YUCCA MOUNTAIN PROJECT

f.S. Department of EnergyOffice of Civilian Radioactive Waste Management

Update on Corrosion Testing

Presented to: .Nuclear Waste Technical Review Board

Pen. .- by:Presented by:~Gerald GordonSeniorienis'ramat o dvance du Pi o

4.-�.. -� �

..

Outline

*Expected Aqueous EnvironmentsQWaste PackageC'orrosion Modeling App'roach and

High ITemperature (• 1500C) Testing Status-Initial results from localized corrosion studies in cad2 with

and wlo NO3-*Bulk brine solutions*Thin aqueous deliquescent brine films

*Summary

* ~~~~~~YUCCA MOUNTAIN PROJCBSC PresentationsNWTRBYMGordon_09/10O/02.ppt 2

Expected AqueousEnvironments

I . - ; .; I

. ~ ~ ~ ~ ~ ~ ~ -.

A...~~~~~~~~~~~~~~.. 1

YUCCA MOUNTAIN PROJECTomwelp-wo-mll"mBSC PresentationsNWTRB_.YMGordon_09/10O/02.ppt3 3

Aqueous Environment Evolution

Temperature .and,. Relative Humidity

S~'.6',.eepage,..,... <.water:.. y.

+Entrained matter

in ventilation I !

1�I . .

Typical Dust Soluble Species.-

....,.M i I d, <<rw.'Carbo'n ,Steel'

('-tim e 'F~~~~~ plan i..* 04..

.7.L 1.4704 .00.5.02

M'.. .1~~~~4 .*4L.254

MSAS *~2..7

"I 44 "

I1

Ti G rade 7 Drip Shi el d .": I I.I

I

Pure Condensate Possible-* 'I *Dfift Dust 0TN: MO 0207EBSDUSTS.020. ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ I _ _ _ _

Was Pckagel SurfaceAqueou~s Environment( m o s t d u s--t- m'i n r s m t to m et a c ev . c e s )s.> S§Som. oi~ st, Us mineral 5scale smetaaomtlceie~zs.voo ~ s..;

o Waste package shielded from seepage while drip shieldo Surface environments expected to exist as thin, aerated

- Formed through deliquescence of solubles in deposits

intactbrine films

MWMM YUCCA MOUNTAIN PROJECT9/10/02.ppt 4BSC PresentationsNWTRB_YMGordon_0

Example Calculation Results for Evaporation of OneSample (high Ca content) Seepage Water Composition*

Preliminary EQ6 Evaporation Run Results (Notyetdocumented)

Starting Composition Taken from THC Seepage Model Calculations (CAL-EBS-PA-0000013 REV 00)

T = 1600 years, Location in Tptpll at Crown of the DriftLoa oCO2 = -4.26: Temrerature = 91.91°C9

8

7

1000000

100000

10000

1000

100Q

6

5

4

3

2

1

10

1

0.1

0.0100.8 /

Halite Precipitation

Starting CompositionTHC Model Resuts Compositon

Species (moles/L)Ca 2.75E-03Mg 3.68E-04Na 3.64E-03Cl 4.18E-03

Si02(aq) 7.46E-03HCO3 6.06E-05S04 1.84E-03K 4.19E-04

Al02 2.47E-08F 3.96E-04

HFeO2 1.11E-09Nu3 3.28E-04

pCO2 (v. frac.) 5.49E-05pH 8.25

a(w) Sylvite Precipitation

*Na+, K+, S0 4=, HCO3 not shown to increase plotclianty

0 pH drops from 8.3 to -5o Concentrated species include Cl-, Ca++ NO3-, Br- and Mg++a F level drops because of CaF2 precipitation

BSC PresentationsNWTRBYMGordon_09/10/02.pYUCCA MOUNTAIN PROJECTpt 5

Waste Package Corrosion ModelingApproach and High Temperature

Testing Status

YUCCA MOUNTAIN PROJECTBSC Presentauons_NWTRBt_YMGordon-09/10/02.ppt 6

mntegrated, Model for WP and DS

t; Material Selection ) (N Radiation )

Me(iallurgica As perturbed by temperature,

- Condition evaporation, deliquescence

Ecor-> -crt. robloga- </ -\.\-< - ~~~~~~~~~~~Effe'ctsLH~~~~~ 6"coir',eciO\

"MOMBSC PresentationsNWTRBYMGordon_09/10/02.ppt 7

