TEML STABILITY OF M-09 CHEMICAL REACTIVITY TESTING

A. C. Tetert .

QUALITY DIVISION

SEPTEMBER 1971 FINAL REPORT

Normal Process Development Endeavor No. 222

2 GQm?llBURON Of THIS DOCUMENT IS UNLIM

P. 0. BOX 647 rhIARI110, TEXAS 79105

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u. 5.

operated for the

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I .

' ,

THERMAL STABILITY OF LY-99 CHEMICAL REACTIVITY TESTING

A. C. T e t u

QUALITY DIVISION

The purpose of t h i s p r o j e c t w a s t o eva lua te t h e thermal s t a b i l i t y of LX-09.

F i n a l Report September 1971

Endeavor No. 222 A c c t . NO. 22-2-34-14-402

Section W

THERMAL STABILITY OF u-09 CHEMICAL REACTIVITY TESTING

ABSTRACT

Several CRT tes ts were performed with LX-09 using sample conta iners obtained from LLL. These containers were used t o help el iminate d i f f e rences t h a t w e r e in - herent i n t h e design of t h e various sample containers used by t h e d i f f e r e n t l abora to r i e s . I n i t i a l experiments showed poor agreement i n test data between LLL and Pantex containers u n t i l Pantex containers w e r e f i t t e d with d i f f e r e n t valves. Later experiments show no s ign i f i can t d i f fe rences i n t e s t data between t h e two types of conta iners a f t e r t h e modification. Fil lers of s t a i n l e s s steel (used i n LLL containers) and of g l a s s (used i n Pantex containers) w e r e interchanged with- ou t any s i g n i f i c a n t d i f fe rences i n r e s u l t s . Resul ts of tes ts with PBX 9404 and with LX-04-1 are included.

I NT RO DU CT ION

The o r i g i n a l purpose of t h i s pro jec t w a s t o evaluate the thermal s t a b i l i t y of LX-09. Information on thermal s t a b i l i t y has been obtained a t LLL and these e f f o r t s have been d i rec ted toward obtaining uniform r e s u l t s of chemical r e a c t i v i t y t e s t i n g (CRT) between LLL and Pantex. Previously, CRT t e s t i n g between these l abora to r i e s has not been as uniform as desired. In some ins tances spec i f i ca t ions of CRT requirements had t o be spread somewhat i n order t o encompass the spread i n r e s u l t s obtained from these labora tor ies . LLE requested t h a t Pantex inves t iga t e CRT t e s t i n g p a r t i c u l a r l y w i t h LX-09 and make recommendations t o ensure t h e best possible agreement between t h e labora tor ies .

EXPERIMENTAL

The experiments w e r e run under standard procedures out l ined i n RM 251080 using sub-ambient temperature programming and a Poropak Q Column 10 f e e t x 1/4 inch. A br i e f o u t l i n e of t h i s procedure is as follows:

One q u a r t e r gram o f HE i s weighed i n t o a g l a s s or s t a i n l e s s steel c a p s u l e and inserted i n t o the sample c o n t a i n e r . A f i l l e r of g l a s s r o d or s t a i n - less steel r o d i s added t o r e d u c e the dead s p a c e volume inside the sample c o n t a i n e r . The a i r i s then removed b y e v a c u a t i n g , f o l l o w e d b y a h e l i u m purge t h r o u g h the c o n t a i n e r f o r a f e w m i n u t e s before f i n a l s e a l i n g under abou t 30 p s i g h e l i u m p r e s s u r e .

T h e sample c o n t a i n e r i s then p a r t i a l l y immersed i n a t e m p e r a t u r e b a t h main- t a i n e d a t 120 C f o r 22 h o u r s . The sample c o n t a i n e r i s immersed to w e l l above the sample c a p s u l e a r e a .

When the h e a t i n g p e r i o d ends, the c o n t a i n e r i s removed from the b a t h and p l a c e d on a s p e c i a l chromatograph inlet s y s t e m des igned for th i s p u r p o s e . A i r i s evacua ted f r o m the i n l e t s y s t e m and the sample i s i n t r o d u c e d a s a l oop i n the h e l i u m gas stream used a s a c a r r i e r gas for the chromotograph.

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The chromatograph oven is p r e v i o u s l y cooled t o -90 C , u s i n g l i q u i d n i t r o g e n ' a s a c o o l a n t . The oven h e a t i s programmed a t 20 d e g r e e s / m i n u t e to 200 c d u r i n g the a n a l y s i s . The peak a r e a s were measured u s i n g a Da tex d i g i t a l i n t e g r a t o r . r e s p o n s e b y the i n t r o d u c t i o n of known amounts of r e s p e c t i v e h i g h p u r i t y g a s e s .

C a l i b r a t i o n was accompl i shed b y c h e c k i n g the chromatograph ic

RESULTS AND DISCUSSIONS

Table I i s a summary of r e s u l t s from t e s t i n g of LX-09 using LLL sample conta iners . These da ta , co l l ec t ed over a per iod of severa l months, were considered good.

