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■HP '"■■ ■ " ■
TECHNICAL REPORT
75-38-CE /
DEVELOPMENT COMPOUNDING AND [
EVALUATION Of PHOSPHAZENE RUBBER
FOR HELICOPTER SEAL APPLICATIONS
by
I Angus Wilson
D C\
AUS 8 7975
ELÜ
Clotniiig, fcquipment & Materials Engineering Laboratory
CE&MEL -136 y
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Approved for public release; distribution unlimited.
Citation of trade names in this report does not constitute an official indorsement or approval of the use of such items.
Dest-cy this» report when no longer needed. Do not return it to the originator.
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THIS DOCUMENT IS BEST QUALITY AVAILABLE. THE COPY
FURNISHED TO DTIC CONTAINED
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PAGES WHICH DO NOT
REPRODUCE LEGIBLYo
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mcuaamBL IICumTY CLASSIFICATION OP THIS PAOE (Wkm> Dm* Mfitond)
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REPORT DOCUMENTATION PAGE nüRwrMüüiir
—^M I 1. OOVT ACCESSION NO
TITLE ran« iukUUol -
Development Ccopounding fL Evaluation of ftoosphksene Rubber for Helicopter Seal Application
ot 7. ggöSL
Angus/Wilson \
-L <V AL
/:
S. PERFORMING ORGANIZATION NAME AND ADDRESS
ion I/O PKOjb
11. CONTROLLING OFFICE NAME AND ADDRESS
US Amy Materials and Mechanic» Research Center Fibers and Polymers Div. AMXMR-RF Watsrtown, Mass.
14. MONITORING AGENCY NAME • ADDRESSf" dlllotmnl Inm Controlling Olli to)
C ' - ': <-' /
READ INtTRUCTIONt P^.fO»I COMPLITWO FORM
I. RECIPIENT'S CATALOG NUMBER
S. TYRE OF REPORT 4 PERIOD COVERED
28 Feb 72 - 31 Aug 73
r PERPORUINO ORO. REPORT NUMBER
i. CONTRACT OR^ORANT NUMBlTväT
TJJ 10. PROGRAM ELEMENT. PROJECT. TASK
AREA • WORK UNIT NUMBERS
1AW-1-Y1-1735-01-AW-BQ, /
71 twyowvooTtr—
if. '4 Huwsw urwan-' 21
IS. SECURITY CLASS. (ol Ihlt rmport)
unclassified
IS«. OECLASStFICATION/DOWNGRAOINO SCHEDULE
JML 1«. DISTRIBUTION STATEMENT (ol Oil» Roporl)
Approved for public release] distribution unlimited. Citation of trade names in this report does not constitute an official indorsement or approval of the use of such items« Destroy this report when no longer needed* Do not return it to the originator,
17. DISTRIBUTION STATEMENT (ol Hi» mbitrtcl rniormd In Block 30, UjKP»tml tnai ««port;
"£ , y s 7- - ! -> V\
IS. 4UPPLEMENTARY NOTES
3 O C
i\ AuG 1975 1-
19. KEY WORDS (Cant)nu* on tont»» old» It atotucy and Identity by block mmbor) D
ff
RUBBER COMPOUNDING RDBBER COMPOUNDING ELASTOMERS mamzm POLYMERS
PHOSPHAZENE POLIHERS HELICOPTER TRANSMISSIONS HELICOPTERS TR .M3MTS.qTnNS (MRT.HaHTnS )
SEALS LOW TEMPS ATÜRE EVALUATION SYNTHETIC ADDITIVES niTRTNn 4GENTS
ABSTRACT (Conltnu» on nmM »I* It mcmv m-1 Idontltr or block number) ,- ,-' r- '- ' L
A polyphosphazene copolymer,-f tf> (IEHJCF;^- NP (OCHgCoF^CFgHLjfc.^ S** «as compounded with a variety of black and non-black relnTorcin| Tillers, curing agents and other rubber additives. Optimum properties were obtained using silicas, silane treated clays, or combinations of these, In conjunction with peroxide curing agents. Tenstte strengths of 116 Kg/cm (1650 psi) were achieved and lip seals were molded and gave evidence of potential use. The cured rubber was flexible to -5U*C and showed good resistance to temperatures up to 150*C.
DO FORM 1 JAN 71 1473 EDITION OF I NO >V«IS
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DEVELOPMENT COMPOUNDING AND EVALUATION
OF PHOSPHAZENE RUBBER FOR HELICOPTER SEAL APPLICATIONS
by
ANGUS F, WILSON
*r
11 » "■-'•Tn ,i .*US 8 i97b
SEDTTElkJ
"DISTRIBUTION STATEMENT A
Approved .'or public release^ Distribt'.üon unlimited
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FOREWORD
This report covers the results obtained from the development compounding and testing of a polyphosphazepe rubber copolymer with the structure:
-£NP (OCH2CF3)2 - NP (OCH2C3F6CF2H)2^
Objective of the work was the attainment of optimum strength, and the evaluation of physical properties and heat resistance with a view toward possible use of the material in helicopter seal applications.
The base rubber was supplied by Horizons, Inc., a contractor of the Army Materials and Mechanics Research Center (AMMRC). Work was carried out for the Organic Materials Laboratory of AMMRC under a customer order, PRON. NO. AW-l-Yl-1735-Ol-AW-BG. Funds for the project were furnished by AVSCOM under Project 1716042.