Alloy 22 Localized Corrosion Susceptiblityin Relevant Environments

* Localized corrosion can occur under very oxidizingconditions in concentrated chloride solutions when

- Chloride to oxyanion molar ratio [c: (NO3- + SO4 )] >-5:1*These conditions lie outsidedthe range of potentialrepository relevant aqueous conditions measured todate for which

- Cl: 'Inhibitor' ion molar ratios < 3:1

-E corr <Ecrit

- Other potentially beneficial species (e.g. carbonate,silica/silicate) also often present

*e.g. CNWRA results in NaCI with and w/o nitrate (D.S Dunn and C.SBrossia, Corrosion 2002, Paper No. 02548, April 2002), and UVa results in 5M LiCI with and without nitrate and sulfate (B.A.Kehler et al, Corrosion2001, Paper No. 01141, March 2001)

YUCCA MOUNTAIN PROJECTBSC PresentationsNWTRB._YMGordon_09/10/02.ppt 8

Higher TemperatureAlloy 22 Measurements

*initial tests in -bulk environments-Electro'chemi-cal determination of critical potentials and

corrosion potentialsCalcium chloride and calcium nitrate solutions up to.1500C

* Initial-thin deliq'ue'sce'nt'surfa'ce fim sudies-Water che'mistry-changes and corrosion-attack that may

occur in thin films. on surfaces exposed to high, Ca contentpotential seepage waters at elevated temperatures

YUCCA MOUNTAIN PROJECTBSC PresentationsNWrRBYMGordon_09/10/02.ppt 9

Crevice Corrosion Evaluation Specimen Types

�'�( �vr I' � ________________�

2 �

r' �

�, �

,,� -�

4t'9<°'tC%'54>Wt eflonwrappewd ecer mc was.hersffiZ " : i S -A- ' Z

Multiple Crevice Assembly (MCA)"Lollipop" Specimen-

Prism Specimen

YUCCA MOUNTAIN PROJECT

B_YMGordon_09/10/02.ppt 10- : .BSC Presentations_NWTR

Benefit of Nitrate on Localized Attack in 5M CaC12 at 900C(Results documented in LLNL Scientific Notebooks)

1 ..~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ ~ ~ ~ ~ ~. Alloy 22, Wrought MA

900C, (N 2) 0.167 mV/s .5MCarC12 + 0.5M Ca(NO3) 24 2 3-2

' ' '~'N_ f~D;T% On'-ll' ._. n IMT%/ rC1fr%)I

C)

U)

.4)_1

0

a4

$:L

1 .2 -J VJ 'L S 2T V 1 ls &a, MV 3 J,- - - 5M CaCl 2

0 .8 - - - - - - - - - - - - --

Ecrit © 20_pAcm2 j0.4-________ _ __

Prism - -Specimens

0.0 -- -- -- - - - - --

-0.4 - -_ - _ _

1xlO' 2 1xlc'10 1x108 1x106 1x104

2

No Localized Attack?

5 ' ' -'C. .

i.-Ii

44-

I I1

- I . -

-?'C'

.- '. I....

- Localized Attack**Initiates at washer/metal interface and

appears to propagate due to1 xI 0.2

Current Density (A/cm2) concentrated HCI formatior+ Initial creviced results based on critical breakdown potential, Ecrit @ 20 pA/cm2 show 10:1 Cl/NO3

addition inhibits crevice corrosion in 900C CaCI 2+ Repassivation potential (more conservative) measurements with Tsujikawatechnique now underway(S.Tsiijkowa.Y. Hisamatsu: Corr.EEng.(Jpn.).29.37(1980));

I

PROJECT11

- _x I-M YUCCA MOUNTAiN FBSC PresentationsNWTRB_YMGordon_09/10/02.ppt

A* 0.1,: t..

0.0

Cyclic Polarization and E in Concentrated CaCI2(Results documented in LLNL Scientific Notebooks)

Deaerated

Corrosion Potential Alloy 22.. . .-... 9M CaCI2 : 0.9M Ca(N03 )2 (150CC)

- - - 8M CaCI 2: 0.8M Ca(N03)2 (140°C),-- Q- 9M CaCI2 (150°C)-a- 8M CaCl2 (140°0)

V(I)a,)

M-4-

G)

4-

0

10

II~

0.10

0.05

0.00

-0.05-

-0.10-

-0.15-

-0.20 -

-0.25 -,

/o. - . .. . .-

I.

