and should be utilized wherever the physical

properties are suitable. It is especially recommended that

these materials, which have exceptionally low coefficients

of friction, be applied in i 02 service as dynamic bearings

192

and seals without lubricants wherever possible because of the

limJ.tationb of the available lubricants. Special high-pressure,

2-hur compatibility tests at 132 C (270 F) and 1000 psig with

90 W 10o 1ý02 demonstrated that Teflon and Kel-F are not ad-

versely affected. The AOL for these 2-hour periods is com-

parable to the percent AOL experienced at 66 C (151 F) in

7 days. Filled plastics such as Kel-F elastomers, 9711

Silicone, and Vitons show swelling at the high test temperatures.

Kel-F elastomeric compounds are generally inferior to Kel-F

itself in compatibility with Iw) 02, and most of theae materials

tested have met the Class 2 criteria.

Aclar, Mylar, and Dacron plastics have demonstrated excellent

compatibility with 1102 in the laboratory. Dacron has been

used fairly extensively as cloth for protective clothing and

reinfo,'cement of other plastics which contact 11202. Mylar

film has been used very little because it does not heat seal,

and a compatible adhesive has not been found. Aclar is heat

sealable and is being used in some applications. Use of these

materials, particularly Aclar 33C film, as bag liners for

storage containers i. currently under study (Ref. 4.9).

There are many plastic materials that break down upon extended

exposure (> 7 days) to 90 and 98 w/o H202 at elevated temper-

atures (151 to 165 F) but exhibit no effect uron 24-hour

exposure. The majority of Viton A, Viton B, Fluorel 2141,

and Fluorel 4121 compounds show this effect. However, most

service applications are at ambient temperature conditions

10 to 50 C (50 to 120 F) and these same plastics and rubbers

demonstrate excellent service at these temperatures.

193

Viton A and Fluorel materials demonstrate Class 1 ratings in

10 to 49 C (50 to 120 F) service. Viton A 271-7, produced

by Parker llannefin Corporation, has demonstrated exceil)edt

service as O-rings in 90 and 98 w/o V102 solenoid vaives and

for component seals. Seuls Ersteru Corporation's Fluorel 2141

and Fluorel 4121 O-rings, seals, and bladders have proved

satisfactory in the moderate temperature range. David Clark

Company's Omnii (Viton A) has proved useful as O-rings and

when used to impregnate glass or Teflon cloth, produces a

material which is satisfactory for use as an 1102 splash

cloth or curtain (Table 4.8).

Polyvinylchlcride-based materials vary in their' reaction with

1102 because of the plasticizer content and because other

additives such as fillers and pigments are used. It is gen-

erally true that such additives reduce the compatibility of

the compound with 11t02. Koroseal 700 (molded) has been ex-

tensively used as a gasketing material in low-pressure service.

The formula for this material was developed specifically for

1102 service. Koroseal 116 and 117 (molded) are both inferior

to Koroseal 700 (molded) for 110, service. Calendered Koroseal

is unsuitable because the 1102 penetrates into the sheet and

develops gas pockets which separate the layers of material.

Calendered materials which do not exhibit Lhis condition can

only be fabricated of materials which are absolutely imperme-

able to 1V02.

Polyvinylchloride plastics are generally permeated by 90 w/o

k 202. This has been determined for both molded and plastisol

types of polyvinylchloride. The absorption of 1202 is indic-

ated by the fact that the materials which are generally clear

or translucent turn an opaque white after a period of contact

with the 10o.. The polyvinylchloride material containing

194

absorbed 11V2 may be shock sensitive although no adverse

experience of this nature has ever been encountered, Polyvinyl-

chloride plastics will also leach chloride ion into the 1 V2

which will cause corrosion of aluminum even when present in

minute quantities.

Silicone rubber elastomers also vary considerably in compdti-

bility with hydrogen peroxide because of the use of pigments

and fillers in some compounds. However, there are a number of

these compounds, mostly unpigmented, which indicated Class 2

compatibility with "202. Of these, Silastic 9711 has demon-

strated the most satisfactory compatibility with 90 w/o 11002.

Silascic 9711 is used in various applications as an 0-ring,

gasket, hose, and bladder material. Although silicone rub-

bers are not subject to heat sealing, welding techniques have

been developed and Silastic 9711 welded with Silastic 2200

indicated satisfactory compatibility with H202.

The compatibility of several possible bladder materials is

reported in Tables 4.26 through 4.28. Compatibility tests

of 90 w/o 11202 at 110 F for 10 days with l.ilastic 9711

(surgical grade), Fluorel 2141, and Aclar 22C (Ref. 4.17)

revealed Aclar to be the most compatible material. A similar

study involved the use of Vicone 185, alone and as part of

a composite structure with aluminum in addition to the pre-

ceding materials. Vicone 185 was not quite as satisfactory

as Aclar in the pure state. In the composite structures,

Vicone 185 with aluminum exhibited the highest decomposition

rate while Fluorel with aluminum exhibited the most stable

combination. Following compatibility tests conducted at

160 F, both Silastic and Fluorel were badly blistered (Ref.

4.12 and 4.15 through 4.17). These results are in slight

conflict with Ref. 4.25 which reported the most compatible

bladder material readily available for 90 w/o 1202 in North

American Aviation's Vicone 185 (Table 4.26). Other satis-

factory bladders are the 1). F. Goodrich Company's 9711 high

purity silicone material, and duPont'. thin film I'4T Teflon

(heat sealed). There are otCer materials that show promise

as bladder materials, such as Viton A aid B.

Some adhesive agents for bonding silicone rubber Silastic

9711 to aluminum b061 were evaluated in the form of finished

washers. Chemloc 607 appeared to be most suitable and DCA

4094 is only slightly inferior to it. With the adhesive

present, compatibility results were reported to be poorer than

would be expected for the silicone rubber and aluminum alone;

however, a control test was not run for comparison.

Silicone rubbers that indicate Class 2 results for !•,O0 service

are considered to be superior to polyvinylchloride maoerials

becaube the possibility of chloride leaching is eliminated

andin general, the flexibility of silicone rubbers varies

much less over a wide temperature range. Permeability studies

of silicone rubber to I 02 indicate slow seepage and layer

separation because of oxygen evolution in the pores. Because

of the permeability of silicone rubber to hydrogen peroxide,

prolonged contact even at atmospheric pressure may make the

silicone rubber susceptible to rapid oxidation should a flame

be encountered.

Host of the plastic materials discussed can be utilized as

gaskets in the proper type of flanges. However, there are

two reinforced Teflon gasketing materials which have exhibited

satisfactory compatibility, and should find application.

Korda-flex, a Teflon-coated glass fabric, has indicated

Class 1 results and Duroid 5600 yielded Class 2 results.

Actual use experience has not yet been gained with either

of these materials.

196

Several tests have been made of built-up diaphragms, usually

a plastic and cloth sandwich type construction using Dacron

or glass fabric. The compatibility of these diaphiagms with

90 w/o 1102 has been satisfactory when using Omni (Viton A)

impregnated glass, Teflon, or Dacron cloth. Polyethylene

and Kel-F sheet diaphragms have been utilized successfully

in pressure transducers with water on the pressure gage side.

Stainless-steel diaphragms have also been utilized satisfac-

torily. In designing equipment for 1102 service, it is best

to avoid diaphragms if possible. If a diaphragm must be

used, there should be adequate testing of diaphragm materials

with 1 02 before the materials for its construction are

chosen.

4.2.2.5 Porous Materials. The results of compatibility tests of

90 w/o hydrogen peroxide with porous materials, prcsented

in Table 4.13, are summarized in Ref. 4.25. In this summary,

it was indicated that porous materials are generally of in-

terest for use in the filtration of hydrogen peroxide to

collect any solid foreign material which accidentally enters

intO the lL0, U 'eeab a minor amount of catalytic dirt

might be tolerated in a large tank of 1202, collection of

this dirt on a filter in a relatively small quantity of U-202

could cause considerable Jecomposition. Therefore, care

must be exercised to keep the use of filters to a minimum

and to select filtering media that will not readily react

with decomposing V202. Therefore, for concentrations of

1202 above 50 w/o, low melting materials such as Dacron are

not recommended for filter elements (Ref. 4.25).

Some porous porcelain bacteriological filters have exhibited

good serive in 1102 power system refueling operations. Tests

indicate that porous Teflon and Kel-F may be suitable for use

as filter media.

197

Stainless-steel filters fabricated of wire, either wrapped

or woven, yield Class 2 or 3 results. When using these mate-

rials for filter elements, welding should be kept to a

minimum. Filters made of 316 stainless steel have been used

successfully in various "202 operations, such as fueling

operations involving flight vehicles. Porous stainless-steel

elements formed by sintering powdered metal have not proved

satisfactory for 1102 service.

Filtros C has been used extensively for filtering tll concen-

trations of 1120 and for filters on atorage and shipping tank

vents, but it is iragile and difficult to back-waih. Replace-

ment of this material for both uses is being investigated.

It is not reconmended for power-system use.

When using filters for 11,0,) service, it is important to keep

them clean and to examine them frequently. When dirt on a

filter is allowed to dry, oxidation may occur which may cause

increased catalytic action. Therefore, it is a good policy

to flush a filter before use, and to back-wash an H 02 filter

imediately after use with distilled or clean water.

4.2.2.6 Lubricants. The compatibility of various lubricants (Ref.

4.25 and 4.33) with 90 w/o 1V02 is p1 sented in Tables 4.14

and 4.14a. The test results indicatt that only the fluorinated

hydrocarbous are sufficiently compatible with 90 w/o 1122 to

be considered. Even these materials can probably react with

the 90 wj" 1202 if there is sufficient force or heat applied

to the mixture. However, the use of fluorinated hydrocarbons

has been satisfactory in transfer pump packing glands in use

with 300 series stainless-steel shafts.

198

The pr-sont fluorinated hydrocarbo&ns do not possess good

lubricating qualities and their viscosities vary widely with

temperature. Some lubricity additives were evaluated sev-

eral years ago, but none was completely satisfactory because

of the difficulty of attaining stable emulsions. In addition,

use of fluorinated hydrocarbons as lubricants for aluminum

threads or in conjunctior with aluminum with a high surface

area in applications where L~at may be created (which is a

natural condition in all applications requiring lubricants)

may lead to detonating reactions without any 1102 present.

Two instances of such an occurrence, one during a thread cut-

ting on aluminum pipe using Fluorolube as a cutting lubricant

and the other when fluorinated hydrocarbon was used as a

thread compound on the aluminum head bolts of a decomposition

chamber, have been reported. This reaction was reproduced

in the laboratory by dropping a fluorinated hydrocarbon on

heated aluminum in powder form.

There also is some indication that presence of a fluorinited

hydrocarbon in intimate contact with an organic materia'L and

90 w/o I,,0 may cause increased sensitivity. Although this

pheaxomenon has not been adequately evaluated, it appears that

the use of fluorinated hydrocarbons in conjunction with or-

ganic materials in concentrated 1102 service should be avoided

unless the specific system to be used has been adequately

tested. The best practice if possible, is to eliminate the

need for lubricants.

In evaluating lubricants for I1V202 service, the results of

the impact test are of greatest significance. However, there

is no standard impact tester, and the reproducibility of most

testers is marginal. The modified Bureau of Mines Impact

Tester used for the results reported in Table 4.14 is simple

to use and has been proved to be generally reliable; but it

199

is subject to vuriations in results with different operators,

and the condition of the anvil plunger or weight is another

variable. Despite the practice of regular calibration of the

tenter with a "known" mixture of ethyl alcohol and 90 w/o

"1202 in equal-volume propcrtions, poor reproducibility has

been experienced. Because of this situation, it is thought

that any positive detonation should be sufficient to place

"a lubricant in Class 4 for H202 service. Thus, even though

"a lubricant or grease may pass all tests with negative re-

suits and then give a positive result during a later check

test, it will be classed as unsuitable for H-0 2 service.

Pump packing lubrication is one problem which can be over-

come by the use of mechanical seals which require no lubri-

cation. Seals fabricated of 300 series stainless steel

with ceramic and glass-filled Teflon mating surfaces and

cooled with the liquid H202 being pumped have been success-

fully applied to centrifuial transfer pumps for several

years.

4.2.2.7 Ceramic and Refractory Materials. A summation of the re-

sults of ccmpatibility tests of 90 w/o hydrogen peroxide

with ceramic and refractory materials, which are presented

in Table 4.16, has been taken from Ref. 4.25. Testing of

materials in this category has been limited because applica-

tions are often limited by fragileness where shock impact

may be experienced. Most of these materials have been coni-

sidered for applications where hardness is important or as

filter elements contained in a stainless-steel housing.

Coors Ceramic AB-2 has been utilized successfully in con-

junction with glass-filled Teflon for mechanical seals on

I202 transfer pumps, which use H202 as a coolant for the

seal. Coors Ceramic AB-2 and AJ-200 have been utilized for

plunger pump parts, but no experience has been obtained with

H202'

200

Selas porous porcelain microbiological filters have shown

satisfactory service with 90 w/o and 98 w/o 112 02 at,d may be

used to filter high-strength 11 202

Aluminum oxide coating materials were evaluated and found to

be unsatisfactory. The poor results may be due to the method

of coating, added agents, or the roughness of the coatifg.

Laboratory glassware is used extensively for carrying out

compatibility and stability tests as well as general lab-

oratory handling. Pyrex glass is superior to soft glaus

and is used extensively as piping in the 11202 manufacturi ug

facilities. Glass linings have been evaluated to a limited

extent; the more common glass used for lining contains

cobalt, which demonstrates poor compatibility with [1202.

Some glass formulas do, however, show excellent compati-

bility with 11202, but there is no use experience available

with these linings.

Synthetic sapphire has not been applied extensively despite

its excellent compatibility with i1202. Ilotameter floats

are probably the only present application.

4.2.2.8 Protective Coating HMaerials. The compatibility of protec-

tive coatings (Ref. 2.25 and 4.29) with 90 w/o H202 is pre-

sented in Table 4.17. Protective coatings are not recom-

mended for H202 storage tank service, but may be of value

for special purpose tanks and to protect incompatible ma-

terials from "202 splash. Of the protective coatings evalu-

ated for service w'.Ih 90 w/o H1202, only Teflon, Kel-F, and

hot air-sprayed polyethylene have indicated suitability for

more than splash contact at temperatures to 71 C (160 F) for

Teflon and Kel-F, and temperatures of 49 C (120 F) for poly-

ehtylene; however, there has been no experience with such

coatings in actual service. The application of such coatings

201

or paints is recomnended for surtfaces of materials subject

to corrosion. Prcvention of rust in 11V2 handling and stor-

age areas is a safety measure because the possibility of

contaminating the 11202 is reduced.

Kanegin-coated (electrolcss nickel) mild steel has shown

good compatibility with 90 w/o 1V02. Tin-plating, followed

by a heat treatment at 215 C (420 F) to seal the pores, has

proved #o be an effective coating for 1102O service.

It is believed that protective liners may be used to ad-

vantage in I 02 service for prevention of corrosion of

aluminum surfaces and for special cases of high-pressure

feed tanks to allow fabrication from metals which possess

high strength-to-weight ratios but are not sufficiently

compatible with the 11202 to allow a practical holding time.

In general, platings, such as tinplate, strip off when ex-

posed to "'0 w/o 11002 unless special precautions are taken

to prevent this. Apparently, the H202 seeps through pin-

holes in the plate or under the edge and then decomposes

when it contacts the undersurface, liberating oxygen gas.

The gas then forms a blister which eventually breaks and

allows more 11202 to contact the undersurface.

4.2.2.9 Protective Clothing Haterials. The results of compatibility

tedts of protective clothing materials with 90 w/o hydrogen

peroxide, summarized in Tables 4a.18 and 4 1 8a, are discussed

in Ref. 4i.25. The study of materials for protective clothing

was directed primarily at finding materials which would not

ignite if 90 w/o !t202 was spilled on them when they were

soiled with catalytic dirt. The chief hazard encountered

when concentrated hydrogen peroxide is accidentally splashed

202

on a worker ic the possibility that the worker's clothing

will ignite. The materials were also evaluated for resimtince

to deter iration by the action of concentrated hydrogen

peroxide.

As a result of this study, it was found that in both the

clean mid soiled condition,"virginuDacron in all forms,

Sarai-monofilament, mid 55 percent Ducrol-145 perceiit woul

cloth resisted ignition. Dynel and Sarai stable fiber re-

sisted ignitiou in the clemn condition sad ignited only

with difficulty when soiled. Dacron was unaffected by 90 w/o

11,202, and Dacron-wool and Dynel were only slight detiorated.

It must be noted that some trcated and dyed Dacron-i iii the

"soiled" condition will ignite with 90 w/o 1I202, and all

samples must be tested before use.

Based on this study, sources were developed for permeable

and impermeable clothing; a recumiended protective clothing

and necessary accessories list for 1t202 handling is pre-

sented in Section 6.4. This list includes safety clothing

and equipment such as goggles, gloves, aprons, and shoe

coverings which are made from plastics or rubbers acceptable

for the purpose. Dacron and Dynel wurk clothing have been

utilized to a considerable extent with satisfactory service.

It must be pointed out that even protective clothing MUST

BE KMPT CLEAN and particularly free of ordinary greases and

catalysts such as potassium permanganate. Grease-soiled

samples of Dacron, Dynel, and 55 percint DacroL-45 percent

wool fabrics have been found to igrnite and burn vigorously

when wetted with 90 w/o H202. When laundering or cleaning

Dynel fabrics, special techniques must be employed because

of Dynel's low softening and embrittling points. Dacron may

be laundered without special precautions. Thus, Dacron id

preferred for this reason in addition to its better resistance

to the 8202.

203

4t.2.2.10 Joint See] llg Compounds. The results of physical and chemi-

cal tewts of joint sealing compounds with 90 W/o hydrogen

peroxide are summarized in Ref. 4.25 and Table 4.15. Host

commerical pipe joint sealing compounds 'ere found to be

unsuitable for high-strength hydrogen pero.ide service. In

systems for concentrations of less than 52 w/o 11202, Aviation

Grade 1'ermatex No. 3 and equivalent have been used satisfac-

torily. There are two thread compounds that have shown good

service in 52 thrvugzi 98 w/o 11202 systems. These a'e T Film,

a Teflon wawer-disp-rsion paste for small pipe threads aid

Teflon tape for 1/4- through 4-inch-size pipe thread. Fluori-

nated hydrocarbon-based materials react vio.enily with hot

powdered aluminum. Therefore, these compounds must not be

used on hot aluminum threads and must never be used as a

thread cuttiij lubricant.

Applications of even the approved joint sealii* compounds

to threads for an 11202 flow sysLem must be made so that no

compound will enter the system. The compound should be usedsparing•ly, only or, the, mamle p-nr -. '--'-d I.- 'r'.f_64 t'6

threads. Thus, the surplus amount will press out. of the

threads, not into the system. Pipe threads should be avoided

in 1I202 syntema; flanges and 37-degree flare connections are

recommeuded.

4.2.2.11 Temperature 1,Lfects. The effect of high temperatures, in

the 212 to 2-0 F region, on materials compatibility with

98 w/o 11202 is shown in Table 4.19. This effect is of par-

ticular intere. t in selection of materials for use in H2 02

regeneratively cooled thrust chambers (Ref. 4.29).

The effect of high-temperature storaje conditions (151 F) on

materials compatibllities with B2l2 is shown in Tables 4.21,

4.22, and 4.24 through 4.30. The appropriate references to

this work are given in each of the corresponding tables.

204

4.2.2.12 Evaluation of iassivation or Surface Preparation Techni ques.

Laboratory tests (Ref. 4.13) have been conducted to: (1)

determine the effectiveness of selected passivation methods

upon 321 stainless steel, 6061-T6 aluminum (bare and anodized),

and Silastic 9711, (2) determine the influence of cyclic ex-

posure of passivated surfaces to hydrogen peroxide; and (3)

investigate the effects of various storage conditions upon

passivity of materials used in hydrogen peroxide service.

The passivation methods employed in these studies are given

in the following references:

CVA-]0-62a (Ref. 4.31)

NAA LA 0110-003 (Ref. 4.35)

Walter Kidde 520007 (Ref. 4.36)

FMC Bulletin 104 (Ref. 4.25)1

McDonnell A/C 13002 (Ref. 4.37)

LTV 308 - 20-3 (Ref. 4.38)

CVA l0- 64a (Ref. 4.39)

The results of these tests are given in Tables 4.21, 4.24,

and 4.27.

The preferred passivation method for 321 stainless steel was

found to be CVA l0-u2a with posttreatment with 35 w/o com-

mercial hydrogen peroxide. For 6061-T6 aluminum (bare and

anodized), the best passivation technique was according to

North American Aviation Specification LA-0110-003. All

pass ivation methods investigated were found to give about .o•

the same results witli Silastic 9711. The ease in passiva-

tion of all materials was found to improve with each exposure

to concentrated hydrogen percu .de. Environmental exposure

tests revealed that 321 stainless steel can be stored best

in clean air with relative humidities up to 1.00 percent;

anodized 6061-T6 aluminum remains more passive in a dry

nitrogen atmosphere. Silastic 9711 appears to retain its

passivation best in a relative humidity of 100 percent.

S~205

The loss of oxygen in 90 w/o H2 02 solutions in contact with

316L and 321 annealed stainless-steel tubing for 3, 5, 7, and

10 days at a constant temperature of 110 F was determined as

a function of two different passivation techniques. One-half

of the tubing specimens was passivated by OVA Specification

10- 6 2a with a posttreatment of 35 w/o hydrogen peroxide in-

hibited with a 0.03-percent H 3P04 solution; the other half

was passivated by Walter Kidde Co. Specification Nor.-520007.

The stability of the H202 solution was also determined after

each test. In general, 321 stainless steel produced less

hydrogen peroxide decomposition than the 316L material. The

best passivation method, as indicated by the AOL results for

both the 316L and the 321 stainless, was found to be CVA

Specification 10- 6 2a plus posttreatment (Ref. 4.18). These

data are summarized in Tables 4.23 and 4.24.

In another study (Ref. 4.9), the effect of surface treatment

on the compatibility of various materials was determined and

expressed in heterogeneous reaction rates (k 2 ), as shown in

Tables 4.31 aqd 4.31a.

4.2.2.13 Effect of Surface Finish. The effect of surface finish on

materials compatibility with 11202, summarized in Ref. 4.1I,

is shown in Tables 4.21 through 4.25. Five different sur-

face finishes applied to 304 stainless steel and aluminum

alloy 6061-T6 (both bare and anodized) were P-!"luated in

contact with 90 w/o hydrogen peroxide to determine the in-

fluence of surface finish on the stability of the peroxide.

The stainless-steel specimens were passivated according to

CVA Specification 10- 6 2a with posttreatment in 35 w/o in-

hibited (0.03 percent H3 PO) hydrogen peroxide. The aluninum

specimens were passivated according to North American Speci-

fication LA 0110-003. Although inconsistent correlations

were obtained bctween the surface finish and AOL with the

304 stainless steel and the bare 6061-T6 aluminum specimens,

2o6

the active oxygen loss resulting from the anodized aluminum

in contact with the hydrogen peroxide indicated an increase

in AOL values with surface roughness. (Surface roughness

may simply be considered as a surface area factor; the

rougher the surface the higher the actual surface area com-

pared to the apparent surface obtained through naasurements

of the linear dimensions of the sarple.)

This investigation has strongly indicated (Ref. 4.14) that

the Industry Staidard AOL test is not an adequate tool for

highly selective screening of materials for hydrogen peroxide

service. The AOL test is considered insufficiently sensitive

to the detection (with any degree of accuracy) of the cata-

lytic decomposition influence exhibited by small variations

in surface roughness or materials in contact with concen-

trated hydrogen peroxide.

4.2.2.14 Effects of Dissimilar Metals. The results of an experimental

investigation of dissimilar metal couples compatibility in

H 202 (Ref. 4.11) are shown in Table 4.30. In this study,

the decomposition rate of 90 w/o hydrogen peroxide was meae-

ured with the following couples: 1060 Al + 6061-T6 Al;

6061-T6 Al + 321 stainless steel; 6061-T6 Al + 316L stainless

steel; 321 stainless steel + 3161, stainless steel. The AOL

and H202 stability was determined during an exposure of

10 days at 110 F an4 7 diva ah i5' F. The tests at 110 F

revealed no significant iafiuence of the dissimilar metal

upon the hydrogen peroxide; however, the 151 F test revealed

that the catalytic decomposition of tb•s hydrogen reroxide

was greater for the dissimilar metal cou.ples thaon for dther

of the single-metal alloys.

207

i• , MATERIALS TREATMENT AND PASSIVATION

General

All material surfaces that come in contact with propellant-

gradý hydrogen peroxide must be specially cicaned and treated

prior to their use to minimize hydrogen peroxide decomposition

and material corrosion. The general terminology applied to

this process, which is designed to provide an inactive sur-

face and eliminate potential contamination sites, is passi-

vation. This section provides a detailed outline of the

passivation procedures normally used for materials in hydrogen

peroxide service.

The passivation procedure essentially consists of three pri-

mary steps prior to the material contact with propellant-

grade hydrogen peroxide. The initial step is a chemical and

physical cleaning procedure designed to remove oxides, scale,

dirt, weld (and heat treat) slag, oil, grease, and other

foreign material from the base material. The second step

is usually the treatment ("basic passivation") of the mate-

rinl with nn ll, lin^. .'- na-i.i . to form •. A ,41....

(probably a complex oxide) on the surface to minimize chem-

ical or catalytic activity betheen the surface and propellant.

Finally, the material is subjected to propellant conditioning

to check the completeness of the chemical treatment and to

eliminate, through further oxidation and chemical complexing,

all remaining active sites. Normally, propellant conditioning

is conducted in 35 w/o H2202 , although many organizations pre-

fer additional propellant conditioning of materials at the

conditions (H2 02 concentration and temperature) that will be

experienced in final application of the material.

The material surfaces should be subjected to passivation

after part fabrication and before component or system assembly.

208

B3sically, items such as valves, pumps, actuators, system

piping, etc., cannot be cleaned properly in the assembled

state, because the solvent, cleaning solution, residual con-

tamination, etc., may be trappe4 in inaccessible areas. The

cleaning should be conducted imnediately before component or

system assembly, unless provisions are made for packaging the

passivated part to protect against re-contamination until

ready for assembly. After assembly, components, such as

valves, should be packaged until they are utilized in the

final system assembly. It is also standard procedure to

check all passivated items with propulsion-grade hydrogen

peroxide prior to assembly in the system.

All cleaning, passivating, and rinse solutions should be

applied by immersing, spraying, wiping, circulating, or other

manner so that all surfaces to be cleaned will be completely

wetted and flushed with the solutions. Any section of the

i ew to be cleaned that can trap or retain any liquid should

be drained or em-.`,,d between the applications of each dif-

ferent solution or chemical mixture. The item should be

rinsed until it is chemically neutral between each operation.

Surfaces should not be allowed to dry off between the clean-

ing and the "basic passivation" steps. The water grade used,

depending upon the passivation stage, should be distilled,

deionized, or potable tap water (which has been filtered

through a 1 O0-micron nominal filter). Unless otherwise spe-

cified, all chemicals should be C.P. (chemically pure) grade

or better.

4.3.2 Passivation Facilities

The passivation of materials for hydrogen peroxide service

should be conducted in an area designed only for that pur-

pose. The area must be kept clean and free of combustible

209

material. Equipment to be used in the passivation procedures

should be large enough to accommodate all items to be placed

in the iintended system and provide a method of complete wet-

ting (with all solutions) of tLe surfaces requiring passiva-

tion.

Procedures for handling hydrogen peroxide and the various

passivation solutions should be well established and obeerved.

Some of the more important requirements are discussed in the

following paragraphs.

4.3.2.1 Personnel Education. All personnel operating in the area

should be well informed of all operating procedures, poten-

tial hazards, safety precautions, proceoures, etc. (see

Section 6.0).

4.3.2.2 Area Cleanliness. The area must be protected from dust and

dirt te prevent contamination of the cleaned parts. Although

a clean room atmosphere is not essential, it is recommended,

partirurilrly, for nsanivatinn nf flight, hardwsarp

4.3.2.3 Drainage. An adequate water supply and drain must be avail-

able for flushing away spilled acid and hydrogen peroxide.

All spillage or dump of chemicals must be heavily diluted

before passage into a drainage system; protected open trough

drainage is recommended.

4.3.2.4 Safety Showers. An adequate number of deluge safety showers

must be provided for area personnel. The locations of these

showers should be such that they can be reached within a few

steps from any location.

210

4.3.2.5 Eye Wash Fountains. An adequate namber of eye wash fountains

should be provided in easily accessible locations.

4.3.2.6 Ventilation. Adequate ventilation must be provided to main-

tain a minimum concentration of solvent and acid fumes, Hloods

with suction fans should be iustalled and used wherever possible.

4.3.2.7 Warning Signs. Safety and warning signs should be placed

where they can be seen and should be appropriate to the haz-

ardb created by the cleaning, passivating, and hydrogen

peroxide solutions.

4.3.2.8 Personncl Protection. Personnel, when handling the various

passivating solutions, should be dressed in suitable protec-

tive clothing. The minimum garb should consist of a face

shield or goggles, rubber (acid-resistant) gloves, rubbers,

and an apron. (For additional infurmation, see Section 6.0).

4.3.2.9 Minor Equipment. Various-sized polyethylene beakers should

be provided for the treatment of small p,.rts. These beakers

are resistant to all reagents normally recommended and used

in the passivation procedures. Although glass beakers can

be substituted for the polyethylene beakers in the use ot

all but hydrofLuoric-nitric acid solution, their easy break-

age can result in a greater hazard. The polyethylene boakers

should not be used for conditioning or surveillance tests

with 1 02.

4.3.3 Cleaning and Passivation Solutions

Generally, the chemical solutions required in the passivation

procedure may be prepared as described in the following para-

graphs.

211

4.3.3.1 Detergent Solutions. A 1 W/o solution of a powdered com--

merical detergent such as Dreft, Naconal, Tide, All, Swerl,

etc., in potable water is normally used for cleaning mater-

ials and glassware. Liquid detergent (of the same approxi-

mate concentration) or a mild solution (5 to 7 ounces/gal)

of a commercial alkaline cleaner such as Turco No. 4090

(or its equivalent) may also be used; however, it should be

noted that a strongly alkaline cleaning solution must be

avoided. The container for the detergent solution should be

rust-resistant and covered to minimize dirt pickup. Since

most procedures recommend the use of hot detergent solution,

provisions should be made for heating the detergent container

to 140 to 160 F.

4.3.3.2 Degreasinp Solvents. Commercial-grade trichloroethylene,

perchloroethylene, or a commercial solvent such as Varsol or

Sunoco cleaner are used for degreasing metals whuich are

heavily soiled or very greasy. Alternate degreasing may be

performed in a vapor degreaser using trichloroethylene (which

meets the Mil-T-7003 specification) or an equivalent gradeof one of t~le . hnve above ,olen..e. Io.-.o-weer, -.• alou- l be noto-

that the working temperatr :e of the vapor degreaser must be

higher than the boiling point of the selected solvent. The

solvent should be stored in a covered galvanized iron, black

iron, steel, or other suitable container. Care should be

taken to prevent entry of water into the chlorinated solvents

contained in the mild steel containers because the resulting

conversion to acids will cause corrosion of the metal and

subsequent contamination of the material during passivation.

t.3.3.3 Sodium Hydroxide (NaOH) Solution, Approximately 1/15 N. A

mild (0.25 w/o) NaOH solution can be used as an alternate

method for cleaning heavily soiled aluminum equipment. A

supply of this solution, which should be available at all

times, can be stored in a stainless-steel drum or polyethylene

212

container which has been previously washed with a detergent

solution and 'inued with clean potable water.

4.3..t Sodiu-z I•ydroxide (NaODi) Solution, 10 wVo. A 10 w/o solution

of NaOll solution is used for cleaning glassware which is

heavily soiled or has contained an unknown solution.

4.3.3.5 Sulfuric Acid (INS04 ) Solution, 35 w/o. A solution of lkS04

is used primarily for passivating glassware. The solution

can be stored in a polyethylene-lined container ur the glass

carboys in which it is received. A lid must be provided if

stored outdoors. Heated storage may be necessary depending

upon the concentration of the acid and the winter tempera-

ture of the locality where stored.

4.3.3.6 Nitric Acid (H1N0 3 ), 42 degrees Baume'. A nitric acid of 42

degrees Baume' (-.70 w/o BNO3 ) is recomnended by F1 (Ref.

4.25) for passivating stainless-steel equipment. It should

always be readily available and stored in the containers in

which it is received.

4.3.3.7 Nitric Acid (BN0 3 ), 45 w/o. A 45 w/o 11N0 3 solution is pre-

ferred by most orgavizations for tha "basic passivation"

step for aluminum and stainless-steel parts. The acid is

normally stored in a polyethylene-lined or AISI 300 series

stainless-steel container. A lid taust be provided to keep

out dirt and confine the acid fumes.

4.3.3.8 Nitric Acid (1ON0 3 ) 33 w/o. A dilute HNO3 solution of 35

w/o is recousended by FMt (Ref. 4.25) for passivating aluminum

equipment. This acid is stored as above (Section 4.3.3.7).

213

4.3.3.9 LVdrofluoric Acid (IIF)-Nitric Acid (1INO ) Mixture, 3 w/o-

10 w/o. A 3 w/o IF-1O w/o lNO 3 solution in used for pick-

ling and cleaning stainless steel when rust or other surface

contamination exists which cannot be removed by the nitric

acid solution. A polyethylene- lined container, with a lid

to keel) out dirt and confine the acid fumes, should be used

for storage.

4.3.3.10 HIydrofluoric Acid (llF)-Nitric Acid (11N0 3 ) Mixture, 1 w/o-

10 w/o. Uuanodized aluminum and aluminum alloy components

that are excessively dirty or contain oxidt film from weld-

ing, heat treating, etc., moy be treated with a 1 w/o ILF-10

w/o ILN0 3 solution. This solution should be stured in the

same manner as the solution discussed ii Section 4.3.3.9.

4.3.3.11 Clean Potable.Water. Drinking water, after filtration?

through a 40-micron nominal filter, is used for rinsing

parts during the initial stages of passivation.

4.73.3.12 Fresh Distilled or Deionized Water. Distilled or deionized

water, which is used for rinsing parts after passivation,

should have a maximum specific conductivity of 10-6 wh1os/cm.

This water should not be stored in aluminum for periods

longer than 1 week prior to or during use. Storage of dis-

tilled or deionized water in an aluminum 11202 storage tank

for any length of time results in slime formation which may

sender the tank unsuitable for 11K202- In the storage and

handling of potable water, distilled water, or deiouized

water, the potential contamination by ttn,, valves, lines,

etc., should be considered (i.e., the use of copper in ihe

system should be avoided). Storage time of deionized or

dis,,illed water should be minimized, preferably less than

1 week. Distilled water should be used for the preparaticu

of deionized water.

214

3.3.-.13 jjydrogen Per oxi~de B~olution, 35 w/o. Although a stabilized

35 w/o hydrogen peroxide solution is available (from various

comercial manufacturers) for the initial propellant-conditiouing

step, many users utilize 35 w/o 1,202 solutious obtained by dilu-

tion of higher concentrations. However, various hydrogen peroxide

manufacturers recomend that if the 35 w/o 11202 is obtained by

dilution of propellaut-grade K1202 (with no or minimum stabiliza-

tion), a stabilizer should be added to the dilute ,202 and the pH

of the solution adjusted so that residual active metal sites can

be deactivated by complexing with the stabilizer (recommendations

of the hydrogren peroxide manufacturers are encouraged in this

area). ihegardles. of the user's preference in the use of stabi-

lizers, any dilution of it202 must be conducted with distilled

or deionized wuter of duitable quality. The 35 w/o solution

should be stored in an aluminum 1060, 5652, or 52511 container.

The storage container must be vented at all times, and the

vent line should be provided with a suitable filter to keep

out dust or dirt. A hydrogen peroxide shipping drum is a

convenient container; however, once removed, the hydrugen

peroxidt uast not be returned to the original drum or con-

tainer. Uydro-en pe~roxide f rom a satisfactory aict iv i t -A~

may be reused, if economics dictate.

I4.3-.l Typical Passivation Technique

Specific passivation procedures that are being or have been

previously used by various organizations involvcd in hydrogen

peroxide usage are contained in the following documents:

Chance-Vought A.ircraft* Specification CVA 10- 6 2a

Chance-Vought Aircraft* Specification CVA 10-6,4a

FW Bulletin 104 (Ref. 4.25)

LTV Astronautics Specification LTV 308-20-3

McDonnell Aircraft Specification 13002

*XiOT: CVA specifications were obtained from-LTV Astronautics(Mef. 4.34 and 4.39).