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TABLE OF CONTENTS _Pa£e_
T. Introduction 5
II. Materials 6
III. Compounding, Curing and Testing Procedures 6
IV. Results and Discussion 7
A. Preliminary Compounding 7
B. Fractionation 8
C. Heat Treatment 9
D. Solution Mixing 11
E. General Compounding 12
F. High Temperature Aging and Seal Testing 17
G. Low Temperature Properties 17
V. Summary and Conclusions 18
VI. Future Work 18
VII. References 19
Appendix A - Identification of Compounding Ingredients 20
Appendix B - Tables of Compounding Ingredients and Test Results 21
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Development Compounding of Fhosphazene Rubber for
M licopter Seal Applications
I. Introduction
Phosphazene rubber (or phosphonitrilic fluoro-elastomer) was
developed under an Army Materials and Mechanics Research Center (AMMRC),
Watertown, Massachusetts contract with Horizons, Inc., Cleveland, Ohio.
The original work was directed toward the development of a fuel and oil
resistant rubber that would remain flexible at low temperatures. Under
the program several polymers were made and one of them, a copolymer with
the st icture:
-tNP(OCH2CF3)2 - NP(0CH2C3F7)29-
underwent development compounding and testing at NLABS from 1968 to 1970.
The data obtained showed the material to be a rubber with excellent fuel
resistance, and with flexibility down to approximately -55 C, although
the physical properties were poor, i.e. tansile strength below 61.2 Kg/cm *
(870 psi). 1'2'3
In 1972 AMMRC expanded the program with Horizons, Inc. to incli''''-
the development of candidate phosphazene rubber compounds for evaluation
as seal material for helicopter transmission shafts. The polymer chosen
for this was a copolymer with the structure:
4NP(0CH2CFJ2 - NP(OCH2C3F6CF2H)2^
and the target properties sought were a Shore A durometer of 75 to 90,
minimum tensile strength of 105.5 Kg/cm (1500 psi), and minimum ultimate
elongation of 175$. After heat aging 70 hours at 150 C the allowable
maximum changes were to be +10 points durometer, -25$ tensile strength,
-30$ ultimate elongation.
As part of the helicopter seal program AMMRC transferred funds to
NLABS for development compounding to attain the target properties, and
for evaluation of the materials produced. Compounding was also carried
out by Horizons, Inc., suppliers of the polymer, and later in the pro-
gram by personnel at the Mobility Equipment Research and Development
Center at Fort Belvoir, Virginia.
♦Tensile strengths are expressed as .Kg/cm in accordance with the ASTM method used in their measurement. If desired, the data can be converted from Kg/cm 'to pascal by multiplying the given value by 9.806 x 10 .
5
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Viscosity, fnl. acetone
1.85
2.41
1.8
1.85
1.71
II. Materials
Five batches of copolyraer-fNPfOCHjCFjg - NPfOCHgC^CFgH)^
were received from April through November, 1972 and were identified
as follows:
Batch Amount, grams
17Q5-47A 246
1829-20 206
1869-34 A50
1?85-47A(2) 450
1931-07 910
The identi y and source of wJier materials used in the compounding
studies are given in the Appendix.
Tests on the raw polymer showed it to be soluble in acetone and
methyl alcohol, and insoluble in bensene and 70/30 isooctane/toluene
by volume.
III. Compounding, Curing, and Testing Procedures
Generally, batches using 5 grams of rubber were prepared.
Ingredients were weighed on an analytical balance and compounded on a
rubber mill with 25-mm (l-rn.) diameter rolls, turning at a 10/7.5
speed ratio. After mixing, the rubber compound was removed from tbe
25-mm mill and sheeted to the desired thickness on a r/6-mm (3-ln.)
mill. It was then molded and cured using a 1.9-mm (0.0?'5-in.) thick
mold of the following configuration and dimensions:
f f "\_ y^ _ 19 mm "'6.35 mm
»i
4 ^y 8^-7 ™m X *.
The use of teflon sheeting on either side of the mold cavity,
required when molding previous phosphazene rubbers was unnecessary with
this copolymer, and a light silicone spray coating was found sufficient
to provide release.
Oven post curing, where used, was done in a circulating air oven
of the type specified in ASTM Method D573-67.
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Tensile and elongation testing was done according to ASTM Method
D412-68, except that a non-standard test specimen (shaped to the mold dimensions shown above) was used.
Shore A durometer values were obtained according to ASTM Method
D-2240-68. The tensile test specimen was used for this test and values
were obtained on the tab ends of doubled specimens, backed up by
another rubber material of similar durometer to provide sufficient thickness.
Low temperature flexibility (Gehman torsional stiffness) values
were obtained according to D-1053-65.
IV. Results and Discussion
A. Preliminary Compounding
In order to compare the new iraterial with the rubber previously
evaluated, a sample of batch 1785-47-A, was compounded in a recipe which
with the previous material ha^ given a tensile strength of 61.2 Kg/cm
(870 psi) - the highest obtained. The recipe in parts by weight was as follows:
Polymer 100
Hisil 233 15
Magnesium oxide 5
Dicup 40C 4
The first three ingredients were mill mixed and bin-aged one
week at room temperature prior to milling in the Dicup 40C. The speci-
men was then press-cured 1 hour at 143 C; press-coooled; and oven--post-
cured 1 hour at 93 C, 1 hour at 104 C, 1 hour at 121°C and 16 hours at
141 C; and gave the following results:
Tensile strength 23.2 Kg/cm (330 psi)
Ult. Elongation 200$
Shore A durometer 45
The compound was repeated but without bin-aging, and the material
was mill mixed and press cured the same day, with the following results:
Tensile strength 44 Kg/cm (625 psi)
Ult. Elongation 200$
"ore A durometer 45
Although part of this higher tensile result could be attributed
to experimental difference, it appeared that bin-aging had no beneficial
effect on the tensile strength of this compound.