,,Y Aerated SM CaCI 2

+ 0.5 M Ca(NO3 )2 @ gooc -

/

-0.2

-0.3 , - W- .4* - Q�- -o- - a-- -Q�- --Q� - O- -t-, --O - -

-0.30

-0.4-I I I 1 - I

0 2000 4000 6000Time (seconds)

8000

1x10 t' 1 xi 0,10 1X10,6 lx104

Current Density (A/cm2 )

1 x1 0,2

* For 9M CaCI2 (1 8M C1-), AE =( Ecrit - Ecorr) 190-240 mV- Similar for both Prism and MCA specimens

* Measured Ecorr values plateau @ <-50 mV SSC for both aerated and _deaerated CaC12 solutions with and without 10:1 Cl1N0 3

YUCCA MOUNTAIN PROJECTBSC PresentationsNWRBY 12

Alloy 22 Corrosion and Critical Potentials vs Temperature in ConcentratedCaCl2 Bulk Solutions with and w/o [10:1 (Cl-: NO3 )]

(Results documented in LLNL Scientific Notebooks)

|OfEcrit, (10)-C: (1)NQ (Prism Specimens)

~ Ecorr (12) .U: (1) NOI 1200 l - | -- |

-D- Er Pure CaC12

E-T -E Ec Pure CaC1 2 T1200 -

1000 -

800 -

I1OM B.P. = 1220C B.P. = 1280C B.P. = 1430C , -* CI- , \ \. B.P.= 1540C

- -- -~ - ~__ _.- _\_ A ,\. (4<1

I

- - 7.17 -- - - - -: � I . , .

1000

800

CnCn

-_4-

0

600 -- -'- 4 A -- - -- IN

I

400 -

200 -

_ ~~I L %- , L -. -

I I1- --

I

- - - -I-- -

I Im I I -

I I- - -1 - -I - - -

&Co

Co

4-J

0

10L

600

400

2.0

lOM

.'-.. :GM - 16MA CI ~ C

-I ~:18M, I . ' ', r- *, clr-

r \_ -1-.

- - - - - - - - - - -

.~ ~ ~ ~ ~ M -I - -- - - - -- -- 4 - - - -

0-

-200 -

-400 -

I

. I I 1

. I I I-(

I I I /-I I f I~

I I .1~~ I

I I I I

L-1- -S

I ',�

I

.1

I

I I

I I

- - B-- qt - -I

I II -IF-- -- a- -2 I I

I0 -111 -

- -- -:- -1 - - -

_ _ _ _ _ _ _ __I

_ , l .~~~~~~~~~~

-_a__

- - - I - -I- -

�_ __* 11111. I I

t. ..... . .. . I

30 45 60 75 90 105 .120 135 150 165 {Temperature (00)

30 45 60 75 90 105 120 135 150 165

- . : Temperature (°0)

* Increase in Ec when 10:1 ClNO3- present leads to less margin at T>-1400C* Boiling point increases to 1540C for 9M CaCI 2 (18M Cl)

BSC PresentationsNWTRB_YMGordon_09/10/02.pYUCCA MOUNTAIN PROJECTpt 13

Corrosion. in, Thin Film Aqueous Solutions

+Ca2~ ~Ni' 2 )*Ni(H,>

Cathodic reactions Typical anodic reaction02 + 2H20 + 4e-40H Ni- Ni2+ + 2e-H+ + e--*H

* In thin surface brine films, concentration changes due tolimitations on diffusion, convection and water mass can

- Increase pH at local cathodes leading to or accelerating* Precipitation of insoluble minerals, e.g. calcium hydroxide

- Decrease pH at local anodes resulting in or accelerating* Acid gas volatility at higher temperatures, e.g. HCIt

YUCCA MOUNTAIN PROJECTBSC PresentatonsNWTRBiYMGordon-09/10/02.fl t 14

Thin Filnm Aqueous Corrosion Studies at LLNL

Custom thermogravimetric analyzer- Controlled temperature and relative humidity (RH) in test

cell

- Continuous measurement of temperature, RH, and sampleweight change as a function of time -,

* Salt deposits were deposited as' aerosols from anatomizer

o Tests so far

- Alloy 22'(also Pt & glass) + CaCI 2 @ 150'C and 22.5% RH'

- Alloy 22 + CaCI 2 @ 1000C and 22.5% RH

- Alloy 22 + CaC12 + Ca(NO3) 2 @ 1500C and 22.5% RH

- Alloy 22 + CaC12 @ 1250C and 22.5% RH

YUCCA MOUNTAIN PROJECTBSC Presentations-NWrRB-YMGordon_09/10/02.ppt 15

Weight Change vs Time for CaC12 Coated Specimens(1 500C and 22.5% RH)

:D~eliquescence Results in -62% CaC02 Solution on Surface2.00

1.50

1.00

0.50

0.00

-0.50

-1.00

; I ^ t~~~~~~~~~~~~~~~~~-".'Gbss Slde .