215

*Eorth American Aviation, Specilication NAA A (010J-O03Inc.

Reaction Motors Division Specification NMI 7000

Walter Iidde Covaany Specification 52O0)7

There are numerous differences in the exact techniques and

procedures used by various organizations for the passivation

of maturials, parts, systems, etc., for hydrogen peroxide

service. glowever, for the most part, these differences are

insignificant and the general techniques used are very sim-

ilar. Although various storability and compatibility studies

"(see Section 4.1 and 4.2) have indicated the greater effec-

tiveness of some techniques over others, it is believed that

no one technique has consistently demonstrated a repeated

superiorit•.

Thus, in developing a procedure to be useO by any facility,

the general or typical technique described below cau be used

as a starting point. More specific (in detail) procedures

or modifications of these typical procedures may be developed

and preferred with the acquisition of "passivation experience";

however, 1he typical procedurer described will passivate m9st

compatible materials. Tire solutions called out in the pro-

cedure are those designated in Section 4.3.3.

,.3.4.1 Degreablt and Cleanin. Excessively greasy metal parts

should be iiitially degreased either by cold flushing with

a solvent for 30 minutes (ripeat with clean solvent if neces-

sary), or through the use of a solvent vapor degreaser for

at liast 10 minutes. All metal parts should then be cleaned

with a hot (140 to 160 F) comaercial detergent solution or

a mild alkaline commercial cleaner. (A 1/15 N NaOH solution

has been used for nonanodized aluminum.) Cleaning can be

accomplished by agitation of the part in the cleaning solu-

tion, scrubbing with a stiff nylon brush, aad/or pumping

the solution through the part (as in the case of tubing and

216

piping). The metal parts should then be rinsed thorough]y

in warm potable water to remove all traces of the cleaning

compound.

Nonmetallic and bonded nonmetallic parts such as gaskets, 0-

rings, chevron rings, hoses, etc., should be degreased by

immersion or scrubbing at 140 to 160 F, with a commercial

detergent or a mild alkaline cleaner, followed by a thorough

rinsing with warm distilled or deionized water. Teflon,

polyethylene, Kei-F, or Viton, except when bonded to metal,

may be cleaued with a solvent, but immersion time should be

limited to a short period (__5 seconds). Items which have

solvent or water remaining on their surface and are not to

be chemically cleaned further, will be dried immediately with

clean dry nitrogen gas or air.

NOTE: Following the degreasing and cleaningstep, the cleaned surfaces of the parts shouldbe handled with clean gloves or tongs only.Any possible means of recontamination of thepart should be avoided frow this point.

4.3.4.2 Descaling. Newly fabricated or reworked meal parts, which

have scale from wel4ing, or heat treatmevt, or impurities

from casting or forging, should be descaled ("pickled").

Descaling solutions should not be used after finish-machining

of precision'surfaces without protection, or on pards that

do not have heavy oxide or foreign material buildups in the

form of rust or scale. The contact time of the descaling

solution with the item ,o be cleaned should be the minimum

time necessary to clean the part or the maximum allowable

time per this section, whichever is shorter. Only plastic-

coated or nonmetallic gaskets should be used with nitric-

hydrofluoric desealing baths to prevent excessive metal

loss caused by electrolytic corrosion.

217

7 777

4.3.4.2.1 Stainless Steel. Stainless-steel parts should be

etched for a minimum period, and not longer than 60 minutes,

at room temperature (60 to 80 F) with a mixture of 3 w/o

technical-grade hydrofluoric acid, 10 w/o technical-grade

nitric acid, and the remainder water.

CAUTION: A close visual check should be main-tained during descaling operations with theIW-IIN0 3 mixture to prevent material pittingor excessive etching. After descaling, thepart should be thoroughly rinsed with potablewater to remove all traces of descaling solu-tiops. Loosely adhering smut or flux may beremoved by spraying with water or scrubbingwith a stainless steel or hemp brush. If theparts are to be passivated immediately afteracid cleaning, they need not be dried. Theparts may be dried completely by purging withdry, hydrocarbon-free nitrogen or air, or inan oven at 140 to 150 F. The AISI 400 series,303S, 303SE, and AM 355 stainless steels will"be descaled by mechanical methods such asmachining, abrasive tumbling, or grit blasting.

4.3.4.2.2 Aluminum and Aluminum Alloys. Nonanodized aluminum and*liinmiinm ii11nu niv'.a inau ho .•aa, n1,la i'_ intr svainn in a 1 'r/o

------------- -J r1 -

HF-10 w/o IIN0 3 solution for 30 seconds to 5 minutes at 115 F

maximum.

CAUTION: A close visual check should be main-tained during descaling operations with theHF-HN0 3 mixture to prevent material pittingor excessive etching. After descaling, thepart should be thoroughly rinsed with potablewater to remove all traces of the acid solu-tion. It should be noted that a 35 w/o H2S04solution at -115 F can also be used as analternate "pickling" solution for aluminumand aluminum alloys.

218

4.3.-4.3 "4asic Passiaration." Immediately following the cleaning

(or descaling) operation, the metal parts should be sub-

jected to ,se "basin passivation" step. Although this step

is always accomplished with HNO3 solutions, the concentra-

tVens used by different organizations vary. The following

procedures are those preferred by the w.jority. It should

b. noted that plastic and synthetic rubbers should not be

sabjected to this step in the passivation procedure.

4.3.-4-3.1 Stainless Steel. Stainlcss-steel parts should be im-

mersed in a solution of 45 w/o HNO3 at 60 to 80 F, for a

minimum period of 30 mi|,'ites. FHC (Ref. 4.25) recommends the

use of 70 w/o BNO3 for a period of 4 to 5 hours as the

stainless-steel passivation step. The parts should then be

rinsed and flushed thoroughly with deionized or distilled

water to remove all traces of the passivating solution.

Unless the part is immediately placed in the propellant-con-

ditioning solution, it should be drained and dried by purg-

ing with dry, filtered, hydrocarbon-free nitrogen or air,

or dried in a dust-free oven at 140 to 150 F; the part shoul 1

then be protected from recontamination by sealing in a sealed

clean plastic bag.

The nitric acid passivation solution should be used for the

AIS! 300 and 400 series stainless steel. The protective film

resulting from this passivation process will not normally be

visible, but surfaces will be uniform in appearance, free

from scale, corrosion, pitting, and contaminants. Normal

* discoloration from welding will be permitted, provided no

scale or rust is associated with the discoloration.

Some organizations recommend electropolishing of stainless-

steel parts (except for AN 355) by the best available cow-

mercial practice as an alternate method for staialesa-steel

219

4'•

passivation. Following electropolishing, the material should

be cleaned with detergent (Section 4.3•4.1) rinsed thoroughly

with deionized or distilled water, and dried in an oven.

4.3•.•..2 Aluminum and Aluminum Alloys. Aluminum and aluminum

alloy materials are usually passivated with a solution of

45 w/o HNO.• ut room temperature for a period of 1 hour; how-

ever, F4C iRef. 4.25) recomends the use of 35 w/o HNO3 as

the passivaticn acid. The materials should be rinsed and

flushed with water to remove all traces of nitric acid, and

unless immediately conditioned with the propellant, the nia-

terials should be drained and dried by purging with dry,

filtered, hydrocarbon-free nitrogen or air, or dried in a

clean oven at 140 to 150 F. Machined aluminum barstock parts

do not normally require descaling or passivating processes

and can be prepared for service by degreasing and thoroughly

rinsing. Welded, cast, or corroded parts will require de-

scaling, cleaning, and passivating. Anodized aluminum parts

will not be descaled or passivated and should be prepared

for service by degreasing and thorough rinsing.

4.3.4.4 Propellant Conditioning. Following cleaning and acid treat-

ment steps, metallic materials should be propellant condi-

tioned to check passivation ("activity testing") and passi-

vate further potentially active sites in the materials.

The nonmetallic materials are propellant conditioned follow-

ing the cleaning step. Normally, most procedures recoumend

initial propellant conditioning with 30 to 35 w/o H202 (see

Section 4.3.-3.13). Following this conditioning, most proce-

dures call for conditioning with hydrogen peroxide of the

grade with which the material will eventually b6 applied.

Propellant conditioning, which should be conducted for a

minimum period of 3 to 6 hours, is conducted on both the

unassembled parts and components and the assembled systems.

220

-- '--77- - -.

.aterials. Parts, and Components. Before the initial

activity tests are conducted, components much as valves,

pumps, etc., should be assembled (care must be taken to

avoid contamination during assembly). The passivated our-

faces should be exposed to the selected 1202 solutions by

either immersion of the part or by filling the composite

assemblies (components) with the H20 2 . Low openings in the

composite assembly may be closed with passivated plugs of

the same material or polyethylene-covered rubber stoppers;

however, there must be a vent to allow escape of gases from

the assemblies. During the tests of the composite assemblies,

all sliding surfaces must be completely wetted (through

valve actuation, etc.) by the 1202.

Acceptance of passivation is contingent upon no reaction of

the material with the hydrogen perioxide (as evidenced by

the lack of gas bubbles evolving from the 1202). If, at the

end of the exposure period, the gas bubble rate is very min-

imal, the unexposed surfaces of the materials are cool to

the touch, and the gas bubbles are not confined to a partic-

ular location, the material or part is considered acceptable.

If rapid bubbling, clouding of solution. or a local hot

spot is observed during the test, the solution should be

discarded and the active part repassivated in accordance

with Sections 4.3.-.1 and 4 .3.'4.3. If it is practical, the

active area should be marked for future observation. A com-

ponent or part should be rejected if it fails three consecu-

tive passivation tests. If a part shows only marginal un-

acceptable reaction, it should be removed from the 1202

solution, rinsed several times with distilled or deionized

water, and reconditioned with fresh H202 solution; the part

should then be repassivated if it continues to demonstrate

marginal unacceptability. Parts which cause discoloration

of the 11202 solution will be reimmersed in fresh H202 solu-

tions; if discoloration continues, the part should be re-

jected and the discoloreJ H202 solution disposed of immediately.

221

S ..... •"''•:' '-'• • •... i,•,, , .. .-. •. .. •. Lw _. ,'.',,p • ' '• ,•-''"-, " ' ':•'7 7-- 7•-'': .• •. "• 7 '

Any part which shows blackenine, rust streaks, or signs of

excessive corrosion should be rejected.

After the materials, parts, and/or assemblies have passed

all activity checks in the selected H2 solutions, they

should be rinsed thorouhbly in distilled or deionized water

and dried with clean dry air or nitrogen. Heat may be used

to dry if the plastic materials are maintained below 120 F

and the metals below 150 F. All parts must be handled with

clean tongs and/or clean neoprene-gloved hands to prevent

recontamination. After drying, the materials should be

assembled in the final system or packaged according to

Section 4.3.7.

4.3-4.4.2 System Assembly. After complete assembly of a handling

installation, storage facility, or any other hydrogen per-

oxide system from compatible and passivated materials (that

have undergone preliminary activity checks), the system should

be conditioned as a whole. The entire system assembly should

be filled with 30 to 35 w/o 1202 (see Section 4.3.3.13) and

activity checks conducted. Again, it is noted that the sys-

tem should be vented and all valves and sliding surfaces

should be operated to wet all surfaces with H2 0 The test

should be conducted for a period of 4 hours unless a local

heated area or excessive gas evolution indicates the test

should be terminated. The observations and conclusions in

the assembled system tests are identical to those of the

materials, parts, and components conditioning (Section

4.3.4.4.1) with one exception; most organizations advoctAte

an activity check of the system using a laboratory-type

"1wet test meter" to measure the actual gas rate.

After successful preliminary testing of .tlhe system with

30 to 35 w/o H202 solution, the system should be condi-

tioned with s202 solutions of the grade it will eventually

222

<~-

utilize. Following this pansivation, the system is con-

sidered ready for hydrogen perioxide service. All such

passivated systems should be protected against further con-

tamination with dust caps. In addition, the system should

be continuously surveyed during use for evidence of exces-

sive H202 decomposition.

!t.3.5 Glassware Passivation

Because glassware passivation is slightly different from

that associated with the materials commonly used in hydrogen

perioxide system fabrication and more often involves a

laboratory-type operation, the technique used has been sep-

erated from the typical passivation sectiin. The procedure

for the passivation of glassware, which includes thermometers

and hydrometers, is contained in the following paragraphs.

Glassware that is heavily soiled should be immersed in a

10 w/o NaO1i solution for 1 hour at room temperature. If the

glassware is relatively clean. a commercia! detergent shouldbe used instead. Following this cleaning, the glassware

should be rinsed thoroughly in clean potable water.

Chemical passivation is accomplished by immersion in 35 w/o

H20 4 for at least 1 hour at room temperature. After the

glass is thoroughly rinsed in distilled or deionized water,

it should be dried with clean air or nitrogen, or in an

oven at 230 F.

The passivated glassware can be stored in a "ready-for-use"

condition by packaging in accordance with Section 4.3.7.

Bottles, flasks, or other containers can be stored by cover-

ing the opening tightly with aluminum foil.

223

4.3.6 .Passivation Aid.

So that materials passivation be accomplished with minimum

difficulty, several general rules should always be observed.

T'he primary rule is, of course, strict adherence to clean-

liness thoughout the procedure. Other considerations, prim-.

arily associated with the materials treatment prior to initia-

tion of passivation procedures, are noted below.

4.3.6.1 Metal Machwing. In addition to the selection of compatible

metals, the effectiveness of future passivation of these

metals for hydrogen peroxide service depends upon eliminating

contamination of the materials with incompatible materials

during machining. Thus, the use of zinc, copper, copper

allo)s (i.e., bronze or brass), tin, iron (low carbon, non-

stainless types), silver, lead, cadmium, carbide, sand, etc.,

should be avoided in tooling and machining operations.

43.6.2 Sirfup Fin i__,. All surfaces which contact hydrogen peroxide

should be as smooth as possible, with manufacturing marks,

identification symbols, and irregularities reduced to a min.-

imum. All surfaces contacting hydrogen peroxide should be

free of cracks, pits, inclusions, and foreign material.

Whenever practical, sharp corners should be broken and a

surface finish of 40 rms (root mean square) or finer achieved.

4 ,k.6.3 Abrasives. Abrasive cleaning methods should not be used if

a suitable chemical method is available. Wlhen abrasives are

necessary, only glass beads, aluminum oxide abrasives, or

stainless-steel wire brushes should be used. AN 355 should

be cleaned only by mechanical methods. Acid descaling should

be avoided if possible.

224a

m - -WV -- &~

4.3.6.4 Anodized Aluminum. Aluminum surfaces which contact hydrogen

peroxide should be anodized. Exceptions are surfaces whose

shape makes anodizing impracticable (i.e., tha interior of

long tubes). Sulfuric acid anodizing is preferred snd should

be used where that process is avail3ble. Sealing of sulfuric

acid-anodized surfaces should be done in hot water (195 ±

10 F for 30 minutes). Deionized water is preferr,.d for seal-

ing although tap water may be used.

4.3.6.5 Rework. All fabrication and fitting of detail parts and corm-

ponents should be completed prior to pasnivation treciment.

Any rework oti passivated areas makes rvipasiivation mandatory.

4.3.6.6 Welded As3emblies. For welded assemblies, each part should

be cleaned prior to welding. Completed weld assemblies muot

be passivated prior to further assembly.

4.3.6.7 Pressure Testing. Pressure testing of a system using various

test fudids ,--rrplaemct of _-- ...... 0 .- eA

will automatically make it mandatory to repeat the activity

testing procedure for that assemly.

4.3.7 Handling of Passivated Materials

Items thdt have been cleaned and passivated should be handled,

stored, or packaged in a manner to prevent recontamination.

Immediately following cleaning and passivation, large valves,

piping sections, vessels, flex joints, subassemblies, and

other prefabricated items should be dried and have ends and

openings capped, plugged, or flanged and sealed with clean

compatible sealing material. Small valves and components

225

should be purged with clean, dry gaseous nitrogen and vrapped

and see.led in clean plastic or metal foil bags. These com-

pouenes should be kept sealed until installation.

4.3.7.1 Acneptable Materials. Small items should be sealed in clann

preformed e,,clopes, rolls, or sheets or: (1) polyethylene

film, polyethylene-backed paper, polyethylene-backed cloth,

or polyethyleiie-backed aluminum foil, (2) vinyl (Vinylite),

(3) Koroseal, (4) Saran, or (5) 'ylar, Materials for short-

"term storage of passivated items can also include aluminum

foil (or aluminum-backed cloth or paper) and celiophane.

4•3.7-2 Indefinite Storage. In the packaging of small passivated

itces for long-term storage, the items should be dried and

packaged as soon as practicable after passivation and activity

testing. Any openings of the itemg should be sealed with

clean new polyethylene or aluminum caps (used closures will

be discarded to prevent reuse). The materials should be

enclosed in a clean envelope and sealed to stop free passage

of air. This envelope should then be wrapped in heavy paper

11.3.7.3 Identification. The passivated Imirts should be identified

with standard markings such as date, part number, part name,

etc., but in addition, a tag should be attached which notes

the equivalent of the following:

PASSI VATI) PART

This part passivated for use with w/o

Ihydrogen peroxide. Activity Test OK

(Date) (Inspector)

NOTI: If a part is contaminated beforepackagingj or if a packalre containing a passi-voted p~art is torn, the part should be re-turned to proper area for passivation oractivity tetst as needed.

226

-'T7

4.4 FACILITIIS AND EQUIPIMNT

1.*I~ Stcrage and Hlandling Facilities

A facility for the utorage and handling of hydIogea peroxide

may exist in the form of; (1) a singular storage facility for

hydrogen peroxide only, (2) a special handling area for hydro-

gen perioxide, such as an equipment passivation area, (3) a

storage complex for oxidizers including hydrogen peroxiue, (4)

an area storage complex for fuels and oxidizers, or k5) a

handling complex for various propellants. Although it is de-

uirabie that any such facility be located in an isolated area,

out of necessity, it may bt: located in the proximity of a test

or launch facility.

The specific desigii criteria for each type of hydrogen peroxide-

containing facility must be considered independently although

most considerations apply to all facilities. This is neces-

sary because any other propellants stored or handled at the

facility also require special considerations. In addition,

a facility located in the proximity of a launch or test in-

stallation, for example, is exposed to vibrational, thermal,

and possibly shrapnel effects, all of which require special

considerations.

The design principles presented in this handbook apply to

those criteria associated With storage atud handling facilities

for only hydrogen peroxide. Thus, in the use of these criteria

in areas where other propellants are sto;-ed and/or handled,

the facility designer must cousider the integration of various

other requirements in his design of the hydrogen peroxide

facility.

.Facility Layout and Orientation. JHydrogen peroxide storage

and handling areas should bc situated in such a manner as to

provide the least hazard to surrounditg facilities and

227

personnel under any given condition. Since the layout of

test areas is depetident upon particular requirements and con-

sideratious, in which many attendant hazards must be accepted,

the i.ayout considered here is related primarily to storage or

handling areas which can be i~ituated as desired. All such

facilities should have adequate drainage and be situated so

that they are exposed to the minimal climate changes for the

particular arca. Some air flow slould normally be available.

•.•.l~l. )Meteorological Considerations. Hydrogen peroxide does

not present a serious toxicology threat to personnel through

vapor inhalation because of its low vapor pressure and cowu-

paratively high threshold limit value. Thus, very little

consideiRtion is usually giveiu to the potential release of

hydrogen peroxide vapor into the atmosphere, either through

venting or gross spillage. Normally, such situations do not

pose a i.hreot to personnel outside of the immediate area,

particularly if spillage is immediately diluted with large

quantitie* cL water. However, site orientation should be

such that ta vent or spill of any conceivable magnitude will

be reduced to relatively harmless concentrations by the time

it reaches downwind population.

.uantity-Distance Considerations. All hydrog4n peroxide

solutions above 52 w/o Ik2 02 are classified as Hazard Group 11

propellants by the criteria established for the Department of

Defense (Ref. 4.52). As Euch, these solutions are grouped with

other strong oxidizers as a fire hazard. The DOD criteria

(R(lf. 4.52) also indicate that solutions above 96 w/o 11202 can

detonate and appropriate precautions should be taken (Ref. 4.53).

Based on the Hazard Group 11 designation, the following criteria

have been recomended iu Ref. 4.52 for the location of hydrogen

peroxide sitew in relation to surround habitations and public

transportation.

228

Propellant Distance in Feet toquantity, Inhabited Buildings, Intragroup andpounds Railroads, Highways, and Compatible Group II

Over Not Over Incompatible Group II Storage Storage

100* 60 30

100 500* 100 50

500 1,000 120 60

1,000 10,000 180 90

10,000 50,000 240 120

50,000 100,000 270 135

100,OOG 30oo00 330 165

3G0,O000 500,000 360 180

500,000 1,000,000 410 205

*NOTE: These criteria do not apply to a single standard minimum sizeshipping container (such as one 55-gallon drum); these should be storedand handled as prescribed by the controlling authority.

4.4.1.2 Storage Containers. The storage capacity of each facility

is dependent upon the particular requirements of that

facility. A user may require one large bulk storage facility

with several ready storage facilities, each to supply a par-

ticular test site. Large sto rage facilities for propellant-

grade hydrogen peroxide may contain one or more bulk storage

tanks with capacities ranging from 5000 to 25,000 gallons.

In addition, the various facilities may require areas for

drum storage.

The propellant-grade hydrogen peroxide tanks and containers

should be stored in an area by themselves and not integrated

with other oxidizer storage (Ref. 4.24). The area layout

should allow for easy access and egress for loading and un-

loading vehicles and adequate separation of the bulk storage

tanks from each other, and from the drum storage area. All

storage tahka and associated valves and piping should be

229

.........

located aboveground to facilitate the detection of leaks.

All main tank connections should be made through the top

portion of the tanks to reducs the possibilities of propel-

lant spill.

4.4.1.3 Buildijns. Hydrogen peroxide bulk storage tanks do tint re-

quire surrounding buildings; however, they should, if possible,

be shielded from direct sun radiation. Drums are usually

stored on a raised pad under an open-wall roof. The struc-

tural framework for either protective covering should con-

sist of either steel or masonry. Wooden supports should not

be used. Any siding should be brick, tile, or other masonry

units; corrugated sheet asbestos; aluminum; or steel with

an approved protective coating. Slate shingles, corrugated

sheet asbestos, aluminum, or coated steel can be used for

roofing; but the use of petroleum-based roofing materials

is prohibited. A vinyl-base, high-temperature aluminum

paint can be used as weather protection for the applicable

structural materials. Floors should be smooth, finished

concrete with a built-in slope for drainage.

4.4.1.4 Dikina and Retainment. Each hydrogen peroxide bulk storage

tank should be installed within a separate dike, revetment,

or walled area to retain spilled propellant. This contain-

ment should have a smooth, impervicus, and acid-resistant

cement lining. The dike or retainment should be capable

of retaining 1.5 to 2 times the tank capacity. The diking

system should be designed so that it will gravity drain

into a collection basin via open-trough, concrete-lined

drainage canals.

4.4.1.5 Safety and Fire Protection. Good system deiiign, develop-

meat and observation of good operating procedures, and

230

good housekeeping are the best safety precautions in hydro-

gen peroxide storage and handling areas. These areas must

be kept neat, clean, and absolutely free of any type of

combustible material. All leaks and spills should be flushed

immediately with large amounts of water. Frequent inspec-

tion of the areas to ensure compliance with these regula-

tions should be maintained.

4.4•.1.5.1 Personnel Education. Standard operating procedures

should be established for all operations and potential sit-

uations that might occur in hydrogen peroxide storage and

handling areas. Thorough education of all operating per-

sonnel with respect to these procedures is mandatory. In

addition, these areas should be restricted to a minimum

number of previously authorized personnel required for

operation and safety.

Personnel ?rotection. Proper protective clothing, an

adequate number of deluge safety showers and eye baths,

and easy egress from the area should be provided for the

protection of operating perasonnrel. This equipment should

be clearly located and marked.

4.4.-15.3 Facility Protection. An adequate water supply must

be available for fire fighiting, flushing and decontamination,

tank cooling, tank dilution, and personnel safety equipment.

In storage areas where the tank temperature may be over

100 F for extended durations, a tank sprinkling system should

be provided to cool the tanks. The locations for floor

flushing, drainage flooding, and fire protection valves

(either for hoses or fixed nozzles) should be clearly marked

by signs and red lights. In the absence of a fixed tank

dilution installation, an adequate hose length should be

available to reach the dome of any storage tank for dilu-

tion in an emergency situation.

231

. . Electrical Concepts. All electrical installations through-

out the hydrogen peroxide storage and handling areas should

conform to thenational, state, and local codes for the type

of area and service involved. The areas should be flood-

lighted in accordance with good industrial and safety prac-

tices for the type of operation involved. Electrical power

distribution within the areas should be through rigid alum-

inum or steel conduits, which are preferably located under-

ground. Spark-proof or explosion-proof fixtures are not

required, but vapor-proof fixtures are recommended. Adequate

electrical receptacies should be strategically located for

miintenance purposes.

All vent stacks, storage tanks, and steel structures should

have integrally mounted lightning protection systems in

accordance with Section 8 of Ref. 4.54. All storage tanks,

pumps, loading points, electrical equipment, and propellant

transfer lines should be grounded and bonded electrically,

in accordance with national, state, and local codes.

4.4.1.7 Access Roads. At least two access roads to transfer and

storage sites should be provided with adequate space at each

site for turning. The use of asplhalt-paved access roads

in close proximity to storage and handling facilities should

be prohibited.

4.4.1.8 Fencing. Storage and handling areas, drainage ditches, and

catch ponds should be fenced and equipped with warning signs,

safety placardls, and other equipment and techniques typical

of good industrial practice.

232

S. . . ....... "_ _"_. _,_ _ __.... ,_- : ...... ... - -.. .. . . . .... . -V,

woo "Mi. "I ~W"3

4.41.2 FEuipment Design Criteria

In the design of an item of equipment for hydrogen peroxide

service, the same basic principles of design apply as far

any other fluid-handling system. For hydrogen peroxide

"service, simplicity in design is essential. Since the de-

composition rate of hydrogen peroxide is a direct function

of the surface area contacted, the material surface area

relative to tile hydrogen peroxide volume should always be

minimized. The number of parts in a system or component

assembly should be kept to a minimum that is consistent with

the mechanical and structural requirements of the equipment,

'.and the equipment must be designed so that all units can be

easily disassembled into component parts for ease in passi-

vation and inspection.

Throughout the design and layout of a hydrogen peroxide sys- 4tem, the potential integrity of the system with respect to

cleanliness and compatibility with the hydrogen peroxide

must be constantly reviewed. The use of each material and

its potential contact with the propellant must be consistent

with the material compatibility data, as illustrated in

Section 4.2.2. Because of the possibility of unforeseen

hydrogen peroxide contamination (with resulting decomposi-

tion and gas release), all systems must be designed so that

they can be completely vented and pressure relieved. When- 4ever possible, the system should be designed to "fail open."

Typical equipment design and selection considerations are

given in the following paragraphs. 'Although these consider-

ations will aid. the hydrogen peroxide user in the design

of hydrogen peroxide storage and handling systems, they are

not intended as a substitute for good engineering practices

nor do they eclutide other competent and kiowledgeable con-

siderations. It is also noted that the f~llowing criteria

are primarily for semipermanent or permanent facilities

233

_j-

and do not apply tc- flight hardware although many of the'"

considerations may be applicable.

4.4.2.1 Storage Vessels. All pressure vessels for hydrogen peroxide,

storage antd feed should be cotrstructed in accordance with

the ASML Boiler and Pressure Vessel Code, Section VIII,

latest edition (Ref. 4.55). Also, all pressure vessel de-

sign and construction should satisfy applicable local and

state codes for such vesscls. All other storage vessels

for hydrogen peroxide service should be designed and fabri-

cated in accordance with good engineering practice for the

pressure and service in which they are to be used. A mini- .4mum safety factor of 4 for vessel and vessel support material

strength should be maintained in all designs with adequate

allowances for local seismic and atmospheric disturbances,

temperature conditions, and externa-l and/or internal

corrosion.

Hydrogen peroxide storage tanks are normally fabrizated of

Class 1 materials. The majority of the tanks used for bulk

btu a'ge1 - .... 1l"ia e f.,hromh a i 99 .6

W/o aluminum. When greater strength is required, aluminum

alloys 5254 and 5652 are normally used for bulk storage.

In considerati~n of requirements for high-pressure light-

weight tankage, AM 350 stainless steel has been used success-

fully. The 17-7 precipitation hardening stainless steel has

been used successfully in 76 and 90 w/o H1202 systems; hoV-

ever, this material is generally more difficult to passivate

than the AM 350 material, particularly when used in 90 and

93 w/o 11202 systems. Both steels offer yield streagths of

160,000 psi.

The hydrogen peroxide tankage used in rocket test facilities

and variou.s other feed and ready storage applications (which

required only short periods of hydrogen peroxide storage)

* 2Y3

are usually fabricated from 347 stainless steel. OtherLmterials successfully utilized in tankage kor these types

of applications are the low-carbon 304, 316, and 321 stain-

less steels.

The cryogenic prestrained 301 stainless steel has demon-

strated excellent compatibility with 90 and 98 w/o 11202, and

the high strength of this material (260,000 psi yield) favors

its use for hydrogen peroxide tankage in flight vehicles

and for high-pressure applications.

•.4.2.1.1 General Considerations.. The particular requirements

of the storage and handling facility will determine the size

and number of storage and feed tanks. If hydrogen peroxide

shipments are received in tank trucks or timnk cars, storage

tanks with capucities greater than 8000 gallons should be

available, and more than one bulk storage tank is recommended

at each particular installation. Bulk shipments should pre-

rerably be maintained in containers of similar size instead

of being transferred to a number of smaller containers. In

addition, the number of hydrogen peroxide transfers from

the initial storage to final use should be minimized. Obser-

vation of these rules will limit the chance of contamination

and the number of hazards involved.

Although atmospheric-pressure, horizontal tanks have usually

been preferred to verticul tanks for the bulk storage of

hydrogen peroxide, any well-engineered tank is suitable.

High-pressure feed or ready storage tanks are usually ver-

tical so they can be fully drained. It should be noted

that the optimum stress-to-weight ratio is contained in a

spherical tank, and this type of tank provides a minimum

surface-to-volume ratio. A 2-to-1 length-to-diameter ratio

tank is also advantageous with reference to strength-to-

weight and surface-to-volume ratios. Regardless of the

shape, the tank should be designed with sufficient volume

235

- 7 P •W W " ... . • . .• • . ... " •••,• '-r . ,,,•,,

capacity to limit the liquid level from rising above the

head attachment weld.

Normally, all hydrogen peroxide tankage should be provided

with openings for filling, draining, ventitig, special in-

strumentatiou (temperature, pressure, and liquid level in-

dication), and pressure relief (usually a large burst disk).

Large storage tanks should be provided with a top opening

manway of at least 18 inches diameter for cleaning &ad in-

spection. All bulk storage tanks should have at least a

6-inch-diameter opening for use during cleaning and passiva-

tion. Many organizations fit the large openings on

atmQsphleric-pressure bulk storage tanks with a floating

cover, which is designed to exclude dirt but free to relieve

pressure buildup in the tank. A cover of this type is

especially effective in providing a large emergency vent to

prevent pressure rupture of the tank in case of massive con-

tamination of the contained hydrogen peroxide.

Top inlet and outlet connections are usually recommended

for large bulk storage tanks; however, a bottom outlet is

generally required fir piropellant feed and ready-atorage

tanks to provide complete drainage. Flanged connections

should be used for all openings whenever possible. Storage

tanks must have a filtered (to protect against inflow of

dirt) vent of at least 2 inches, which cannot be inadvertently

closed. Pressure vessels should be designed with fail-open

vents. In addition, many storage tank designs incorporate

a temperature alarm, in which a thermocouple is installed

in a protective aluminum tube inside the tank or fastened

to the outside wall of the tank below the liquid level

(with external glass wool insulation). Mercury thermometers

and liquid-type manometer gages should not be used in direct

contact with the liquid.

236

4.a.2.l. Pressure or Volume Changes. Throughout the design,

fabrication, and application of hydrogen peroxide storage

vessels, the pressure and volume changes resulting from hy-

drogen peroxide decomposition must always be con~sidered. A

liberation of oxygen from decomposition results in a subse-

quent change in gas volume and/or pressure of a sealed con-

tainer. To illustrate this point, Fig. 4.10 shows the volume

of oxygen liberated per uaiit volume of hydrogen peroxide as

a function of hydrogen peroxide concentration and temperature,

assuming a decomposition rate of 0.1 percent AOL per year

and a constant pressure of 14.7 psia. Figure 4.11 demon-

atrates the pressure increase resulting from this decomposi-

tion in an unveuted system with an initial ullage volume of

10 percent. Pressure increases observed under actual stor-

age conditions are illustrated in Fig. 4.3 and 4.6.

For these reasons, venting of systems for normal long-term

hydrogen peroxide storage is necessary. This venting may

be either continuous or of the intermittent variety. The

latter is used when the rate of pressure increase is used

as p measure of stability. Commercial shipping containers

are Inormaliv of the continuous-venting type. A eo-.ewhat

labyrinthine path is made with holes drilled through the

cover material. The geometry is such that the possibility

of contaminants entering through the holes is neglible, and

the possibility of trapping and subsequenit blowing overboard

of liquid hydrogen peroxide is insignificant. For most

aerospace applications, nonvented systems are employed and

allowances for pressure increase during the storage period

must be made in the design.

4.4.2.1.3 Self-Heating. Another important consideration in the

design of storage tanks is related to self-heating of the

hydrogen peroxide. This behavior, thoroughly discussed in

Ref. 4.56, can be briefly summarized by the followilug

comments from that discussion:

237

"All h3drogen peroxide solutions decompose ata finite rate, and this decomposition releasesa relatively large amount of heat (1200 Btu/lbof hydrogen peroxide consumed). Consequently,every Ihydrogen peroxide storage vessel mustcontinually transfer heat to its surroundings,a corollary being that such storage vesselsare always warmer than the surroundings. Themagnitude of this temperature difference isestablished by the balance between heat re-leased by decomposition and heat transferredto the atmosphere. The actual mechanism, ofcourse, involves a gradual ,eriperature rise inthe contents of the vessel until the rate ofheat transfer to the surroundings becomes equalto the rate of heat liberation by decomposi-tion. however, the rate of heat transfer to"the atmosphere increases only linearly withtemperature, vdhile the rate of decompositionincreases exponentially. As a consequence,for any particular storage vessel there emistsa critical decomposition rate beyond which therate of heat liberation will always exceed therate at which heat can be transferred to thesurroundings. Once a storage vessel passesthe critical condition, a self-acceleratingdecomposition will set in wdhich, unless checked,may reach a very high rate. As hydrogen per-oxide solutions are nearly impossible to detonateand vapor explosions are possible only oververy strong solutions, the primary hazard is%A A%. %#4A3 %I- L~ LI J bAU t £ j~&

of the container."

Because of this potential effect in storage, the design of

any hydrogen peroxide storage container should incorporate

features which control seli-heating. Assuming various hy-

drogen peroxide decomposition rates, a maximum safe-tank

size can be calculated for a given hydrogen peroxide con-

centtration stored at a given temperature in a given tank

material (Ref. 4j.56). flydrogen peroxide tankage should be

located so as to permit free movement of the surrounding

air, and since heat dissipation from the tank is necessary

to prevent self-heating, the insulation of hydrogen peroxide

storage vessels under normal earth ambient storage condi-

tions should be prohibited. Because knowledge of impending

238

- , , - ,- -.. . .

self-heaLing is desirable, adequate instrumentation should

be provided for all bulk storage tanis; this instr-tmeaation

is discussed more thoroughly in Section 4..2.11.t

4.4.2.1.4 Surface Area Effects. One (if tht, important c'nsidera-

tions in the design of hydrogen peroxide storage tanks is

the effect of surface area. This is discussed in many other

sections of the handbook, and the system desigoer should be

well wware of its contribution to the decomposition of hy-

drogen peroxide. With proper knowledge of this effect, it

can be minimized by proper design. Since the current high-

purity of propellant-grade hydrogen peroxide minimizes the

homogeneous decomposition reaction, the primary cause of

decomposition results from the heterogeneous reaction. This

is the controlling reaction under the normal ambient stor-

age conditions assuming inadvertent contamination of the

hydrogen peroxide does not occur in sufficieut quantities

to initiate the homogeneous reaction mechanism.