7
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-—jw °iw^"" ■ ' JnfiAwpptn11"!11 . .^w> Jit»iwuwii4aiaiu.wiijjiyii,..iwwiv*j*w<ww^ m *.-
Essentially the same compound was again mixed, except that 1.5
parts of steario acid was added as a lubricant, and to remedy a
tendency of the compound to stick to the small, mill rolls during
mixing. The addition, while resulting in a smoother sheet off the mill,
did little to relieve the tendency to stick, and the cured material
had many small surface bubbles. This batch also was mill mixed and
press-cured the same day, and gave these results:
Tensile strength 42.2 Kg/cm (600 psi)
Ult. Elongation 250$
Shore A durometer 46
Since the recipe used above was a basic and simple formula,
compounds were mixed eliminating various ingredients to determine
their effect on physical properties. A compound was mixed containing
only the polymer ana dicumyl peroxide as follows:
Polymer 100
Dicup UOC U
Press cured 60 min/l27°C
Oven cured, for: 1 Hr/93°C, 1 Hr/l04°C, 1 Hr/l21°C, and then
16 Hr/l41°C
This gave a tensile strength of less than 0.7 Kg/cm2(l0 psi),
comparable to that of a specimei of press-molded gum rubber.
To test the effect of magnesium oxide, the compound was again
mixed, this time with the addition of 5 parts of the oxide, and press-
cured and oven cured as before. The results this time were 2
17.6 Kg/cm (250 psi) tensile strength, and 330$ ultimate elongation.
Thus, this initial series of compounds shows that dicumyl peroxide
alone causes little, if any. effective curing of the phospliazene
copolymer. Addition of magnesium oxide to the peroxide causes a
marked improvement in the tensile strength, and the addition of a
silica filter to these two ingredients increases the tensile again^ I
by a factor of 2.5,
B. Fractionation I
To check the possibility that the tensile strength of the
rubber could be improved by removing its lower molecular i
portion, a small quantity of the raw gum was fractionated by
8
.,.,. ^ ^ . ^^ ...M-^„.^«^ m ^^^^^^^MtdomMm^min <Kmmm*amM
- -
tU'i)U MUMW^PÜI^A|L!'.WW|jg^MWIjWU.!UlB..-;i.-. ■ K miUW..A*l.," " ^—^-^-~T-~- "~: 1
coagulation from an alcohol solution: 25 grams of raw polymer were
dissolved in 200 ml. of reagent methanol, and 300 ml. of benzene was
added dropwise, with stirring, over a period of 1-fc hours. The coagulated
polymer was allowed to settle out and the liquid decanted. The polymer
was air-dried at room temperature for 18 hours, and at 05° to 88°C for
one hour. The yield was 80$, i.e. 20 grams, and the material was less
tacky, and appeared somewhat tougher, than the parent polymer. The
decanted liquid was evaporated at room temperature and the residue dried
for one hour at 93 C. This material was flowable, soft and very tacky,
with apparent low viscosity.
The coagulated rubber portion was cured according to the following recipes,
with the following results:
100
15
5
4
60/143
1/93
1/104
1/121
16/141
47.1(670)
180
45
The data, when compared with that obtained on whole polymer, compounded
in similar recipes (see above), shows no real superiority for the fractionated
material, and would indicate that the presence of low viscosity material was
not, cr at least was not alone, responsible for the low strength values
obtained on +.his copolymer.
C. Heat Treatment
The effect of heat applied during various phases of compounding was
investigated using the following recipe:
Fractionated Polymer
Hisil 233
Magnesium oxide
Dicup 40C
Press cure Min/^C
Oven cure Hrs/ C
Tensile, Kg/cm (psi)
Ult. Eleng., %
Shore A duro.
100 100
25 15
5 r
2.5 2.5
60/143 60/143
1/93 1/93
1/104 1/104
1/121 1/121
16/141 16/141
47.1(670) 40.8(580)
1.0 180
67 46
•
bamamsk^. memtM
100
5 lS
J.
··'·'l 1 !' .t ·l "\' ~::: .. .., It' I 12'°C . 16 °C d h <> '·-':· ;~.· c.1.:, •. u:: v~ "+J 1:1. :. . .t. ? an11 hours at lh3 P an gav~ t e
3ho\.'e .'4. durometnr
:3go7 Kg/,~m2 (550 psi)
280% 50
'J'lH:: :-:w:p·.··u:n•i was :t:"epea+.od and all the ingr·edients except the di.c..-umvl
}-:er·)X.7.d.c vrere. milled tcgether and oven heated for 16 hours at 100°C. It
VJ!-.' s · 1~heD. r·et1xr.·ned t.o the mill for addition of the perox:!.de and was cured
::.ts abr:.ve 9 W::.th ".:.h.;;se :r·esults~
Ul.t. FJ.u:1gat:i.or;.
56.3 Kg/cm2 (800 psi)
26Cff, Sl:.o:r·~~~ A 61.11')C·m~:te:c 51.
llhe or:'i.e;·:~1c ~l_ ~::.Jlrl})Ourld was aga.in r·epeated but no oven cm~e vms used, and
66o8 Kg/cm2
(950 psi)
200% 43
J\~:<ri,n·~Y· n'.x oi' t.h::: c::m!pom1d was rr.ade, ~LTr which all ingredients except the
:c;o:'cx~ .. :ie T.·rc·cc.; mU.:l. :nixed and oven heated for 16 hours at 100°C 9 prio.r• to
··:.'!:~"'.. ·r.::::'l.:i.n;; 9 a:r!r~[ ~trh::.cn was not cven-post,cured. gave the following:
'hns.~.I'5 sr,~·engtr.t 70.3 Kg/cm2 (1.000 psi)
;nt. :ETc:Jr'.g<:;:t:.ioCJ. 26C!fo
TJ:.L~ se:d.E:s shows that mill mixing and oven heat:L'I'lg of ingredients before
L;.''""~~- nL~.x!.~.g and ~~'.ll·:.i_r,r~ :Lmp!•oves phjs:L,~al pr(";perties 9 and that el:lrnination '
,Ji.' :Jv~m··<>::steo;·c::-·~ also :t:esults in improved properties. However, the combina-
i~.i. ·,,n r: f p>.·ehf~aling mvl ov~m c1ire elimination gave only slightly higher values
XA 1?~~ :is ar; o:r·gar~o silane (see Appendix) 9 one of a class of materials
·:>:cr:r.'ent.ly f:J.!"~din.g use :1.n rubber compounding to promote interg-;tion between
····,:1·:1-:.er :md nclrl .. l::l:J'.:k .(.U.te:~'S (5).