_ w. 5 a#;'m ...................................................... , ri2s sz.................Glas......

< ?6iX ' , <1 i 9. .;~~~~~~2. i ,,, y R bw , ,, ..1iX

-/Ha~~~~~~n W n Ms~~PatnuI

-5 0 5 10 15 20 25 30 35 40 45

Time (hours) *Scatter likely due to slight differences in aerosolI_ _ .' -_ J . _ _ .__ -. _ ._ ._ . - _ - _. _. _

o Initial weight gain from deliquescence of CaCI 2 Ueposinion, arying antransfertothermo-balance

o Weight loss due to volatilization of HCI leading to increased pH, precipitationof Ca and resultant water loss

- Losses similar for Alloy 22 and controls* Within expected scatter

CaCI 2 + Alloy 22 at 1500CPre-test specimen Raman spectroscopy'

Post-test specimren.

on'selected areas.

White, Ca containing precipitates formed by deliquescencePrecipitates (analyzed only on Alloy 22) contain significant Cl

- EDS analysis indicates Ca:Cl atomic ratio ~1:1, consistent withHCI volatilization-

- Wet chemical analysis confirms A1:1 ratioe No surface degradation observed visually after deposits

removed- Highly polished sample being tested to confirm

absence of surface attack using SEM IM.-BSC PresentationsNWrRB-YMGordon_.09/10 /02.p

YUCCA MOUNTAIN PROJECTpt 17

-SummaryWaste package (WP) surface environment stronglyinfluenced by Titanium Gr 7 drip shield (DS)

Seepage waters diverted from WP while DS intact

Aqueous brines on WP will exist as thin deliquescent films

WP calculated to maintain corrosion resistance forregulatory period

Even if DS fails, recent tests in bulk and thin film brinescontinue to confirm expected WP localized corrosionmargin at temperatures approaching 1500C

o A comprehensive materials testing program iscontinuing to'LA and beyond to reduce remaininguncertainties in long-term degradation behavior

_ _ _-. _*. _YUCCA MOUNTAIN PROJECTBSC Presentations..NWTRBEYMGordon_09/10/02.ppt 18

.1

tBacsup,~~. ...

.. ......... .. .I.I... I .. .. ....

YUCCA MOUNTAIN PROJECTat 19BSC Presentations_.NVTRB-Y'MGordon_09/10/02.p

...

Potentially Relevant Alloy Compositions

Composition of Ni-Cr-Mo Alloys

UNS No. Alloy Cr Mo W Fe Co Mn Si C P S Ni OtherName

N06022 Hastelloy 20.0- 12.5- 2.5- 2.0- 2.5 0.50 0.08 0.015 0.02 0.02 Rem V: 0.35C-22 22.5 14.5 3.5 6.0 max max max max max max max

N06455 Hastelloy 14.0- 14.0- 3.0 2.0 1.0 0.08 0.015 0.04 0.03 Rem Ti: 0.70C-4 18.0 17.0 max max max max max max max max

N10276 Hastelloy 14.5- 15.0- 3.0- 4.0- 2.5 1.0 0.08 0.02 0.030 0.030 Rem V: 0.35C-276 16.5 17.0 4.5 7.0 max max max max max max max

N10002 Hastelloy 14.5- 15.0- 3.0- 4.0- 2.5 1.00 1.00 0.08 0.040 0.030 Rem V: 0.35C 16.5 17.0 4.5 7.0 max max max max max max max

N06059 Nicofer 22.0- 15.0- 1.5 0.3 0.5 0.010 0.010 0.015 0.010 Rem Al: 0.1-59 24.0 16.5 max max max max max max max 0.4

N06686 Inconel 19.0- 15.0- 3.0- 5.0 0.75 0.08 0.010 0.04 0.02 Rem686 23.0 17.0 4.4 max max max max max max

N06200 Hastelloy 22.0- 15.0- 3.0 2.0 0.50 0.08 0.010 0.025 0.010 Rem Cu: 1.3-C-2000 24.0 17.0 _ max max max max max max max 1.9

Composition of Titanium AlloysUNS No. Grade Intentional Elements Residual Elements OtherR52400 Grade 7 Pd: 0.12-0.25 C:0.03 max; Fe: 0.30 max; H: 0.015 max; N:

0.03 max; 0: 0.25 maxR52402 Grade 16 Pd: 0.04-0.08 C: 0.10 max; Fe: 0.30 max; H: 0.010 max; N: Other residuals: each 0.1

0.03 max; 0: 0.25 max max; total 0.4 maxR56403 Grade 24 Al: 5.5-6.5; V: 3.5-4.5; Pd: C: 0.10 max; Fe: 0.40 max: H: 0.015 max; N: Other residuals: each 0.1R56405 0.04-0.08 0.05 max; 0: 0.20 max max; total 0.4 maxR53400 Grade 12 Mo: 0.2-0.4; NI: 0.6-0.9 C: 0.08 max; Fe: 0.30 max; H: 0.010 max; N:

10.03 max; N: 0.020 max; 0: 0.25 max _ _ _

YUCCA MOUNTAIN PROJECTpt 20BSC Presentations.._NWTRB_..YMGordon_09/10/02.p

180

160

- 140

2 120a)

' 100

E 80Ea) 60I'.