Surface area effects, which are the basis ol the hetere-

geneous reaction, can be minimized by optimizing container

design for minimur surface area per unit volume (the ulti-

mate design being i sphere). Further optimization requires

a minimum number of storage containers. Previous produc-

tion plant storage data show that the active oxygen loss

in the storage of hydrogen ptroxide can be reduced 50 per-

cent by going from an 8000-gallon storage tank to a 25,000-gallon storage tank (Ref. 4.25). Since such volumes are

not practical for many applications, compromises have to

be made with respect to convenience of handling and minimum

quantity required at the storage site for assurance of

continuing operation.

239

h.I .2.2 Piping Systems. Information of a general and specific nature

relating to pipe, pipe material, and piping itistallation is

extensively covered in Ref. 4.3"1 through 4.60.

4.4.2.2.1 System Desigi. All piping used in the storage, vent-

ing, and transfer of hydrogen peroxide should be designed

in bccordance with Sections 3 and 6 of Ref. 4.57. Allowable

tensile stresses for pipe materials are listed in Table 12

of 'ief. 4.57. Material specifications for pipe, fittings,

valves, flaugcs, tubing, and boltings are listed in Table 8

`1 ot lif. A.57.

In design of hydrogen peroxide. piping systems, all piping

and items of equipment, especially valves and pumps, should

be designed for complete drainage on shutdown. This can

be accomplished by providing easily accessible draincocks

at the low points as~l by placing equipment containing dams,

such as some types of valves, in vertical rather than hor-

izontal positionis.. A piping system which holds hydrogen

.peroxide in stagnant pools, Wveu if properly vented, may

be subject. to excessive cnrrosion eve,, when fabricated

from the recommended riterials of construction.

There should be no places in the flow system where hydrogen

peroxide can be trapped for any period of time without a

vent path or a relief arrangement. Since hy)drogen peroxide

solutions will constantly decoripose at a slow but steady

rate, the resulting gas, if completely cenfined, could even-

tually build up sufficient pressure to cause rupture."Dead ends," of which a Bourdon tube gage is an example,

should be avoided since foreign material can accumulate in

these spots. Ball, plug, and gate valves are examples of

valve designs where the hydrogen peroxide can be trapped

rwhen the valve is closed; if one of these types of valves

240-__ _0~ ----...----- . *

4.4.2.2 Piping Systems. Information of a general and specific nature

relating to pipe, pipe material, and piping installation is

extensively covered in Ref. 4.57 through 4.60.

4.t.'2.2.1 System Design. All piping used in the storage, vent-

ing, and transfer of hydrogen peroxide should be designed

in accordance with Sections 3 and 6 of Ref. 4.57. Allowable

tensile stresses for pipe materials are listed in Table 12

of Ref. 4.57. Material. specifications for pipe, fittings,

valves, flanges , tubing, and boltings are listed in Table 8

of Ref. 41.57.

In design of hydrogen peroxide piping systems, all piping

and items of equipment, especially valves and pumps, should

be designed for complete drain~age on shutdown. This can

be accomplished by providing easily acces3ible draincocks

at the low points anix by placing equipment containing dams,

such as some types of valves, in vertical rather than hor-

izontal positions. A piping system which holds hydrogen

peroxide in stagnant pools, even if properly vented, may

be subject to excessive corrosion even when fabricated

from the recommended numterials of construction.

There should be no places in the Jlow system where hydrogen

peroxide can be trapped for any period of time without a

vent path or a relief arrangement. Since hydrogen peroxidc

solutions will constantly decompose at a slow but steady

rate, the resulting gas, if completely confined, could even-

tually build up sufficient pressur' to cause rupture.

"Dead ends," of which a Bourdon tube gage is an example,

should be avoided since foreign material can accumulate in

these spots. Ball, plug, and gate valves are examples of

valve designs where the hydrogen peroxide can be trapped

when the valve is closed; if one of these types of valves

240

is to be used, the cavities must be vented to relieve any

gas formation. It is recommended also that the number of

valves in a system, be kept to a tainimum to prevent trap-

ping of the hydrogen peroxi e between valves.

In the use of pumps in the system where the point of pump

discharge is lower than the storage ÷,ank liquid level, the

pump suction line from the top outlet should have a valved

vaLuum breaker to prevent siphoning after the pump is stopped.

The pump installation should also be designed to prevent

hydrogen peroxide from flowing back to the storage tank

upon pump shutdown.

4.4.2.2.2 Pipes and Fittings. Pipe and welding fittings are

normally manufactured according 0r standard thickness and

weight, as proposed by the American Standards Association.

Adherence to these standards ii, the design of hydrogen

peroxide piping systems will eliminate unnecessary costin the purchase of pipe and will facilitate purchases insmall lots. Pipe wall thicknesses should be determined in

accordance with Ref. 4.57, Section 2, Chapter 4, Paragraph

214(

The most compatible piping for hydrogen peroxide service is

1060 alumiuum, and this material is generally recommended,

particularly if the liquid hydrogen peroxide is to remain

in long-time static contact with it. However, where greater

strength or hardaess is required over that of aluminum 1060,

or where other aluminum alloys (3003 ard 6063) may be more

readily obtainable in piping, other Class 1 or Class 2

aluminums may be used, Piping of 300-series stainless

steel may also be used in certain Class 2 (Sectiorn 4.2.1.2)

applications.

241

_7 _ __

, i

Welded and flanged construction is recommended in hydrogen

peroxide piping with a minimum of fittings and joints. Bends

are preferred to elbows, and joints should be stud-ends with

lap joint flanges or flanges welded to the piping. The use

of stainless steel and galvanized or aluminum-clad bolting

with galvanized steel back flanges is recommended, because

rusting of carbon steel would afford a source of possible

contamination of the piping when the flanges are opened.

If popsible, threaded fittings and connections should be

avoided; however, where they must be used, it is recommended

that the tapered pipe thrLads be sealed with Teflon thread

tape. Normal pipe thread compounds must never be used.

4.4.2.2.3 Pipe Hangers and Supports. Pipe supports, hangers,

anchors, guides, and braces should be designed to prevent

excessive stress, deflection, and motion in operation of

the system, or too large a variation in loading with changes

in temperature, and to guard against shock or resonance with

imposed vibration and/or critical cqnditions. Design and

selection of the pipe supports should be in full accordance

with Section 6, Chapter I of Ref. 4.57. Additional inform-

ation is included in Ref. 4.58 through 4.63.

4.4.2.2.4 Flexible Connectious. A corrugated, seamless hose of

304 or 316 stainless steel, witih open pitch construction

and welded flanged ends is recommended as a flexible con-

nection for hydrogen peroxide service. Flexible hose lineswith Teflon or Silicone S-5711, fitted with flanged con-

nections, also have been successfully used. Another type

of flexible connection tVat has been applied successfully

in hydrogen peroxide service is aluminum piping with swing

joints of stainless steel and Teflon.

242

"-•:-: , _ .. . ... .- AIh-L i, -; -lo il l i iiiAMM•I "i iil i li• • I'i !i ' '

A%

/I. h.2.2.5 Identification. Hydrogen peroxide piping should be

identified in accordance with MIL-STD-10IA(10). The prim-

ary warning color (band) is green. The secondary warning

colonr (arrow) is blue.

4.4.2.3 Stainless Steel Tubing and Fittit!gs. Tubing and fittings

of 300 series stainless steel are used almost exclusively

for pressurized hydroger peroxide systems. (It should also

be noted that the X-15 experimental aircraft uses an all

stainless-steel hydrogen peroxide system.) All systems

designed with stainless-steel tubing should conform to M1I,-

T-8808A (for type 321) MIL-T-8606A (for type 347), or

MIL-T-8504 (for type 304). Fittings should conform to AN

or MS standards for flared tube fittings.

4.4.2.4 Valves. Sele.ction of valves for hydrogen peroxide service

imposes certain design requirements that are more stringent

or critical than with most other propellants. The designshould be such that trapping of hydrogen peroxide in anypart of the valve is impossible during any operation cycle

of the valve. As a result, globe or Y-type valves are

usually recommended for hydrogen peroxide service. Modifi-

cation of some types of gate, plug, and ball valves to pro-

vid..- s ,fventing has also permitted their use in certain

applications.

Materials used in approved hydrogen peroxide valves are

normally Class 1 or 2 (see Section 4.2.1.2). Stainless steels

321 and 347 have been employed successfully as valve mater-

ials; however, some aluminum alloy valves have been sub-

V jected to severe galvanic corrosion *dhen used in conjunction

with stainless-steel poppets 3r fittings. A metal-to-Teflon I(or Kel-F) seal between the plug and valve seat is normally

243 S:I* -. * -- ---- -- -- _ _ _ _ ~ - ---

preferred over metal-to-metal contact. Materials approved

for gaskets are normally used as valve packing.

4.4.2.5 Relief Devices. The preferred relief device for hydrogen

peroxide systems is a rupture disk. The relief device

should be rated at not more than 100 percent of the vessel

or system rating when used as a primary relief device or

105 percent when used as a secondary relief device. Sizing

of the device should be large enough to prevent the pressure

from rising 10 percent above the maximum allowable working

pressure of the system under any projected condition. Burst

relief devices on hydrogen peroxide tank cars are designed

to relieve at 45 psig pressure.

4.4.2.6 Regulators. Regulators are used primarily to supply i-egu-

lated nitrogen gas for transfer, purge, and control systems.

The selection of r regulator for service in hydrogen perox-

ide systems depends upon its particular intended service.

If the regulator is in an attendant system which cannot be

contaminated with hydrogen peroxide, no special requirements

are necessary. However, when contamination is a possibility,

the regulator materials must conform fo compatible material

specifications. 44.4.2.7 Pumps. Pumps manufactured from wrought or forged 300-series

stainless steel (304, 316, 321 and 347) and pumps made with

aluminum alloys B356, 356, or 43 which aloo have a 300-series

stainless-u~eel shaft, are recommended for pumping hydrogen

peroxide. Cast stainless steel should be avoided because

it is subject to chromium leaching, which seriously contam-

inates the propellant and hastens decomposition. Self- "

priming pumps should be used for transferring hydrogen

peroxide from tank cars or storage tanks with top outlets;

2411

AE

21 itt

the pump normally used in this service is a 2-inch, self-

priming centrifugr.l. Wfhiere higher pressure or low capac-

ities are desired, a special rotary pump is reconmended.

Pump shafts should be stainless steel, and any packing must

be made of compatible materials. W!,ere used, packing should

le rings of either Teflon or Vitrium, lubricated with a

fluorinated hydrocarbon; excessive gland tightening of the

packing should be avoided, because overheating could result

in the rupture of the gland. Stainless-steel mechanical

seals wvith glass-filled Teflon and ceramic faces are recom-

mended. Ail pumps should be equipped with drain valves and,

where desired, temperature alarms to warn against overheat-,'-.

if. I.'2. 8 Filters. Liquid filters have been used in hydrogen p)eroxide

storage and transfer systems to maintain propellant clean-

liness from insoluble contaminants. Because of the massive

surface area available (for promoting heterogeneous decompo-

sition), the filter should be selected from Class 1 or 2

materials, and should be located where it is not constantly

immersed in the liquid (such as the inlet or outlet of a

transfer line). Also, it should be located for easy and(

repeated opening and cleaning. A 25--micron, tyiu 316

stainless-steel filter with a 1000-sq in. minimum element

area (100 gpm 11202 at 15 psi AP) has been used success-

fully in large handling systems.

It.t.2..9 Gaskets. The selection of gaskets for hydrogen peroxide

service is related to the type of service to be provided.

Materidls normally used as gaskets are Teflon, 11el-l",

certain silicone rubbers, some polyvinyl plastics, Koroseal

700, pure tin, and either a combination of spirally wound

stainless steel and Teflon (Flexitallic) or a Teflon

245

envelopm over asbestos. The metal-containing gaskets

are usually recomended for high-pressure and vacuum

systems; however, contact between dissimilar metals should

be avoided to prevent galvanic corrosion. The use of

certain elastomeric meterials as gasketu =ist be avoided

because the plasticizer or filler material may be incom-

patible or impact sensitive (see Section 4.2.2).

* i.4.2.10 Lubricants. The use of lubricants in propellant-grade

hydrogen peroxide service should be minimized or avoided

wherever possible. Results of compatibility tests (Sec-

tion 4.2.2.6) indicate that only the fluorinated hydro-

carbons are sufficiently compatible with hydrogen peroxide

to be considered, and even these materials may react

under certain conditions.

Ia.4.2.11 Instrumentation. In the design of instrumentation inter-

nal probes or sampling tubes for hydrogen peroxide storage

and handling systems, the proper selection of compatible

materials is the primary consideration. Dissimilar metals

in contact with hydrogen peroxide demonstrate a tendency Afor electrolytic corrosion, with the more concentrated

solutions showing lea3s galvanic action. However, even

with 90 w/o hydrogen peroxide, the use of dissimilar 4metals should be avoided. Attempts at insulating one

metal from the other by a plastic have not been very

effective in past applications where intermittent wetting

occurs. If two dissimilar metals must be in contact, the

anodic metal should have a larger surface area than the

cathodic metal. In addition, the use of soldered joints

(particularly silver solder), idrich is common in various

types of probes and sensors should ie avoided (because of

catalytic decomposition of the hydroge' peroxide).

246

I.. &•k •-,•

An noted previously, "dead ends," which are those places

that could be filled with hydrogen peroxide without per-

mitting adequate recirculation of the fluid, should be

avoided wherever possible. (A common example of this in

instrumentation design is the typical Bourdon tube pres-

sure gage.) The disadvantage of having a dead e:"7 in.,

piece of apparatus is that there is a possibility that

small impurities will accumulate in the dead end until

extensive hydrogen peroxide decomposition results. If

dead ends cannot be avoided, they should be placed above

the low point in the system so that liquid hydrogen per-

oxide solutions will not collect in them.

i.i.2.11.1 Pressure Gages. If gages are required or used in

hydrogen iperoxide service, they should be constructed of

compatible materials and meet the other considerations

noted above. Where Bourdon tube-type pressure gages are

used, their design and assembly should allow for proper

passivation and inspection of the gage inlet, and there

should be no welds in contact with the hydrogen peroxide.

For example, a stainless-steel diaphragm held between

two bolted stainless-steel flanges should be used in con- 4junction with a Bourdon tube pressure gage. with the

-~ebY placed &it a Vertical Pubitionl. Gas legs and

diaphragm protectors have also been used with success in

preventing direct exposure of the gages to liquid hydro-

gen peroxide.

4.4.2.11.2 Storage Tank Temperature-Measuring Devices. A study

of temperature-measuring devices fr high-strength hydro-

gen peroxide storage sysLems has been reported in Ref.

4.64. A summary of this study, shi#n in Table 1.32 iillustrates the presently available techniques. Selec-

tion of' any one of these techniques is dependent upon

the requirements of the particular facility. However,

247

regardless of which technique iL used, its limitations,

operating characteristics, and relationship to potential

"red line" conditions must be fully understood by facility

personnel to ensure the usefulness of the system.

In consideration of the various techniques described in

Table 4.32 , the surface measuring eystem with its sensing

point at the bottom of the tank (Method 3) would be less

affected by high vapor space temperature than any of the

other measuring devices. The Manufacturing Chemists'

Association (Ref. 4.65) has, in effect, recognized this

technique as a suitable method by stating."The tenijera-

ture of a tank may be monitored by temperature indicators

attached to the exterior of the tank below liquid level

which records the temperature automatically or an operator

may record the temperature on schedule." While not di-

rectly measuring liquid temperature, such a system would

show tank temperature changes (although it would probably

be uisuitable for inventory purposes). Using a dial

thermometer, this type of system would be the most econ-

omical direct temperature indicating system.

The use of a dial thermometer inserted in a thermal well

below the liquid level (Method 4) would more closely

indicate the true liquid temperLture and be less affected

by ambient temperatures than surface mounted systems.

High vapor space temperature would not, affect such a sys-

tem unless the liquid level fell below the well.

Another type of surface measuring system (Method 7) en-

cotmpsses the vapor space using a capillary sensing ele-

ment which is sensitive to the warmest spot along its

length. However, any time the vapor space is warmer than

the liquid, this instrument will indicate the vapor space

tank surfcce temperature rather than the liquid. One

organization reported that it was necessary to set the

248

alarmi point of such a systeLi at 14t3 F to eli irinaLte false,

alarms resulting from sun heating effects transferred into

the vapor space. One maitufacturvr of this type of inistru-

ielnt does not recommend it for this use.

Anuithier organization reported the use of an averaging sur-

face measuring system covering the lower quadlnit of the

tank (Method 6). This system was affected in a manner

similar to that of Method 7 at lower liquid levels, but

to a lesser extent, since it tverages the temlperature

rather than selects the warmest spot.

The Weston System (described ais Method 10), using a re-

sistanefc temperature element installed from top to bottom

of the tank in a well, will average the liquid temperature

from the liquid level to the bottom of the tank. A manual

switch is provided to change the temperature-sensitive

segment of the element to that position below the liquid

level in up to six steps. This system gives good average

liquid temperatures at any one vertical plane in the tank.

Several elements installed in one tank or in several tanks

could be used with one indicator. Such a system is expen-

sive but might prove extremely valuable in the checkout

of a nev, storage area, particularly by a group inexperi-

enced in hydrogen peroxide linul lijg and stnorae.

The use of automatic temperature alarms connected to the

sensing device would be of little value in determining

self-heating of the tank in the early stages. For example,

in cold weather, self-heating could be progressiing very

rapidly by the time the alarm point set for 120 F would

be reached. Conversely, in hot weather, the effects of

the sun coupled with low liquid levels could result in

frequent false alarms at this temperature. As a rezult

of these false alarms, the alarm would soon be ignored (or

if the alarm were set high edough to eliminate the false

249

_ : . c• • .•. . . . ••i• • ....... .. .... • , M, _ tssi '. •idl •, ."arn , .s' 'l • ••• : :"

alarms, it might providle a false sense of security). An

alarri system could be set up to operate oin a given tern-

perature differential between ambient and storage týmp -a-

tures; ho,'ever, this involves additiuial expense.

It is generally recommended that the use of continuous

plots of tank (with any of the indicated devices) and

ambient temperatures beý used as the method of evaluating

storage conditions, at least until personnel have suffi-

cient experience to evaluate the fac'lities properly.

.4.3 _System Fabrication and Assembly,

Hydrogen peroxide storage and transfer systems tire similarto tlhose employed for" handling ortlinary fluids, except

for matterials of construction. Pump motors, solenoid

valves, electrical switch-gear, and other electrical equip-

ment in thle hlydrogen peroxide transfer and storage systems

should be selected and installed in accodlance with the

requirements of the National Electric Code, Article 500,

Class 1, Division 2. All seals and joints in the propel-

lant system should be peziodically and frequently inspected 4for leaks aud damage.

In the layout, placement, and arrangetment of operating 4systems and units, ample spacing should be proviled for

proper maintenance clearances anid adequate ventilation.

In many cases, the removal, replacement, and servicing of

valves, pumps, piping sections, instrumentation, and other

equipment must be done by personnel in protective cloth-

ing. Ample room and access must be provided for use of

tools and for easy movement of equipment. Where possible,

equipment, valves, and lines should be located so that

250

S - ' m . .. . . -

mainitenance and service wvork can be accomplished from a

position above the piping level to prevent propellaut

drips and leaks from falling on personnel.

Priot to fabrication and assembly of the systen, the

nmaterials and equipment to be used should be carefully

_selected from the recommended lists as given in Section

4.2.2 and 4.4.2. Any questionable or unknowni (with re-

spect to compatibility) material or piece of equipment,

which is to b used in the system, should be thoroughly

checked in accordance with the procedures given in Suction

4.2.1. In addition, the identity of each nmterial used

in the fabrication and assembly of hydrogen peroxide sys-

tems must be ensured; test kits are availttuie for the

identification of metals in the field (Ref. 4.60).

These selections should be judiciously reviewed by knowl-

edgeable personnel who have had prior experience in the

operation of hydrogen peroxide facilities. The selected

materials and equipment should then be cleaned, passivated,

and "activity" checked and the system fabricated and

assembled according to the considerations given in the

following paragraphs.

I.4.3.l Generc.l. In the fabrication and assembly of hydrogen

peroxide systems, the user is again reminded of general

"rules of thumb" that should be observed in the design,

preparation, and assembly of the system. These are noted

as follows (Ref 4.25).

1. All hydrogen peroxide tanks should be designed with

a minimum surface-to-volume ratio for maximum storage

stability (ie., a sphere is the optimum shape).

251

2. All storage tanks, vessels and drums should be designed

so that sampling of their contents may be accomlplished

witlhout the use of a sample thief or i nscrt ion of aly

device into the storage container.

3. Various seamless stainless-stcel tubing call be used for

high-pressure systems, but tile 304tL, 316L, 321, or 3P17

alloys should be used if welding is itquircd.

4. Stainless-steel and aluminum components should not be

coupled in the same system bccause electrolytic corro-

sion may result.

5. Free-machining, staitiless-steel alloys should not be

used.

6. Cast stainless-steel components should not be used un-

less the particular casting is thoroughly proved to

be suitably compatible with hydrogen peroxide.

7. All markings should be removed from stainles-steel

plates before they are formed into a tank.

8. Lap joints should not be used in fabrication of materials.

Lap joints provide cracks, crevices, etc. (which can-

not be readily cleaned), and may furnish a source of

contamination; they also provide dead spaces for re-

tention of hydrogen peroxide.

*• .lt '.I 1 equiijeri mu bL U se .. ... in I .ru t le

fabrication.

10. Head forming dies should be free of rust and smooth.

11. It is often advisable to degrease atnd passivate the

tank head and bottom closures prior to fabrication.

This eliminates difficulties in future tank and sys-

tem passivations.

252

12. Flux ald carbon formed in fabrication 1 should be

cleaued from welded areas in stainless steels by a

30 seieas $taillCss-steCl wire brush. Any inclusions

remaining should be ground out. Fuor the grinding, of

cast surfaces, welds, and weld spatter on surfaces

that will contact proplllanIt-grade hydrogeien pieroxide,

a clean white aloxide (aluminum oxide) abrasive is

recommended.

13. Carborundum is not recommended for grinding because

the iron in the carborundum is catalytic with hydrogen

per oxide.

14. Metallizing or sprayed metal coatings are not suit-

able techniques for preparing surfaces for hydrogen

peroxide service. It is possible for the hydrogen

peroxide to seep behind the coaiting or vn exposed edge,

and cause the coating to blister.

15. Sandblasting is not recommended because it reduces the

compatibility of metals with hydrogen peroxide due to

the formation of a porous or pitted surface. The

rougher surface decreases its compatibility with hydro-

gen peroxide.

16. Mechanical polishing of aluminum alloys is not advis-

able because of the possibility of introducing materials

which are not compAtible and could cause decomposition

of the hydrogen peroxide. Electrochemical polishing

(anodization) of aluminum is the recommended method.

17. If an aluminum system is employed, it should be ano-

dized per Specification Mil-A-8625 (with no dyes),

followed by a 1-hour rinse in boiling distilled water.

18. Aluminum materials and componenits should be handled

carefully to prevent the possibility of embedding

metal particles in the surface.

19. Hlydrogen peroxide system components should not be

brazed or silver soldered.

253

20. All plastic m:,aterials must' be checked for 1tinal

particles, inclusions, etc., pri or to use. The ell-

traprlent of organic solvents in po-ous muate'ials should

be avoided during cleaning opeilltions.

21. Chromic acid soluti!91s should not be used fUi clean-

ing because chromium i s one of the better decomposi-

tion catalysts for hydrogen p)eroxide.

4.4.3.2 WeldinjL. In general, the standards for welding pipe wAIii

conform to Chapter It )f Rlef. 4I.57. Pipe fittitngs shot'ld

be iprocured frVom reputable sour'ces who iper'uaiently il

thcir fittings as to: (1) manuflcturei, (2) size and schied-

ule of pipe, and (3) material and heat code. The fittings

should be of the butt-welded type to facilitate system

cleauing and purging operations. A typical set of stand-

ards for the acceptance of pipe welds is as followe:

1. Cracks of any natture, whether crater, underbead, trans-

verse, longitudinal, or parent metal will be cause for

rejection.

2. Crater cracks which are determined to be only surface

defects auty be removed by machiiiing or grinding. They

nxeed not be rewelded provided buildup is not less than

10 percent nor more than 30 peircent of the metal thick-

ness, nor if drop-through is not less than flush nor

more than 30 l)ercenlt of the metal thickness.

3. Normally acceptable defects occurring in conijunctioon

with or adjacent to cracks will be cause for- rejection

if they occur within a dictance of 2 inIches eachi way

from the crack.

4. Butt joints will have 100-percent penetration through-

out 100 percent of the linear length of the weld.

254

5. Any lack of fusion will ot be accepted.

6. Uaderccut, excessive drop-through, and excessive rough-

ncss will be cause for rcjcction. Folds in drop-through

wil! bt accepted if they are yot greater in depth than

10 percent of the thickijess of the pareiit metal.

7. Ploropity or inclusions occurring it, the weld meta!,

exclusive of tile weld reinforetments in which 13 any

radiographic image is darker than the iparent metal or

inrger in its greatest dimension than 15 percent of

tile p|arent metal thickness will be rejected.

8. Porojit. and inclusions in the weld reinforcement will

be accel,'.able ip rovided they do not, extend through the

surface of the reinforcemente and provided they d,, not

result in an objectionable stress riser.

9. Porosity and inclusions whose grenttst di tensl!!ris are

equal to or less than 15 percent of the parent metal

thickness will be acceptable to the extent of one pore

per inch of weld length.

10. Tungsten inclusions located in the penetration zone

will be accepted provided the greatest dimension of

any particle is not o~er 25 percent of the parent metal

thickness.

.I- taie wl!Ai1E&i of hydrogenl peroxido SastemS, Specific col-

siderations must be observed to ensure the passivation and

compatibility -f the fabricated and assembled symtem with

hydrogen perexide. These considerations, noted in Ref. 4.25,

are essentially dependent upon the design of tanks and

equipment, which should be such that good welding techniques

and machining practices can be readily utilized. Since

weld splatter on surfaces which will contact, the hydrogen

peroxide will cause excessive decomposition, tihe design

should allowfor removal of weld splatter if it should occur.

255

Staitiletis-(-teel welds exposed to hydropen peroxide should

a.so be Machilked smooth if possible; however, aluminum

uelds should not be wire brushed or machined because this

mny inturoduce impurities and thus do wore haii than good.

Allowanuce for good niachi iiiiig will result in smooth surfaces

Which wIill (icause less decomposition of the hyd rogen pCer-

o()ide tLan rough or poorly machined surfaces.

4.4 . . 2. 1 Aluminum Allo"s . Weeldability of ailuminum atd aluminum

alloys varies over n wide range. The same procedures and

techniques are employei in wcldintg aluminum and its alloys

as are used iil welding other weldable alloys. Ii general,

the less constitutents in the alloy, the more weldable the

al loy.

The wcldi:;g 1. 1 •o L e t1~d sihouia be oa the same compo-

sition as the parent metal. Unlike other alloys, the

aluminum alloys do not lose any appreciable amount of the

alloying A.einni.8s during weldi tg. Il most cases, dissimilar

alurninuiti alloys, which cul be welded individually, can also

be readily welded in combinations; the weldding rod to be

used should be of the harder material in the conmlinatioti

(i.e., in weld i ugalumiii nuwiiwill oy a 1060 and 5652, a 5652 rod

would be used). The use of 5-perceut silicon rods such

i• •• w~Jwichi alr cOMMo*;ly uS"M ili auniou'u,-wcldi W- g, is

not recommended for propellaut-grade hydrogen peroxide

service. During passivation and contact with hydrogen per-

oxide, such welds turn black and may cause decomposition of

the solution. If use of the 43S rod is required, subsequent

sulfuric adid anodization is necessary to stop the weld

frow turniutig black during passivation. During anodization,

there nwv" still be some blackening of 43S welds, but this

dicoloratiov does noý seem to be a prior indication of

an active site. Normally, a 5254 welding rod is recommended

for welding of the 606] alloy to other alloys.

256

Aluminum welds should not be wi r- biushed or machined if

at ill possible, because impurities may lbe inttroditced i|ito

t lie mieta li in ttt'iicrs where wire brutshintg i s a iiecessi. y

a 50 scries staitileH-Ot-eel brush will be used, and care

must be takesi to confine the bvushiiiig Wo the immodiate weld

area.

Automatic inert-gas welding processes, such as the Aircominatic

or Sigma processes, give excellent results wdhen uticd with

the prope " weldintg rod. The welds, in gencral, are iiouiporou4,

soft, alnd utniform. Electrode tip cups should be of stain-

less steel athIer 'thalt copipler (or other such nmaterials) be-

cause the latter might melt into and contaminate the weld.

Ilcliarc inert-gas welding is, ini genieral, a satisfactoty

Irovess. Although it hits many of the advantages of the

automatic processes, it does have the disadvantage of

"spitt ng" of tungsten from tile tungsten electrode into the

weld when the arc is initiated and when the arc is discon-

tinued; these exposed tungsten deposits will cause decompo-

sition of the hydrogen peroxide. The tungsten "spitting"

may be decreased and, iu amany cases, eliminated by using

a pure tungsteni electrode, striking the arc on a separate

piece of material and currying the weld into the work,

and then discontinuing the arc on a separate piece. For

inert-gas welding, where the welding rod is not coated,

it is recommended that strips be cut off the work scrap

and used as the welding rod. Stainless-steel electrode

tip cups should be used,

The weld resulting from the metal-arc process has two dis-

advantages: (1) porosity, and (2) brittleness. These

characteristics are highly undesirable in hydrogen peroxide

systems, and for this reason, the inert-gas processes are

usually preferred aud recomiended. The metal-arc process

257

( '-ucii It m a tilt slit Iom ii. () oj X rup.~, ) itiid i a qi it c sui it hi) I c

fn I thiis ph jI'ome.

O\ -Yit c 'ty I etiC gii H liv I dI it, iit I ;o itoH twio iti d v i rit I I c fel't u ic

ifl ltNd zugeit pocr-ox ilt sy xiUrn wi VId I) wloteul V0rpIredI-( to tltc

ii('trt -aIc pro(cesses. Theetl 111.(: ( I) tle excc~ivc l't' tn re-

tj ircd til(t'Lilt 8M d ajiigt ('11(() tilie flux tt'd. ix to be 1 Clpped

ill tile' wl d . 11(1 Wevr Vt' ~i.lilit' 1tH Irt MT i Wti sfII''to a 11-orn a

Htl'(eilgtlit p0J)itt Of View tkitd , if tilie i tl ed HUlIVsItivit ilge s Call

be toleraited, tiii8j4rcs 1)'H'#1 iM ep aCC)ide. XVI(Jxyi 'txcuiIC PIuS

ve Idii jg mHn licen itt i Ii ized for pii pei aind eniil I partus mande oif

III it1Iti 111118 WliiCII 1t igl ý i lt i I Ied Miid VX'V IE' i Ciii'i' We' idt'I- Lire

avi4l il1~J~'I'.Tiil mIect~i 011 Cail bet WC Itiedl iitvte' mtitisfatoilt y

wi I C I tIt i b typIeo o f m, Id i I g. Napo! Ii hta we 141inti flux or its

equitivulentii is recomarnd'eid fuk tif 111e 1,1118wed u

3 .1 .2. 2 Staki iti ss steel . I itert-gaN anid flictal are-we hii tg pro-

cebmes are liati sf actory iit tile lield i fig of Sttainless steel

fO Ilty 11FO1-g~i'tje'Oiley H.StrnIH . Tue iitert -gusH 111-0tess is

[)ie fV ared bVCInubt' tie i Ie utL-gutS b I ailte I. resu Its illit weld

wi th less fore igii matiter~ ial. lII gezzerau1, tliorinted tuuigsteu

eci c .rudes tir ut tsed(. Stanidard we dittiq; procedures should be

timed for both of these procemses, antd it is n ecessary that

uilli we Id be oif hiight quality , smnoothi, lhowogetiious , iand free

of intcl usi ons muid bIoufitoles . Carb))i de precipi tati on du.rinug

we Iditig must. be avoided by the use of stabljjIized alloys

muchi aa 3117 Jr. 321 or thle extrit Iow-tctthoh il loym, 3011 or

316,.

After it weld is completed, ill] weld scal~e shouldl( be remuoved

with at 300 series statiilesms-teeI brush, and tile iunner weld

mu rface should be ground wit itid whitiie aiox ide uiieel to it

maux imuam 32 rms finiusih.

Any instailation of a flange or disiclanrAge pipe at the low

p,,itit of a1 hydrogenl peroxide tanllk should be Welded from hthe

tank j ititerior and ground stwooth 1 iior to wcldiiup, the Luot tu

Clum 'e ill place.

NQIF: A carboru,,d(m wheel mhould not beused for grinditig, or else ironi will bedeposited in the wetal surface.

A narrow and thin mtaiio esss-steel backiing ring should be

insttalled at the weld placement in vertical tanks.

Polishling of stainless steels following wcldiiag is geCl(r'ally

unueccesary but, for certain burderlinc cases, it may mi-pruve the compatibility of the metal With the hydrogen per-

oxide by smoothing the surface. N'a general, the smoother

surface will pirovide a louer rate of hyd rogen peroxidt,

decompositLion. For mechanical 1politihi ng, a wet or dry

paper (aluminuim oxide abrasive) with a Jkcroaelle lubricant

can be used.

l;leCtFOl)oliahkillg of stainless 3tteI has also been cffective

in improving the cowpatibility of steel for hyd - ogen per-

oxide service. For routine hydrogen i-eroxide applications,

electropolishing is not required Leccuse stainless steel

. ... , IIA) oliLY , LU Aa Limlete CoU _ct1 !1nii j t•er'vkce.

For special applications, electropolishing of stainiless

steel might be justified, and in such cases, standard

electropolishing techniques should be used.

4.4.3.3 Brazing and Soldering. brazing and soldering techniques

are not recowezaded for application in hydrogen peroxide

systems. The joints ptoduced by these methods are usually

incompatible with the propellant.

259

It I7 I

14•.11.3.1, Mc.vllioaiitil_ ;•i/ ut . The Cdviiantugs of relutaiclC 11 Ii'-f lrce

S n1ll-•c lded t -atIINIVI &)i , t'1118 (III 1J iUb~iu , IJuW I ~I,, (IC 1 1

i iit Idpo i [t, I I ,owevu , I" usol type of .j (Ii t , Whet lie I flIui..•d or

(Ith I I'Wi H1 i s I equli red to pruvide IlduquIt Cm. iHttevl(lH fle A 1) iity

bmall I o.l~ and c4mpeonen'a ts should bI.e 1 'C ctd 'With AN

1'mill d-typ c•c(, t(ioInsM. LOUrge %11%Vt4 d 11111(d l,-UI CIIVlItS M1hIIC ltj" I 4eIc c t ed u i h t l1 fI t Igv'd c oiltI c c t i 1)1 . Til C uinl, ll tlit~ iit ( 'tIII c l-

tiect ion (hIM lld liu Of the AN t-ie, aind (-ti be pirovided b',

velding boss fittiungm u 1(11(' l~i ,,eliiies iir by iitiuml oI r4

tee fittii 4 t8 oil suriill lilies.

Ll 1.*.34 ll= 1 Ie (.j5 10I1. II tihe c'o IMtIU) t r ioil, iiiit illLti(111, 41l!d m0di fi -

cat ion of I1ll(Irogetil pel roxide systews, inlspection it; 1Im o t I llit

tu iusuvc qumlity of miateriuls; dhLeCIreCe to desit., eir' i

at ions; anid l11 'uplcr fabrication teclntmiqueti. Before instal.-

lit iul, eitch pii ece of equiiplcit, sutch as pumlpl-., flex ,j,,ints,

Valves, filters, etc., wi.1 be iniispeted and tc8ted fox:

C. 1"1 c 11l i lie S

2. l'rupv I I uori it ( tt4 (if t 11 o wal Ic)

3. Leakigc , Intcrtial i1ud externIcr

4. i'erssuie-liroof test

5. Seiliitm alld gasket uateri Ir

0. P'ropivr operlitioil

7. Freed!omu frow defects

8. Adhirenice to appllicable specificati)iirs--type, nize,

=i4t. ilti4, (i im witliois, etc.

Piping And tubinig sections Will be irsapected alud tested for:

1. Conformn'uce to design specificatiouns aid buildii. codes

2. Identity rild quality of materials of construction

3. Adequacy of supports; freedom from "cold Bpring" IIt . C'l eliil i liess

260

gI

5. l'rpe fitb ii tat io wo: rkmansIhIip

(,. I'ruof-prcsuuxe aild leakh tests

-, PIA,1per filhtakl litioul of ( ICA joa'1t I

I'l ec tla x i (li a ~sLn 1 hIt i on aid cqtxi pmcijt ui 11 bv instouected

I I 1. Cuuizrosaincc to deusign speci ica tti ons awli apil cable

2. Adeqjuitte grounidinxg

3. liiutit~tiii ista*ttce

4.Circuitry con~tIinuity mi~d ptopvr tertuiiitt1igi

5. Wut-kakishrj' and fabricationx tecmiqiiqti

[ (~j. Proper suU5lJj(t of Conaduitsanuid wi.xritig

Irrutrumezits (fluwmeterm, giigestraxsducers, etc.) will be

shop tested, wiid calibrated awad ccris'i 'ed u.ith due regard

to usiiuj, ctaiditiummx, fluid deiiuity, ojbvrutliti range,

Umater-if1 idenrtitLy. reperitiiilit' , vnd vieal Lg (:atuiabi it).