:1.0 BEST AVAILABLE COPY
miiuinii JJL.IIH,JH|l!ll.l.lWilUpi,»,IW|I ppppmwvyujMun WWJKP" w w»
tnan elimination of oven ,cure alone, and the difference, in fact, can be
attributed to normal test variation. The results strongly indicate that
lengthy oven-postcuring is unnecessary with the dicumyl peroxide cure
system.
There was a possibility that the heat resistance of the cured rubber
could be improved by heating the raw rubber prior to compounding, on the
hypothesis that such treatment would eliminate those portions of polymer
most heat susceptible and leave a residue of heat resistant material.
Accordingly a 15-gram sample of raw rubber was heated for 96 hours at
149°C. The materiil lost 0.5$ of its weight and became dark, trans-
parent, and flowed out flat and level. It was compounded using the
recipe given above and gave a soft putty-like mas^, which when press-
cured for 60 minutes at 143°C gave a tensile of less truin 0.? Kg/cm (<10 psi).
A second sample of i*aw rubber was mil] mixed with the Hisil ?33
(from the above recipe) and then heated for 96 hours at 149 C. This»
material lost 1% of its weight but did not darken t-*' the extent that the
raw rubber had, and did not flow, or lose its shape. Ti; was compounded
with the remaining recipe ingredients and press-cured, and gave a
tensile strength of less than 0.7 Kg/cm (.10 psi).
These mixes clearly show that the heating at 149 C in air results
in severe degradation of the base polymer, probably due to depolymerization.
Allcock, Kugel and Valan had demonstrated that methoxy, ethoxy, trifluoro-
ethoxy and phenoxy derivatives of (NPC19) suffered depolymerization below
200 C, and that solution viscosity measurements showed a viscosity de-
crease after heating 8 hours at 150 C. Further, their work showed reten-
tion of form and integrity when treated in a vacuum at 200°C, but depoly-
merization in nitrogen at 15C°C arid 200°C.
D. Solution Mixing
Jo check the efficiency of the milling procedure, especially in the
mi^ng of the filler into the ba«e rubber, a compound was made by dissolving
the rubber and then adding the filler-, as fol'.ows:
Twelve grams of polymer 17Ö5-47A were dissolved in 100 ml of methanol,
and 2.16 gms of Hisil 233 (equivalent to 18 parts per hundred parts of rubber)
were stirred into the solution. The mixture was allowed to stand for three
11
;?.;fr'^>^jrfe^^
.S....1.v;.'.'. .. ... .:,:.■... ,.....,.-„■,lJJAiii~>i2»J
!'' ,;:· r:.. l'ht~ ;n..:l::hmwl wns alluwed to evaporate away at:. room temper-'':I -•' f: • · .• '· dny·.. Tt10 po:i;ymer/f.iller residue was dried for 2 hours at 00°0,
, j ·:': -'·"-~ \f. 1:·•"> r:ng,le:r:.'.;l:: cuc~d~l and d:!.c:Jmyl perox.idl'"::p and press and oven
72.1 Kg/r:i (102) psi)
:na,t 36
'f!tese reSLlU.s v1ere ~orr::parable t.o the results obtained on mill mixed stoci<e
cU_s,.•lElned :l.n the pr:~v:Lous sectJ..on and showed rrd.:x.tng on the 1" mill to be an
Eo Cir:nm·al Ccmp(lU:Y!ding
·• b.r.t khes t)f po.lymur s ( 1785-h 7 A a.n<l 1829-20) were used t,o make a
series c.f , .potmds i.n wh:lt;":h both rubbers were formulAted in the same recipes I
T'b.~.s, :)_n effe,-:;t ~ gave a dupl:Lcat.e test of the indiYidiml recipes md provided
ar: oppc·-::-·':·'J.!').:L-t.;y- to observe ar.y t:::-end toward a <iLfference in t,he properties of
t.h':J +.~,.;o base :rubbers. 'l'he compounds forrrmlated and the results obtained,
1isLc:d ·in TabJ.e I, sho\-: that :ln most instances there was no significant
di.f:'er~:r:c:e bet·..,een the two mtz~hes of pol.ymer. '!'he sole exception was the
~n5r· L,'?··.A-··10 and 20···10 n·ade with filler of silica and carbon black, with
•.irLL: h the 1.82Q--:20 J.-'oJ.ymer· gave a tensile strength of 70 Kg/cm2 (995 psi),
··>rr!J.:cl!'ed tc) ;_;.. Kg/cm2 (200 psi) for 'the 1785 ~ 47A polymer.