40

20

0

Waste Package Surface Temperature and RH vs Time forTypical High and Low Temperature Operating Modes

_ 10,000 year regulatory perio-._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .9 0 .. . . . .

, - . , , High' Tempe'ratur'e' Mo'de'' 80 - . . . . CLow Temperature Mode,)~~~~~~~~~~~~~~~~M , 80 L .,' 1' 1"' 8 0r' ,C r . e ...)- ,- 16 p .-. 5oC peak temperature 6

30

) 5 1- -> 1 - , .. ........ .. ... .. .. em per turi)~ ~ ~ ~ ~~ ~~ ~~ ~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~6 .. . ... .er ... .. .. .. ................... .. ... .. ... .. ... .... .\..... . ......

-~~ ~~~ ..... ............... .. .. ov 140 . .. 0-... ... ... ..

20

) ..................... T.................... . ....................... . ., ...... . .. . ... .. T i e ( s ) 0 .1Ot 102 1~~~- 0 3 yea E0 40 0 < 0 0 0 0 0... .... .. y...a r...) ....... ... ..... ..... s

~Ik

gE

r,

1 .00

0.75

0.50

1.00

0.75

0.50

0.250.25

0.00o i i4 i l j

01 1 0o2 10 3 1 0 10 1 tI0 . 10 2

Tim e (years)

W_~~Waste emplacement/ventilation periods*OCRM "FY01 Supplemental Science and Performance Analyses, Vol. 2: Performance Analyses," TDR-MGR-PA-000001.July 2000. pp. 4F-36-37

o0 1t0'

Time (years)

106

.I. -

Path Forward on Susceptibilityof Alloy 22 to Localized Corrosion in Bulk Solutions

0 Use different ratios of C[l/N03

- Cl/NO3- = 1O. 5 and 1

0 Vary the Initial Cl- Concentration- [Cl-]=2M,10M,16M

a Vary the Microstructure

- Base Metal (Wrought Mill Annealed), Aged Base, As-Weldedand Aged Welded

* Different Surface Finish on the Specimens

- Freshly Polished, Solution Grown Oxide Films, Furnace GrownOxide Films, Laser Peened Surfaces, etc.

I Different Methods

- Cyclic-Polarization Test, Tsujikawa-Hitsamatsu Electrochemical(THE) Test, Constant Potential Test

YUCCA MOUNTAIN PROJECTBSC Presentations.NNWTRBYMGordonr09/i0/02.ppt 22

Thin Film Corrosion Path Forwarde Low RH sample holder for surface analysis

- Additional Raman spectroscopy,

X-ray diffraction

Quantification of elemental composition of deposits- Wet chemistry'

o Quantification of surface degradation- Scanning electron microscopy (SEM)

- Optical microscopy

o Effect of different salt combinations; matrix has beendeveloped --

- for example, NaCI + CaC12

-. .. -

YUCCA MOUNTAIN PROJECT-BSC Presentations_NWTRBYMGordon_09/10/02.ppt 23

Key Elements For License Application

0 Resolution of Key Technical Issues (KTI)- Container Lifetime and Source Term

- Evolution of the Near-Field Environment

o Mechanistic basis for environment evolution onwaste packages and drip shields

Mechanistic basis for amount of corrosion per unit ofdeposited salt

* Bulk aqueous solution electrochemical studies andthin aqueous film studies complement each other togain'the mechanistic bases

_ YUCCA MOUNTAIN PROJECTBSC PresentationsNWTRB._YMGordon_09/10/02.ppt 24

Electrochemical Confirmation of General CorrosionRates from Weight Loss Measurements

(D~at documented in LLNL Sdentific Notebooks)

Arrhenius Plot'Alloy 22, Wrought MA Passive Dissolution Rate Measured

8 - I X SAW (I hr-N2). Potentiostatically in 900C SAWSAW (1 week-aIr) 1.E05

0C)

V- 5-

4-

900 C -

In k, -EJ/RT + In A 300C

'0.1 u/vr © 90°C

I

0

0

.1a

C,

I.E-06

1 .E-07

For 2100 mV data:i = 1.710-5' (Titne)-0-49"7, (in A/cmCalculated rates at 100 mV:I day 0.46 um/yr1 week - 0.1495 pIm/yeI month - 0.0726 1Im/vear @ +400 mV (Ag/AgCI |

de-nerated SAW. 900C/_ 7._ .. "..- -1

I

iPN--14fm W.