These instutiuents must be jinspe~cted foi cicazil ineM prior

to i tasLa IlItiti oil.

Itunds, build ings, structures, etc. should beinsjupected

for conifuranuaxce to design ispecificatxoznn anid buildinig codes.

4.4-.6 yd'ojitittic aiid/ur hieuwmatic Trests. All compoaenitti anid taniks

to be placed iii hydrogen peroxide service should undeugo

appli cablec hydrostatic w~dlo /0pnueutuit ic Ij~ruox temLi rig be-

fore they are cleanted atid passivated.

NOTE: lHydrosttuLic testing ahould beConducted with water.

261

After paosivation, all proof and leak testing should be

conducted only with deionized or distilled water, or with

clean, filtered, hydrocarboti-free nitrogen gas or air.

4.5 DECONTAMINATION AND DISPOSAL

Tihe initial step in the decontamination of equipment or

facilities and subsequent disposal of hydrogen peroxide is

its dilution with large quantities of water. All facilitiesI

which store and handle hydrogen peroxide should be equipped

with an adequate water supply to ensure a maximum dilution

of the hydrogen peroxide prior to its flush into the

facility drainage system. Normally, dilution to 3 w/0II202 or less should be completed before the hydrogen per-

oxide solution is damped or pumped into the drainage sys-

tem (which should terminate in a large body of water).

Further dilution is required before dumping into a public

water table. Under no circumstances should hydrogen per-

oxide be dumped into sewers or drains that lead to public

water tables, unless this maximum dilution has been per-

formed at the originating site.

4.5.1 Equipment Decontamination

Equipment being removed from service, temporarily flushed

of residual propellant, and/or being decontaminated of

possible impurities, is normally flushed with distilled

or deionized water. Emergency decontaminations may use

water supplied by the normal facility water or "firex"

(fire-fighting equipment) systems. Once flushed from the

equipment, the hydrogen peroxide should be diluted further

with facility or "firex" water.

"262

,-!

Elk,-~

4. 5.2 Fa cility Decontamint iati0

The decontamination of gross spillage or leakage at a

facility is best accomplished through the use of a facilityfloor flush or n flooding water spray system. Large-volume

fire hoses may be used as a substitute technique, but the

method of attack should preclude washing concentrated hydro-

gen peroxide solutions into the drainage system ahead of

the dilution water. Ordinary garden-type hoses can be used

for small spills or for rinsing hydrogen peroxide from theout•-'ide ---f equipment.

CAUTION: Unless an emergency exists(and massive water spray of equipmentis required), care should be taken influshing the outside of the equipmentto prevent water damage to the attend-ant electrical and control systems.

All facility flushing should be thorough and can be con-

ducted with normal facility water.

'* 5. •Drainage

All hydrogen peroxide facility drainage ditches (or otherspillage catch basins) should be open and lined withimpervious acid-resistant concrete. These ditches and

catch basins should be kept clean of debris and combustible

material. The use of the hydrogen peroxide drainage sys-

tem for other chemical dumps should be prohibited unless

an adequate water flow is maintained to ensure maximum

dilution and drainage system flushing of all chemicals.

The mitin drainage ditch should be supplied with a large

water flush outlet at the highest point of hydrogen peroxide

drainage and should be fenced from the facility to the

catch basin. The desigil of the facility should be such

that all areas are adequately drained by gravity into the

main drainage system.

263

-2-TV .. -. -.

I!I

4.5.4 Catch blasins

Because hydrogen peroxide dumping into public water tables

can be potentially hazardoi:s if it has not bAen sufficiently

diluted, most facilities utilize a catch basin whiich either

stores the water for facility recirculation or acts as a

settling or dilution pond prior to drainage into a public

water table. In either situation, the hydrogen peicoxide

is diluted or reacted further O.itl other chemicals (con-

tained in the catch basil?) to form water solutions that

are nontoxic.

4.5.5 Final Dilution Requirements

Althoigh local, state, and federal codes are not sufficiently

clear with respect to regulation of hydrogen peroxide dump-

ing into public streams, lakes, etc., it has been generally

accepted that dilution to less than 3 w/o 11202 concentration

is required to ensure human safety.

In a bioassay study conducted by the Academy of Natural

Sciences of l~hil-delphia fr a. 1A. dul ont de Nemours and Co.

(lef. 4.67), a concentration of 165 ppm 1120O in water at

"-70 F (with a dissolved oxygen content of 5 to 9 ppm)

resulted in a 100-percent mortality rate of fish (4 to 10

centimeters long) of the Lepomis macrochirus IRaf. (blue-

gill) species, which had been exposed to the contaminated

water ior a period of 24 hours. The resulting 24-hour TLm

(maximum threshold limit) for these species was 65 ppm at

a solution phl of 7 and 90 ppm at a solution pll of 8.5.

Internal regulations used by the liocketdyne Division of

North American Aviation, Inc., have established a maximum

concentration of 100 ppm 11202 for water dumped into public

water tables; these regulations have been accepted by

local, state, and federal authorities.

264

-. , -rv

AA

-I4.6 REFERENCUS

4.1 Shell Decvelopment Company, Emeryville, Californiap Concen-

trated Storable h~ydrogen Per-oxide, Report No. S-13971t,

Report period: May 1964 - August 1965, Contract

DA-04-200-AMC-569(Z).

4.2 McCormick, James C., F.M.C. Corporation, Buffalo, New York,

Hlydrogen Pei-oxide Rocket Manual, 1965.

4.3 Shanley, E. S. and F. P. Greenspan, "Highly Concentrate~d

Hydrogen Peroxide -Physical. and Chemical Properties,"

Ind. Eng._ Chem.,, 1536-43(1947).

t-.h LTV AStronautics Division, Dallas, Texas, Peroxide Contam-ination Study, Final Summary Repor,;, Report No. E 320

30 April 1965.

4.5 Roth, E. M., Jr., and E. S. Shonley, "Stability of Pure

Hydrogen Peroxide," Ind. Eng. Chem., 4ri 33-9 (1953).

4.6 E. 1. DuPont de Nemours and Co., Inc., Wilmington, Delaware,

Final Report, Research on the Stability of High StrengthI1 0 - nnrf. No AV'fPL-TR-.66-.1 It; Manrrh 1066 (Vnnfad=9j.a)P- 1 1 - - - ', -'. . . .

AFO4(611)-10216.

ia.7 F.M.C. Corporation, Buffalo, New York, Storage of 90% and

98% byWei ght Hydrogen Peroxide in Sealed Containers for4

Extended Periods, Report No. SSD-TR-61-29, September 1961,

Cont~ract AFO4(611)-6342.

4.8 Shell Development Company, Emueryville, California, Storable

Concentrated ilydroxen Peroxide, Report No. AFRPL-TR-606--207,

Report period: March - May 1966, Contract AFO4(611)-mW1.6

265

S.. . .... . ' • , •

1. *4 Shell DeveIuPmezit Company, law'ryvi11c, California, Storable

Concent rated llyd ron l'en Pj oxide, Report No. AlAL,-T11-66-26-,

Rlepor period: June -, Augus1 19(6, Co(jitract Al'Oli(ill)-11416.

1.. 10 1TV .\tFronauttics D)i vision, Dl)alas, lexas, "Re'lationshipt of

Active Oxygen loss (AOL) anid Surface To Volume Watio of

Materitt ls in Contact with Concentrated Hfydrogen uPeroxide,

leport No. 3-52100-0043-111, 23 July 1965.

It. 11 IAV Astronautics Division, Dallas, Texas, "Effects of Dis-

similar Metals on the Stability of Concentrated Hydrogen

Peroxidc," Report No. IJI-3-52100-0039, 30 July 1965.

14.12 MIV Astronautics Division, Dallas, Texas, "Compatibility

of Various Materials with 90% Hydrogen Peroxide at iO0 F

and 7501, for 10 I)ays," Report No. 3-52100-0011, 17 December

196',.

1.13 LTA' Astronaulics Division, Dallas, Texas, "Establishment

of Effective lifetime of Hydrogen Peroxide PIassivated Sys-

tems," Report No. LR-3-521OU-0047, 28 April 1965

.1. lITV Astronautics Division, I)allas, Texas, "Evaluation of

the Influence of Surface Finish of Material- on the Stability

of' Concentrated Hydrogen Peroxide," Report No. 3-52100-0049,

5.15 L11V Astronautics D)ivision, Dallas, Texas, "Verification

of the Classifice kion of Materials Used in the Scout Vehicle

Hlydrogen Peroxide System," Report No. I{-23-TR-0005, 30 April

1965.

4.16 JIA Astronautics Division, Dallas, Texas, "Compatibility of

Various Bladder Materials with Concentrated Hydrogen Peroxide

and 6061 Aluminum at 160°F," Itejiurt No. 3-52100-0041,

5 February 1965.

266

I .-.-.

4.17 LTV Astronautics Division, Dallas# Texas, "I'1ydrogen plerox-

ide Compitibility Evaluation of Three Candidate Expulsion

Bladder Materials," Report No. TR-3-52100-0038, January 1965.

4.18 LITV Astronautics Division, Dallas, Texas, "Evaluation of 316L

and 321 Stainless Steel Tubing for Service in fLydrogeni Perox-

ide Systems," Report No. TR-3-52100-0037, February 1965.

4.19 Explosives Research and Development Establishment, Waltham

Abbey, Eigland, The Behaviour of Starinic Acid Sols in Con-

centrated 1lydrogen Peroxide, Part 4. Quantitptiiv Evalua-

tion of the P'recipitating Efficiency of Aluminum lons,

Report No. 25/11/63, November 1963.

4.20 Lewis, T. J. and T. M. Walters, "The Behaviour of Stannic

Acid Sols in Concentrated Hydrogen Peroxide. I. Factors

Affecting the Stability of Stannic Acid Sols in Concentrated

llydrogen Peroxide," J. Appl. Chem., 1-0, 396-403 (1960).

4.21 LTV Astronautics Division, Dallas, Texas, Effects of Ele-

mental Ions on The Stability of Concentrated hlydrogen

Peroxide, Report No. LR-3-52100-004'i, 30 April 1965.

4.22 United States Naval Underwater Ordnance Station, Newport,

Rhode Island, Condition for Self-Heating of Exothermnlly

Decomposing Liquids (e.g. Hydrogen Peroxide), Technical

Memo 227, Janrary 1960.

4.23 United States Departmert of the Navy, Bureau of Aeronautics,

Handbook for Field Handling of Concentrated Hydrogen Perox-

ide (over 52 w/o H Report No. NavAer 06-25-501,

January 1957.

4.24 United States Government, Office of the Director of Defense

Research and Engineering, Washington, D.C., The Handling

and Storage of Liquid Propellants, January 1963.

4.25 F.M.C. Corporation, New York, New York, Materials of Con-

Struction for Equipment in Use with Hydrogen Peroxide,

BECCO Bulletin 104, 1966 Revision.

267

4.20 Shell l)evelopment Company, Dneryville, Californxia, Shell

Annlytical Methods for flydrogen Peroxide, SMS 705,'58, 1958.

4 27 Milit ary jei'Liiic( L It ionj, Propellaunt, Hlydrogen Pleroxide,

Mil-lP-1I0051), 18 Muarch 1965.

4•.28 l'rivi, ,,•it . ..- i n ion, S 4, i, i , 116ll Aerosystems, buffi lo,

New York, to m. T. Constantine, ltocketdyne, Canogn P'ark,

California, December 1966.

4.29 Aerojet-Gencral Corporation, Sacramento, California, Final

Report, Advanced Propellant Staged Coombustion Fenfsibilily

Program, Phase I, Parts I and 2, Iteporit No. AFRI"I,-Th-66-6,

April 1906, Contract AF0'(6 11)-10785, CON"IDI2lTIAL.

4.30 The lattelle Memori i n 18stitute, ( oiIumbus, Ohio, _Compatibil- I

ity of Rocket Propellaxts with Mate rials of Construction,

Defense Metals Information Center Memo 201, January 19()5.

4.31 U. S. Department of the Navy, Bureau of Aeronautics, Field

Handling of Concentrated Hlydrogen Peroxide (over 52 w/o),

Report No. NavAer 06-25-501, January 1957.

4.32 Private Communication, U. H. Robinson, LTV Astronautics

Division, Dallas, Texas, to M. T. Constantine, Rocketdyne,

Canoga Park, California, January 1967.

4.33 Fisch: K. I.. L. Peale, .1. Messinai and II i "C•irm-

patibility of Lubricants with Missile Fuels and Oxidizers,"

ASIE Transactions, 5, 287-96 (1962).

4.34 [TV Astronautics Division, Dallas, Texas, "Preparation of

Metallic Surface for Exposure to Concentrated Hydrogen

Peroxide," GVA lO-62aSpecification.

4.35 North American Aviation, Inc., El Segundo, California,

"Process Specification, Processing of Wydrogen Peroxide

System Components and Assemblies," No. IAOllO-003, April

1961.

268

- ' . ... - t 7 •

Aj t

4.36 Walter Kidde and Company, Inc., Belleville, New Jersey,

Specification No. 520007, as given by Ref. 4.2".

4.37 HeP!uaiell Aircraft Company, St. oKuis, Missouri, Specifics-

tion A/C 13002, no reference located; see Tables 4.21, 4.23,

4.26, and 4.29.

4.38 LTV Astronautics Division, Dallas, Texas, LT'V bIUc.LticatioII

308-20-3, as given by Ref. 4.13.

4.39 LTV Astronautics Division, Dallas, Texas, "Preparation of

Non-Metallic Surfaces for Exposure to Concentrated Hlydrogen

Peroxide," CVA l0-64a Specification.

4.40 Shell Chemical Company, New York, New York, Concentrated

Hydrogen Peroxide. 2nd Ed. Properties, Uses, Storage,

Iandling, Report No. SC: 62-23, 1962.

4.41 Liquid Propulsion Information Agency, Ljiquid P'ojellant

Manual, "Hydrogen Peroxide," 1958.

4.42 The Battelle Memorial Institute, Columbus, Ohio, Liquid 4Propellants Handbook, "H1ydrogen Peroxide," Vol. 1, 1958,CONFIDENTIA L.

4.23 Jlocketdyne, a Division of North American| Aviation, Inc.,

Canoga Park, California, Review of Materials Compatible

w~iA ch!I-,drogen Peroxide, Ruport No. R-755

It.It1 Private communication, W. C. DeKleine, F.M.C. Corporation,

Princeton, New Jersey, to J. C. McCormick, F.M.C. Corpora-

tion, Buffalo, New York, 11 January 1967.

4.45 Bell Aerosystems Company, Buffalo, New York, Compilation

of Materials Compatibility Test Data with Propellants,

Report No. 2084-939-001, Coitract AF33(657)-8555,

December 1962.

4.46 'Bellinger, F., I1. B. Friedman, W. !H. Bauer, J. W. Eastes,

and W. C. Bull, "Corrosion and Stability Studies," Ind.

Eag. Chem., ., 310-20-(1946).

269

IIII

4.47 F.M.C. Corpor-ation, Neh York, New York, Firial Rle;'i

Iydrog'en Peroxide: Catalyitic P)ecompomi)tion . Comi"Itibi lillHatetiptls at llih Tmperature. and Surveillntiict' )c'ijcrm

Report No. 2214-17, Contract NOas 58-689c.

4.48 Acrojet-Gcnrial Corporation, Sacramrnto, California, Com-

imitibility of O-lting. Materials with 90%( if • Naterials

Sectioni Ieport No. 1847, as given by lRef. 4 .29.

4.49 Monsanto Research Corporation, Dayton, Ohio, Uvai luatioli

of Elastom(ers as O-]iuii Seals for Liquid Roc'ket Fuel aIid

Oxidize.r Sy'.stems, Report No. ASI)-Tlflt-63-496, Contract

A1'33(6l6)--8'i3, September 1963.

4.50 Mcl)onr|eLAir'craft. Corporation, St. Louis, Missouri, Evl lul tiorn

of "0" lings for' Conipt ibility with 90 Percent Hydrogen• l'e.x-

ide at- 1i501, Report No. A7:21, June 190?1.

4.51 Explosives llesearch and Development Imbsiabiiilnent, Waltht i

Abbey, Fnugland, The Sensitiveness of Fluorocarbon Lhricant,/.

RrP mixturts, E.R.1).E. TecCi Memo 1,/M,152, October 1952,

CONFIDLI'IAL.

14.52 Department of Defense, Qua•.tity-Distance Storage (Criterin

for Liquid Prop~ellants, Instruction 4145.21, 26 Miy 190•'.

4. .53 Naval Ordnance . . ... boruto•ry , Wh . c. 'i a A,," "-" 1 ii' 1 i u .... cIIu I

NOLTR 63-12.

4,.54 United States D)epartment of the Arm', Or'dnance Safety

Manual, Rleport No. Ol) M7-244.

4.55 ASME bioiler and Pressure Vessel Code, Section VIII, "Hiules

for Construction of Unfired Pressure Vessels," latest

edition.

4.56 Shanley, E. S., "Self Hleating of Hlydrogen Peroxide Storage

Vesselsu" Ind. Ung. Chem., A5, 1520-4, (1953).

270

7

-. ,' ;-.• r-r -~W .. r T•- ; .NWA~A

,.4-

4.5"1 Auericeni Standard Code for Pressure Pipting, ASA D131.1,

1955 l!ition.

4.58 Crocker, Sabin, Pipinig Handbook, McGrow--lilt book Comnpany,

New York, New York.

14.59 H. W. Kellogi. Company, Jersey City, New Jersey, IPesipAl of

Piping Systems, John Wiley & Sons, Inc., New York, New York.

4.b0 Littleton, Charles T., Industrial Pjping, McGraw-llill Houk

Company, New York, New York.

4.61 The Grinnell Compmny, Pipit% Pesign and Enginevring.

4.62 Crane Company, Catalog No. 53.

4.63 The Grinnell Company, Catalog on Pipe Hangers and Supports.j4.64. Shell Chemical Comlpa,.., New York, New York, Technical hklelt~in,Study of Teni)erature Mensuring Systems for Hligh Strecngth HIy-

drogen Peroxide Storage, Report No. IC:63-7, May 1963.

4.65 Manufacturing Chemists Association, Washington, D.C.,

Supplement II. Chemical Safety Data 'hieet SI) 53.

4.66 International Nickel Comimny, l!.!)id Idcittilicution (Spot

Testing) of Stone Metals and Alloys.

4 67 Academy of Natural Sciences of Philadellphia, Department

of Linu~ology, Philadellphia, Pennsylvania, bioassay Tests

for the Engineering Department, E. 1. duPont de Nemours

and Company, December 19b2.

271

777.7-

.. . . .... .. ...

TADLE 4. 1

STOIRAUL STA14 I '1111 01" ll11)IIRiLN !'IMIO2WIW1 )

Wcighlt ptIccut I,,0,, Sturuge o Iouyear (2).......... .~ 0 I iu{ l"1I

(ozitainiir Timfl 2Initial, lill matcari I monthls •vight Irceit

We tabi Izcd (.K, v.'.ý l,0,, (Storcd(3) 1945-1948)

90.5 8( 3 7. 0-251,

"90.5 89. I - 30 0. 21087.8 - 3I 0. 381

90.3 89.3 - 30 0.16990.5 89.3 - 30 0.16990.5 HS. 7 0 36 O'25t

Unstabilized 90 v o 1L.02 (Stored(3) 11, 19511 to 121'1955)

91.23 t39.27 1060 Al 13 0.6090.72 90.56 10(00 Al 13 0.o0390.91 90.-45 5652 Al 13 0.42588.13 87.54 5(652 Al 13 0.5490.91 90.81 5254 Al 13 0.03990AI1 90.17 523" A 13 0.20

,iaatabiIljzed 98 w 'u !L,0o (stored(3) 8 1900 to 5/1963)

98.59 96.47 _(4) 33 0.02198.14 97,- I 33 o A.o-1

98.6 9e3. f - 33 0.08691.59 98.28 - 33 0.05408.8 48. 36 - 33 0.07796.11, 97.79 - 33 0.06198. 8 98.311 - 33 0. o989.1___ 97.143 _ 33 [ 0.125

:tabilized lorpedo-Gradc I•f,% (Storage(3) Completed 811J,902)

90 88.51 10(00 Al 62 0.129% 80.75 1000 Al 63 0.2070 (8.32 1000 Al 76 0.088

(1 ~1ata Iti uen from Reuf. 4.2 (3) lit storage in 30-gallon(r)o drum (s/V *-O. • iD.-)

(2)(),) IvL year does n•ot correcpomd °(IV0)8 i.%)P u material wim m;asum!ed

With concentration change to be aluminum alloy

,27

_ •#•:; .,,.

S~TAULL i4. 2

A COHW'AI WIS N CY 1 IL AL 01T l)LtC0NI JsF 1 0M 01 , 90 u o IIYDItmtoON PI xtWXIJ .

H,%NU1ACTUILLD IN 1947, 19)3, AND 1905(1)

L.ifect ol lmit'czaturw

Rate of Dccompositioni (AOL)

lemperu ture , F 19 ,7,(2) 1953(3) 190_,__ ,,M

8b 1% per ycar 0.5 to 1.0%. per year 0.02- to 0.01" per year

131 1j pur week 10% per year 0.1% per yA r

2 12 2% Ip e d ay 41 p er w eel 1 • pcir yc ar

Effect of Contamination

Decomposition RIate at 212 F

Additive to 90 w,"o 1)O, 1947(2) 1965(5)

None 2% per day 1% per day

Al 10 mig/liter 2% per day

Cr 0.1 mg,11iter 96% per day 2% per day

Cu 0.01 mg 'liter 24% per day 10 per da .

Cu 0.1 .,'liter 85%, pe r day 6bj per da)

Fe 1.0 mg/liter 15% per day 25% per dayi gn 10 -.,iliter ' i0% p ai do)-

Sn 10 mg/liter 2% per day --

IIO()Data reported an generalized criteria from tests using assortedtest parameters and techniques; da!. generally represent teatsp runder minimum S//V conditions.

(2) Data reported in Ref. 4.3

(3)( Data reported for 99-1 w/o .IL)O) in borosilicate glass containers tef. 4.5)

( Data reported in Ref. 4.1

Data reported in Wef. 4..4

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KAIITABLE 4j.14&

COMPATIBILITY OF 90 w/o HYMROGEN PIOXIIDE

WITH POTENTIAL LUMIICANTS(l)(2)

NO VISIBLEk REACTION

Halogenated Aliphatic Hydrocarbons

Polytetrafluoroethylene (solid)

Tetrafluorocthylene-hexafluoropyropylene copolymer (solid)

Polychlorotrifluoroethylene (molecular weight < 800)

Polychlorotrifluoroethylene (molecular weight > 800)

Perfluorokerosene

Dispersion of Polytetrafluoroethylene in Trichlorotrifluoroethane (solid)

Perchloropentacyclodecane (solid)Perfluorodiethylcyclohexane (mixed isomers)

Dichlorodecafluoroheptane

Chlerofluoro HydrocArbon (approximate molecular weight 725)

Chlorofluoro Hlydrociarbon (approximate molecular weight 1000)

Fluorinated Hydrocarbon (77.4 percent F; approximate molecular weight 640)

Polychlorotrifluoroethylene (approximate molecular weight, 775;80 percent halogens)

Si l icon Compounds

Silicon Fluorides

Tri(p-trifluoromethyl phenyl) Silicon Fluoride

Trilaurysilicon Fluoride

Tris (3,5,5-.trimethvlhexyl) Silicon Fluoride

Dimethylpolysi loxanes

Dimethylpolysiloxane (2 -to 500 Cs)

Fluoropolysi loxanes

HCF 2 (CF )5 CH2 0[Si(C13 )2 03nCli2 (CF2)5 0F2 11, Fluoropolysiloxane, n 1-26

311

.44S:,fT : J,• . . .. .... L • • • ,e•- .... , -.. . ,,• • - -- .. .. . . .•

(Continued)

NO VISIBLE REACTION (Continued)Cyclic Fluoz'osiloxanee

Cyclic Fluorosiloxane (3olid)

CH (R)SiOSi(CH, (R)OSi(CtI3)(R)O

RB CF CF2CF CH-3222

Cyclic Fluorosiloxane (solid)CH (R)SiOSi(C113)(R)Osi(C113)WBO

Fluorosiloxane Elastomer (solid) Made From

CF (CH2)S (I)C 2

Cyclic Fluorosilaxane (solid)

CH1 (R)SiOSi(CH, )(R)OSi(CH~ )(R)?9

R = CF CF 2CF 2CII-4I

Mixed Cyclic Fluorosiloxane (solid)

CH (R)SiO[Si(CH )(R)OJ Si(CH )(R)O

R =CF CFCFCI n 3 anidhigher .4322Dimethylpolysiloxane-Cyclic

Fluoropolysiloxane Blends

Fluorosiloxane Grease (No. 33 + inorganic gelling agent) .Fluorosiloxane Girease (No. 34& + inergan.-c gelinari ageniAt

Mixed Diwethylpolysiloxane and Cyclic Fluoropolysiloxane

Mixed Dimethylpolysiloxane (average molecular weight < previouscompound)

Halogenated and Nonhialogenated Aromatic Hydrocarbons

3-Heptyl-ni-terpheny 1

Isopropyl-ni-terpherayl

Dinonyliiaplithalerie (mixed isomers)

1,3-Big (trifluoromethyl) Benazene

312

77

TABLE 4..14a

(Continued)

NO VISIBLE BRUCTION (Continued)

fw,3,5,6-Tetrachlorofluorobefl5Oie (solid)

l,3,5-Trimethyl-2,4,6-Trifluorobenzene (solid)

1,3,5-Trimethyl-2,IA--Difluorobenzene

2, 5-Dichiorobenzotrifluoride

2-Fluorobiphenyl (solid)

3,31-Difluorobiphenyl (solid)

4,4'-Difluorobiphenyl (solid)

3,6,4'-Trifluorobiphenyl (solid)

Estere

Mixed Fluoroalkyl Camphorates Fluoroallcyl-HCF (C2)n CII- n 3,5,7

Bis-lH, 1H,511-perfluoropentyl Camphorate

Bin-lU, LU,IIHl-perfluoroundecyl Camphorate (solid)

Tetrabutyl Pyromel11itate4Mixed Fluoroalkyl Pyromellitates

Bis (2,2,3,3,4,4,5,5,-octafluoropentyl)3-methylglutaratt

Bis (2,2,3,3,4 ,4,5,5,6,6,7,7,-dodecafluoroheptyl)3-uaethylglutarate

2,2,3,3,4,4,-Hexafluoropentyl 1,5-bis (triwetiayl acetate)

big(I-m-eth-eyey! ehezy AInctahy'AI/ Sebacate

Poly (1,1,5,5-tetrahydrohexafluoropentazmethylene adipate)(solid)

B in (2-ethylhexyl) hoedtDibutyl Chlorendate

Nitrogen Compounds

Jlexadecytriphenylurea

2,2'-Dinitrophenyl Ether (solid) -

4,%'-Dinitrophcnyl Ether (solid)

313

TA~b,, 4. l4a

(Continued)

NO VlISBIX REACTION (Continued)

2,bý-Difluoro-3,5-dinitrochlorobenzene (solid)

2,I4-Dinitro-5--fluorobromobenzene (solid)

Per! luorotr ibutylaniine

Per! luoro Compounds

Polytetrafluoroethylene (solid)

Tetrafluoroetliylene-hexafluoropropylene Copolymner (solid)

Perf luorokerosene

Perfluorodiethylcyclohiexane (mixed isomers)

Mixed Perfluorocyclic Ether, C F 16 0 (five- or six-miembered ring withaide chain, oxygen in the ringi

Per fl1uor ot ribu tylaw in

Per! luorodihexyl Sulfide

4-Chiloro-3,5-difluoroniitrobenzcne (solid)

3,3'-Difluoro-li,4'-dimethoxybiphenyl (solid)I

Bis(m-phenoxyphenyl) Ether

I ,4-bis(cresoxy) Benzene (mixed isomers)

CF CF o(CF ) SF5

2, 2-Dinitrodiphenyl Ethei (solid)

Ia,4'-Dinitrodiphenyl Ether (solid)

4-Fliuori-6-wctiaoxya~cctanilide (solid)

3,3'-Difluoro-'4,4'-dimethioxydiphlenyI Sulfoxide (solid)

3,5-Difluoro-6-methoxyacet~anilide (solid)

Mixed Per! luorocyclic Ether, C FJ6 (fv- or six-membered ring with

side chain, oxygen in the ringi

TABLE 4.14a

(Concluded)

SOLUBLE IN 90-PERCENT 11202 WITH NO VISI&LE SIGN OF REACTION

2,2,3,3,4,4,5,5-Octafluorohexyl 1,6-bis (trimethylacetate)

2,2,3,3,4,4,5,5-Octafluorohexyl 1,6-bis (3,3-diwethylbutyrate)

Diethylene Glycol Succinate Polyester

Chlorotetraf luorobenzotrif luor ide

p-bisu(m-trifluoromethylphenoxy) Benzene

PARTLY MISCIBLE

2,4,6,3',5' Pentafluorobiphenyl (10-percent decrease in volume)

3,3' Difluoro-6,6' dimethoxybiphenyl (solid; 20-percent decreasein volume)

p-chlorobenzotrifluoride (20-percent decrease in volume)

SOME COLOR CHANGE

Bis(p-phenoxyphyenyl) Ether (solid)

3,5-Difluoronitrobenze ue

GELLED ON MIXING

Tetrachlorodiphenyl Ethe- (solid)

(')Data taken from Ref. 4.33(2 )Wring testing, 1 milliliter (liquid) or I gram (solid) was mixed

with I milliliter of 90 weight percent H202*

315

-7, M mom,

TABLE ,. 15

RECOMMENDED JOINT SEALING COMPOUNDS FOR USE WITHMI)

90- AND 98-JPERCENT HIYLDOGEN PEROXIDE

Name Supplier Formulation Class Remarks

Dixseel Dixon Corp. Teflon 1 Suitable forsmall-pipe service

T-Film Eco Engineering Dispersion 1 Suitable forTeflon-Water small-pipe service I

Teflon Tape Various Teflon I Suitable formost applications

NOTE: Use sparingly to prevent carry-offinto the 112.02 stream. Avoid threaded con-nections; use AN flares and flanges.

Compoundti Not Recommended

Compound Supplier

Calbar CB Pipe Seal Calbar Paint & Varnish

Crane Thread Lubricant Crane

Fel-Pro, C-5 Felt Products Mfg.

Graphite Paste Key Graphite

Goop (blue) Carl A. Pearson

Goop (silver) Carl A. Pearson

Cyl-Seal West Cheater Chemical

Mo lybd•en i•te Pipe Dope

Permatex, Aviation Form A Gasket No. 3 40S-18 Lubricant Monsanto Chemical

Pecora Compound Pecora Paint

Plastic Metal No. 22 National EngineeringProducts

Rutland Pipe Dope Rutland Fire Clay

Skydrol Monsanto Chemical

Weco No-Gall Well Equipment Mfg

X-Pando X-Pando Corp.

316

zo",ý

TABIE Ji.15

Comp~ound (ocue)Supplier

Kel-F Grease No. 90 Minnesota Mining & Mfg.

Tin Plating on Aluminum 6061

Alcoa Thread Lubricant AlcoaRectorseal No. 15 Rector Well Equipment

(')Recommendations taken from Ref. 4.25

317

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327

TABII he. 20

COMP1ATIBILITY 01' 90-PERCENT IIYILtOUEN PEII3OXIVE WITH!

1060 ANP 1100 ALUMINUM ALLOYS(I)

Exposure Per,-eut

Mate'i 1 Surface Temlpcrature, Time, Stnlbi- ExpesureForm 2 Coudi tion " days AO1, ].ity ieliepollse

1060 Alloy1 Uitanodized 110 10 0.2 92.3 No effectlt•S 96

1060 Alloy, Unianodized 110 10 0.2 92.3 No effect1112 Temper lat21 89

1060 Alloy Anodized 110 10 0.3 97.2 No effectlulS 96

1000 Alloy, Anodized 110 10 0.3 97.5 No effect1112 Temper I. Ls 89

1000 Alloy Unanodized 75 10 0.6 98.8 No effect

100 Alloy Una iodized 40 10 0.7 99.0 Discolored

1100 Alloy lUinanodized 110 10 1. 1 95.2 WhiteIlos 20 coat ing

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TABLE 4.31a

PROCEDURES USED FOR SURFACE PREPARATION

IN TABLE 4.31

Nate Preparation Procedure

a Sample degreaserI in aromatic solvent followed by a rinse inacetone, all at room temperature

b Sample submerged in I-percent NaOll for 10 minutes at roomtemperature

c Sample submerged in 10-percent NaOH for 16 hours at roomtemperature

d Sample submerged in I-percent 1N013 for 5 miuutes at roomtemperature

e Sample submerged in 35-percent HNO3 for 16 hours at roomtemperature

f Sample submerged in HP-90 until used for test, at roomtemperature

. Sampl.e submerged in stabilized HP-90 at the t3mperature of thetest for 1- to 16-hour periods, followed by repeat treatmentswith fresh 1&-9O until steady-state conditions appear to beachieved

h Sample submerged in fused stearic acid for 1 hour at 80 to 100 Cimmediately after treatment by Procedure b

i Sample submerged in 2-percent ethylene-diaminetetraacetic acidin 30-perrent H 2 S0 4 for 30 minutes at 80 to 90 C

Sample submerged in 1-percent diaodium ethylenedianinetetraaceticacid in 35-percent BN0 3

k- -Sample submerged in fused phthalic anhydride for I hour at 140to 150 C immediately after treatment by Procedure b

I Sample submerged in Viscasil 100,000, then wiped dry with absor-bent tissue

m Sample submerged in 85-percent H3PO4 for 16 hours at roomtemperature

"357

TABLE 4.31a

(Concluded)

Note Preparation Procedure

n Sample submerged in 35-percent IINO3 for 1 hour at 50 to 70 C

p Sample submerged in I-percent Viscasil in benzene, dried, re-submerged, and dried

q Sample anodized in 25-percent ISP04 at 1 amp/sq decimeter for6 minutes at room temperature

6 Samples submerged in 2-percent NaOll for 2 hours, then in 2-percentHNO for 10 minutes, then zincated. Samples zincated in 16-percent Na ZnO? - 40-percent NaOOl solution for 30 seconds at roomtemperature. Samples were then rinsed well and submerged in2-percent JIN0 3 for 1 minute. Samples were then zincated again,rinsed, and submerged in 2-percent IN03 for 1 minute again.Samples were then electroplated by submerging in 6.4-percentstannous sulfate, 5.0-percent sulfamic acid, 0.5-percentdihydroxydiphenyl sulfone solution with the current on and main-tained for 6 minutes at room temperature at 0.022 amp/cm2

(20 amp/sq ft). Samples were then rinsed well and submerged inHr-90 for 20 hours.

t Samples previously plated by procedure s were given an additionaltin plate by submerging in 5.0-percent stannous sulfate, 5.0-percent sulfuric acid, 5.0-percent sodium sulfate, 0.4-percentgelatin, 0.2-percent m-cresol solution with the current on and

~L~IVC A.A VJ UL1U to ~ £UUI W1A U L , V. d Q WF/ LAU-.

Samples were then rinsed well and submerged in ffl-90 for 20 hours.

u Samples were treated as in procedure S through the first zincatingstep. Samples were then zinc electroplated in 0.05-percent zincchloride, 0.05-percent sodium cyanide, 1-percent sodium hydroxidesolution for 1 minute at room temperature at 0.02. amp/cm2 .Samples were then rinsed and submerged in 2-percent LINO for1 minute and then tin electroplated as in a. The tin plate wasthen fused in a furnace at 265 C and then tin electroplated asecond time. Samples were then rinsed well and submerged inIEP-90 for 20 hours.