D::11:-bJ.e bat-::hes of these two compounds were prepared, split in half,
.':rd p!'".'3S·-(:t:.red. One specimen of each was uven-postcured and the other was
':r::·l_,, Co'T'pound :i.829-·20 gave a tensile of 67 Kg/cm2 (955 p.,.:..) with oven cure
:.m: 56 I<g/em2 (?95 psi) •rtithuLi+;;- 17S5..:47A gave h6 Kg/cm2 (655 p~i) with oven
c~.1rc; E~nd 39 Kg/cm2 (555 psi) without." Although the 11329-:-20 polymer again
t~r:.ve the h::.ghe::.· st:r·ength results~ the difference .was not as gl;'P'i.t as with
l~h,.:: ::~·ev-icms rrd.x. Another m:i.x of' the compounds was prepared, this time with
J'esu.l~>s ~·f 67 and ~ Kg/cm2 (955 and 355 psi) respectively. The two compounds
wer•e the-~ m;bced w:l ... :.h a 9a ~ ·-bis( t-butyl peroxy) diisopropylben.e (Vulcup 40KE) . 2
subs~.:Li.,,c::;~::(l J.'or the d.:i.curnyl peroxi.de w' .. t.h similar results of 65 and 17 Kg/em
(~~25 and 21-+5 ps~.). 'I'hus the results show tht tensile values obtained with
polyrre~· 1829-~20 to be ~onsistent 9 while those with polymer 17S5-47A to be
er:ri1"LJJ;: :l.ndicat::Lng u se:n.s:"Ltivity of this material to the silica/carbon black
:'iller in ccnjur'.cl;i•:m ~r.i:Lh peroxl.de cures. The basic reason for this is not
.J.prc~.re!'lt.j,')
12
ii .jii. ii^ t * n M .Wn» !■!■ •- i^|i|i.ip» ^m ■ i ™
«
Otherwise, a review of the results contained in Table I (see Appendix B)
shows that the highest strength values were obtained with the silica filler,
dicumyl peroxide cure (54.8 Kg/cm ) (780 psi) and with a HAF black filler, 2
dicumyl peroxide cure (59 Kg/cm ) (840 psi), values still short of the target
value of 105 Kg/cm2 (1495 psi).
The use of phenol-formaldehyde resins (Amberol and Durez) in conjunction
with either peroxide or amine cures gave poor teni.dle properties. Likewise,
the use of the Diaks, developed for curing fluoroelastomers, resulted in
complete degradation of polymer strength properties. This could have been
due either to the effect of materials themselves, the higher temperatures
required for their activation, or a combination of these factors.
In order to conserve polymer, since the amounts .available were relatively
small, the practice of making a group of compound's from two different batches
of polymer was discontinued. Instead a series of compounds was made to
evaluate the effects of various curing agents, fillers, coupling agents, and
other additives. The recipes used and the physical properties obtained are
given in Table II.
Analysis of the data allows several conclusions to be drawn.
The use of a base, such as TETA or 2,6-diaminopyridine in conjunction
with dicumyl peroxide (47-A-12, 57-A-16, 34-K) resulted in tensile reductions
of up to 50??..
A silica/HAF black filler combination (47-A-17) gave mediocre physical
properties.
The blending of polyphosphazene polymer with ethylene propylene ^iene
rubber (20-11, 20-12) gave tensile properties inferior to those of straight
polypho spha z ene.
The use of dibasic lead phosphite (Dyphos) in a silica filled and
dicumyl peroxide cured stock (20-13, 20-14) slightly improved tensile
properties.
A grojp of compounds made to investigate dicumyl peroxide levels and cure
times (34~A thru 34-H) showed that 2 party of Dicup 40C gave tensile
properties tsquivaxent to, or slightly higher than, those obtained with 4
parts, and that better properties were attained without oven postcure than
with it. This is in agreement with results contained in Table I, pre-
viously discussed»
13
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^'■i.i^tnwi'fl'-'-'Vrr'"fifg"r{ . mm*;,'"JI*iMrtT'ia'(ft&&Tfr-:/~iS
' 1:
T
· ~··l -:~~>- ·:.· ·-- f't;·:: .. >t:'.:l(• 1f:<'0is :!.n t).mjtmd;i:m with tho use <Jf dibll6ic
J., '· : >.<::JJ)~;l.Lc;;. >: ,_~o:r!•otu:ds subjected ·t:.o O'<!en hM.t:tng prior- to peroxide
:.>:':.'.:.~:~: ()1.;.-:: .. }'.~~Tr :34-J: Rpt and :,:3.!,.-.J Rpt) showt~d no difi'eronce between
•· : •• r.:). n ,f' ~!:~.-.:,~p l/lGr o.~1d :l'~ -!:.F.c.r;~,J.e 1\np:-:·:;·v·l!l!':':~r .. t resulting from
.:·, .. ·~~ _.,,,1·,~,\i. ·:.1.:~::,. 1· ::·,.; "·:r:~? tJ.1e d:\bas:L·:;; 1.e&.d phcsphi te, eold commer•cia~ly
>:·1• '!:ifl:~' .. ':·'~ (3\ .. J.) gave ~l ve!."/ low t.e:ns::..le.
C·'!::l ·~''-'-~::.i:'.:>::; w"-~·1:.L a h::_gh level of sj_l:'Lca ( )() pn..:::•i:.s) witli a.nd without
~.b:· c···:>.gr.:::·.,':, Ct'J0ri'J:Lr:_~(: ~)() (3h--Mp 3h·-N) gHYe a stiff material incapable of
v,~:l:.~·.:r !,OJ.ffi (~c1 .o.-~a 0 b1.s( t--b1~t.yl peroxy) d1.:l.sopropyibenzenf3 on clay)
:Lr~ ··:c::.•.j~;_r,d,ion v,.D .. ~.:.h va::•:;;dr.\g a.mucJ:~ts of silica. (34...0D 34.··P 9 34-Q) gave 2
-:.e::.\s:iJ .. cs u:~·· to 9lo4. ~.hm (1300 ps:t) ~ but :l.n the presence of 2,6-diarrd.no-
:pyr·:~..-.n.rw (.':31.;··::1.) gave poo::o res1~lts, 'I'he use of a. (:oagent 0 Chemlink 30,
',•(.') ·:,;.:; Vr:~0·n:-J ( 'JL: .. ,S) '~.:l.d :~ot :i.mprove the strengtho
'j_';te ·~·:se c).~·· ~>. c ~-as f111.~:>:· 0 sueh as Bu.'i."gess OPE (3/+-T through 34-W)
::·;.:; :.~,_·t~: ·t-,G·) :]~~:. pr'·;~ .. ' .;..,,:, !r~ed.:1.()C:r."e ":;"'l!"e s.. The 1.1se of a silane trea't,ed clay,
Bur:,se~'s .i<_E:, .--~::.'~-t·.~~ :(~· :l.n. ::.c·mbinat.i-;m w:it.h a s:l.l:J.ca (34-AN, 34-AO) showed 2 s;:~'~:3:·.:l.r·lj~.s.~~ ~-'':~_,::--:..-:;•::rr.r.-.r-:·1~, 56 to 74 Kg/em (800 ta 1055 psi) compared to
')
~.:: ~~:J ~-:;. 'iSi!)r:::t (21.5 t.o 625 ps:i.).