.~ 3-

. I.

t I ,I I -, I I

@ +100 mV (AgIAgCI)

de-aerated SAW, 90C

1.E-08 i . . . . . 600 700 900 1 000 00ff lz|0 10000 20000 30000 40000 50000 60000 70000 80000,k9O000 100000

. . .,

.

Time (seconds)

I-J\~ La).0026 ;. 0.0028 0.003

1/T (K 1)0.0032 0.0034

Potentiostatic Polarization

Linear PolarizationTSPA currently employs corrosion rates obtained from descaled weight lossmeasurements on 2 year exposed specimens from LTCTF

+ Electrochemically measured rates consistent withrates measured by descaled weight loss NTAIN PROJ'EcTr

22MOMM&C"CU-Ma1BSC PresentationsN4WTRB_YMGordon...0/10/02.PPt ' 25

General Corrosion Rate at 900C vs Exposure Time(Based on electrochemical and weight loss measurements)

y \= .0963x Alloy 22R = 0.9685 1

Maximum measured values

o y = o0274°C Range of very limited2 ~~~~~~~~~~~~~~~~~~~initial 5 year LTCTF

Eg R2 = 0.8712 \ results for Alloy C-4

4g o 1nlvl0.1

.r0 Mean valuesi |0o .\

0.01

Lian, potentiostaticpolarization, SAW, sCW Rebak, linear MTI weight loss, LTCTF weight loss,(Data documented in LLNL polarization,SAW BSW (Data from SAWSCWSDWScientific Notebooks) (Data documented in LLNL McDermott Technologies dAocumneWiLScintfi

Scientific Notebooks) Final Report DE-AC08- (datadocumentedinLSc

0.001 O~~~~~~~~~~~~~~1RW12101, June 2002 Notebooks)0.001

0.001 0.01 0.1 1 10

Exposure Time, years* Two-year LTCTF rate distribution currently used in TSPA* Five-year exposed samples now under evaluation

- Initial results consistent with expectationsYUCCA MOUNTAIN PROJECT

BSC Prosentations.NWTRB.YMGordon-09/10/02.ppt 26

Pitting Susceptibility of Candidate WP Outer Barrier andDS Materials in Acidic NaCl Solution

Molar Ratio = oo

.. . ................ .... .... .. ....... . .......... p; ..

. .~' 44.,t..

.. -. .-.. # s~tZA+W.+ .+*.._

1 ? * :4 ... _277,'v4 ' .t= ... , S5X .. *'''',.'..'&

,~ ~ lo 825 t .t7,. ..,"..,,*'"...wt'; 4* {F

PREjtt.-VA, Chic

.1 .i, ,�i�- � -1- II -, , , , - 4 - - ,

owt� ,.I , -, - , ... - . , � . -V. I I -, -,

,-I -6: .- PA~ZI.1z

1>7�.:"" *-* -< A.�.

"I- t "

-_e__

Alloy G-3 Alloy G-30

V;� b6Ibfli1e&-1h 1011C;,'0H,,�42.7;',1 0%:"aCI.Soll"tion

* 'P

.... -7

0'��

- �t �M10JJ4UA..r*, 4..*

.- --. : .- -4 ~~~4 p ~~~~Aj wet

?

A'ASN-2 '

4fl"�. A��A��PA"11 4yA'A'St.

A4dA��AA 2 �

'A�

n�s�r W4

Alloy CA4--v. b-., z... A .. - ..