358

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TET CONDUCTED AT 212 F INPYREX GLASS FOR 24 HOURS

75 -

90 92 94 96 98 100

H2 0 2 CONCENTRATION, WEIGHT PERCENT

Figure 4.1. Stability of Hydrogen Peroxide as aFunction of Concentration (Ref. 4.2)

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T I ME, DAYS

Figur,! 4.2. Typical Decomposition Rates for Various WdrogenPeroxide Samples at 32 F (Ref. 4.6)

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TEMPERATURE, C

102_0 0 60 40 20

, ELECTROLYTIC TIN& 1260 ALUMINUM

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363

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SPHERICAL TANK VOLUME, GALLONS

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H202 TEMPERATURE, F

Figure 4.8. Effect of StAbilisation of 98 Weight Percent H102 as aFunction of Temperature (Ref. 4.7)

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Figuve 4.9. Effect of Stabilization of 90 W/o if 0 oas a Function of Stabilizer Concentraioat 212 F (Ref. 4.8)

368

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HYDROGEN PEROXIDE CONCENTRATIONe W10

Figure 4a.11. Pressure Increase in a Sealed ContainerResulting From Hlydrogen Peroxide Decompo-sition at a Itate of 0.1 Percent AOL/Year

370

SECTION 5: TM NSPORTATION

5.1 SHIPPING CONTAINE[S AND V1II1CLES

Approved hydrogen-peroxide shipping containers are available ill

the following capacities (Ref. 5.1, 5.2):

Reagent quantities: 1 pint (3/4 pound) (iC.U. lReguIltion

73,266)

Drum quantitivs: 30 gallons (300 pounds) (I.C.C. Regulation

42D)

Tank cars: 4000, 6000, and 8000 gallons (I.C.C. Regulation

"10 3-A-AL-W)

Tank trucks: 2000 and 4000 gallons (I.C,C. Regulation

MC 310-H2202)

Portable tanks: any desirable size (I.C.C. Special Permit)

All hydrogen peroxide storagv or shipping containers are equipped

with a dustproof vent to rel'dase oxygen produced from decomposition

"and to p'event the G 0 o

5.1.1 Reagent Quantity Containers

Reagent quantity containers are glass bottles with dustproof vents

on top. For concentrations above 52 w/o H2 02 , the glass container

capacity should not exceed 1 quart (Ref. 5.3). When packing these

7 containers for shipping, I.C.C. Regulation 73.266, Specifications

15A, 15B, 15C, 16A, and 19A apply (Ref. 5.2). The applicable

reagent bottles must be packed in a metal container vented at the

bottom and packed in another metal container vented at top. Cush-

ioning material shall be used between the bottle and inner container

371

and between the inner and outer metal containers. Cushioning

material shall be vermiculite or the equivalent in an amount

at least 10 times the volume of the solutibn x!hipped, and shall

be wet with at least 10-percent water 'by volum'e to which a sta-

bilizing agent has been added (Ref..5."). TI9se containers should.-

then be crated in a wooden box.

5.1.2 Drum3

There are two types of druns available for shflppina -concentrated

hydrogen peroxide. One is a double-head drum &Utitb.lee or all

freight shipment, and the other is a single-head drý4m suitable

only for full-carload and full-truckload shipments.. The vent

on the double-head drum opens into the compartment between the

two heads. This compartment will trap any 11202 lost through

splashing or leakage (Ref. 5.4, 5.5).

Both types of drums are fabricated according to I.C.C..$pecifica-

tion 42D (Ref. 5.2). Each of these drums is made of high-purity

aluminum with a vented closure in the top head. The rated pcapa-

city does not exceed 30 gallons, and side openings are not per-

mitted. The closure is Pealed to prevent removal in transit.

The top head should be plainly marked 'WEEP TIIIS END UP" or "KEEP

PLUG UP TO PREVENT SPILLAGE." For shipments other than carload

or truckload lots loaded by consignor and unloaded by consignee,

the drums must be of a design and venting arrangement approved

by the Nureau of Explosives.

The approximate tare weight of a single compartment drum is 42

pounds, and that of a double compartment drum is 50 pounds. The

net filling weights of 70 and 90 percent hydrogen peroxide are

'280 and 300 pounds, respectively. These weights correspond to

about 26 or 27 gallons of liquid in the drum. The volume will

vary with temperature (Ref. 5.4).

372

5.1.3 Tank Cars

Tank care suitable for hydrogen peroxide use are available in

4000-, 6000-, and 8000-gallon capacities. These cars, constructed

"according to I.C.C. Specification 103A-AL-W (Ref. 5.2), are cylin-

- drical, fusion-welded aluminum tanks with a dome containing a

manhole, a vent with a porous-stone filter to exclude dust, an

unloading dip-pipe, a fill connectLion, and a bursting disk de-

signed to blow out a I5-psig pressure. The temperature of the

hydrogen peroxide is measured by a thermometer or thermocouple

ca-ried in a protective aluminum tube inside the tank or fastened

to the tank's outside wall below the liquid level; the outside

thermometer or thermocouple is insulated with glass wool (Ref.

5.1). All fittings, gaging, venting, loading, discharging, and

air-inlet devices are constructed of materials compatible with

hydrogen peroxide. Venting devices are Of a type approved by

the Bureau of Explosives.

5.1.1* Tank Trucks

I.C.C. Specification MC-310-H12 02 (Ref. 5.2) applies to shipment.

by tank trucks with-2000- to o000-gallon capacity. These trucks,

which have been special.l.. -ast.iu••`-t for _x ._ ....e I I* O"roxide

service, are equipped with complete unloading facilities, includ-

ing a connecting hose and fittings for attachment to the consignee's

storage system (Ref. 5.1, '5.4).

5.1.5 Portable Tanks

Portable tanks, commonly of 500- and 1300-gallon capacity, are

subject to I.C.C. Special Permits. These tanks, which can be

filled at the plant and used as storage vessels at the user's

site, offer many advantages, particularly for remote, overseas,

or temporary sites.

373

5.2 SIIIPPING RUGUIATIONS

For shipping, the I.C.C. has classified concentrated 1120 as a

corrosive, "white, label," liquid. Each container must be'cleprly

marked "TllIS SIDE UP" or 'KEEP PLUU UP To AVOID SPIIAAGE." In

addition, each container must carry the specification marking

and number and the statement of the contents. "FOR HYDROGEN

PEROXIDE USE ONLY" must be stenciled above the specification

markings.

5.2.1 Commercial Air (Federal Aviation Agency)

%lhen hydrogen peroxide is shipped by commercial air travel, the

Official Air Transport of Restricted Articles, Tariff and Civil

Air Regulations No. 49 regulates packaging and handling informa-

tion.

5.2.2 Military Air (Department of Defense) .

Regulations n~t.ed in AFM 71-4, Packaging and Handling of Dangerous

,.tri a1- for'Tuaiisportu'ion by hi].iinry Aircre -ft, a .nd NA,

15-03-500 govern all hydiogen peroxide shipments by-military

aircraft.

5.2.3 W.•aterwas (U.S. Coast Guard)

Hydrogen peroxide shipments on Coast Guard-controlled waterways

are controlled by I.C.C. Regulations and U.S. Coast Guard Regula-

tions NAV-CG-108, which note packaging and handling information.

374

5.3 OPEiRATION AND AINTENANCE OF EQUIIMENT

5. 3.1 Drums

uo prevent spillage through the venting device, drums containing

""-hydrogen per')xide should not be tilted or rolled during loading,

transfer, or handling; they must be moved and stored in an upright

position.

Siphoning or pumping arc the recommended methods for emptying drums.

The siphoning system is used when small quantities of hydrogen

peroxide are involved. A siphon known commercially as the Model D

Golden Thief Vacuum pump (manufactured by the W&W Manufacturing

Co., Box 9311, Chicago, Illinois) or its equivalent is usuallyused for transferring or sampling of small. quantities of liquid.

Although the vacuum portion of the noted device contains aluminum

alloys unsuitable for peroxide use, the only part that contacts

the solution is a compatible plastic tube. This siphon can be

used for sampling tanks as well as drims and can deliver liquid

from a considerable height. The plastic tubing and the sampling

pump should be properly cleaned and passivated before use. Suit-

able cleaning and packaging between use times is also required.

A combination of glass and plastic tubing is also possible in a

siphon arrangement. Pouring or gas pressurization should be

avoided in emptying drums containing hydrogen peroxide. (Gas

pressurization can introduce contaminants or overpressurize the

drum.) (Ref. 5.A).

Although direct pouring is not a recommended technique, a special

hydrogen peroxide drum valve suitable for attachment to the stan-

dard 30-gallon drum is available from the Shell Chemical Company.

This valve enables a direct pour from the drum and is suitable

for short use times only (1 to 2 days) (Ref. 5.4).

375

After being eptied, the drum (and compartmenta) should be con-

pletely flushed with clean water and drained. The bung cap

should be replaced immediately and tight.ened securely. All pipe-

lines and hoses should be drained when transfers are complete.

%lihen emptying a drum by pumping or vacuum, a trap should be placed

in the auction line to pievent feedback of the hydrogen peroxide

into the container after withdrawal.

5.3 2 Tank Cars and Trucks

Tank cars and tank trucks may be unloaded by either pumping or

pressurization with clean, dry, hydroca:rbon-frce nitrogen gas.

The use of a self-priming pump is quit- comwon and is particularly

desirable when fast delivery under pressure is required. 'The

majority of the pumps are a cvntrifugal design, although air-

driven reciprocating pumps are also available. Pump unloading

is recommended for both tank cars and trucks.

The pressure fed system (sometimes called the ejector system)

is a method of feeding by gas pressurization and qho,,ld not be

used on drums or smaller containers, There are mixCd fteli:-.

about pumping by this technique. In addition to the possibility

of overpressurization that exists with this technique, it is

felt by some organizations that the possible introduc.tion of water

or oil with the pressurant gas and/or the insertion of the pump

-inlet line into thesupply tank offers the possibility of vehicle.

c.ontainer contamination. Thus if this unloading system is used,

it is recorzmended that the. com)ressed air or nitrogen used for

p, resaurization be filtered for' ntrain'd solids as well as water(water-pumped gaa. is -referrcd to oil-pumped"gas), and its pressure

carefully controlled.

The standard tank car compressed gas fitting has been designed

for nitrogen. The gas pressurization line should be equipped

376

4,

with a suitable pressure reduction valve, a safety relief valve

(act for approximately 13 psig), and a pressure gage. A pressure

of 5 to 10 psig is norumlly sufficienot to unload a 4000-gallon

tank car in '2.hours. This will consume about 6- to lO--cu ft/miin

n.itrogen. Pressures in excess of 15 psig shouid not be used.

The compressed-gas feed line should be blown out before introduc-

tion into the hydrogen peroxide supply. Details of the unloading

procedures should be obtained from the particular hydrogen peroxide

manufacturer that supplies the tank car.

Tank truck unloading is normally handled by the thydrogen peroxide

producer oe his carrier. Each tank comes equipped with the neces-

sary fittings, a hose, and h pump designed for hydrogen peroxide

service. Trained drivers 3nd/or other qualified personnel repre-

senting the producer are present to make the necessary connections

for the unloading operation. After unloading a tank with pressure,

the vent shall be opened at once. When pressure transfer is used

on tanks, a line shall be attached to the safety vent and extended

to the ground so that the vent may be quickly opened to stop the

flow in an emergency. The tank should not be flushed after emptying

unless it is to be entered for inspection or repair.

When either the tank car or truck have been emptied, the outside

of the tank and the ground sIhould be washed thoroughly wherever

spillage of the hydrogen peroxide could have occurred during the

unloading. All lines, hoses, and the pump should be drained free

of hydrogen peroxide and flushed with clean water. All lines and

.hoses should then be covered with aluminum blind flanges or poly-

ethylene bags to prevent contamination, from dust (Ref, 5.4).

5.3.3 Handling

When transporting hydrogen peroxide, the following handling

procedures and safety precautions should be followed;

3V7

1. At least two trained operdtors should always be assigIred

to any operation involving the handling, transfer, or

storage of bydrogcni peroxide.

2. 'Drivers and operators involved in deliveries of hkydro-

gen peroxide should be instructed to identify the mate-

rial as hydrogen peroxide of the correct concentration

and grade. Carelessly calling it by another name such

as "acid" may result in its being unloaded into the wrong

tank with possible serious consequences.

3. Leaking pipes, hoses, pumps, etc., from concentirated

hydrogen peroxide tank trui:ks or tak cars are fire

hazards. The presence of combustible materials, espe-

cially wood, paper, or cotton waste, at the filling or

unloadin'g site, should be avoided. Spilled hydrogen.

peroxide should be immediately removed by flushing with

copious quantities of water.

Ai. Operators unloading hydrogen peroxide should wear pro-

tective clothing and use only the designated equipment.

5. There should be water hoses, showers, and eye fountains

in the immediate vicJ nity of the unloading area. The

.locat.ion and proper function 6 "this"equipment ;hould. " ~be checked before beginningo)ruA,

6. Sampling of hydrogen peroxide, if necessary, should be

' : . done only under very carefully controlled conditions

and only by authorized personnel. All sa.mples should

be discarded after use and never rellurned ;o the utorage

container.

7. Sampling devices or any other material should not be in-

serted into a hydrogen peroxide contalrer. Samples

should be taken by pumping or draining from system feed

lines.

378

8. If, for some reason, it is necessary to put some instru-

ment, device, sampler, etc.,into a hydrogen peroxide

solution, the device must undergo the appropriate clean-

ing and passivation procedure. With each addition of a

foreign body to hydrogen peroxide, the chance of con-

taminati~orn is increased.

9. Freezing may cause localized concentrations of contan¶-

inants which, on thawing, may r'esult in accelerated

decomposition.

10. Freezing will cause concentration gradients to develop

as the material thaws. Thorough agitation is required

to ensure uniform concentration of the solution. Hydro-

gen peroxide solutions are difficult to freeze, and

supercooling of 70 to 90 F is not uncommon. Handling,

vibration, or motion of any kind should be avoided dur-

ing possible supercooling periods to avoid freezing and

subsequent concentration stratification.

11. Pressure vents should be shielded so that the possibil-

ity of dust return or other contamination is minimized.

12. Routine inspection of 3torage facilities should include

hosing down storage containers as well as the storage

area at regular intervals to minimize the accumulation

of dust, dirt, debris, etc.

13. The outside of storage cuntainers should be thoroughly

cleaned before removal of outlet covers. This may be

accomplisIled by menz of an air hose, a water hose, or

a combination oY these.

14. Cleaning of tht threaded sections before connection of

the mating parts should be carefully done to minimize

the possibility of contamination.

379

15. In the opening of a pipe line or similar item that has

previously been used in transferring hydrogen peroxide,

it should always be assumed that there may be some hydro-

gen peroxide left in the line, and a supply of water

should be available.

14. Storage of equipment such as transfer hoses should pro-

vide for venting any pressure built up from decomposition

of residual peroxide. All drained materials should be

diluted and discarded.

5.4 REFEXENCFS


Research and Engineering, Washington, D.C., The IHandlin*

and Storage of Liquid Propellants, January 1963.

5.2 General Services Administratiort, National Archives and Records

Service, Federal Register Division, Code of Federal Regula-

tions, Title 49, Chapter 1, "Interstate Comerce Commission,"

Parts 71 to 90, revised 1936.

5.3 Schumb, W. C., C. N. Satterfield, and R. L. Wentworth,

Hydrogen Peroxide, A.C.S. Monograph 128, Reinhold Publish-

ing Corporation, New York, 1955.


Hydrogen Peroxide, H202. Properties, Uses, Storage, Handling,2nd Edition, Report No. SC: 62-23, 1962.

5.5 McCormick, James C., Buffalo, New York, Hydrogren Peroxide

Rocket Manual, F.M.C. Corporation, 1965.

380

SECn Nw 6: SAFry

6.1, HAZARDS

The potential safety hazards in dealing with hydrogen peroxide

fall into the following general categories: detonation and/or

explosion,, uncontrolled decomposition, fires, and personnel

injury. While these hazards may sound ominous, it must be

remembered that similar hazards exist for various other com-

pounds which are in widespread use and are safely handled by

industry. If operating personnel are arr~ed with knowledge of

the potential hazards'-and how to avoid them, there is no reason

why concentrated hydrogen peroxide cannot be safely employed in

commercial processes.

6.1.1 Physiological Effects

6.1.1.1. Vapor Inhalation. Hydrogen peroxide solutions and vapors are

nontoxic, but they are irritating to body tissue. This irrita-

tion can vary from mild to severe, depending upon the concentra-

tion of hydrogen peroxide. Concentrated hydrogen peroxide has

little odor unless deliberately inhaled. The sensation iE then

somewhat""E Like that produced by ozone or the halogens (Ref-J. 6.1').

Inhalation of hydrogen peroxide vapors causes irritation and

inflammation of the respiratory tract and many result in burning

of the nose and throat, running of the nose, and coughing. pro-

longed breathing can produce swelling of the respiratory mem-

branes or accumulation of fluid in the sinuses and lungs. Short-

time exposure will not cause lasting harm, but a physician

a should be notified in extreme exposure cases (Ref. 6.2. and 6.3).

The toxicity level. for 90 w/o hydrogen peroxide is expressed as

a threshold limit value (TIN) of 1 ppm (1.4 mg/cu m) (Ref. 6.4

381

and 6.5). The TLV represents tho average concentration over a

normal work day to which the average human can be safely exposed

on a daily basis without adverse effects.

The vapors can also irritate the eyes, producing burning, red-

ness, and watering.' The effect is short-lived except in extreme

or continuous exposure. When hydrogen peroxide contacts the

eyes, the eyes should be flushed immediat~ely with water.

6.1.1.2 Cutaneous Ex~posure. The vapors, mists, and solutions of hydro-

gen peroxide are very irritating to body tissues. Whena the

liquid touches the skin, there is a burning sensation and the

areas affected are bleached. If contact is brief., the effects

will usually disappear within 2 or 3 hours. Continued exposure,

however, will result in slight water blister formation which

should heal quickly. Contact of the hydrogen pero~xide with the

more sensitive parts of tY, body, such as the thighs, neck, or

under the fingernails, will cause more severe effects than con-

tact with the hands. If hydrogen peroxide contacts the skin,

the area affected should be flooded immediately with large quan-

tities of water (Ref. 6.2 and 6.3). If the irritation does not

subside after flushing with water and burns persist, a physician~

should be notified.

Various experiments have been conducted with animals. to show

the effect of hydrogen peroxide on skin surfaces. With rabbits,

it was observed that 90 w/o hydrogen peroxide applied to the

skin was absorbed and caused death by gas embolism (rabbits are

susceptible to embolism, however). Cats, guinea pigs, rate,

pigs, and dogs,, although mtuch leer, susceptible to embolism,

showed a greater reaction on the skin (Ref. 6.1). (There were

no results sho''ing possible lethal effects of 11202 o hsanimalb, however.)

382

In studies on human skin, 90 w/o hydrogen peroxide on the palms

azid fingertipn, where the keratin is thick and nerve endings are

abundant, causes strong prizkling and formation of opaque white

patches. This is extremely painful under the fingernails. "On

other skin areas where the keratin is thinner, irritation occurs,

but with lens itching and the white appearance is confined to a

fe'h areas at the base of hairs. There in no evidence of pene-

tration deeper than the first layer of skin, or stratum corneum,

and all these effects disappear without trace" (Ref. 6.1, page 426).

6.1.1.3 Ingestion.. If hydrogen peroxide is swallowed, e.g., during

pipetting, it may cause bleeding and severe distention of the

stomach due to the liberation of oxygen. In some cases, injec-

tion~ or ingestion of hydrogen peroxide can be fatal, depending

,upon the amount end concentration. Intravenous injections of

dilute hydrogen peroxide solutions are more lethal than concen-

trated solutions, since the dilute solutions are able to pene-

trate the system more deeply before decomposition and blocking

of the circulation occur (Ref. 6.1).

In the mouth, an effervescence occurs as the hydrogen peroxide

decomposes, giving a prickling sensation. At high concentra-

tions, the effects in the mouth are heightened, to the point

of pain~fulness, to say nothing of the hazard of burns; and such

contact is to be avoided.

6.1.2 Fire Hazards

Hydrogen peroxide by itfself iis not flammable, but soluticas of

high concentration may react with combustible materials and

4 generate enough heat to cause ignition. When involved in a

fire, hydrogen peroxide actively supports combustion by liber.-

ating oxygen, and this results in a "flare" fire that may ter-

minate in explosion. Elimination of air, however, does not

control or put out the fire. Hot, concentrated, liquid hydrogen

383

peroxide (> 65 w/o), once ignited, will "burn" rapidly an a

continuous, hot, nearly invisible vapor decomposition flame

close to the surface of the liquid. Such a decomposition

flame will continue without an external source of heat until

the liquid is entirely consumed, unless the liquid concentration

is reduced or the liquid is cooled sufficiently to extinguish

the flame (Ref. 6.2).

Hydrogen peroxide solutions greater than 65 w/o can release

enough energy to heat the decomposition products to a relatively

high temperature (1382 F for 90 w/o solutions). Ignition of

nearly inflammable material may then be expected. Solutions

of less than 65 w/o may also cause fires due to the fact that

upon exposure to air, water in the solution may evaporate faster

than the peroxide, increasing the concentration of the latter.

Naturally, the lower the initial concentration, the less likely

this would happen (Ref. 6.2).

Fires can be started easily by dampening combustible materials

with hydrogen peroxide solutions stronger than about 70 w/o,

provided that the proper catalyst is present. In the absence

of catalysts, many materials buch as clean cotton or wood may

not even react with 90 w/o hydrogen peroxide. (The absence of

any catalytic material, however, is rather unlikely according

to Dev. 6.6.) Secundary fires may also occur. Consumrnptic of

the hydrogen peroxide does not necessarily eliminate the fire.

If the ignition temperature liwit of any fuel-air mixture in

the immediate vicinity has been achieved, combustion of these

materials will continue. This may, however, occur at a con-

siderably different burning rate.

An empirical test was devised (Ref. 6.7) to compare the flamma-

bility hazard of the various concentrations of propellant-grade

hydrogen peroxide. A spill test was developed using a green

felt of 90-percent wool and 10-percent vegetable fiber. (Num-

elous other organic materials were tried, but this was the first

384

material to give reproducible results.) The test simnply consist~s

of placing two drops of concentrated hydrogen peroxide on the

piece of felt and measuring the time to visible flame. The ig-

nition time decreases with increasing concentration as shown in

Fig. 6. 1.

Ignition (i.e., initiation of rapid decomposition) limits have

been determined for hydrogen peroxide vapor (Ref. 6.8 and 6.9)

for pressures above atmosp~heric; these data are presented in

Fig. 6.2. The ignition limits of hydrogen peroxide are actually

the ignition limits of the vapor and are, therefore, a function

of the vapor-phiase comp~osition. In turn, this vapor-phase compsi-

tion is a function of the liquid temperature and the total pres-.

sure on the system. The ignition limits are not sharply defined

but are general areas, as illustrated by the positive and nega-

tive test results shown in Fig. 6.2

General areas where the vapor phase in contact with the liquid

phase has reached the probable ignition level are shown in

Fig. 6.3 (Ref. 6.10).

6.1.3 Explosion Hazards

Although hydrogen peroxide solutions are not ordinarily classed

as explosives (see Section h.4k.1.1.2), certain conditions can

exist in which a detonation or an explosive-like release of

energy can occur. Typically, most "explosions" involving hydro-

gen peroxide are a result of decomposition of the hydrogen per-

oxide, which may occur as a result 'of gross contamination and/or

excessive temperature rise of the hydrogen peroxide. The decompo-

sition reaction produces large amounts of heat (which further

accelerates the decomposition reaction) and gas with subsequent

effects of gas overpressurization in any confining areas. The

"explosion" usually results from the rupture of the confining

surface and release of the gas pressure.

Normally, this decomposition process is relatively slow, and the

final pressure release is preceeded by a slow thermal and pressure

buildup. However, there are also coaditione in which the decompo-

sition process reaches an explosive !.,te. Although such conditions

are usually associated with the vopor phoss, separation of the

cause-effect relationship between the liquid and vapor phases is

difficult. In addition to the normal liquid-vapor equilibrium,

the entrapment of vapor (and a subsequent vaI)or-Ihuse decomposition

within the liquid phase) is always possible with a material that

decomposes so readily inte liquid ard gaseous products.

6.1.3.1 Vapor-Plase Hazards. When the coiicentration of hydrogen peroxide

in the vapor phase exceeds 26 mole percent (40 w/o) at atmospheric

pressure, an explosive decomposition reaction is possible (Ref. 6.8

and 6,9). This limit is increased with decreasing pressures

(43 w/o at 200 mm Jig and 70 w/o at 40 mm 1ig) and decreased with

pressures above ambient. Ignition of these concentrations may

occur as a result of a spark, contact with a catalytic surface,

or contact with a heat source in excess of 300 F.

During vapor detonation velocity measurements (Ref. 6.8), a detona-

tion velocity of 6700 ft/sec was recorded at atmospheric pressure

in a minimum c,,ncentration of 50 w/o hydrogen peroxide. No deto-

nai: ionis were otserved in hydrogen peroxide vapor at total pressurvs

of 4•2.6 an4 09.5 psia. Measurements of detonation velocities in

higher concentrations at atmospheric pressure were geierally un-

obtainable because of spontaneous decomposition or premuture igni-

tion of the test gases.

Under ordinary storage and handling conuitions, explosive vapor

concentrations are not reached. However, when heated under atmos--

pheric pressure to temperatures of -264 F, liquid concentrations

above 75 w/o will produce vapor concentrations in the explosive

range. These explosive regions correspond to the ignitable regions

shown in Fig. 6.3 as a function of liquid composition, liquid

temperature, and pressure.

386

6.1.3.2 Liquid-Phase Hazards. Although earlier experimental efforts, par-

ticularly those of the Germans, had indicated that liquid hydrogen

peroxide solutions with concentrations greater than 88 w/o could

be detonated, more recent efforts have demonstrated the absence

of shock sensitivity in the liquid phase below concentrations of

95 w/o. however, there are still more conflicts in the data ob-

tained from a variety of shock sensitivity tests on hydrogen per-

oxide concentrations greater than 95 w/o. Consequently, these

higher concentrations are still considered (Ref. 6.11) potentially

explosive under certain conditions. In addition, concentrated

hydrogen peroxide solutions are thermally sensitive (see Section

6.1.3.1) although the direct participation of the liquid phase in

detonations involving the heated vapor phase is ques'ionable.

The validity of positive result6 from some types of sensitivity

tests used in the early efforts on the hydrogen peroxide liquid

phase are questionable (Ref. t.12) for the following reasons:

1. Shock sensitivity in earlier work was usually done by

setting off relatively large explosive charges in the

hydrogen peroxide. This technique is questionable

because the mixture of organic vapors from the explosive

charge may have initiated the reaction, and the heatliberated by the explosive charge uay vaporize efough

hydrogen peroxide to result in a vapor explosion.

2. Thermal tests in early work were limited to open containers.

Because of localized heating and distillation effects, it

was not known what concentration of hydrogen proxide was

actually involved in the explosion.

3. Subsequent sensitivity tests (Ref. 6.9) on the vapor phase

above a hydrogen peroxide liquid phise of 90 w/o indicated

that none of the detonations found in this concentration

range involved the liquid phase.

387

The results of various experimental efforts, which have involved

three primary areas of sensitivity testing (thermal sensitivity,

shock sensitivity, and detonation propagation), are summarized

in the following paragraphs to provide a guide to the potential

explosion hazards of the hydrogen peroxide liquid phase.

6.1.3.2.1 Thermal Sensitivity. To expand previously available liquid-

phase thermal sensitivity data (sumutrized in Table 6.1) thermal

sensitivity tests were conducted by dul'ont (Ref. 6.12) on hydrogen

peroxide in open and in closed containers. The open-container tests

(at atmospheric pressure) showed that the vapor above 90 w/o liquid

hydrogen peroxide exploded at 248 to 284 F. The liquid did not

explode but decomposed rapidly, producing temperatur 4 up to 752 F.

Similarly tested 98-percent hydrogen peroxide vapor exploded at

212 to 248 F and gave evidence of liquid participation in the reac-

tion. Resultq from tests on 35--percent hydrogen peroxide were

similar to those with 90-percent hydrogen peroxide. In sealed

glass bulbs, 90-percent hydrogen peroxide explodet: at 320 to 356 F

and the liquid was involved in the reaction; however, the explosions

were attributed to pressure buildup from relatively slow decomposition.

A low-order explosion was produced with 95 and 98 w/o hydrogen per-

cxide at 27.8 to 2814 F. The results of representative tests from

these efforts are reprinted in Tables 6.2 through 6.4.

In a further effort to determine liquid-phase participation in

vapor-phase detonations resulting from thermal sensitivity, field

tests (Ref. 6.12) were conducted using larger quantities of material.

These tests, which eliminated the possibility of complete vaporizalion

of the liquid, consisted of placiing approximately 2 gallons of con-

centrated hydrogen peroxide in old, well-used "Albone" (35 w/o

stabilized I12 0) drums. These drums were placed in a pit with

remote heat contol and temperature recording systems. The drums

388

were heated at a controlled rate, and the temlperature-time profile

of each was recorded. The following results were •eported on the

five tests run:

1. Two gallons ef 90 w/o tlydrogetn peroxide. The drum started

belching foam at 271 F. Much liquid was dispersed, but

the stainless-steel containcr was undamaged.

2. Two gallons of 95 u/o hydrogen peroxide. Vapor ignited

at 268 F and burned with several white puffs with ni,

resulting damage to thle stain ess-steel container.

3. Two gallons of 35 w/o hydrogen peroxide. Vapors ignited

at 248 F. Burning continued for 30 seconds. both ends

of the drum were bulging and the thermocouple had been

ejected from the drum during the test.

4. Two gallons of 95 w/o hydrogen peroxide. Vapors ignited

at 295 F and burned for 3 minutes. The drum was undamaged.

5. Two gallons of 95.2 w/o hydrogen peruxide. At 289.4, the

drum ruptured, spewing high-strength liquid hydrogen per-

oxide. The maximum j'ressure recorded was 75 psi.

It was concluded (Ref. 6.12) as a result of these tests and the

other available data that in concentrationb up to 95 W/o the liquid,

or at least a good piart of the liquid, does not larticipate (except

to form more vapor from heat feedback) when vapor--phase burning

or explosion occurs. This is true even though the adjoining vapor

temperature exceeds 572 F. Hlowever, concentrated liquid hydrogen

peroxide is susceptible to overheating, which makes possible the

formation of vapor within the liqui'! phase and consequent "belching."

Thermal hazurds increase for liquid hydrogen peroxide concentrations

above 95 w,/o, even though direct participation by the liquid phase

in resulting detonations is questionabl..

3F9

6.1.3.2.2 Shock Sensitivity. Hydrogen peroxide and hydrogen peroxide-

water solutions are considered non-impact sensitive in both the

solid state (low-temperature studies) and the liquid state up to

212 F (Rcf. 6.2, 6.4, 6.6, 6.12, and 6.13). No imimct sensitivity

was noted (Ref. 6.13) for 98 w/o Iiydrogen percxide at. 212 F and

an impact height of 300 kg-cm.

lkydrogen peroxide grades of 90 and 98 w/o 11202 have ben subjected

to adiabatic compression test, loading rates of 23!,000 lb/sec at

7P to 72 F and 160 F with no effect oil the hydrogen peroxide. Load-

ing rates of 3,000,000 lb/sce at 70 to 90 F have been achieved on

90 w/o hiydrogen peroxide with no adverse effects (Ref. 6.3).

Shock teets with No. 20 PETN boosters set off ill 30-gallon alutuinum

drums, and tests with 15 grams of llercowite dynamite exploded in

the same quantity at 70 to 72 F and 160 F showed no propcllant

detonation for 90 and greaier w/o hydrogen peroxide solutions

(Ref. 6.3).

Card gap tests, using an atiporatus in which 30 gms of liquid sample

was separated from a 30 gm tetryl charge by a thin (5 to 10 mils)

aluminum membrane, indicated no evidence of detonation in 90, 95,

and 98 w/o hydrogen peroxide (Ref. 6.12). The iesults of these

tests are shown in Table 6.5, and are si-mila 1 0 ,"4u,' . y•-•ut"Ii

from earlier tests conducted by the Navy (Ref. 6.3) to dewonstraic

the relative insensitivity of 90, 95.5, and 99.5 w/o hydrogen

peroxide at ambient temperatures and 160 F.

Other types of shock sensitivity tests have also been conducted

on 90, 55, and - 100 w/o hydrogen peroxide (Ref. 6.12 and Table

6.6). Although some of these data do indicate shock sensitivity

in hydrogen peroxide concentrations above 95 W/o, the data are

suspect (Ref. 6.12) because of poteiitial vapor-phase detonation

and contamination contributions.

396

6.1.3.2.2 Shodc Sensitivity. Hydrogen peroxide and hydrogen peroxide-

water solutions are considered non-impact sensitive in both the

solid state (low-temperature studies) and the liquid state up to

212 F (Ref. 6.2, 6.4, 6.6, 6.12, and 6.13). No impact, sensitivity

was noted (Ref. 6.13) for 98 w/o hydrogen peroxide at 212 F and

an impact height of 300 kg-cm.

lybdrogen peroxide grades of 90 and 98 w/o 112 02 iys been subjected

to adiabatic compression test loading rates of 231,000 lb/sec at

70 to 72 F and 160 F with no effect on the hydrogen peroxide. Load-

ing rates of 3,000,000 lb/sec at 70 to 90 F have been achieved on

90 w/o hydrogen peroxide with no adverse effects (Ref. 6.3).

Shock test3 with No. 20 PETN boosters set off in 30-gallon aluminum

drums, apd tests with 15 grams of Htercomite dynamite exploded in

the same quantity at 70 to 72 F and 160 F showed no propellant

detonation for 90 and greater w/o hydrogen peroxide solutions

(Ref. 6.3).

Card gap) tests, uping an app~aratus in which 30 gins of liquid samplewas se,)araip, fromtn a %gm char-e by a thin (• 4o 10 _;IS-

I---------------' -' Ný J -~" .p 1 %_ _ L' A LA

aluminum membrane, indicated no evidence of detonation in 90, 95,

and 98 w/o hydrogen peroxide (Ref. 6.12). The results of these

tests are shown in Table 6.5, and are similar to those resulting

from earlier tests conducted by the Navy (Ref. 6.3) to demonstrate

th: relative insensitivity of 90, 95.5, and 99.5 w/o hydrogen

peroxide at ambient temperatures and 160 F.

Otler types of shock sensitivity tests have also been conducted

on 90, 95, and - 100 w/o hydrogen peroxide (Ref. 6.12 and Table

6.6). Although some of these data do indicate shcck lsensitivity

in hydrogen peroxide concentrations above 95 w/o, the data are

suspect (Ref. 6.12) because of potential vapor-phaie detonation

and contamination contributions.

'90

Although it is generally con.-luded that hydrogen peroxide iolu-

tions are not normally shock sensitive, it should be noted that

hydrogen peroxide with additives (or contaminants) capable of

being oxidized are highly impact sensitive. This sensitivity

theoretically depends upon the concentration and type of additive

and, in actual practice, upon the sample size and the method and

typc of impact. Various mrixtures involving hydrogen peroxide of

various concentrations with minimum (< 10 percent) quantities of

organic materials such as ethylene glycol, ethyl alcohol, benzene,

etc. have been found to be particularly hazardous (Ref. 6.11).

These mixtures will detonate violently when subjected to the

slightest mechanical shock with detonation velocities approaching

those of nitroglycerine, TNT, RDX, etc.

6.1.3.2.3 Detonation Propagation. Under normal usage, it seems im-

possible to obtain a propagating detonation in hydrogen peroxide-

water solutions. The only tests where a propagating detonation

has been observed were under conditions of extreme confinement

with an exceptionally heavy booster charge. Although these con-

ditions are not likely to be encountered in any normal storage

or handling condition, studies by the Navy (Ref. 6.11) have demon-

strated some conditions at which hydrogea peroxide concentrations

above 95 w/o will propagate a detonation.

In another study (Ref. 6.3) propagation tests were conducted on

98-percent hydrogen peroxide by placing explosives (having energy

rates of 1,860,000,000 ft-lb per second and pressure generation

rates of 576,000 atuospheres which develop within 12.5 micro-

seconds) in a 1.5-inch schedule-80 stainless-ateel pipe. The

pipe was connected to at, aluminum drum containing 250 pounds of

hydrogen peroxide. Although a detonation was vet off in the pipe,

the hydrogen peroxide was unaffected.

391

Siwilar results v;ure obtained (Ref. 6.3) by the Burvau of Mines

in tests on 99 w/o hydrogen peroxide contained ill 0.5--inch tubing.

A large booster charge was located in l-iinch tubinig of hydrogen

peroxide, which was connected to the smaller tubing. The detona-

tion of the booster charge, which detonated the material in the

1-inch tube, failed to propagate into the hydrogen peroxide in

the smaller tubing.