A ss:--·~_es (;£' <:.r)\!!fKit::.nds using a va.r~e-c.y of clay, black and silica
fl ~--l-'.' ~~ .s {:1!,.·-X ~ ,3!~-1' ~ 34-Z P 3~.--AA through 34-AP P 34--AT through 34-AZ v and
Jij--m, t.!':,:c·rngh :3L:-·BH) ~ ir. c:Jmbj_nation ~Lth Vulcup curiP..g agent ranged i..'l
·~~,·::.s:U.e s:.':e:.~gth . .f:r.c\m. ;21 :to .116 "$g./em (300 to 1650 psi). Those meeting
sr.8 t·.r,:..·gs~; 1~e':ls:U .. e v.:- 105o 5 ~/cm2 (1500 psi) we:re compou."l.ds using a
t.rea.'l:.ed clay ( 31.;.-AC), a. silane
~_:..··e;J. 1>-'J ~;U_i';e. 3h·-ABv ~m~ combir.atJ.ons of silane tr~at.ed clay and silane
t:::·G~,.·;-.~~d s:~h~::t. (3L.--Air 34-A,J? 3~~-AK)o .In all of' the batches additional
s:~ .. Jane 1N';)s .~idd~~d t(\ the i'illers prio:t· to m:tlJ.:l.ngo '!'he highest tensile
si;:rc·!".f?th b.c:h:Le-v<"d was :!.n compound "34-AI w.i:l::.h a value. of 116ott Kg/cm2
(li))O pcd) 9 ev:i.d(~ntly ber.~ause of •':,he eomb:i.nation of clay, silica, and
•
wu*m ummm^m^mmgf^m'f^m'W'iVf^if-' W '■ [l - 'I'jpfPPl^iPlg^wy^PfW ■ .V. «ULMPII»»«
:-
Three additional peroxides; 2,5-dimethyl-2,5-bis(t-butyl peroxy)
hexane; 2-5-dimethyl-2,5-bis(t-butyl peroxy) hexyne-3; and di-t-butyl
peroxide (34-AQ, 34-AR, 34-AS) all failed to achieve the tensile strength
achieved with the Vulcup 40KE.
Two additional batches of raw rubber evaluated in Vulcup cured stocks
using silica/clay filler combinations (07-A, 07-B, 47-A through 47-D) gave
slightly lower tensile values than those obtained with the previously
evaluated rubber (34-AI), i.e. 98.4 and 102.0 Kg/cm2 (1400 & 1450 psi) 0
compared with 116 Kg/cm (lo50 psi).
A series of compounds containing varying amounts of silane coupling
agents in conjunction with a fumed silica filler (Aerosil 200) and cured
with Vulcup (47-£ through 47-V) showed no advantage over the base compound
made without silane (47-F). Of the four silanes used: A151, vinyl-
triethoxy silane; Al71, vinyltrimethoxy silane; A172, vinyl-tris
(beta-methoxyethoxy) silane; and A1100, gamma-aminopropyltriethoxy silane;
2 parts of Al100 gave the highest tensile value, 91.4 Kg/cm (1300 psi);
but this also was attained with no silane and the results indicate that no
beneficial effect is obtained from addition of silane to this filler, in
this polymer.
Use of alumina filler or alumina/silica blends (47-Alon, 47-Alonsil A,
47~Alonsil B) gave mediocre strength values, 81 Kg/cm (1150 psi) or less.
The use of hydrophillic precipitated silicas (47-W through 47-AB), or
naturally occurring amorphous silicas (47-AE through 47-AH) resulted in low
strength values.
As previously discussed the highest tensile achieved in the Table II
compounds was 116 Kg/cm' (165O psi). However, Horizons, Inc., producers
of the various batches of polymer had achieved tensile values in the 140 2 ?
Kg/cm (2000 psi) range, and with one compound had obtained 150.8 Kg/cm
(2145 psi). In order to evaluate the consistency of properties between
different batches of raw rubber, Horizons' recipe was used with polymer
1785-47A (47-AC and 47-AD). Samples of the individual compounding ingred-
ients were obtained from Horizons and used to mix the compound and, except
for the peroxide, were either oven dried, milled together and bin aged; or
vacuum oven dried, milled together and bin aged prior to peroxide addition
and cure— the latter procedure being one followed by Horizons. The high- p
est tensile obtained was 80.9 Kg/cm (1150 psi). A s^Tiilar series prepared
15
.■i,,.,,^,,.,, &S8&aaäsaaaai^i^^
™i!9Pi"«'f^r'; 'WP^^I ^ipippilipp^ *.- . ■«■
using Vulcup 40KE,. instead of the Luperox 500 40KE provided by Horizonsr gave
a high tensile of 91,4 Kg/cm (1300 psi). The difference of 70 Kg/cm (lOOO
psi) between Horizons' and our compounding of the same recipe is strong indica-
tion of either basic strength differences in various batches of the polymer
or strong sensitivity of the polymer to differences in compound mixing
procedures.