^SR & LAChoice _TiGr-1 2

.

Results from A.K. Roy et al, "Localized Corrosion Behavior of Candidate Nuclear Waste Package ContainerMaterials," Materials Performance, V. 37, 3, March 1998, p. 55

BSC Presentations-NWrRBYMGordon_09/10/02.pYUCCA MOUNTAIN PROJECT

,pt 27

Alloy 22: Exceptional Corrosion ResistanceULterature Results

Boiling Green Death Solution Potentiostatic Polarization at 500 mV, SSE11.5% H2S504+1.2% HCI+1% FeCI3+ 1% CuCI2 1 M NaCI, pH 1

Ho- . . 1.6E-06 1 -1. 1 i.

E

0U)

-0

a-

b-00.

10U

80

60

40

20

.46. 6��46 '�"666'.6''') 6466 66, 6)6',

6. 44',6. 6 '�,, 6646..' 6�< 'k6'6.��.td6,) ,#.�,A..-66 4 6' <��'6''6

†;6 6�i

- '666,.-.��. '�666'6 �466'

6666 -

6 " '6 66

'.6 646 6666 '6'�" 66 6'' 66')" '6

rU

U

U

1 .4E-06 -

1 .2E-06 -

1 .OE-06 -

8.OE-07 -

6.OE-07 -

4.OE-07 -

2.OE-07 -

O.OE+00 -

004

C..

Do

014C.

A {o

-.Alloy

UoCq

00(0

en(I)-Jto

290 310 330 350 V 3UTemperature, OK 850C

Passive current vs temperatureA.C.Lloyd et al, Stainless Steel World, 2001

170

A less resistant predecessor of Alloy 22(16.5% Cr, 17% Mo, 4.5% W, 6% Fe, <0.15% C)Alloy C exposed at Kure Beach, North Carolinasince 1941 (-50 years)

- 250 meters from oceanOriginal mirror finish still intact after salt anddebris washed from surface

- YUCCA MOUNTAIN PROJECT

BSC PresentationsNWTRBYMGordon..09/10/02.ppt 28

Localize Corrosioll Initiation:

Current versus Future iviuu'v'%

o TSPA-SR/SSPAIFEIS Model

- Process ModelBased onlpotentio dynamic data

AE .=.Ecrt Ecorr = fT, PH,

log(CI )]

- Abstraction: Model

. implemented in TSPA,-ModelAE =.Ecr E corr f[lP-lH

0 TSPA-LA Model

- Ecrit and Ecorr Modeled Separat* AIIows independent

adjustments for MIC andAging.

amV

DO

i-

K:.ely

aEmV

- fIT, pH, log(CI), log(CIl N0 3-)F

-Will incorporate inputs for most aggressive relevant cation(s)

,1 -n nnc

- jnJ

-~~ YUCCA MOUNAN PROJECT

BSC PreettoSNBYGf1fOIOO

ZIj

.Ppt

Expected In-Drift Environmental ConditionsConstiutunt J-13 Well Water 'Perched Watery PIa ore Walb I000X J-13 * -I(OX) Pore W\:ater**

(We/) (no/) (RCI1) (H10) (Jim/I

0 Aqueous solutions in contact with wastepackage and drip shield will become thinaerated brine films through

- Evaporative concentration of dilute 'seepage waters to dryness andsubsequent deliquescence and/or

- Deliquescence of hygroscopic saltsnresent in duist dennoits formed from

Na+Si(aq)Q-14K'-

4,s.802851105.042.01

V 2.18Cs 7.14NO.- &78So:- 184Pb'ASIICC; 12&9

p1 .)lar 4 tio 1;.W

pli 7.41

36.037.025.01.72.2

0.76.3401.20

147.0

0.76a&

35-1l552-432-1222-8.1-24

-_

20-185.4-3218.260

74-220

<2.79.2-&6

43iOI

2747010.1

16195S07548213209

6223221.643264U

.c5$42521)-15Y'2098

24255 c45

0-58 1.17-10.3 6-6.5

*Basic brin*Near neutr*- EO. md ff~dwrab

es (pH -8-12) from carbonate dominated J-13 or perched watersral brines (pH -6-7) from rock pore watersotba ln.Ias sernd *.nnLEm USWSD&47 ard 9) n i )I Ta 2i-; Pb "dAs M Arqb Nowell a b Iq Gls WV~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~%. .. A__ . .. _. WHI"A.-

particulates and aerosols introducedduring construction and ventilation Coiisfituent

phases N&

* While drip shield remains intact, Cs+'any aqueous films formed on waste N t+