6.1.3.3 Explolsion Potential Criteria. A criterion (Ref. 6.14) has been

developed for the estimation of the potential explosive and

detonation hazard of hydrogen peroxide systems. This involves

the calculation ef what is called the "critical exceis energy"

of the system and is the heat of reactioni for the formation of

all gaseous products from all compounds in the mixture. Before

continuing with the correlation procedure, a discussion of bal-

asicing combustion-explosion type reactions seem appropriate.

Briefly, these are the rules for balancing these reactions:

1. Carbon is first oxidized to CO

2. lf additional oxygen remains, form water

3. lf additional oxygen remains, oxidize CO to CO2

Addition of readily oxidizable wetals to this system would intro-

duce it step betweeni 1 and 2; however, there are a number of quali-

fications to this procedure so that the reliability of this, teclhique

as a hazard criterion for metals is questionable.

After balancing the equation with the particular ratio of ingredients

which are of interest, the heat of reaction is computed, assuming

that all of the reaction products are in the vapor form. Heats

of formation of the reactants in their actual form (solid,, liquid,

or gas) and of the end products in their gaseous form, all based

at 298 K, are used for this computation. A heat, of reaction in

392

excess of 450 cal/gw implies a possible explosive hazard for that

porticular mixture. A heat of reaction in excess of 900 cal/gm

predicts a possible detonation hazard. Thes't "critical energy"

values were selected after a very careful study of experimental

data accumulated from explosive anid detonation tests on mixtures

of organic comnpounds with concentrated hydrogen peroxide. A heat

of reaction can be computed for a number of compositions and the

compositions for the "critical excess energy" values of 1650 and

900 cal/gm determined. These computed compositions may thcn be

plotted to map out hazard areas in the use of mixtures of these

materials. It should be noted, however, that these values are niot

infallible. Mixtures should always be tested experimentally before

actual handling operations begin.

Expressions, which may be solved by pure mathematics, have also

been generated for the determination of the critical energy compo-

sitions (Ref. 6.15). However, for those handbook users who are

willing to balance the chemical equation, the following heate of

formation of the common prcductb of combustion are given. The

heats of formaition of various concentrated hydrogen peroxide solu-

tions are shown in Fig. 2.12 to 2.13a and are discussed in Section

2.2.3.1 of this report.

CO -26.417 kcal/mol at 299 K; molecular weight - 28.01

H20 -57.80 kcal/mol at 298 K; moleculur weight - 18.016

2C0 2 -94.315 kcal/mol at 298 K; molecular weight 4 4.010

Heats of formation or heats of combustion (from which heats of

formation can be computed) of v large variety of organic com-

pounds are available in practically all chemical handbooks.

In the computation of systems where the coupononts are not mutually

soluble or are not soluble in all proportions, consideration should

be given to the possible existence of hazardous concentrations at

393

liquid-phuse interfaces. The solubility of a large inmber of

compoUid-s in hydrogen peroxide ig givena iii Table 4.l['a, Sectioni

1. This method of evaluationi iti not really ajojproiriatc for

Immiscible myst(Le.

Despite the apparent success of the corielation methods, a safety

hazard evaluation must always be obtained ior it new system when-

ever the safety of ptersoniel or equipment is concerned. These

wy-thods should only be used to define limits for exjii'riuentill

test des igii.

The explosive regions ini systews of hydrogenl peroxide and organic

compounds surround the cowj)ositiori ratios of ii,0,/organaic compound

which lead to complete reactioun to carbon dioxide and water. Exj'lo-

sions are generally unobtainablc if tCe fital solution contains less

thatn %,:Tr'ximately 30 w/o hydrogen peroxide.

The sensitivity of these explosive mixtures toward explosion is

of the Oame order of magnitude as that for molten TNT or nitro-

glycerine. Oxygen-deficient mixtures or water-rich mixtures are

less sensitive (to mechanical ialpact, for example) than oxygen-

balanced or oxygen-rich mixtures. Expluaions can be ititiated

by mechanical shock, explosive shock, beat, electric discharges,

hot surfaces, etc.

The following factors should not be overlooked in the investigation

of a new system:

1. The possibility of reaction, such as the formation ofperformic acid in the system containing formic acid.

In this case, the explosive region increases in urea as

a function of time because performic acid is generated

at a measurable rate.

2. The addition of a new species suhi as sulfuric acid,whicih at high lI ,O 4/f2 0 ratium caused the autIodctonlu--

tion of conpositioan• which had yieldt,( ncgi tivc imlpact

teet rueultm. Tlis is usually a time-d peindent reaction.

3. limnincible mystews call ex)lodC at iltelrf.tcCS. Increased

disI)V'lIoaIA raLky cause an itmuiacible tqwytra tu be aus dan-

gel'ou8 as a misciblc flystcwl.

4. Solids such as iou exchange resinb, or jla licos such

asj PolyvinAYl-chloride, cian exjelodc whean eaturiated with

conaccntrated hydrogen peiox ide.

5. The first, iaipa(t tests on a new systew should probably

be wade a$' high hydrugen pcioxide couw entrationts and

low organuic comp)I,)ad concentratioaNs since this regi on

lk where the deto0',atUoIA limit is closest to thCi limit

dtcterwined via impact test or cal)-in-pipe tCet. Fo r

thin same reason, defisiahiv e positive t~ests (as oppoped

to doubtful tests as often obtained with oxygen-

dclicieut mixtures) will bc obtained ii; this region

(Red. 6.l,)

6,2 UZ JI)JLELAU7104N

As described in the Hazards Section (6.1), spills and leakage

of hydrcgen peroxide can result in hazards to both personnel

and facilities. The beat possible means of avoiding theve

hazards is to eliminate or minimize the potential cuuse lactors.

Lffective reduction of leakage, spills, contamination, avd other

potentially hazardous situations can be best accomplished by the

use of properly desigued equipment and thoroughly truined

personnei.

:95

6.2.1 Ey stew L ClnItc'iy

The importance of the design il tLcgrity of jpropellant storage,

trunsfer, 'And hualdling myettems cu.wot be overzempllhaized. The

systems should bu reliable, operationully 1fI4xible, and easy

to riaintain. Some of the suggested design criteria that should

be invcorporated in a system are:

1. The siystem 'AiUst be constructed of waterials which are

definitely knowi, to be compatible with Ihydrogen

pcroxide.

2. The system will be designed wid operated in such a

Amwnuer as to prevent contamination of the system with

kuiown reactive materials.

3. The number of mechanical joiltrs will be reduced to a

minimuw, thus reducing the probability of propellant

leakage.

4. The system will be designed to safely withstand the

v:aximum operating pressure.

5. The 1,runsfer lines will be free of liquid traps.

... A i rt-g'a. (moistlure-free) system must be provided

to purge the transfer lines without the x~ecessity of

dumping the residual hydrogen peroxide or disconnect-

ing any system joints.

7. The system components muot be reliable, compatible

with hydrogen peroxide, and properly serviced (cleaned

and passivated).

8. Sufficient remotely activated control equipment must

lie provided to isolate portions of the system duriug

emergencies or component replacement.

The continual observation of an operational system for possible

malfunctions can prevent serious propellant spills.

396

0 .2.2 Tirai ned l'ersoxiual

lProperly trained personnel are required to handle IProp• 1lUn t-

grade hkydrogen porozide. All pervounnl coucvriied with the

handling, storage, or transfer of hydrogen ptruxide should be

thoroughly familiar vith the following:

I. The nature and properties of propellunL-grudv hydrogen

peroxde

2. Compatible materials of construction gid thL veccsaity

of essential pausivation techniques

3. Operation of the transfer and storage systelu

4. Toxicity and physiological effects of hydrogen

peroxide

5. Operation and use oi safety equipment and clothing

6. Fire and spill prevention techniques

7. Fire and spill control mueasures

8, Disposal and decontaziinati ,n teclaiquvs

9. Local operating procedures Lui regulations

10. First aid techniques

No person should be allowed to handle hydrogen peroxide unles

thoroughly familiar with the previously listed items and should

be confident that the propellant can be handled safely with the

equilment and facilities available, lu addition, ill operations

should be controlled by a procedures checklist, which has been

prepared and thoroughly checked by personiel most familiar with

the potential problem areas. As further safeguards, close

supervision should be maintained to ensure adherence to safety

practices, and all operations involving the handling of hydrogen

peroxide should be performed by groups of two or more persons.

397

6.3 UMZAJW CONMtOLQ

G .. ,1 1F ciliti' Sufvt-t. Equipgent

Lquipwant for facility protectiot; tvhould consist of a water deluge

system and fire hoses (chemical fire extinguishers are nut to be

used on hydrogen peroxide fires). This equipment should be stra-

tegically located and easily accessible, fjther facility items to

be pioYided for peraonnel ,iutectiun include bufe'ty showers, eye

Wash fouwtairia, and apprupriutel) locuted first eid lits.

All operating personnel shouid be thoroughly familiar with the

locution and operation of each piece of safety equipmrent. The

operutinu condition of the eyuipment must be verified periodically.

6.3.2 §pil,1 Control

A propellant spill can be most efficieutly controlled by, peororm-

ing the following steps in thv order 3ieted:

1. Stop the propeljant-handling operati(oLn

2. Isolate the propellant tanks from the tfanifer Jintsa by

closing the necessary vuhles (by remote control if possible)

3. Locate the source of the spill

4. Ioolate the components affected by closing the necessary

valveb

5. Diepoae of the spilled propellant

The performance of tOe first four steps should be autouatic and

can be performed in a very short time.

The disposition of the spilled propellant should not be too diffi-

cult, especially when propellant hbundling is performed during sati-

factory weather conditions and the first four steps listed previously

are quickly executed.

398

ilydiogen peroxide spills can best be cnitrolled b.1 deluging the

spil~ed propellunt with laige quaniLities of water. A 'tev the

spill is controlled, tne entiie area must be thoroughly cieunod

to prevent the possibility of fire.

6.3.3 Fire and Explosio n Control

Since most woodCLn flooring, straw, ragA, clothing, lCUth'r, etc.,

Contain enough cutuly ?ic material to cause rapid ignition with

90-perceut bydrogen peroxide, proper precautions should bi- taken

With this fuct ilk wtild. Storage Ureas for uoncentrutcd solutions

should be of fireproof construction, and provision should bc mnade

for the fluohing a•td druining of spilluge.

Fires involving hydrogen peroxide should be controlled with water,

because it diluteh, the hy'drogen peroxide und reduces the intenSuity

of flare burninlg. The prompt applicution of copiouts amoulits of

wuter dilutes amd cools, eliminating or minimizi~ig the possibility

oX violent reaction. ClIII=ltLL FIRE 1IINOUISlI i61 IIOULI) NMI lie USU).

CLannr t0 WCinŽ 101 vach pitt. ui'

hydrogen peroxide present should be applied. Because c".tainers

may burst, creating a fragmentatioIi hazavd, fighting these fires

with hand lines is daugerous; therefore, pxrefir'e rrungewemnts

(i.c., the provision of fixed systems, etc.) should be mode. In

a hkdrogeix peroxide-fuel fire, cvery possible effort should be

exerted to stop the flow of both fuel and lhdrogen peroxide. If

a fire breaks out neaarby, coutainers of 90-percent hydrogen peroxide

should be kept below 230 F to prevewt vapor-phuse explosions. A

temperatre.-uctuatled sprinkler systom oii the storage tanks could

be employed as a further precaution.

To prevent an explosion, hydrogen peroxide shouldcbe stored at a

temperature low enough to prevent excessive Sas formatioa due to

decmposition. (A temperature below 145 F io recommended for

399

long-term storage as noted in Ref. 6.4~). Hydrogen peroxide that

has become contaminated or shows an abnormal temperature rise

should be diluted and disposed of. Phosphoric acid (H?04) may

be added as an emergency stabilizer to reduce decomposition

(Ref. 6.4~) before disposal.

6.4' PERSONNEL PROTECTI ON

6.)4.1 Personnel Safety Equipment

The main personnel hazard in handling concentrated hydrogen per-

oxide is probably not from the contact of peroxide with the skin

but the danger of burns caused by ignition of clothing. Protec-

tive clothing is necessary for all personnel handling concentrated

hydrogen peroxide. Ordinary fabrics made of cotton, rayon, leather,

or wool should not be used, because these are apt to ignite when

splashed with hydrogen peroxide. Unnoticed splashes on ordinary

clothing may cause fire sometime after the occurrence. Conven-

tional permeable clothing of Dlacron, Dynel, or Orlon, when used

with eye goggles, gloves, and boots, normally gives adequate pro-

tectioni. For- full body protection, v'inyl coveralls or aprons of

Koroseal or Neoprene should be used. The clothing must cover all

parts of the operator's body and must be adjusted so as to prevent

drainage into the gloves or boots. Permeable clothing wet with

peroxide must be flushed with water and removed promptly, and the

affected body parts must be thoroughly washed.

The hands and feet are always subject to contamination during the

handling of liquid propellants or associated equipment. Gloves

ovid boots will keep hydrogen peroxide from touching the skin.

(Leather reacts quite readily with hydrogen peroxide, however.)

The gloves used should protect against hydrogen peroxide and also

should allow free movement of the fingers. Tb~e vinyl-coated gloves,

Type R1-1, Mil-G-1i244 (Ref. 6.16) meet these requirements. Surgical

rubber gloves or lightweight Neoprene gloves are suitable for hand-

ling small parts. Sin~ce boots of the approved protective materials

are not conmmercially available, an overboot, designed to be worn

over regular safety footwear and high enough to fit comfortably

undler the protective trousers, is suitabl~e. Boots mutde of natural

or reclaimed rubber or GIL-S may be used with reasonable safety if

any contamination is washed off quickly. Thc boots should be

frequently inspected to detect flaws which might result in personal

injury. Severe foot burns can result from splashes on ordinary

sh~oes.

Respiratory protection against vapors is not ordinarily requi'red.

Respirators approved for protection against hydrogen peroxide

mists, however, should be available for use where exposure to the

aerosol or mist is possible (Ref. 6.17 and 6.18).

In selection of protective clothing for H,,O 0) handling, the degree

of hazard involved and the workers' comfort and agility must be

considered. Overdressing and use of protective accessories when

not warranted can actually be hazardous. A hood and full suit of

impermeable clothing is only required where danger of gross spill-

age or spray directly on the worker is involved. In a pump trans-

fer operation of hydrogen peroxide above 50 W/o, at least one man

should be fully outfitted with impermeable clothing if detachable

equipment such as a hose is being used. For handling hydrogen

peroxide in drum quantities and in pump transfers in a permanent

piping system, the permeable uniform worn with face shield, or

eye goggles, rubber gloves, apron, and boots or rubbers will be

sufficient. When wearing permeable Dacron or Dynel shirts and

trousers, it is good practice to wear Dacron or Dynel underwear

and socks. Goggles which afford complete eye protection should

be worn during all handling and transfer operations. Water must

always be available and two persons must always be present when

high-strength hydrogen peroxide is handled even if protective

clothing is worn.

Protective clothing and accessories recommended for personnel hand-

liug propel lant-grade hydrogen peroxide are listed in Table 6.7.

401

6 .Ih.2 First Aid

IF HYDROGIN PL10XIDE CONTAC17S TYE SKIN. Flood the area involvedw'ith water. If burns arc present, refer to a physician.

IF IIYDRUG•N PEiOX)UI)E CONTACTS TIH EYES. Flush iumwdiately andfreely with water for at leakit 10 to 15 minutes; or if water isnot available, saliva can be uae4l to absorb the hydrogen peroxideand decrease the effect upon the tender eye membrane (Ref. 6.3).This should be done if even minute quantities of solution haveentered the eyes. For any case of exposure involving the eyev,

refer to an eye specialist.

IF HYDROGEN PEROXIDE IS SWALLOWED. Encourage vomiting. Givelukewam water freely and encourage belching if there is evidence

of distention. Call a physician.

IF HYDROGEN PEROXIDE VAPOR OR MIST IS INHALELD. Remove victimimmediately from further expost, If irritation of the noseand throat is severe, refer to .)ysician.

6.4*.3 Medical Treatment

IN CASES OF EXTRME EXPOSURE OR CONTACT, OR PERSISTING IRRITATION,A PHYSICIAN SH(KJL) BE NOTIFIED.

02

6.5; RE•F•UCES

6.1 Sochumb, W. C., C. N. Satterfield, and It. L. Wentworth,

IiSdrogen Peroxide, A. C. S. Monograph 128, Reinhold Publish-

ing Corporation, New Yor, New York, 1955.

6.2 Shell Chemical Company, New YorL, New York, Concentrated

Hydrogen Peroxide. 1_20. Properties, Uses, Storage llandling,

2nd Edition, Report No. SC: 62-23, 1962.

6.3 McCormick, J. C., F.H.C. Corporation, Buffalo, New York,

Hydrogen Peroxide Rocket Manual, 1965.


Research and Engineering, Washington, D.C., The Handling and

Storage of Liquid Propellants. January 1963.

6.5 Sax, N. I.# Dangerous Properties of Industrial .Mterials,Reinhold Publishing Corporation, New York, New York# 1957.

6.6 Shanley, E. S. and F. P. Greenspan, "Highly Concentrated

Hydrogen Peroxide," Ind. Eng. Chem., 3 1536-43 (1947).

6.7 Explosives Research and Development Establishment, Waltham

Abbey, England, Some Properties of 100 per cent Hydrogen

Peroxide.

6,8 Monger, J., H. J. Baumgartner, G. C. Hood, and C. E. Sanbornt"Detonations in Hydrogen Peroxide Vapor,! J. Chem. Eng. Data,

2(l), 124-7 (1964).

6.9 Satterfield, C. N., F. Feakee, and N. Sekler, "Ignition

Limits of Hydrogen Peroxide Vapor at Pressures above Atmos-

pheric, " J. Chem. Eng. Data. 4., 131 (1959).

6.10 Laporte Chemicals Ltd., Luton, England, Hydrogen PeroxideData Manual. 1960.

6.11 Naval Ordnance Laboratory, White Oak, Maryland, Report

NOLTR 63-12.

6.12 E.I. duPont de Nemours & Company, Inc., Wilmington, Delaware,

A Report for North American Aviation, Inc., Rocketdyne Division,

October 1958.

403

6.13 Bloom, R., Jr.,and N. J. Brun3vold, "Anhdydrous Hydrogen

Peroxide as a Propellant," Chem, Eng. Progress, 2, 541 (1957).


Wydrogen Peroxide. Summary of Research Data on Safety

Limitatipues Report No. SC: 59-44R, 1959.

6.15 Shell Development Company, Emeryville, California, Hydrogen

peroxide by Oxidation of Isopropyl Alcohol. XVI, Vapor

Explosions and Miscellaneous Explosion Test Data, Technical

Report 7-60, January 1960.

6.16 Private communication, J. C. McCormick, F.H.C. Corporation,

Buffalo, New York, to H. T. Constantine, Rocketdyne, a

Division of North American Aviation, Inc., Canoga Park,

California.

6.17 "Military Specification, Gloves, Protective, Acid Resistant,

Vinyl Coated Cotton, Type P-l," Mil-G-42'4A(AF), 6 May 1954.

6.18 "Respiratory Protective Devices," AITP61-1-1, 20 August 1962.

6.19 "Respiratory Protective Devices," TB MED-223.

0.20 F. M. C. Corporation, New York, New York, Materials of

Construction for Equipment in Use With Hydrogen Peroxide,11 § vi0ion.

404

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90-- TO 100-4JMtUN2T lMI0OG&I I'MO)tLID 8UOUG 8tIMITIVlTY J)ATA*

______,90- .0

lJbpact Tests ---- No czplovios op-

Rifle Fire -a- No explosions - so

No. 6 rud 8 Bllastiug a- .No detunutio-s SOCape

AleuI

N,. 6 and 8 blasting Cape lucou'lete detonation -. -v Cosq)leteWith Pentuerythtritol

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Lead Block ulnargm•uet 5 cc/gm 7 cc/gV, 9 to 12 cc/am

Explouiozi Velocity <I00 meter/ I50u meter/ 6200 meter/Aluminum Pipe eec Dec sec

Closed Steel Tubes, 175 milli- No Detonatedliters ILB,0 * 50 grams Penthrite DetonationPrimed V•tE Fulminate

*Data takeu from work of varioub investigatoru and summarized in Ref. 6.12.These data, whichi are not referenced or otherw•Ase detailed with regard toadditional test p•arameters and techniques, are ineluded ae a gene-ral sxjiryof twe efurto preceding ibe dat& reported in Ref. (.12.

410

TAI" 6.7

PlYrkUCTIVE GLO`11UNG AND) ACCESSULES ILECOKML&12I) FOil

kaUNN1IL 11ANI)LING CONCINTRATkIX H1111 O) 111ON IQLU1DE

I tem j •t sjri i Sour

Shirts, Dacron fabric, Polystyrene buttons, Workion, Inc., N.Y., N.Y.

Trousers no front or side pocketu, no cuffs

Dyuel Fabric Mine Safety Appl. Co.

100-percent Dynel Chum-Weav,, Chum-Wear, lnc.,medium weight Darien, Couw.

Delta Vinyl plastic, witb plastic buckle Numerous commercialsources

fUndvrshirts Dacron Alamac Knitting Mills,N.Y., N.Y., Special lot.minimum order, 10 doýoen

Dacron-cotton (can be ignited if Carmi-Aiusbrooke Corp.,*oiled) Caurli, Illinois

Shorts Dacron Carmi-.Ainsbroohke Corp.Mianhattau Shirt Co.,N.Y., N.Y.

Socks Knit Dacron, no elastic, whiLe JRolston Mfg. Co.,Vynel fabric anoxville, Tenn. Numerous

commercial sourcesfbes 1-inch Netourene Cuaedi- Nu_. QgG !run Aue Div.. Childn &

steel toe Co., Inc., Pittsburgh, Pa.

Rubbers Full, Neoprene with tongue Numerous commercial sources

boots Neoprene, knee length Numerous comuercial sources

Goggles Nqo. 93 AV large nose, clew, Willuon Products, Inc.,Willson Honogoggle Urading, Pa.

Model 293607 "AF-I-(EUR, Series 29 UJ.S. Safety Service Co.clear lens Karmas City, MKo

Face Shield No. 324 clear Sellstrom face shield Watson Co., Buffalo, N.I.

Gloves Sureseal,, gauntlet, Vinyl or Curety Rubber Co.Neoprene, No. 116 lightweight for Carrollton, O~iolaboratory use. No. 136 mediumweight for work use

Aron -ail vinyl plastic. Surgeon's Milburn Co.type, extra long, overlappingq in Detroit 7, Mich.back, ties in front.

ftef. 6.19

tll

TABLE 6.7

(Concluded)

Item Description Source

Coveralls Vinyl plastic. One-piece, light Mine Safety Appliance Co.weight disposable unit. Grey color

Cups Dacron fabric. Baseball type, with Worklon, Inc.removable sunshade for neck.

Dynel fabric Chem-WearMine Safety Appliance Co.

Hood 8-rmil vinyl methacrylate window, Milburn Co.detachable head band, adjustable Detroit 7, Mich.for size

Impermeable Fiberthin Raynster, Neoprene coated U.S. Rubber Co.Jacket Nylon, MRS-107 Washington, Inkl.

Impermeable Fiberthin Raynster, MRO-107 U.S. Rubber Co.Overalls Washington, Ind.

OMTDOOR WINTER-WEIGHT PROTECTIVE CLOTHING

Shirts 55-percent Dacron-l5 percent wool Worklon, Inc.Sport-type shirt, polystyrene New York, N.Y.buttons

Trousers 55-percent Dacron-45 percent wool Worklon, Inc.No pockets, cuffs New York, N.Y.

Cap 100-percent Dacron pile lining, Borg Fabric Div.outer material Gý W. Borg Co.

Delavan, Wiec.

Pants 100-percent Dacron pile linin6, Borg Fabric Div.outer material

Boots Neoprene, insulated boots. Hood Rubber Co.Similar to U.S. Army all-rubber, Watertown, Mass.insulated combat boots

Jacket 100-percent Dacron pile lining, Borg Fabric Div.outer material

412

5

aM

IL

I-r

i--I

S3

LU

1-

0 -

LAV II%

HYDROGEN PEROXIDE, WEIGHT PERCENT

Figure 6.1. Ignition Delay of HydrogeiA PeroxideWith Felt (Ref. 6.7)

413

ID 0.1 0.41

COCETATO OF. RYRGNPROIEI.APRPAEMOliRCTO

Figure ~ ~ ~ ~ ~ ~ ~ ~ ~ l 6.2. Igito LiisoI!rgnProieVpr(e.68

I Mi

'so

UJ~ ISO

GOILN

140*

I~ hi h~I

760 75 Sl SB1 Ti0 95l IB M

1111 GEN PEROX1!E, W/F' igure11 6.13 Liq id HoAoi on 1 hc Rsl i gntb1 ao

0ocnrtc& (Tt .0

140 poll

IT! Ti I I I I:

1501

" I

8SETION 7: DIECOMPOSITION

7.1 DECOM UI ION ECBHANISM

The decomposition of hydrogen peroxide may be represented by

the equation:

.+ 1/2 02

This decomposition process is irreversible. Kineticists study-

ing this particular decomposition process can theoretically

illustrate 10 to 20 intermodiate reactions which may exist in

hydrogen peroxide decomposition; however, the above equation

is the effective result of these intermediate steps in the

decomposition. Although the rate contralling reaction has not

been identified, it is generally believed that it is one in-

volving an electron trarisfer.

Since its discovery, when Thenard (Ref. 7.1) reported on the

effect of over a hundred materials on the decomposition reaction,

many decomposition studies have been conducted on hydrogen

peroxide in attempts to characterize the decomposition process.

Throughout these studies, it has been recognized that hydrogen

peroxide decomposition is a result of both homogeneous and

heterogeneous reactions. This decomposition, when both the

liquid and vapor phases of hydrogen peroxide exist, has been

considered as the sun of five types of reactions:(l) homogeneous

reaction in the liquid phase between the hydrogen peroxide and

dissolved catalytic or oxidizable components; (2) heterogeneous

reaction of the liquid phase with surfaces of the container

and/or suspended particles; (3) heterogeneous reaction of a

film of condensed hydrogen peroxide on surfaces in contact with

the vapor phase; (4) heterogeneous reaction of the vapor phase

on Ory surfaces; and (5) homogeneous decomposition of the vapor

phase (Ref. 7.1).

417

In a recent investigation ( af. 7.2) to define the contribut-

ions of these individual reactions to the ambient temperature

decomposition of 90 w/o hydrogen peroxide, reaction types (4)

and (5) were ignored. Reaction type (4) probably does not occur

when the temperature of the surfaces is below the hydrogen per-

oxide boilirn point ard the effects of reaction type (3) were

considered insignificant at the temperatures under consideration.

In addition, it was indicated that reaction type (1) could

probably be separated into further types of reactions; however,

for the purpose of the particular study, the liquid phase homo-

geneous decomposition was considered as being essentially ionic

catalysis. The differenxces betveen reaction typves (2) and (3)

were considered to be in the effective concentration of hydrogen

peroxide on the surfaces, the concentrution of contaminants

which may build up in this condensed liquid film, and in the

concentration of inhibitoru which would be present in the con-

densed film (unless agitation of the vessel caused frequent

wetting and washing of all surfaces with the hydrogen peroxide

liquid phase).

Assuming these three types of reactions are the only contri-

buting effects to hydrogen peroxide decomposition in the ambient

temperature range, the rate of decomposition can be represented

by the following expression:

S- kl • , H /v)liq. (Up) (s/V)por

dt

where HP - concentration of hydrogen piroxide

1I - liquid phase homogeneous reaction rate

k2 - liquid phase heterogeneous reaction rate

k3 - vapor phase heterogeneous reaction rate

5/V smrface to volume ratio of the liquid phase

s/V - surface to volume ratio of the vapor phase

t - time

Through the use of various purification techniques, relatively

inert sarfaces, and the absence of a vapor phase, the experi-

menters of Ref. 7.2 were able to isolate, for all practical pur-

poses, the effective homogeneous reaction rates of the liquid

from 20 to 100 C (68 to 212 F). Using these data, the effects

of solubl' additives (such as stabilizers) on the liquid phase

were also determined. Although the data rosulting from this

work varied from test to test and as a function of stabilizer

concentration and type, temperature, and manufacturing process,

the homogeneous decomposition rate of the stabilized and

unstabilized liquid was generally found to be less than

~ 0.03 w/o active oxygen loos (AOL) per year at 100 C (212 F).

In addition, it was indicated that for future comparisons of

results at different temperatures or the estimation of decom-

position rates at various temperatures, the activation energy

for the homogeneous decomposition of hydrogen peroxide caii be

assumed to be 18 kcal/mole.

As a result of this work, the experimenters indicated that the

predicted homogeneous decomposition rate of hydrogen peroxide

would correspond to the following expression:- 1800

D 1 10 7 .2 01987T

where D1 - homogeneous decomposition rate in weightfraction/year

and T te•perature in K.

Using an overall decomposition rate with a correction for the

effect of the homogeneous rate, heterogeneous decomposition

rates were also determined In this study. Values were calcu-

latod for k2 using experimental decomposition rates obtained for

hydrogen peroxide storage in 5-gallon storage tanks fabricated

from different materials. In these tests it was assumed that

the rate constants for both vapor phase and liquid phase hetero-

geneous decomposition were equivalent at the lower temperatures

419

(on the basis that the rate of decomposition was sufficiently

slow mo that mass transfer of hydrogen peroxide to the vapor

space surface was not the controlling rate); thus the heter-

ogeuecus decomposition rate for both phases was equivalent to

k2 (I/V) where (S/V) represented the total exposed surface

area of the tank relative to the volume of the liquid hydrogeiz

peroxide. Results of these tests indicated that k2 for the

different materials at 25 C (77 F) appeared to be as follows:

1260 aluminum - 0.0065 weight fraction AOL, cm/year

5052 aluminum 0.0160 weight fraction AOL, cm/year

tiul plate - 0.286 weight traction AOL, cm/year

Kel-I" - 0.0031 weight fraction AOL, cm/year"

Additional studies in this and the homogeneous area are being

conducted by the same investigators and have been reported

thus far in Ref. 7.3 and 7.4.

A study of hydrogen peroxide homogsneous decomposition rates

in the complete absence of catalytic surface effects (Ref. 7.5)

was attempted through the use of solid hydrogen peroxide as

the container wall. Unfortunately, during the period of the

contracted work, the desired experimental conditions were not

obtained, although definitive techniques uere proposed for

future study. However, during the study, total decomposition

rates .ere " .... *uvea L-f'k*- acdi muia'uilized grades

of 90 and 98 w/c hydrogen peroxide in both the frozen (-60

and -30 c) and the cooled liquid (0 C) state. The resulting

decomposition rates from these tests, which were effectively

.due to homogeneous decomposition effects, were below 0.023

w/o A01/year.

Throughout the various decomposition studies that have been

conducted on hydrogen peroxide, it has been, generally in-

dicated thbit the homogeneous decomposition rates of liquid

hydrogev peroxide were found to be dependent upon:

1. Eydrogen peroxide concentration

420

2. Type of additives or contamuinants present

3. Concentration of additives or contaminants

4. pAt

5. Particuler combinxations of foreign materials present

6. Temperaturn

Similarly, the heterogeneous reaction rates were found to be

dependent upon:

1. Hydrogen peroxide concentration

2. Temperature

3. Passivation or cleanijg technique

4. Surface area

5. Surface finish (area ratio)

6. Localized concentrations of impurities in the solid

surface

7. Pressure (under certain zonditions)

Numerous investigators have reported decomposition and

stability data for hydrogen peroxide as a function of these

variables and with hundreds of various materials. Because

of the uncertainty involved in trying to se, 4rate any one of

the contributing parameters in the decomposition process,

illustrations of the individual parameters are not presented

in this handbook. However, these decomposition data are

summarized as total effects relative to engineering parameters

such as storability (Section 4.1), materials compatibility

(Section 4.2), passivation effectiveness (Section 4.3), etc.,

in other parts of this handbook.

For those users of this handbook who are inteheftted !.n more

details of various reaction rates and other aspects in the

decomposition of hydrogen peroxide, the use of the previcusly

referenced literature (Ref. 7.1, 7.2t 7.3, 7.4, and 7.5) as

well to the use of references to literature on decomposition

pi'ovided in the attendant bibliography (Sectioi, 8.9) will

provide the basis for further invastigation.

421

7.2 CONTOLL DI•I 'J1IT51WION

The hydrogen peroxide decomiponition process is used under

controlled conditions to provido a high temperature gas as

the wo.king fluid for reaction control systems, auxilIar7

power wilts, turbopumsp drive, underwater propulsion. etc.

Ordinarily, to achieve effectivc use of the decjpouition

process for theme applications, the hydrogen peroxide must

undergo a rapid and complete decomposition to ILO and 02

within the confines of e combustion chamber; the decomposition

must be immediately initiated upon entry to the chamber amd

must be cuokpleted upon exit. The process must occur smoothly

without radical surges or oscillations in the working pressure.

There have been two primary methods employed to initiate ani

maintain this type of a controlled decomposition of hydrogen

peroxide in a combustion chamber: (1) catalytic decom1,oition

and (2) thermal decomposition.

7.2.1 Catalytic Decomposition

Catalytic decomposition of hydrogen peroxide is, as imlied,

dependent on the use of a catalyst, either as a liquid in a

fluid-type catalytic chamber or as a solid in a fixed bed

chamber. In the use of a liquid catalybt, a suitable cata-

chamber with the hydrogeu peroxide and ejected out of the

combustion chamber with the decompositioaI gase,. The liquid

catalysts normally employed are aqueoub solutions of calcium

or potassiumi permangaante.

Solid catalyst beds normally consist of packed columns of

porous materials or screens, which have been coated with the

catalytic agent. The solid porous materials are usually re-

ferred to as catalytic stones and are activated by impregnation

422

with the catalytic agent contained Iii a mulveiat with subse-quent removal of the solvent (usually by dryriug. )Materials

that have broen camonly uped for this type of solid catalyst

are aqueoub solutions ol calcium or potassius permanganate.

or the metallic nitrates. Calcium permauganate is usually

pref6red to potassium p.rmazhganate, primarily due to its

higher solubility in water. The most effective results from

tbis type of catalyst are usually obtained with altaiina or

carborundum particles as the porous carrier medium.

Silver in probably the beut known and the most active cats-

lyat for the decomposition of hydrogen peroxide. This cata-

lytic material is usually applied i;. a rcreen type of con-

figuration. Since pure silver has proven somewhat tudesirable

frow a physical integrity standpoint (ispecially at the

teaperatures obtained in this type of application) and be-

causo of it,- hi4. t.A. the silver cttaiyst is also used is

a plating on brass, uicke.* * etAnless steel screens. To

further reduce the cost impomvd b.ý the silver, stainless or

nickel screens rre auLe.,mngled with the silver or silver

coated screens, without reducing catalybt effectiV7 less; of

course a minimum number (4hich is dependent on the particular

configuration) of catalyst screens, is required for satis-

factory oper tion. The use of the silver plated screens

usually ofters better initial starting characteristics than

the catalyst does and provides more structural integrity in

the bed; however, such screens are more subject to catalyst

stripping during operation. Because the initial activity

of previously umused silver catalysts is normally low', they

cre usually "activated" by pretreatement vith samarium

nitrate (by immersion) and hot fired in. a furnace prior to

their use in the catalyst pack.

4L23

Although the silver and the permanganate catalysts have

been the catalysts of choice for most of the controlled

decomposition concepts, there are a number of other types

of materials which have been investigated as hydrogen per-

oxide catalysts. Identification of these different materials

and a more detailed discussion of the catalytic decompobi-

tion process are contained in Ref. 7.1, 7.6, 7.7, and 7.8.

A complete bibliography of other data in this area has been

compiled in Ref. 7.9.

7'.2.1.1 Catalyst Pack Design and Descriptions. The permanganate

liquid catalyst was initially used by the Germans during

World War II for application in torpedo propulsion and in

a gas generator to drive the turbopumps for the V-2 rocket.

Although the liquid permanganate catalyst is still used

for some underwater propulsion applications, the solid

catalysts have proven to be more applicable to most of the

present monopropellant hydrogen peroxide propulsion and

gas generation concepts.

The first effective application of the solid catalyst con-

cept was in the Redstone Missile gas generator system.

This catalyst (Ref. 7.10) was used to decompose a 76 w/o

hydrogen peroxide solution to provide working gases for a

turbine which was used to drive the main propellant pumps

of the missile system. The catalyst was a polysurfaced

silicon carbide "stone" which had been impregnated with

calcium permanganate. These "permanganate stones" (FMS)

were screened to +16 mesh and packed into a catalyst bed

of approximately 3 inches depth, where they were held in

place by an inlet screen of 16 mesh and outlet screens of

16 and 80 mesh, supported by rigid perforated steel plates.