The effects of various heat stabilizers- Ifyphos (dibasic lead phosphite),
Dythal XL (dibasic lead phtalate), and Leadstar (normal lead stearate) -
in prevention of deterioration during cure were investigated in compounds
47XX0 through 47XX3 and 47ZZ0 through 47ZZ3. Dyphos slightly improved the
tensile strength, Etythal XL slightly decreased itf and Leadstar resulted
in approximately a 50% reduction. One part of SRF bl'ack was also evaluated
(47XX4 and 47ZZ4) because work by J. A. Williams showed that a small amount
of black acts as a heat stabilizer in silicone rubber» In these poly-
phosphazene rubbers, however, it had l^ctle effect.
In Table III are shown results obtained on a series of compounds majs
with polymer batch No. 1931-07. These include various black and non-black
fillers, blends with another polymer, and the use of various compounding
additives - all compounds being cured with Vulcup 40KE. The series again
clearly demonstrates that little tensile strength can be developed without
a reinforcing filler, and that the best tensile values could be achieved
using the fumed silica or a silica/silane-treated-clay combination,, The
highest value obtained was 98*4 Kg/cm (J.400 psi), using such a combination.
The results clearly demonstrated that carbon black fillers generally gavp
very poor results and in many cases prevented curing* The best tp-'i^e
obtained with a black was 63-3 Kg/cm (900 psi), and this was in a compound
using a blend of polyphosphazene rubber and EPDM rubber (02-G). Blending
of the two rubbers resulted in low tensile values, the above value being
the highe t obtained.
The series also showed that a satisfactory cure could be obtained by
substituting zinc oxide for magnesium oxide, and that the use of ultra-
fine talc particles as a filler produced stocks with moderate tensile
strength; i.e. approximately 49 Kg/cm (700 psi).
16
MMwaiffi^^
'i.JVM.'u^JiwtatjiMiiJi^
*- ■•
F. High Temperature Aging and Seal Testing
In order to evaluate the ability of the polyphosphazene rubber
to meet the target requirements for resistance to heat aging, compound
34-AC (Table II) was mixed, press cured 20 minutes at l60uC and oven
cured 18 hours at 100 C. Physical properties were measured before and
after aging 70 hours at 149 C, with the following results:
Original Aged Change Target Change
Tensile, Kg/cm* 112.5 91.'. -1995 -25$ Max. Elong., % to 75 - 6$ -30$ Max.
Shore A, Duro. Points 85 88 + 3 +10 Max.
The tests showed good retention of properties, under these aging
conditions, and as a result a 50-gram batch of the compound was milled
without peroxide for fabrication into test seals. A small portion of
the compound was sampled at NLABS, milled with the peroxide curing agent,
cured and tested, with these results:
Tensile: 112.5 Kg/cm2 (l600 psi)
Elongation: 90$
Shore A: 79
The remainder of the compound and curing agent was sent to
Federal-Mogul, Inc. a contractor engaged in testing prototype helicopter
seal materials supplied by Horizons, Inc. The curative was milled into
the compound and seals were fabricated by Federal-Mogul for evaluation
on their test equipment. g
As reported by Federal-Mogul , the test conditions were:
MIL-L-7808F, 230°F, 5500 RPM, 20 hours on, 4 off, test to be terminated
when measurable leakage (of the lubricant) occurred; with these results:
Seal 1: dry at 18.0 hours, leaked 16 grams after 42 hours.
Seal 2: dry at 17.5 hours, leaked 5.9 grams after 89.5 hours.
These values were intermediate between those obtained by
Federal-Mogul on other polyphosphazene compounds.
G. Low Temperature Properties
A compound containing 15 parts of silica, 5 parts of magnesium oxide,
and 4 parts of Dicup 40C fwhich, when press and oven cured, gave a tensile
strength of 23.2 Kg/cm and a Shore durometer value of 45) was tested for low
17
4ifttolffifcffi.irf fi» ".i nitV^tinani'ftirt i ' , ■»- -ii-f
mil** «U,..#'H.M .j^iuiMiuii^qpp^iRPia^^m^^^pnupp^apiii i II iiii *j n "
temperature stiffness according to AST* Method D 1053-65, with the follow- ing results:
T2 -47.5°C
T5 -54.5
-57.5
-66. ü
l10 r 100
V. Summary and Conclusions
The copolymer, -£NP (0GH2CF )2 - NP (0CH2C,F6CF2H)2^c is curable
with various peroxides, and the best results were obtained with dicumyl
peroxide (3?« 5 - 41.5% active supported calcium carbonate) and a
a-a*-bis(t~butyl peroxy) diisopropylbenzene (39»5 - 41.5$ active
supported on silane treated clay).
The best reinforcing fillers for the copolymer were precipitated and
fumed silicas, silane treated clays and combinations of these. Carbon
blacks in general gave poor result? and in some cases interfered with peroxide cures.
The cured rubber exhibited good aging resistance and low temperature
flexibility down to -5A C,
The target properties were exceeded, and tensile strengths of
116 Kg/cm (165O psi) were achieved, and with the use of proper heet
stabilizers higher strengths might be obtained.
VI. Future Work
Work will continue at NLABS on compounding of these and other
polyphosphazene rubbers, under an AMMRC customer order. Emphasis will be
placed on achieving optimum physical properties and en developing compounds
suitable for specific fabrication techniques, including dipping and coating»
18
fr
ÜMM MNNMMVNV
fe*fc^riÄi^^.:^4J^4^^^.i>^^ri.i ±xi;'^tä3MJäf''•''&
iMwm -^^mwiw* ."■-«^■v'iw.-o-.t»!»-^!»" s^ipuu«««^«»». iu»i»™™jiiimi ! ! i | > _.IJJI.W-...-^M--»P-» J.M..UI. *-uW ■.•»■«P"»'
VII. References
(1) Wilson, 1. Initial Compounding Studie3 of Polyphosphazene Rubber.