package will result only from --deliquescence of soluble species present C-NC.c-

in dust deposits 4

IiC(:-

* In all cases ClINO.- Molar Ratio <3 'iarRti

Tllpical in-driftUust+ (mg/l)

3638260720434

14.5181418816

0.00124/0.0962

11.27

T3 pial atmosphericallydeposited species++ F

(kg/ha)

.09-.271

.53-1.47.013.092.043.254

.06.39.70-4.41.38-2.20

(. 15- 01.3.3

___ ____ __ -_- - _- _

+Preliminary in-drift data from Zell Peterman, USGS; ++Atmospherically depositedspecies from Southwestern Nevada from National Atmospheric Deposition -ProgramrNational Trends Network; Site ID NVOO, web site: http:n/nadp.sws.uiuc.eduJed1

YUCCA MOUNTAIN PROJECTBSC Presentations_N.VTRBE.YMGordon_09/10/02.ppt 30

Brine Evolution by Evaporative Concentration at Boiling Point(Simulated 100-fold J-13 Carbonate-Based Groundwater and Perched Water Starting Solution)

J-13 conce

*Boiling Poi

*pH-12250000 -: __ n15-,~ y

r- L /

kntrated -45,000-fold

int A1120C

2% NO3-, 1% S0 4 -

[Cl- /(NO - + SO4 ] = 1.90

I

0)(UI-f

a)

0aU

200000 - 200/c* ~*1 3.5% Cl-, 1

*Molar Ratio

..AU .

150000 - 150/t

. I-~ ~ ~~* ':".

100000-10%

50000 -5%_`11�

MW"Ma6U T - ~- _ n , I _ ~ _ ; -

10. 20 30 40 50 60Liters of 100-fold J-13 solution evaporated to 150mL

Ca Mg z From G. Gdowski, "Environmental Specification for Drip Shield and Waste Package," presentation to WastePackage Peer Review, Las Vegas, May 23, 2002. Data In LLNL Scientific Notebook

chloride, high nitrate basic brine formed )

-AiU

U.

70

70

'A MOUNTAIN PROJECT

HighVYUCC

BSC Presentations-NWTRB YMGordon_09/10/02.ppt 31

, I,

Principal test environments for general and: ' ocalzed -- corosion measurements

(Data from J.C. Farmer, "General and Localized Corrosion of Waste Package & Drip Shield Materials", presentation to Waste Package Materials Performance Peer Roview Panel,February 28, 2002 and from LLNL Scientific Notebooks)

*Long Term Corrosion Test Facility Other corrosion test bulk Thermo-(LTCTF) Large tank environments environments gravimetric_______ _______________________________________ _ - -Analyses

Concentration (mg/L) Water films

Ion Simulated, Simulated': Simulated Basic Simulated Pure PureDilute Concentrated 'Acidified: Saturated Saturated CaCd2 *CaCd2Water '. ,Water: , Water Water Water (with and (with and

:___________ ~'(SDW)* (SCW)*- (SAW)* (BSW) (SSW) without nitrate) without nitrate)

K 34 3,400 - 3 '3,400 81,480 141,600

Na 409 40,900 40,900, 231,224 487,000 _Mg . 1 '1 1,000 ...Ca 0.5 <1 . 1,000 1M-9M -220,000

F 14 1,400 0 1,616 ---

C ' 67 6,700 24,250. -169,204 128,000 2M -18M -390,000

NO3 64 6,400 23,000 177,168 1,313,000 0 - 2M variable

SO4 167. '16,700 38,600 16,907

HCO3 947- ' 70,000 0 107,171

Si 27 (60°C); 27 (60°C); 27 (60 0C); 9,038- 49 (90.C) 49 (90°C) 49 (90°C) . ., . _.

Molar Ratio 0.7 0.7 0.9 1.6., 0.2 1- °° 1- 00CI/NO3+SO4

pH 10.1 10.3 2.8 >12 6.7 5.8-6.4 |

Temp. °C 25-90 25-90 25-105 25-105 25-120 30-150 |< 1500c

Environments evaluated cover range of relevaconcentrated brines, pH's, Cl-/NO3- ratios and t

Tnt and accelerated hefilmsemperaturesu

YUCCA MOUNTAIN PROJECTBSC PresentationsNWTRBYMGordon_09/10/02.ppt 32