A hydrogen peroxide flow rate of -,6.0 lls/sec resulted ina bed loading rate of - 10 lb/sq in.-min and a 20-to 30-psi bed

pressure drop. The catalyst was required to give suitable

operation for 600 sec~ond3; the start transient was&~ -.70-150

ms from propellant entry into the chamber to 90% Pc.

Although the TF(S catalyst provided a suitable catalyst for

76 w/o hydrogen peroxide, the use of concentrations in ex-

cess of 85 w/o H12 02 stripped the catalytic material from

the porous carrier. In addition, the 1PIS catalyst had a

tendency toward fracturing or "dusting" in handling with

a resultant loss in catalytic efficiency. Thus the dev-

elopment of a more suitable catalyst for higher hydrogen

peroxide concentr~ations was sought.

In the middle 1950's, silver catalyst screens were developed

for use with 90 w/o If 20 2. Since then, there have been a

number of different types of silver catalysts developed for

different applications. Each bed is unique to the appli-

cation for which it is developed, thus each particular de-

sign way be silightly different. Because there are a number

of different catalyst beds for decomposition of 90 W/o R 02in existence today, a listing of each in this handbook would

be prohibitive. Therefore the description of a catalyst pack

for 90 W/o 112 02 given in the succeeding paragraph represents

a general description of the silver screen catalyst pack and

does not represent any single design.

Silver catalyst screens may be (as mentioned previously)

fabricated from pure silver or from silver plated-brass,

-nickel, or -stainless steel screens. The screens are

usually 16 to 20 mesh with a wire diameter of -,-0.014 inches.

Some specifications for catalyst screens call for a 66 to 71

percent light-transmission. After "activation" by samarium

nitrate immersion and baking, the screens are packed into

the combustion chamber (with a light force fit against the

walls) at right angles to the combustion chamber. Usually

4~25

the packing is such that a stainless steel or nickel screen

(inactive screen) is placed between two catalyst screens.

The number of catalyst screens is dependent on system require-

ments (operational life, bed size, throughput, pressure drop

limitations, start transients, etc.) and may vary from 15 to

as many as 100 catalyst screens.

Usually, the bed is terminated with several "inactive"

screens. Perforated stainless steel supports are used Ps

screen retainers, and also may be placed at different points

in the bed to act as anti-channel baffles. The entire column

is compressed to some specified compacting pressure to limit

pressure oscillations and assure reproducible performance

(pressure drop, flow rate, temperature gradient, etc.) from

bed to bed in the same hardware. Most silver screen catalyst

beds are operated at bed-loadings of - 20 lb/sq in-min; these

bed loading rates may vary although it should be noted that

higher catalyst bed loading rates will result in highe' bed

pressure drops and silver erosion rates. Bed pressure drops

usually run from 75 to 125 psi.

The standard silver and silver-plated screen catalysts were

found to be inadequate for sustained decomposition of 90 w/o

H2 02 that is pre-heated to temperatures above lOOto 150 F,

or for concentrations of hydrogen peroxide with adiabatic

decomposition temperatures above 1400 to 1500 F. Because

many present applications involve preheating of the hydrogen

peroxide (as a result of its use as a regenerative coolant)

and the use of 98 w/o H202 which decomposes at - 1800 F, the

development of a catalyst which retains physical strength

and chemical reactivity above this tepnperature has been

pursued.

426

The initial development of a high temperature hydrogen

peroxide catalyst was undertaken by Rocketdyne, first

under company-sponsored funding and later under Contract

NWas 56-1052J. Although this catalyst, which ii described

in Ref. 7.11, has been used successfully at Rocketdyne for

several year& in thE decomposition of 98 w/o H1202' the

catalyst's physical and chemical stability at temperatures of

2000 F is questionable. Thus under Air Force Contract

AF0o(611)-11208, FHC initiated the development of new de-

composition catalysts for 98 w/o 11202. Their progress in

these efforts have been reported in Ref. 7.12.

For those users of this handbook who are interested in the

detailed design of catalyst beds for various concentrations

of propellant-grade hydrogen peroxide, the use of data con-

tained in Ref. 7.13, 7.14, 7.15, and 7.16, in addition to

thove already cited, ere suggested.

7.2.1.3 Catalyst Poisoning. There are a number of impurities that

may be contained in hydrogen peroxide, which will cause

catalyst poisoning or catalyst pack malfunction. Although

these impurities are normally associated with those addi-

tives used in stabilization, any non-volatile contaminant

or additive in the hydrogen peroxide is a potential cata-

lyst poison. Residual or nongaseous products from the

decomposition process, such as tin or aluminummay act as

a catalyst poison by depositing on the catalyst to decrease

the effective catalytic surface or by physically plugging

the flow paths. Other materials such as the nitrates,

chlorides, and phosphates may cause excessive erosion and

lose of catalytic material, which reduces the effective

activity of the catalyst. Additives which act as stabilizers

during hydrogen peroxide storage by complexing and "tying

up" the activity of heavy metal ions also tend to complex

with the catalyst material in the combustion chamber.

U.7

* Although the particular details of catalyst poisoning by

various potential contam'inants are not completely under-

,stood, most of the important hydrogen peroxide catalyst

poisoners have been identified. Attempts at characteriz-

ing limitations for each of the individual species and

the contributions and limitations of their interaction

have met with little success. However, the limitations

(which were determined under an extensive Navy "crash"

program and further refined through extensive use) placed

on inorganic contaminants in the hydrogen peroxide by the

procurement specification MIll-P--16005D (see Section 3.3)

for 90 w/o hydrogen peroxide have been effective in con-

trolling poisoning of catalysts used for decomposition

of propulsion grade hydrogen peroxide.

7.2.1.3.1 Effect of Organics. For some time there has been

considerable controversy over possible differences between

hydrogen peroxide produced by the various production tech-

niques with respect to silver-screen catalyst performance

and failure. Organic contaminants found in hydrogen per-

oxide produced by the organic process (namely the anthra-

quinone and propane-derivative oxidation processes) were

suspected of being responsible for various catalyst pack

failures that occurred periodically in various hydrogen

peroxide decomposition systems (Ref. 7.15). Although

there were a few catalyst pack failures (in contrast to

the many successful operations) during operation of the

packs with organically derived hydrogen peroxide, there

was a lack of clear-cut analytical evidence indicating

that the organic contaminants were c~ontributing causes.

Because there was a belief that the higher carbon content

of the organic materials either caused the reaction to ex-

ceed the melting point of the catalyst or caused a carbonate

formation on the surface of the catalyst (to effectively

poison it), a study was conducted by Rocketdyne (Ref. 7.11)

to determine the potential effect of carbon content on

4-W

catalyst performance. The performances of three types

of organically derived hydrogen peroxide were compared with

that from the electrolytic process in silver screen catalyst

packs of the configuration used in the Rocketdyne Super Per-

formance Aircraft Rocket Ekgine (Models AR-i, -2). The

results from these tests indicated that the performance of

one of the organically-derived hydrogen peroxides (with a

carbon content of 150 to 200 mg/i) was equivalent or better

than that of the electrolytically-produced reference

hydrogen peroxide. The failure of the catalyst in the

use of the other two organically-derived hydrogen peroxides

(with similar carbon contents of 120 to 270 and 194 to 212

mg/l, respectively) was theorized to be a result of either

(1) the specific nature of the carbon compounds present,

(2) synergistic effects of organic and inorganic contamin-

ants, or (3) synergistic effects of the purely inorganic

impurities.

Later, after apparent improvementa in the process for the

manufacture of organically-derived hydrogen peroxide, pro-

duction models of the Rocketdyne AR-2 engine system were

qualified using 90 w/o hydrogen peroxide (which met the

requirements of Mil-P-16005C)*from the three manufacturers

of propellant-grade hydrogen peroxide. No catalyst failures

were experienced during these testd that were attributable

to any particular type of hydrogen peroxide, either organ-

ically-or electrolytically-derived.

Recently, studies were conducted by the Air Force Rocket

Propulsion Laboratory (Ref. 7.17), in which 90 w/o hydrogen

peroxide (procured under Hi1-P-16005D from the various

manufacturing processes) was catalytically decomposed in

an LR-99 gas generator using a simulated flight feed system.

No differences were observed in the operation or performance

between the three types of propellant-grade hydrogen peroxide.

*NOTE: Mil-P-16005C was superceded by MIlr-P-16005D

429

It was concluded that "there was no evidence to indicate

a desirability of a change in the current hydrogen peroxide

specification".

As a result of these recent comparisons of hydrogen peroxide

catalyst performance with both organically-derived and

electrolytically-derived hydrogen peroxide, it is concluded

that the propellant procured according to lil-P-1b005D re-

quirements should not be detrimental to the performance of

the present silver-screen catalysts. However, the roles of

the individual contaminants of both types as well as their

inter-relationship in catalyst poisoning are still not

completely defined.

7.2.1.4 Operational Problems. Although reviews of the operational

problems that frequently occur in the catalytic decomposi-

tion of hydrogen peroxide appear in many sources (including

in particular, Ref. 7.1 and 7.15), a very adequate and

concise discussion of the problems is given in Ref. 7.18

as follows:

"It is now opportune to consider the various factors. Iwhic-h lead to a loss of efficieilvY of a (caiaIVyis-E "

pack.

The first is that of increase in pressure dropacross the pack during use. In this case, althoughthe pack is still active, it may become impossibleto maintain the desired rate of Iflow of H.T.P.(propellant-grade hydrogen peroxide-Ed.) due to theincrease of resistance to flow through the pack.Such increased resistance may be caused by the de-position of large amounts of non-catalytic mater-ial such as tin stabilizer. The deposition of pre-cipitated silver dissolved fiom the entry end of thepack can also cause an increaee in pressure drop ifthe amount of free space provided downstream is small.Increased pressure drops have also been observed whenlarge amounts of silver were provided oi the downstreamgauzes (screen-Ed.). This effect may result from thepartial fusion of the silver, causing the gauzes tobecome 'welded' together and is likely to be accen-tuated when H.T.P. of high concentration is used.

.30

A second factor leading tc the loss of catalyst packefficiency is the erosion of silver. This may occurin two principal ways; (1) When the adhesion of thesilver plating to the base metal of the gauze is poor,mechanical stripping of silver may occur at high flowrates of H.T.P. through the interstices of the gauzes.The type of silver catalyst known as 'activated silver'which is a loose powdery deposit of silver made bydipping copper gauze in ammoniacal silver nitratesolution, is particularly prone to mechanical stripping.(2) Erosion occurs by solution of silver metal in theliquid l.T.P. near the entry end of the pack: most ofthe dissolved silver is redeposited downstream but asmall fraction is blown out, and this leads to a grad-ual reduction in the total amount of silver available.However, more important than the gradual overall lossof silver is te fact that the gauzes at the entry endof the pack eventually become completely stripped ofsilver and then cease to contribute towards the decom-position of the H.T.P. This leads to a gradual shorten-ing of the effective length of the pack, the liquidphase penetrating further towards the downstream end.Eventually the penetration reaches the downstream endand the efficiency of the pack falls rapidly.

The use of l.T.P. at low ambient temperatures, andthe repeated stopping and restarting of the decomposerwhen cold, both accelerate the loss of efficiency ofa pack, due to an increased rate of erosion of silver.Since the rate of decomposition of hydrogen peroxideat a silver surface decreases with decrease in tempera-ture, the uee of a decofposcr at low temieraiuren in-volves a greater penetration of the pack by liquid

.H.T.P. and in consequence a higher overall rate ofsolution of silver. As mentioned above, the rapidstarting of a decomposer involves a greater pene-tration of H.T.P. than occurs during steady 'running,1and there is in consequence a higher rate of solutionof silver during the starting period. Repeatedstopping of the decomposer and restarting when it hascooled down will therefore lead to an overall higherrate of loss of silver than occurs during a continuous'run.' It is also a consequence of the greater pene-tration of liquid during a start that a decomposerwhich is losing efficiency, but is still usable, maynot restart satisfactorily from cold if the'run'isstopped at a late stage during its potential lifeunder continuous 'running' conditions.

431

in connection with the erosion of silver it in nec-essrTy to consider the phenomenon kuown as 'chanueling,'which is the term given to the preferential erosionof silver over certain parts of the gauze area. Asa result of thanneling' the gauzes become completelystripped of silver over certain areas whilst the restcf the gauze still retains silver. This process inturn, leads to penetration by undecomposed HI.T.P.along the channels. This condition brings aboutvery inefficient usage of the available silver onthe pack, since once a 'hannel' has been producedthe lI.T.P. begins to flow more freely along it thanthrough other parts of the gauze area.-

thanneling'is caused by two principal factors, (1)irregular distribution of !I.T.P. on the gauzes bythe injector, and (2) the cooling effect at theperiphery of the gauzes due to loss of heat to thesurroundings. The presence of 'chanieling'due toirregular distribution of II.T.'. is noticeablewhen an injector consisting of a number of holes ina plate is used, as each hole ii the injector ismatched by a channel on the gauze in the entry endof the pack. The cooling effect at the peripheryof the gauze leads to a somewhat lower rate of de-composition in this region and a greater distanceof penetration. This leads to more rapid erosionof silver at the periphery, and 'channeling' alongthe walls of the decomposer.

Finally, it is necessary to consider a third factor

namely loss of activity of the silver catalyst.This may occur in two major ways, (1) by ti'e cata-lyst becoming covered with a layer of non-catalyticmaterial, or (2) by direct chemical 'poisoning'ofthe catalytic surface. The first type of effectoccurs whenever non cataly-tic material, such asalumina and tin oxide, is deposited on the gauzesdownstream thereby redicing the efficiency of con-tact of ll.T.P. with the catalyst surface. The sec-ond type of effect occurs when the II.T.P. containscontaminants which reduce the rate of decompositionat the catalyst surface."

*Editor's Note: It is also believed that channeling can causerecirculation of the hot decomposition gases within the cata-lyst chamber. These gases can preheat the liquid stream enter-iug the catalyst bed, which results in an increase in the normaldecomposition temperatures in the bed. This increase in tem-perature is a probable major contributor to the failure of thepresent silver-screen catalyst packs.

432

7.2.2 Thermal Decomposition

The use of self-heatiug thermal chambers to maintain

controlled decomposition of hydrogeu peroxide has beca

limited to laboratory studies. In tbe thermal concept,

the design of the decomposition chamber i, similar to

that employed in packed bed catalytic chambers, except

that the chamber material is selected on the basis of

thermal conductivity criteria rather than for catalytic

activity. The thermal pack is heated with a "pilot

light" either by diverting a small flow of hydrogen

peroxide through a small catalyst chamber (and direct-

Ing the decomposition gases into the thermal bed) or by

bypergolic ignition slugs of fuel and oxidizer. When

the thermal bed achieves a suitable temperature level,

the main flow of hydrogen peroxide is initiated and the

pilot flow is terminated. The assumed advantage of this

operation is an elimination of most of the problems

associated with the effects of temperature, poisoning,

and erosion in the catalyst bed.

This concept was investigated with both 98 w/o (Ref. 7.19)

and 90 w/o (Ref. 7.11) hydrogen peroxide and found to

have limited usefulness. Although decomposition could

be maintained with smll bed loading rates, large pro-

pellant flows usually quenched the decomposition process

within 3 to 5 seconds after "pilot light" termination.

It wan conclude~d that the slow rate of thermal deco.-

position of hy'lrogen peroxide cannot compete with the

rates obtainable with catalytic decemposition.

433

7.3 na~u"ECES

7.1 SchImUb, W. C., C. N. Satterfield, and It. L. Wtietwort'h, Wiydrozo'tu

1'croxide, A.C.S. Moograjih 128, Reinhold iPublish~ing Corporation,


7.2 Shell DevclojRinet C6qi&atky, Emeryville, Califorznia, Final ivjort,

CoweuLratcd Storable Ib-droLgen Peroxide, Report No. S-139714,

August 1965, Coutract IA-04-200-AHC-5b9(Z).

7.3 Shell levelolmmit Comwpau, Emeryville, California, Storable

C!!ncentra~ted Ib'dro,&en l'erox ide, Report No. ALkt'L-11I-G6-20",

Report period: M-mrch--May 1966, Contract AF'014(wil)-lila lb.

7.4 Shell Development Cowpauy, Emtryvillc, Californiu, StorableConcentrated ll~ydotaii Peroxidj., Report No. AFiUtL-TH-66-2b2,

Report period: June-August 1966, Contract AF0 (611)-i1,16.

7.5 E. 1. duPont de Nemours & Company, Inc., Ilinal Report, Research

on the Stability of High Stren4gth I R02, teport No. AFRPL-TH-6b-13,

15 March 1966, Contract AF0(6i1)-10216.

7.6 liauwgartner, if. J., G. C. Hood, J. H. Monger, It. H. Roberts, and

C. E. Sanborn, "1)ecomposition of Concentrated Hydrogen Peroxide

on Silver., 1. Lown Te'mperatu-,re Reaction1 ann_ Kit-wtice," J. -.-

Catalysis. 2, 405-14 (1963); "I1. hligh Temperature Decomposition,"

J. of Catallsis, 2, 413-20 (1963).

7.7 Hart, A. B. avid H. A. Ross, J. Catalysis, 2, 251 (1953).

7.8 Rocket Propulsiou Establialunutt, Westcott, Buckirgliwm.a.ire,

England, Some Aspects of the Catalytic Decolaosition of ILydrogen

Peroxide by Silver. Part IV. The Rate of Decompos-tion, R.P.E.

Tech Note 197, December 1960.

7.9 F.M.C. Corporation, Princeton, New Jersey, Heterogeneous DecMposition

of Ihydrogen Peroxide by Inorganic Catalysts, Report No. AFIUL-TIt-66-

136, June 1966, Contract AF04(bll)-1120t3.

7.10 Rocketdyue, a Division of North Amnericau Aviation, Inc., Canoga Park,

California, Redstone Catalyst Improvement Program. Final Ruport for

Period October 1958 to December 1960, Report No. R-2985, 29 May 1961.

7.11 Rockctdkae, a Division of North American Aviation, Inc., Canoga Park,

California, Summary Report, Research Program on Hydrogen Peroxide,

Report No. R-2091P, March 1960.

7.12 F.M.C. Corporation, Princeton, New Jersey, Investigation of

Decomj'ositiou Catalysts for 98% •_ydrogen Peroxide, Report No.

AkFPL-IT-66b-1-3, June 1966, Contract AF10(611)-11208, CONFIrNTIAL.

7.13 Aerojet-General Corporation, Sacramento, California, Advaunced

Propellant Staged Combustion Feasibility Program, Phase 1, Parts

1 and ", Report No. A.L-T1t-66-6, April 1966, Contract AF04(611)-

10785, CONFILIMIAL.

7.14 Aerojet-.General Corporation, Sacramento, Califiraia, Advanced

Propellant Staaed Combustion Feasibility Progaram, Report No.

10785-Q-3., August 1966, Contract AF04(611)--10785, CONFURiWNTIAL.

7.15 McCormick, J. C., F.M.C. Corporation, Buffalo, New York, Hydrogen

Peroxide Rocket Manual, 1965.

7.16 Davis, N. S., Jr., and J. C. McCcrmick, "Design of Catalyst Pack

for the Decomposition of Hydrogen Peroxide," A.R.S. Paper No.

124,6-60, 1960.

7.17 Barclay, L. P., Air Force Rocket Propulsion Laboratory, Edwards,

California, "Hydrogen Peroxide Evaluation," k3th Liquid Propulsion

Symposium, Cleveland, Ohio•, November 19bb, Vol. 2, COIWIDEMfIAL.

7.18 Rocket Propulsion Establishment, Westcott, Buckinghamahire, England,

Some Aspects of the Cmtalytic Decomposition of Concentrated Hydrogen

Peroxide (H.T.P.) by Silver: Part IX. Tests With l&compopers, R.P.E.

Report No. 42, June 1963.

7.19 Kazaajian, A. R., "Thermal Decompositiou Rate Studies of 98% H202,'

Unpublished Data (RX 316-92), Rocketdyne, a Divisiou of North Aaerican

Aviation, Inc., 19 March 1958.

'35

.:7.20 ::United States Naval Air Rocket Test Station, Lake Denmark, Dover,

.-New Jersey, Mollier Charts for the Decomposition of lHydrogen

Peroxide-Water Mixtures, NARTS Report 43, November 1954.

436

SECTION 8: BIBLIOGRAPHY

In addition to the references actually used in compiling the data appear-

ing in this handbook (these references are listed at the end of each

section), many other articles and reports were reviewed. These addi-

tional references are listed b.elow in the proper category for further

information. In addition, several general, secondary references contain-

ing extensive physical property and/or handling data for H 0 are included.2 2

Although these compilations are not repeated for each category, most are

applicable to all sections.

4137

8.1 tGENERAL RLFE2kCES

Aerojet-Goneral Corporation, Sacramento, California, Final Report,

Advanced Propellant Staged Combustion Feasibility Program, Vol. I

and Vol. II. Report No. AFRPL-TR-66-6, April 1966, Contract

AF•4(611)-10785, CONFIDENTIAL.

Aerojet-General Corporation, Sacramento, California, Physical

Properties of Liquid Propellants, Report No. lRP 178, 13 July 1960.

Ardon, H.,Oxygen: Elementary Forms and Hydrogen Peroxide,

W. R. Benjamin, Inc., New York, New York, 1965.

The Battelle Memorial Institute, Liquid Propellants Hlandbook,

"Hydrogen Peroxide," Vol. I, 1958, CONFIDENTIAL.

Bloom, R., Jr., and N. J. Brunavold, "Anhydrous Hydrogen Peroxide

as a Propellant," Chem. Eng. Progr., 52, 541 (1957).

De Castro-Ramas, R., "One Hundred Percent Hydrogen Peroxide,"

Rev. cienc. aplicada, 4, 49-54 (1950).

Dierdorff, L. II., Jr., Hydrogen Peroxide Physical Properties

Data Book, F. M. C. Corporation, New York, New York, 1955.

Laporte Chemicals Limited, Luton, England, Lydrogen Peroxide

Data Manual, 1960.

Liquid Propulsion Information Agency, Liquid Propeilant Manual,

"Hydrogen Peroxide," 1958.

McCormick, J. C., F.M.C. Corporation, Buffalo, New York,

Hydrogen Peroxide Rocket Manual, 1965.

Military Specification. Propellant, Hydrogen Peroxide, MIL-P-

16005D, 18 March 1965.

Military Specification, Hydrogen Peroxide, E-Stability 72%_

and 90% (for Torpedo Use), MIL-H-22868 (Wep), 21 March 1961.

Schumb, W. C., C. N. Satterfield, and R. L. Wentworth,

lLydrogen Peroxide, A.C.S. Monograph 128, Reinhold Publishing

Corporation, New York, New York, 1955.

438

Shell Chemical Company, New York, New York, Concentrated Hydrogen

Peroxide, H1202, 2nd ed. Properties, Uses, Storage, Handling,

Report No. SC: 62-23, 1962.

Wood, W. S., Hydrogen Peroxide, The Royal Institute of Chemistry

Lectures, Monographs, and Reports, No. 2, 1954.

8.2 PHYSICAL PROPERTIES

8.2.1 Phase Properties

8.2.1.1 Melting (Freezing) Point

Cuthbertson, A. C., G. L. Matheson, and 0. Maass, "The Freezing

Point and Density of Pure Hydrogen Peroxide," J. Am. Chem. Soc.,

50, 1120-l1 (1928).

Foley, W. T. and P. A. Giguere, "Hydrogern Peroxide and Its

Analogues. IV. Some Thermal Properties of Hydrogen Peroxide,"

Can. J. Chem., 22, 895S-903 (1951).

8.2.1.2 Boiling Point

Shanley, E. S. and F. P. Greenspan, "Highly Concentrated

Hyd,-ogen Peroxide-Physical and Chemical Properties," Ind. Engr.

Chem., J9, 1536-43 (1947).

Simkin, D. J. and C. 0. Hurd, "Vapor Pressure and Heat Contents

of Saturated Liquid and Vapor Hydrogen Peroxide," Jet Propulsion,

21, 419-20 (1957).

Uchida, S., S. Ogawea, and M. Yamaguchi, Japan Sci. Rev_. En•.. Sci.,

jNo. 2, 41 (1950) (Eng.

439

84. Density Solid

Maaso, 0. and W. H. Hatcher, "The Properties of Pure Hydrogen

Peroxide. I," J. Am. Chem. Soc., 42, 2548-69 (1920).

8.2.1.4 Density, Liquid

Cuthbertson, A. C., G. L. Matheson, and 0. Haase, "The Freezing

Point and Density of Pure Hydrogen Peroxide," J. Am. Chem. Soc.,

50p 1120-1 (1928).

Huckaba, C. E. and F. G. Keyes, "The Density of Aqueous Hydrogen

Peroxide Solutions," J. Am. Chem. Soc., 70, 2578-81 (191i8).

Iluckaba, C. E. and F. G. Keyes, "Error in the Average Coefficients

of Specific Volume Change From 0 to 200 in Aqueous Solutions of

Hydrogen Peroxide," J. Am. Chem. Soc., 72, 5324-5325 (1950).

Kubaschewski, 0. and W. Weber, "Freezing-Point Diagram, lleats

of Mixing and Densities of the System Water-Hydrogen Peroxide,"

Zeit. fur Elektrochemie und angew. physik. Chem. , 5, 300-4 (1950).

8.2.1.5 Coefficient of Thermal Expansion

Giguere, P. A. and P. Geoffrion, "Changes of Density of Hydrogen

Peroxidc "olutions on Cooling aud C•- - Can. j. Researeh, 28B,

599-607 (1950).

fluckaba, C. E. and F. G. Keyes, "The Density of Aqueous Hydrogen

Peroxide Solutions," J. Am. Chem. Soc., 70, 2578-81 (19'i8).

Maass, 0. and W. If. Hatcher, "The Properties of Pure Hydrogen

Peroxide, I," J. Am. Chem. Soc., 42, 2548-69 (1920).

440

8.2.1.6 Parachor

Cuthbertsou, A. C., G. L. Matheson, and 0. Maass, "The Freezing

Point and Density of Pure lydrogen Peroxide," J. Am. Chem. Soc.,

-0, 1120-1 (1928).

Phibbs, M. K. and P. A. Giguere, "Hydrogen Peroxide and Its

Analogs, 111. Absorption Spectrum of Hydrogen and Deuterium

Peroxidee in the Near Ultraviolet," Can. J. Chem., 29, 173 (1951).

8.2.1.7 Surface Tension

Maass, 0. and W. 11. Hatcher, "The Properties of Pure Hydrogen

Peroxide, I," J. Am. Chem. Soc., 42, 2548-69 (1920).

8.2.2 Thermodynamic Properties

8.2.2.1 Heat of Formation

Coughlin, J. P., Contributions to the Data on Theoretical

Metallurgy. XII. Heats and Free Energies of Formation of

Inorganic Oxides, Bulletin 542, Bureau of Mines, U.S. Department

of the Interior, U.S. Government Printing Office, Washington, D.C.

Schumb, W. C., C. N. Satterfield, and R. L. Wentworth, Ib-drogen

Peroxide, A.C.S. Monograph, 128, Reinhold Publishing Corporation,


8.2.2.2 Heat of Fusion

Giguere, P. A., I. D. Liu, J. S. Dugdale, and J. A. Morrison,

"Hydrogen Peroxide: The Low-Temperature Heat Capacity of the

Solid and Third Law Entropy," Can. J. Chem., L2, 117-28 (1954).

Naass, 0. anj W. HI. Hatcher, "The Properties of Pure Hydrogen

Pecoxide. I," J. Am. Chem. Soc., 42, 25118-69 (1920).

8.2.2.3 Heat of Vaporization

Egerton, A. C., W. Eute, and G. J. Miiikoff, "Some Propertics of

Organic Peroxides," Discussions Faraday Society, 1951 (10), 278-82

(1951).

Foley, W. T. and P. A. Giguere, "Hydrogen Peroxide and Its

Analogues. I1. Phase Equilibrium in the System llydrogen

Peroxide-Water," Can. J. Cheu., 29, 123-32 (1951).

Giguere, P. A., B. G. Morissette, A. W. Olmas, and 0. Knop,

"Hydrogen Peroxide and Its Analogues. VII," Can. J. Chem., •,

804 (1955).

8.2.2.4 Beat of Sublimation


Analogues. 1I. Phase Equilibrium in the System Hydrogen

Peroxide-Water," Can. J. Chem., 29, 123-32 (1951).

8.2.2.5 Heat Capacity. Liquid


Analogues. II. Phase Equilibrium in the System Hydrogen

Peroxide-Water," Can. J. Chem., 29, 123-32 (1951).

Giguere, P. A. and I. D. Liu, "Recommended Values for the

Thermodynamic Properties of Hydrogen and Deuterium Peroxides,"

J. Am. Chem. Sec., 77, 6477-9 (1955).

Maass, 0. and W. H. Hatcher, "The Properties of Pure Hydrogen


Papousek, D., "Intermolecular Interaction in Liquids. I. Adiabatic

Compressibility and Structure in the System Hydrogen Peroxide-Water,"

Chemicke Listy, 21, 1781-6 (1957).

8.2.2.6 Entropy and Enthalpy

Mitchell, A. G. and W. F. K. Wynne-Jones, "Thermodynawic and

Other Properties of Solutions Involving Hydrogen Bonding,"

Discussions Faraday Soc., , No. 15, 161-8 (1953).

8.2.3 Transport Properties

8.2.3.1 Viscosity, Liquid

Shanley, E. S. and IF. P. Greenspan, "Highly Concentrated Hydrogen

Peroxide-Physical and Chemical Properties," Ind. Eng. Chem., 12,1536-43 (1947).

8.2.3.2 Viscosity. Vapor

Svehla, R. A., "Estimated Viscosities and Thermal Conductivities

of Gases at High Temperatures," NASA Tech Report E112, 140 pp.

(9Q629)

8.2.4. Electromagnetic and Optical Properties

8.2.4.1 Index of Refraction

Cuthbertaon, A. C. and 0. Haass, "Hydrogen Peroxide. VIII.

The Dielectric Constants, Refractive Indices and Ionizing Power

of Hydrogen Peroxide and Its Aqueous Solutions," J. Am. Chem.

Soc., 52, 489-99 (1930).

"443

Egerton, A. C., W. Emte, and G. J. Minkoff, "Some Properties of

Organic Peroxides," Discustions Faraday $rtet-y, 1951 (10), 278-82

(1951).

Ioffe, b. V., "Heasurement of the Index of Refraction for a

Mixture of Volatile Liquids on a Pulfzich Refractometer,"

Zh. Fiz. K1im., •3-, 1133-35 (1960).

Maass, 0. and W. H. Hatcher, "The Properties of Pure llHdrogen

Peroxide. I," J. Am. Chemw .Soc., 42, 2548-69 (1920).

Phibbs, H. K. and P. A. Gigucre, "Hydrogen Peroxide and Its

Analogues. I. Density, Refractive Index, Viscosity, and Surface

Tension of Deuterium Peroxide-Deuterium Oxide Solutions,"

Can. J. Chem., _2, 173-81 (1951).

8.2.4.2 Dipole Moment

Penny, W. G. and G. B. B. H. Sutherland, "Structure of Hydrogen

Peroxide and Hlydrazine With Particular Reference to Electric

Moments and Free Rotation," Trans. F draday Soc , 20, 898-902 (1934).

Randall, J. T. , "Structure of Liquid Hydrogen Peroxide," Proc.

Roy. Soc., A159, 8Y-92 (1937).

Theilacker, W., "The Dipole Moment of Hydrogen Peroxide,"

Z. phyaik. Chem., B20, 142-4 (1933).

8.2.4.3 Dielectric Constant

Cuthbertson, A. C. and 0. Maass, "Hydrogen Peroxide. VIII.

The Dielectric Constants, Refractive Indices and Ionizing Power

of Hydrogen Peroxide and Its Aqueous Solutions," J. Am. Chem. Soc.,

52, 489-99 (1930).

Gross, P. M., Jr., and R. C. Taylor, "The Dielectric Constants

of Water Hlydrogen Peroxide and Hydrogen Peroxide-Water Mixture,"

J. Am. Chem. Soc., 1 2075-80 (1950).

Linton, C. P. and 0. aass., "The Electric Howent of Hlydrogen

Peroxide," Caiu. J. Research, 7, 81-5 (1932).

Shanley, E. S. and F. P. Greenspen, "Highly Concentrated Hydrogen

Peroxide-Physical and Chemical Properties," Ind. Egg. Chem ,1536-43 ( 1947).

8.2.'..'. Electrical Conductivity

Gross, P. H., Jr., and R. C. Taylor, "The Dielectric Constants

of Water Hydrogen Peroxide and Hydrogen Peroxide-Water Mixtures,"

J. Am. Chem. Soc., 72, 2075-80 (1950).

Hatcher, W. 11. and E. C. Powell, "Conductivity Data of Aqueous

Mixtures of Hydrogen Peroxide and Organic Acids. Il," Can. J.

Research, 7, 270-82 (1932).

Hatcher, W. H. and H. G. Sturrock, "Conductivity Data of Aqueous

Mixtures of Hydrogen Peroxide and Organic Acids," Can. J. Research,

Ai, 35-8 (1931).

8.2.4.5 Magnetic Susceptibility

Gray, F. W. and J. Farquharson, "Improvements in the Curie-

Cheneveau Magnetic Balance," J. Scientific Instruments, 2, 1-5

Maass, 0. and W. H. Hatcher, "The Properties of Pure Hydrogen

Peroxide. I," J. Am. Chem. Soc., .#2, 2548-69 (1920).

Neiding, A. B. and I. A. Kazarnovskii, "Magnetic Susceptibilityasd Structure of Hydrogen Peroxide," Doklady Akad. Nauk S.S.S.R.,

-h 735-8 (1950).

Ne.ding, A. B. and I. A. Kazarnovskii, "Magnetic Susceptibility

and Structure of Peroxides," Zhur. Fiz. Kl0im., 26, 1167-72 (1952).

445

Savithri, K. and B. Ramachandra, "Magnetic Susceptibility of

Some Peroxides," Proc. Indian Acad, Sci., I{A, 221-30 (194,2).

8.3 SU"L7TRE

Feher, F. and F. Klotzer, "The Crystal Structure of Hydrogen

Peroxide," Z. Elektrochem., 41, 850-1 (1935).

Feher, F. and F. Klotzer, "Crystal Structure of Hydrogen

Peroxide," Z. Electrochem., A3, 822-6 (1937).

Giguere, P. A., "Properties and Structure of Hydrogen Peroxide

and of Deuterium Peroxide," Bull. Soc. Chiw. France 1

720-3 (1954).

Giguere, P. A., "The 0-0 Bond Energy in Hydrogen Peroxide,"

Can. J. Research, 28B, 17-20 (1950).

Glocker, G. and G. Matlock, "0-0 BoinJ Energy in HydrogenPeroxide," J. Chem. Phu's., 1L,, 50405 (1940 ).

Hunt, R. H., "The Determinatio, of the Hindered Motion in Hydrogen

Peroxide From Its Far Infrared Spectrum," University of Michigan,

AD 420638 (1963).

Kazarnovskii, I. A., "Structure of Inorganic Peroxides,"

J. Phys. Chem. (U.S.S.R.), _lb, 32-31 (1940).

IKazarnovskii 1 I- Aý "The -Structure of inorganic, Peroxidaca."

Khim. Referat. Zhur., A, No. 1, 30-1 (1941).

Natta, G. and R. Rigamonti, "Crystal Structure and Molecular

Symmetry of Hydrogen Peroxide," Gazz. chim. ital., 66, 762-72 (1936).

Neiding, A. B. and I. A. Kazarnovskii, "Magnetic Susceptibility

and Structure of Peroxides," Zhur. Fiz. Khim., 26, 1167-72 (1952).

Neiding, A. B. and I. A. Kazarnovskii, "Magnetic Susceptibility

and Structure of Hydrogen Peroxide," Dokla&y Akad. Nauk S.S.S.R. L

1-4 735-8 (1950).

446

Parsons, A. E. and A. W. Searcy, "Prediction of the Shapes of

Two Centered Covalent Molecules and Ions," J. Chem. Physs., 20,

1635-6 (1959).

Penney, W. G. and G. B. B. M. Sutherland, "A Note on the Structure

of Hydrogen Peroxide and HYdrazine With Particular Reference to

Electric Moment@ and Free Rotation," Trans. Faraday Soc., J0,

898-902 (1934).

Penney, W. G. and G. B. B. N. Sutherland, "The Theory of the

Structure of H,.•rogen Peroxide and alydrazine," J. Chem. Phys.,.2,Ik92-8 (1934).

Randall, J. T., "Structure of Liquid Hydrogen Peroxide," Proc.