TR 70-lO-CE, (C4FLSEL-68) US Amy l.'atick Labs., August 1969.
(2) Wilson, A. Polyphosphazene Rubber. Horizons. Inc.. No. 1436-16,
1436-19, and 1438-Q5. Memo Report, US Army Natick Labs., November 1969.
(3) Wilson, A. Polyphosphazene Rubber; Horizons: Inc., No. 1487-12.
Memo Report, US Army Natick Labs., April 1970.
(4) Reynard, R. A.,*Sicka, R. W., Vicic, J. C«, Rose, S. H., Develop-
ment of Thermally Stable PolyCFluoroalkoxyphosphazene) for the UH-1
Helicopter, Final Report - Contract DAAG. 46-72-C-O073, September 1973
(5) Ziemianski, L. P., Pagano, C. A. and Ranney, M. W. Silanes in
Elastomers? New Route to High Performance Pigmented Products. Rubber World,
October 1970.
(6) Allcock, H. R., Kugel, R. L., Valan, K. J. Phosphonitrilic
Compounds. VT. High Molecular Weight Poly(alkoxy and aryloxyphosphazenes).
Inorganic Chemistry, Pg 1709-1715f Vol. 5, No., 10, October 1966.
(7) Williams, dohn A. Carbon Black as a Heat Stablizer in Silicone
Rubber Vulcanizates. SWERR-TR-72-28, Weapons Laboratory at Rock Island,
US Army Weapons Command, April 19172.
(8) Inter-Office Memorandum, R. Hinderer to J. Born, Federal-Mogul,
May 24, 1973.
19
üa&t&MiäMaaemMm,. :,. . ..- . . . . J
mi.i.it »HpagiiLiiLJijjs ^W!||ISJ<p»J'«.W«W#^pwi!W."Wi^«Wl.,'!PiBiPliwi"
■fatsrial
Aerosii 200 Aeroail 300 Aerosii R972
Agerits Resin D
Ai or. Amberol ST-137X 3'j.rgess KE ßurgess OPE Cebbowax 4000 Chemlink 30 Diak 5 Dxak 6
Dicup <*0C
Durea 1268? Djiphcs Dythal SL Elastomag 170 Hisil 233 1msil A10 Imsil A15 Leadstar Luperco 101 XL
Lupercc 130 XL
Maglite D Mistron Vapcr
Nerdei 104C Nulok 321 SP QUS0 F22 QUC0 G32 QUSO HU0 QUS0 WR82 Fcyalene 400 Silane A151 Sllane A171 Silar.e A172 Silane A1100 Silanox 101 Silene EF Vulcup 40KE
Appendix A Identification or Compounding Ingrsdlsnts
Composition Source
Hydrwphiillic fumed silica Hydriphillic fumed silica Fu.med silica treated with
dimsthyldichloro silane Fc j yvee i> iaed 1,2-dlhydro-2, 2, H
triiiethylquinoline Famed Alumina Phenol-formaldehyde resin Silane treated aluminum silicate Aluminum silicate Pclyethyiene-glycol Tnmethyloi Propane Trimethacrylate Treated hydroquinone Proprietary^ fiuorocarben curing
agent H0% Qicunyl peroxide on calcium
carbonate Pher.ei-fcrmaldshyde resin Dibasic lead phosphite Dibasic lead phthalate Magnesium oxide Precipitated hydrated silica Amorphous silica Amorphous silica Normal lead stearate 2, ~--Dinethyi-2,5-bis(t-butyI peroxy)
nexane 2,5-dimethyl-2,K-bis(t-butyi peroxy)
hexyne-3 Magnesium oxide Magnesium silicate
Ethyi^ns-propyiene-diene terpolymer Silane treated aluminum silicate Precipitated silica Precipitated silica Precipitated silica Precipitated silica Ethylene-prcpylene-diene terpolymer Vinyltriethoxy silane VinyItrime•hoxy s ilane Vinyl silane
Gamma- aminopropyItriethoxy silane Fumed silica Frscipitated hydrated calcium silicate 40% a-a 'bis(t-butyl peroxy) di-
isopropylbenzene on Burgess KE clay
Degussa, Inc. Degussa, Inc. Degussa, Inc.
F. T. Vanderbilt Co., Inc.
Cabot Corporation Rohm S Haas Co. Burgeas Pigment Co, Burgess Pigment Co Union Carbide, Corp. Ware Chemical Corp. E„I„ duPont daNemours 6 Co. E.I. duPont deNemours £ Co.
Hercules, Inc.
Hooker Chemical Corp. National Lead Co. National Lead Co. Morton Chemical Co, PPG Industries Illinois Minerals Co. Illinois Minerals Co. National Lead Co. Penwalt, Lucidol Div.
Penwalt, Lucidol Div.
Merck & Co.., Inc. Cyprus Mines, United
Sierra Div. E.I, duPont deNemous 6 Co. J.M, Huber Corp Philadelphia Quartz Co. Philadelphia Quartz Co. Philadelphia Quartz Co. Philadelphia Quartz Co. Unircyal Chemical Div. Union Carbide Corp. Union Carbide Corp Union Carbide Corp. Union Carbide Com. Cabot Corp, PPG Inudstriess Inc. Hercules, Inc.
;"■':',»
j'T'j|"3l"Wtfh'l'il"trfT .
20
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yet,.„mmm^fM,! ■ LUJLUUIU,,! L JjUlilU^^PP f... JliyjLUJLUWI IIIIIIMIIHWJIJIJL
■
Appendix 1
Tables of COBpoundini Ingredient» and Teat Results
Table I Duplicate Compounds of Base Polymers 1785-47A and 1829-20.
Table II Compounds of Base Polymers 1785-47A, 1829-20, and 1869-34.
Table III Compoun of Base Polymer 1931-07.
21
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