Roy. Soc., A&I., 83-92 (1937).

Sisler, H. and L. F. Audrieth, "Structural ai.4 Chemical

Similarities of Hiydxogen Peroxide, Hydroxylomine, and Hydrazine,"

Trans. Illinois State Acad. Sci., 31, l144,-5 (1938).

8.4 SOUDILITY

Akerlif, G. and H. E. Turck, J. Am. Chem. Soc., 51, 1746 (1935).

F.M.C. Corporatiob, New York, New York, Safety Code for BECCO

90 Percent Hydrogen Peroxide (H.202), May 1947.

Floyd, J. D. and P. M. Gross, Jr., "Solubilities of Some Strong

Electrolytes in the Hydrogcn Peroxide-Water System. I., Sodium

Chloride, Fluoride and Nitrate, Potassium Chloride and Nitrate,

and Lithium Nitrate," J. Aim. Chem. Soc., U, 1435-37 (1955).

Husain, S., Z. anorg. allgem. Chem., M2, 215 (1928).

Jones, H. C., J. Barnes, and C. P. Hyde, "Lowering of the Freezing

Point of Aqueous Hydrogen Peroxide," Am. Chem. J.,27, 22 (1902).

Jones, H. C. and C. G. Carroll, "Lowering of the Freezing Point

of Aqueous Hydrogen Peroxide, Am. Chem. J., 28, 284 (1902).

"447

Kazanetzkii, P. V., "Behavior of Hydrogen Peroxide With Salts,"

J. Russ. Phys. Chew. Soc., 46, II0 (1914).

Maass, 0. and W. II. Hatcher, "The Properties of Pure Hydrogen


Matheson, G. L. and 0. Maass, "Properties of Pure Hydrogen

Peroxide. Vi," J. Am. Chem. Soc., 21i 674-87 (1929).

Menzel, II. and C. Gabler, "Concerning Compounds of Alkaliphosphates

with Hydrogen Peroxide," Z. anorg. allgem. Chem., Jj_, 187 (1928).

Minnesota Mining and Manufacturing Company, Chemical Reactions

as Related to Advanced Solid Propellants, Report No. 1, Ml.M-

0209-C, Report Period: 1 January - 31 March 1966, Contracts

NOsO5-0209-C and NOw-66--0466-C.

Price, T. S., "Depression of the Freezing Point of Aqueous Solutions

of Hydrogen Peroxide by Potassium Persulphate and Other Compounds,"

J. Chem. Soc., 91, 531-36 (1907).

Schumb, W. C., C. N. Satterfield, and R. L. Wentworth, Hlydrogen

Peroxide, A.C.S. Monograph 128, Reinhold Publishing Corporation,


Shanley, E. S. and F. P. Greenspan, "Highly Concentrated Hydrogen

Peroxide-Physical and Chemical Properties," Ind. Eng. Chem., 39,

1536-43 (1947).

8.5 HANDLING AND STORAGE

Aeronutro..ic, Newport &ach., California, Explosive 'lazartd jf

Rocket hAunchings, Technical Report No. U108:98, 30 November 1960.

The Battelle Memorial Institute, Columbus, Ohio, Liquid Propellants

Handbook, "Hydrogen Peroxide," Vol. I, 1958, CONFIDENTIAL.

Bethlehem Steel Company, Shipbuilding Division, Bethlehem, Pennsyl-

vainia, Design ýIf Prototype System for Shipboai'd Storage and

lHandling of Liquid Propellants for Guided Missiles: Concentrated

Hydrogen Perioxide, Contract NOas 45349, Task Order V., CONFIDENTIAL.

448

Davis, N. S., Jr., and R. Bloom, Jr., New Techniques for Transferring

H202 at High Pressures, 9th Annual Meeting, American Rocket Society,

December 1954.

E. I. duPont deNemours & Co., Inc. Wilmington, Delaware, Research

on the Stability of High Strength 11202, Contract AFO4(611)-10216

Final Report AFRPL TR-6b-13, 15 March ]966

QPR December 1964 AD610853

QPR March 1965 AD615036

QPR June 1965 AD619179

General Electric Co., Rocket Engine Section, Cincinnati, Ohio,

Handbook of Operation and Maintenance Instructions, X-405i Rocket

Engine VEGA Second Stage Propulsion, 1 June 1960, COfhYIL*NAL.

Keefe, J. H. and C. W. Raleigh, "Field Transportation of Concentrated

Hydrogen Peroxide," Jet Propuls.on, 27, 663 (1957).

Laporte Chemicals, Ltd., Luton, England, Hydrogen Peroxide Data

Manual, 1960.

Liquid Propulsion Information Agency, Liquid Propellant Manual,

"Hydrogen Peroxide," 1958.

Manufacturing Chemists Association, Washington, D.C., 1jydrogen

Peroxide Properties and Recommended Practice for Packaging,

Handling, Transportation, Storage and Use, Supplement B, Chemical

Data Sheet SD-53.

McCormick, J. C., F.R.C. Corporation, Buffalo, New York, Hydrogen

Peroxide Rocket Mauual, 1965.

McCormick, J., A. Livewski, and G. Carmine, Storage of 90 & 98%

* by Weight Hydrogen Peroxide in Sealed Cortainers for Extended

Periods, U.S. Dept. CGmm. Office of Tech. Services, AD268,379 (1961).

Mecker, G. W., Jr., Hydrogen Peroxide: Problems and Operating

Procedures at the Air Force Flight Test Center, New York (1952).

449

Rocketdyne, a Division of North American Aviation, Inc., Canoga

Park, California, "Handling of iydrogen Peroxide," Engineering

Procedures Manual, April 1963.

Rocketdync, a Division of North American Aviation, Inc., Canoga

Park, California, Passivation of Stainless Steel Parts for hydrogen

Peroxidi, Process Specification PR 601-3, Amendment 1, January 1960.

Rocketdyne, a Division of North American Aviation, Inc., Canoga

Park, California, Passivation of Materials Used in Contact With

Hydrogen Peroxide, Process Specification PR 1-17, September 1951;

PR 1-37, October 1958.

Satterfield, C. N., "C & EN Commodity Series; Hydrogen Peroxide,"

Chem. Eng. News, 32, 2726-30 (1954).

Shell Chemical Company, New York, New York, Concentrated Hlydrogen

Peroxide. 2nd Ed. Properties, Uses, Storage, llandling, Report No.

SC:62-23, 1962 (revision of SC:58-16).

Shell Chemical Company, New York, New York, Concentrated lydrogen

Peroxide Sumrary of Research Data on Safety Limitations, Report

No. SC:59-44R, 1959.

Shell Chemical Company, New York, New York, Study of Temperature

Measuring Systems for High Strength Hydrogen Peroxide Storage,

Report No. IC:63-7, 1963.

Shell Development Company, Emeryville, California, Concentrated

Storabl_' Hydrogen Peroxide, Contract DA-04-200-AMC-569Z

Final Report, S-13974, August 1965

QPR 1, May-July 1964, S-13928

APR 2, August-October A964, S-13938

QPR 3, November 1966 - January 1965, S-13950

QPR 4, February-June 1965. 5-13961

450

Shell Development Company, Emcryville, California, Hydrogen

Peroxide by Oxidation of Isopropyl Alcohol. Part XVI. Vapor

Explosives and Miscellaneous Explosion Test Data, Tech. Report

No. 7-60, January 1960.

Shell Development Company, Emeryville, California, Thermal

Stability of 90% Hydrogen Peroxide, Final Report S-13801, Report

Period: July 1958-31 December 1979, CONFIDENTIAL.

Southwest Research Institute, 5an Antonio, Texas, Missile/Space

Vehicle Launch Site Fire Protection Study, WADC Technical Report,

No. 59-464, June 1959.

Technidyne, Inc., West Chester, Pennsylvania, Feasibility of

Modifying Certain Physizal Chemical Parameters of Liquid

Propellants, Report No. RR-65-26, April 1965, Contract DA-36-04-

AMCO-153Z, CONFIDENTIAL.

Thiokol Chemical Corporation, Denville, New Jersey, "Water,

Specification for General Purpose Rinse and Dilution," Reaction

Motors Division Specification 4085.

Thiokol Chemical Corporation, Denville, New Jersey, "Rinse and

Dilution Water for H1202 Systems," Reaction Motors Division

Specification 7253.

Thiokol Chemical Corporation, Denville, New Jersey, "Passivating,

Conditioning, and Stability Testing - Hydrogen Peroxide System

Components,' Reaction Motors, Incorporated, Specification 7000.

Thiokol Chemical Corporation (Reaction Motors, Incorporated),

Denville, New Jersey, Field Handling and Storage Pf90 Percent

Hydrogen Peroxide."Threshold Limit Values for 1960," Adopted at the 22nd Annmal

Meeting of the American Conference of Governmental Industrial

Hygienists, Rochester, New York, April 1960.

Tschinkel, J. G. and A. E. Graves, "Development of an Apparatus

for Warming Hydrogen Peroxide by Its Own Controlled Decomposition,"

Jet Propulsion, 27, 796-8 (1957).

451

Air Force Flight Test Center, Edwards Air Force Base, California,

Safety Procedures for Rocket Propellants, Report No. FJR-TM-58-1,

November 1958.

General Services Administration, National Archives and Records

Service, Federal Register Division, Washingtohi, D.C., Code of

Federal Re,.ulations, Title 49, Chapter I - Interstate Commerce

Commission, Parts 74 to 90, revised 1956.

United States Department of the Air Force, General Safet

Precautions - Mispile Liquid Propellants, Report No. AITO 1C-1-

6C, August 1962.

United States Department of the Navy, Ammunition Ashores, Vol.Is

Handling, Storage, and Shipping, Report No. OP-5, revised 9 August

1957.

United States Naval Underwater Ordnance Station, Newport, Rhode

Island, Hydrogen Peroxide and Its Application to Ordnance, NAVORD

Report No. 5215, 8 July 1957.

United States N&val Underwater Ordnance Station, Newport, Rhode

Island, "High Performance Thermal Propulsion Systems for the

Future," Torpedo Propulsion Conference, Vol. HI, July 1963,

CONFIDENTIAL.

Vedenkin, S. G. and V. S. Sinyavskii, "Aluminum Alloys for

Railroad-Car Construction," Tr. Uses. Nauchn. - Is-1z4. Inst.

Zheleznodor. Transp., 1959, No. 171, 5-66 (1959).

Victor, M., "Rockets," Rev. aluminum, 24, 69-74 (1947).

8.6 MATERIALS COMPATIBILITY

The Battelle Memorial Institute, Columbus, Ohio, Compatibility

of Rocket Propellants With Materials of Construction, Defense

Metal Information Center Memo 65, September 1960.

4552

Connecticut Hard Rubber Company, New Haven, Connecticut, Development

of Rubberlike Materials for Applications InvoAving Contact With

Liquid Rocket Propellants., Report No. WADC-TR-651, Part II, 1960.

Davis, N. S. and J. H1. Keefe, Jr., "Equipment for Use With High-

Strength Hlydrogen Peroxide," J. Am. Rocket Soc., 22 (2), 63-9 (1952).

Explosives Research and Development Establishment, Waltham Abbey,

England, The Sensitiveness of Fluorocarbon Lubricant/IITP Mixtures,

E.R.D.E. Tech Memo 16/M/52.

General Electric Company, Cincinnati, Ohio, Handbook of Operation

and Maintenance Instructions. X-4O5HRocket Engine. VEGA, Second-

Stage Propulsion, 1960, CONFIDENTIAL.

Kopituk, R. C., "Materials Compatibility with 90% Hydrogen Peroxide,"

Presented at the 42nd National Meeting A.I.Ch.E., Atlanta, Geogia,

February 1960, A.I.Ch.E. Preprint 1.

LTV Astronautics Division, Dallas, Texas, "Influence of Oven Bauing

of 321 Stainless Sýeel Tubing Upon Its Compatibility With Concentrated

Hydrogen Peroxide," Report No. LR-O00-TR-005, 1965.

McFarland, R.,Jr., "Rigid Polyvinyl Chloride as a Construction

Material for Valves," Corrosion, 11, 103t-4t (1955).

Monsanto Research Corporation, Dayton, Ohio, Evaluation of Eleatomers

as O-Ri•g Seals for Liquid Rocket Fuel and Oxidizer- Systems, Part II,

Report No. ASD-TDR-63-496, August 1964&, Contract AF3B(616)-8483.

Reichert, J. S. and R. H. Pete, "Materials of Construction Versus

Hydrogen Peroxide," Chem. Enx., 58, 263 (1951).

Rlocket Propujlsion Eetablwent, W tt, Englacd, Thie Co..Li)hi iij

of Silicone Rubbers With Concentrated Hydrogen Peroxide (H.T.P•.)

R.P.E. Tech Note 233, August 1964, CONFIDENTIAL.

Rocket Propulsion Establishment., Westcott, England, The Nature of

the Oxide Film Formed on Stainless Steel Immersed in Hydrogen

Peroxide, R.P.E. Tech Note 187, January 1960, CONFIDENrIAL.

4153

Rocket Propulsion Department, Royal Aircraft Establishment, England,

The Compatibility and Engineering Applications of Various materials

With Concentrated Hydrogen Peroxide, February 1955.

Rosen, A., "Evaluation of Lubricants for 90% 11202 Service," Un-

published Data (RM 245-93), Rocketdyne, a Division of North American

Aviation, Inc., Canoga Park, California.

Royal Aircraft Establishment, Rocket Propulsion Department, Westcott,

England, The Compatibility and Engineering Applications of Variods

Materials W.th Con centrated Hlydrogen Peroxide (1I.T.P.), Report

No. R.PD. 24, February 1955, CONFIDENTIAL.

Schuler, F. T., "Evaluation of AR O-Rings in 90% IV02 at 160 and

180 F," Unpublished Data (tM 249-93), Rocketdyne, a Division of

North American Aviation, Inc., Canoga Park, California, November 1957.

Schuler, F. T. and A. Blitstein, "A Study of the 17-7 P11 Stainless

Steel and 42B Aluminum Alloy for Service in Ninety Percent Hydrogen

Peroxide," Unpublished Data (RR 57-27), Rocketdyne, a Division of

North American Aviation, Inc., Canoga Park, California, 20 June 1957.

Southwest Research Institute, San Antonio, Texas, Survey of

Lubricant Compatibility Test Methods for Missile Systems, Technical

Documentary Report No. ASD-TlDt-62-190, January 1962.

I.Ltman-Duoin Laboratories Group, Frankford Arsenal, Philadelphia,

Pennsylvania, Lubricants for Missile Systems, Report No. R-1522,

December 1959.

Rocket Propulsion Laboratory, Air Force Systems Command, Edwards,

California, A Compatibility Evaluation of Plastic Membrane Filters

With Liquid Propellants and Solventa. Report. No. RPT.-TDRi-64-38,

February 1964.

U.S. Army Rocket and Guided Mirsile Agency, Redstone Arsenal,

Iluntsville, Alabama, Minutes of the First -yujiosium on Materials

Compatibility With Liquid Propellants, 27 October 1961.

454

8.7 TRANSPORTATION

laporte Chemicals Limited, Luton, England, jj[drozen Peroxide

Data Manual, 196C.

8.8 SAFETY

Aeronutronic, Newport Beach, California, Explosive Hazards of

Rocket Launchings, Technical Report No. U-108:98, 30 November 1960.

Aeronutronic, Newport Beach, California, Toxic Hazards of Rocket

Propellants, Technical Report No. U-108:9, 30 November 1960.

Ahlert, R. C., "Explosive Limits for Vapor Phase Ikydrogen Peroxide,"

Unpublished Data (RRl 56-77), Rocketdyne, a Division of North American

Aviation, Inc., Canoga Park, California, 1956.

The Battelle Memorial Institute, Columbus, Ohio, Liquid Propellants

Handbook, "Hlydrogen Peroxide," Vol. I, 1958, CONFIDETrIAL.

Bethlehem Steel Company, Shipbuilding Division, Design of Prototype

System for Shipboard Storage and Handling of Liquid Propellants for

Guided Missiles: Concentrated htydrogen Peroxide, NOas 45349, Task

Order V, CONFIDENTIAL.

Edwards, J. 0., editor, Peroxide Reaction Mechanisms, Conference,

Providence, Rhode Island, 1960, Interscience Publishers (Published

1962).

Explosives Research and Development Establishment, Waltham Abbey,

England, The Sensitiveness and Detonability of Certain FuelZO-xidant

Mixtures and Emulsions, E.R.D.E. Tech Memo 23/R/58.

Jacobson, E. 11., U.S. Army Chemical Research and Development Labora-

tories, Army Chemical Center, Maryland, "Propellant Toxicity,"

Presented at the 3rd JANAF Meeting, CONFIDENTIAL.

Levine, D. and C. Boyars, "Measurement of Ixiapact Sensitivity of

Liquid Explosives and Monopropellants," Advanced Propellant Chemistry,

Advances in Chemistry, Series No. 54, pp. 201-78, American Chemical

Society, 1965.

455

Hanufacturing Chemists' Association, Washington, D.C., "Properties

and Essential Information for Safe Handling and Use of Hydrogen

Peroxide," Chemical Safety Data Sheet, Manual Sheet SD-2), 15 pp.

(1953).

MHanufacturing Chemists' Association, Washingtor, D.C. "iydrogen

Peroxide. Properties and Recommended Practice for Packaging,

Hlandling, Transportation, Storage and Use; Supplement B," Chemical

Data Sheet S§-_1.

Meckert, Gi. W., Jr., Edwards Air Force Base, California, "Hydrogen

Peroxide; Problems and Operating Procedures at the Air Force Flight

Test Center," New lork, 1952.

Monger, J. M., It. J. Baumgartner, G. C. Hlood, and C. E. Sanborn,

"Explosive Limits of Hlydrogen Peroxide Vapor," J. Chem. Eng. Data, 2,119-124 (1964).

Poesehl, 11. and 11. Seidel, "New Testing Procedures for Determination

of Friction, Impact and Heat Sensitivity," Chem. Tech. (Berlin),

18 (9), 565--7 (1966) (Ger.).

Rocketdyne, LA Division of North American Aviation, Inc., Canoga

Park, California, "Handling of Hydrogen Peroxide," Ei~ineering

Procedures Manual, April 1963.

Rocket Propulsion Establishment, Ministry of Aviatioa, London,

England, The Effect of Some Hlalogenated Methanes on the LimiLs

of Inflammability of Oxygen-Enriched Ethane-Air Flames, R.P.E.

Tecb. Note No. 183, October 1959.

Satterfield, C. N., E. Kchat, and M. A. T. Mendes, "Ignition of

and Flames Above hiydroget Peroxide Solut ions," Co,,,bus-on. and

Flame, I, 99 (1960).

Satterfield, C. N. and T. W. Stein, "Decomposition of Hydrogen

Peroxide Vapor," Ind. Eng. Chem., 49, 1173 (1957)$ J. Phys. Chem.,

61, 537 (1957).

456

Shanley, E. S. and J. R. PerriL., "Prediction of the Explosive

Behavior of Mixtures Containing Hydrogen Peroxide," Jet Propulsion,

2 8, 382-5 (1958).


Storable Hydrogen Peroxide, Contract DA-04-20G-AMC-5b9(Z):

Final Report, May 1964-August 1965, S-13974

QIHt-l, May-July 1964, S-13928

QPR-2, August-October 1964, S-13938

QPR-3, November 1964-January 1965, S-13950

Qllt-4, February-June 1965., S-1396i

Shell Development Company, Emeryville, California, Storable

Concentrated Hydrogen Peroxide, Report No. AFRtPL-TR-66-262, Report

period: June-August 1966, Contract AFO4(6l)-11416.

Sheil Development Company, Emeryville, California, Final Report,

Thermal Stability of 90% Hydrogen Peroxide, Report No. S-13801,

Report peripd: 1 July 1958-31 December 1959, CONFIDENTIAL.

Southwest Research Institute, San Antonio, Texas, Hissile/Space

Vehicle Launch Site Fire Protection Study, WADC Technical Report

No. 59-464, June 1959.

Thiokol Chemical Corporation (Reaction Motors, Inc.), Denville,

New Jersey, Field Handling and Storage of 90 Percent lHydrogen

Peroxide, "Threshold Limit Values for 1960," Adopted at the 22nd

Annual Meeting of the American Conference of Governmental Industrial

Hygienists, Rochester, New York, April 1960.

Ul 1,, "An.e+,er Lecture Experiment in C-ombus'ionx Chew'... -"

Ang•ow. Chem., A2, 619-20 (1936).

United States Bureau of Mines, Pittsburgh, Penasylvania, Review of

Fire and Explosion Hazards of Flight Vehicle Combustibles, Progress

Reports No. I and 2, 1960.

457

United States Bureau of Mines, Pittsburgh, Pennsylvania, Review of

Fire and Explosion iHazards of Flight Vehicle Combustibles, Report

No. ASD-TR-61-278, April 1961.

United States Bureau of Mines, Pittsburgh, Pennsylvania, Review

of Fire and Explosion Hazards of Flight. Vehicle Combustibles,

Information Circular No. 8137, 80 pp. (1963).

Air Force Flight Test Center, Edwards Air Force Base, California,

Safety Procedures for Rocket Propellanta, Report No. 171t-TM-58-1,

November 1958.

General Services Adminiistration, National Archives and Records

Service, Federal Register Division, Code of Federal Regulations,

Title 4.9, Chapter 1 - Interstate Commerce Commission, Parts 71

to 90, revised 195b.

United States Department of the Air Force, General Safety Precautions -

Missile Liquid Propellants, Report No. A•TO IlC-1-6C, August 1962.

United States Department of the Army, Ordnance Safety Manual,

Report No. 0111 7-2,4.4.

United States Army Chemical Center, Medical Division, Maryland,

Health Hazards of Military Chemicals, Report No. 4, 3. February 1950.

United States Department of the Navy, Bureau of Aeronautics, Han•.book

for Field Hlandling of Concentrated Hydrogen Peroxide (over ,)2w/

H1202), NavAer Report 06-25-501, January 1957.

United States Department of the Navy, Ammunition Ashore, Vol. I,

llandlinjk, Stowing and Shipping, Report No. OP--5, revised 9 August

1957.

United States Naval Underwater Ordnance Station: Newport, Rhode

Island, Hydrogen Peroxide and Its Application to Ordnancc, 8 July

1957.

United States Naval Underwater Ordnance Station, Newport, Rhode

island, Safety of 92g Aqueous HIydrogen Peroxide Based on Its Physical

and Chemical Properties, December 1957.

4a58

The Safety Equipmnent Manual, NAVWXOS P-422, November 1900.

Victor, H., "Rockets," Rev. alumirnum, 2_4, 6•¶--74 (1Y47).

8.9 DECOMPOSIT10N

Abel, L., "Instability and Stabilization of lhydrogen Peroxide,"Z. anorg. allgem. Chem., 263, =29-32 (1950).

Aerojet-Gerieral Corporation, Sacramento, California, Advanced

Propellant Stuaged Combustion Feasibility Program, Report No.

10785-Q-l, September 1965, Contract AFO4(bll)-10785, CONFIDENTIAL.

Aerojet-General Corporation, Azusa, California, Final Report,

Developxnent of Self-Generating Propellant Pressurization System8,

Report No. 1890, AkftC-TR-6-68, Part 1, October 1900, CONFIDMNTIAL.

Aerojet-General Corporation, Sacramento, California, Performance

and PropjŽrties of N2 0 4 /Aerozine 50 Selected Metal ized Storables,

Report No. LRI 302, March 1963, CONFIDENTIAL.

Ahlert, R. C. , "Comments on Catalytic Stone Production," Unpublished

Data (ON 73-92), Rocketdyne, a Division of North American Aviatioa,

Inc., Canoga Park, California, 5 September 1956, CONFIDENTIAL.

Ahlert, A. C., "Identification of Materials That 'Poison' PMS

Catalyst Stones," Unpublished Data (I1 100-92), Rocketdyne, a

Division of North American Aviation, Inc., Canoga Park, California,

15 October 1956, COIDENTIAL.

Ahlert, I. C., "Low Pressure Evaluation of Hydrogen Peroxide,"TUn-pu-. lish 4a V - A t (M.4- ID I I N'' ID 1,-r 1

American Aviation, Inc., Canoga Park, California, March 1956.

Ahlert, R. C., "Test Tube Evaluation of 90% 11202 and .g Screen

Decomposition Catalyst," Unpublished Data (*R 56-12), B-Icketdyne,

a Division of North American Aviation, Inc., Canoga Park, California,

January 1956, CONFIXENTIAL.

'59

Ahlert, R. C. and S. E. Stephanou, "Research Support of AR-1

Engine Development," Unpublished Data (Rlt 56-40), Rocketdyne, a

Division of North American Aviation, Inc., Canoga Park, California,

August 1956, CONFIDENTIAL.

Ahbtrt, R. C. and C. A. Younts, "An Investigation of Ag Screen

Catalyst, for the NAA 75-110 Gas Generator," Unpublished Data

(OR 59-36), Rocketdyne, a Division of North American Aviaticvn, Inc.,

Canoga Park, California, October 1959, CONFIDENTIAL.

Ahlert, R. C. and C. A. 'Younts, "Low Temperature Starting Character-

istics of PMS Catalyst Stones," Unpublished Data (RN 218-92), Rocketdyne,

a Division of North American Aviation, Inc, Canoga Park, California,

September 1957 ,CONFIDENTIAL.

Anonymous, "Temperature Dependence of the Degree of Dissociation

of Water and Hydrogen Peroxide," Theor. i Eksperim. Khim.. Akad.

Nauk. U.K.R. S.S.S.R., 1 (6), 833-6 (1965).

Barclay, L. P., Air Force Rocket Propulsion Laboratory, Edwards Air

Force Base, California, "Hydrogen Peroxide Evaluation," Presented

$,at th h Liquid PropulsiLon Sy-mposium, Cleveland, Ohio, -Novewber

1966.

Bender, R. W., "Chemical Arc - Jet Rocket Feasibility Study," Proc.

Astronautical Aeron., 2, 95-120 (1963).

Bianchi, G., F. Mazza, and T. Mussini, "Catalytic Decomposition of

Acid Hydrogen Peroxide Solutions on Platinum, Iridium, Palladium

and Gold Surfaces," Report No. AFOSR-4236, reprint from Electrochimica

Acta, 1, 457-73 (1962).

Broughton, D. B., D. H. Mauke, M. E. Laing, and R. L. Wentworth,

"Activity of Metal Hydroxides as Catalysts for the Decomposition of

li 2 02 ," Unpublished Data, Massachusetts Institute of Technology,

Cambridge, Massachusetts, 28 February 1946.

Broughton, D. B., R. L. Wentworth, and H. L. Farnsworth, "Mechanismof Decomposition of llydrogen Peroxide With Cobalt Compounds,"

J. Am. Chem. Soc., 1., 2346 (1949); Anal. Chem., 19, 72 (1947).

460

IBroughton, D. D. , R. L. Wentworth, H. E. Laing, and D. M. Mauke,

"Mlecbanism of Catalytic Decomposition of 11202 Solutions With

Manganese Dioxide," J. Am. Chem. Soc., 69, 741 (1947).

Droughton, D. B., R. L. Wentwort'h, M. E. lAting, and D. H. Mauke,

"Mechanism of Catalytic Decomposition of 11202 Solutions With

Maniganese Dioxide," J. Am. Chew. Soc., 62, 744 (1947).

CLykalo, A. L. and A. G. Tabachnikov, "Calculation of the

Thermodynamic Properties of Hydrogen Peroxide, Allowing for

Dissociation, From 273 to 20000 K and 0 to 5000 Bars," Lepjofiz.

Vys. Temp., 4 (no. 6) (1966).

Pedman, A. J., Explosives Research and Development Establiehmtent,

Waltham Abbey, England, Automatic Methods of Rtecordirng Decomposition

Rates of 11ydrogen Peroxide ut Ambient Temperatures, E.R.D.E. Tech

Memo 8/M/61, 13 March 1961, CONFIDENTIAL.

Dedan, A. J., P. Flood, T. J. Lewis, D. 11. Richardh, and D. A. Salter,

"Acid-Base Properties of Hydrogen Peroxide - Water Mixtures,"

J. Chem. Soc., 1965, 3505-12 (1965).

Dedman, A. J.,T. J. Lewis, and D. 11. Richards, "Peroxy-Complexes of

Inorganic Ions in Hydrogen Peron-id-Wer ixtu.s. .... t W.

Decomposition by Tungstate Ions," J. Chem. Soc., 1963, 5020-24 (1963).

E. I. duPor'tdeNemours and Co., Inc., Wilmington, Delaware,

Stability of High Strength 11202P Quarterly Report No. 2, March 1965,

Contract AFO/,(611 )-l0216.

E. I. duPont de Nemours and Co., Inc., Wilmington, Dolaware,

Stability of Hligh Strength 11202, Quarterly Report No. 3, June 1965,

Contract AF04(611)-10216.

Edwards, J. 0., Editor, Peroxide Reaction Mechanisms 1 Conference,

Providence, Rhode Island, 1960 (Publ. 1962, Interscience Publishers).

Fiesel, 11., "Experimental Investigation of the Kindling Temperature

and the Reaction Velocity of the Hydrogen-Oxygen Mixture," Z. Physik.

Chem.__, U, 158-78 (1921).

461

Flood, P., T. J. Lewis, and D. H. Richard*, "Peroxy-Complexes of

Inioganic Ions in Hydrogen Peroxide-Water Hixtures. Part II.

Decomposition by Chromate Ions," J. Soc,, 12, 2446-55

(1963) (Explosives Research and Development Establishment Tech

Mcmo 5/R/62).

Flood, P.JT. J. Lewis, and D, H. Richards, "Peroxy-Complexes of

Inorganic Ions in Hydrogen Peroxide-Water Mixtures. Part V.

Decompositýon by Vanadate Ions," J. Chem. Soc., 1262, 5024-29

(1963) (Explosiveo Research and Development Establislhnent Tech

Mero 14/R/62).

F.M.C. Corporatikon, Princeton, New Jersey, Heterogeneous Decomposition

of Hydrogen Peroxide by Inorganic Catalysts. A Literature Survey,

Report No. AtRPlr-TR-66-136, June 1966, Contract AFOli(611)-11208.

F.M.C. Corporation, Princeton, New Jersey, Investigation of

Decomposition Catalysts for 98% Hydrogen Peroxide, Report No.

AFRPL-TR-66-66, March 1966, Contract AF04(611)-11208, CONFIDENTIAL.

F.M.C. Corporation, New York, New York, Isothermal Reaction of 90%

Hydrogep Peroxide With Silver at 20°C, Report No. Ti 213-2, September

1958, Contract NOas-56-921-d, CONFIIWNTLAL.

F.M.C. Cor.poration. lj-,f"falo, New. YorL ,.Storage of 9,U16 and 281: by

Weight Hydrogen Peroxide in Sealed Containers for Extended Periods,

Report No. SSD-TR-61-29 (Propulsion Dept. Report No. 3504-7),

November 1961.

Foner, S. N. and R. L. Hudson, "Ionization and Dissociation

of Hydrogen Peroxide by Electron Impact," J. Chem. Phys., L6,

2676-80 (1962).

Fontana, B., J., "The Heat of Reaction of the Cerous-Ceric Couple

in 0.5 Molal Perchloric Acid at 250C," in The Chemistry and Metallurgy

of Miscellaneous Materials. Thetvodynamics, NNES, Division 4, Vol.

19B, lot edition (L. L. Quill, editor), McGraw-Hill Book Co., Inc.,

New York (1950).

462

Giguere, 1'. A., Chemical Reactions in the Electrical Discharge,

U.S. Dept. of Commerce, Office of Technical Services, I'll Report

14'. 2-, 6 vpI. (1959).

Gray, P. D. , "Effects of the Space Enviroiwient on Liquid Rocket

Systems," Ch•m, Entgr, Progr. Sywp, Series, 60(52), 180-4 (196'.).

Greiner, N. R., "Flash Photolysis of 11202 Vapor in the Presence

of D 2, Ar, and 11 20," J. Chem. Phys. , A2 (1I), 99 (1966).

Hart, A. B. , "Thermal Decomposition of Hydrogen Peroxide in the

Vapor Phase," Nature, 163, 876-77 (1949).

Islein, 11. S. , G. C. Williams, and C. N. Satterfield, "Theoretical

Analyses of the Decomposition of high Strength hlydrogen Peroxide

Solutions," J. Am. Rocket Soc., March-April 1952, p. 70.

Kataen, G. A. and L. N. Rozanova, "Kinetics of the Reaction Betueen

hydrogen Peroxide and Germanium," l(him. Perekisnykh Soedin. , Akad. Nauk

S.S.S.R., Inst. Obshch. i Neorgan. Khim., 120, 63-7 (1963).

Kazanjian, A. R., "Thermal Decomposition Irate Studies of 98% 11202"s g..... LI1; ... 0. , a W, A W ,i-•; Iu RokteLdvyne U Divigion ox Nortf

American Aviation, Inc., Canoga Park, California, 19 March 1958.

Kehat, E., A. Wechuler, L. Israel, R. S. C. Young, and C. N.

Satterfield, Quarterly Periodic Status Report of the Hydrogen

Peroxide Laboratories Hassachusetts Institute of Ttchnology,

CamLridge, Massachubeits.

Levis, I'. J., Explosives Research and Development Establishment,

Waltham Abbey, Engiu4n, The Corrosion of Aluminum in Concentrated

Hydrogen Peroxide, Report No. 20/1R/60, CONFIDENTIAL; J!. Appl. Chem.,

11, 4.05 (1961).

Lewis, T. J. and D. H. Richards, "The behavior of Stannic Acid

Sole in Concentrated Hydrogen Peroxide, III. The Ageing of Stannic

Acid Sole in Water and )*ydrogen Perozide," J, Appl. Chem., 11,

443-49 (1961).

463

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of lnorgaiic IoJns in IHydrogen P'eroxide-.huter Mixtures. Purt. I.

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J_. AopI. Chew., 1_, 396-403 (1960) (Explosives Rtsearcih and Develop-

went Estaubiishment Tech Mewo 21/11/59, Part ).

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SolI in Conicentrated HIydrogen Peruoxide. 11. The Meciuanisaaa of

Stabi I izationt of' Concentrated Hydrogen Perox ide by Sodium

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CONFII)EN.LAL.

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AMC-569(Z), CONF1J1, L.

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U.S. Naval Research Laburatury, Wý%mbiugtuai, DJ.(. , 1,1t -e II ~v of1

l11a1rKlIlic Coxit~amiunuts fil thff Caa4tu ko~stjf ~'lyjjy

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Huuuachumettu, Quarterly Periodic Staitus Rteport of the 11 0

Laboratories, 3J December 1900.2

Youtits, C. A. , ~'Tevelopz..ut of NAA 75-110 Gam Geiwzrutor CuaLlYst"

Unpublished Data (RM 390ý-92), Itocketdytiev a Divisioni of North

Ainericau Aviatioin, luc. , Canoga Park, Calif ornian, 6 Augurt 1958,

C ONFI ILMN IA L.

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Unpub~lished Data (HR 58-38), lRocketdyneI, a Divisiov of North Aweinuacaz

Aviation, Inc., Cano~a Park, Califwiuia, 7 October 1958, CONYIMM1AL,

Swcuriy ClassiicitionODOCU441&T CONTROL. DATA - R&D

(I&NSo *40wiftt*4d, Ott I$*6dU 04. *&t.*,.t ad i s otod sad a dwooph on must 60 0"0w wMarvt of e..b.5 to ww. dA ia ta...I .)

F Iocketdlyne, a 1Nvinion of North American Aviativu, NAS &U

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9.lu ONIOIATON M.ON I , .~1

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of AMPiL-711-07 -1 'i'i10 A VA IL AOILITY/LIMIYATION 060TICKS

Thfis documenit is subjvct to special export controls and each tranauiittul tofourvign goverz1*Iw~jvntF 0S forvign Liatioxialm way be wade onlyN with prior aj)Jir'ovalto AIIJ'L (JU'1PII/fT INFO), Edward., Cali-forn - a 93523.

11IBJUP1Pj.9Sd9# ThEY NOTES I 1 PkPAING0 WOLTAN. ACTIVITY

Alr Force Rockvt I's-opulwuiozi Labora~toryI itvearch a-nd Ttc -uoiogy &Dv~iii"

ILEAw*rdis Air Force Biase. Culijrginia

This haudbook ii' a compilation of the dvngiueering 1ropertive and handling

charac teristics of 1propel laut-grudv hydrogen 1wroxide. The huadbook includes

data and itiforwatiou on hy-drogen jperwiide physicochemical properties, Pru

ductiozi, storability, materials compatibility, miaterialip treatmezit and

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Rocketdyne-Hydrogen Peroxide Handbook