Table I1 shows da ta obtained from regular Pantex conta iners and i n d i c a t e s high ni t rogen, oxygen content , and considerable f luc tua t ions of o t h e r values. This w a s apparently caused by trapped a i r i n t h e t e f l o n sea led diaphragm valves being used a t the time.

Table I11 shows r e s u l t s obtained with t h e Pantex conta iners a f t e r t h e diaphragm valves were replaced with K e l 9 seated needle valves. very favorably i n quant i ty of gas evolved and t h e p rec i s ion of the tests appear acceptable.

Tables I and 111 compare

T a b l e IV is t h e r e s u l t of t h e same comparison tes ts with LX-04-1, again showing good agreement between the t w o types of containers .

Table V conta ins values obtained with PBX 9404 which are included f o r comparison purposes.

A s e r i e s of experiments w a s performed t o ind ica t e v a r i a t i o r s t h a t might be ex- pected under less r i g i d temperature cont ro l . LX-09 samples were run a t t h e temperature ind ica ted using a Benco-Gran& constant temperature bath with a ten- pera ture c o n t r c l range of 20.02 C (Table VI1 ~ The temperature con t ro l s p e c i f i - ca t ions w e r e confirmed using a Hewlett Packard quartz thermometer with recorder . The table shows t h a t a va r i a t ion of t h e f e w degrees makes a considerable d i f f e rence in the q u a n t i t i e s of gases evolved.

The e f f e c t s of enclosing the sample i n t h e container under e i t h e r higher or lower pressure than 30 ps ig a r e shown i n T a b l e V I I . PBX 9404 w a s used as i t s l a r g e r gas evolut ion would tend t o show g rea t e r d i f f e rences than o ther PBX's.

I t appears from the da ta t h a t t h i s parameter d id no t s i g n i f i c a n t l y a f f e c t values .

F ina l ly t h e s t a i n l e s s steel i n s e r t s i n t h e LLL conta iners were replaced with g l a s s i n s e r t s (Pantex containers use g l a s s ) without any apparent change i n r e s u l t s . S t a i n l e s s i n s e r t s w e r e a l s o t r i ed i n t h e Pantex conta iners with t h e same r e s u l t s . The conta iner configurat ions are shown i n Fig. 1.

whitey O m - 2 stainZess steeZ needZe vaZve a

bBenco-Grant high temperature thermostatic bath Mode 2 HB3X, Osbcm Engineering, Inc., Tulsa, OkZahoma

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P

3.5(

1 1/8" ss

SS Body

Glass Filler - Stainless Filler Stainless Capsule .

Glass C a p s u l e

4

c

1 I-

PANTEX SAMPLE CONTAINER

LLL SAMPLE CONTAINER

Fig. I.. Sample Containers

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CONCLUSIONS AND RECOMMENDATIONS

It is now apparent t h a t t h e cause of d i f fe rences i n CRT analyses between LLL and Pantex w a s t h e Teflon diaphragm valves being used on t h e Pantex sample container. N o s i g n i f i c a n t d i f fe rences i n values w e r e obtained by changing space f i l l e r s and v i a l s from g l a s s t o s t a i n l e s s steel. Very small d i f fe rences were noted when t h e helium sample pressure w a s var ied from 10 t o 50 ps ig .

The l a r g e s t problem w a s apparently due t o entrapped air i n t h e sample container system. saurces of entrapped a i r are eliminated from the sample container system.

Reproduction of t h e analyses shown should not be d i f f i c u l t when a l l

Variations of values overlapped when t h e temperature of t h e cons tan t temperature bath w a s var ied F 3 C from t h e spec i f ied 120 C.

It is apparent, however, t h a t b e s t results should be obtained when t h e temperature is control led t o t h e k 1 C required by t h e t es t spec i f ica t ions .

Container No.

30 32 30 32 32

TABLE I. LX-09 WITH LLL SAMPLE CONTAINERS (CC-STP)

N2 + 07 CO 4- NO co2

0 0 011 0.026 0.015 0.010 0.023 0.016 0.005 0.017 0.013 0.011 0.015 0.012 0.007 0.022 0.014

TABLE 11. LX-09 WITH STANDARD PANTEX CONTAINERS ( CC-STP 1

Container N o .

3 9x 3 9x

N2 + 02 CO i- NO co2 . 0.016 0.03.5 0.018 0.024 0.016 0.039 0.017 0.014 0.020 0.016 0.006 0.014

0.006 0.006 0.006 0.004 0.005

0.005 0.009 0.006 0.005

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TABLE 111. LX-09 WITH MODIFIED PANTEX CONTAINERS ( CC-STP)

Container No.

18

19

1 2

0.002

0 e 009 0.003

-

T o t a l 0.014

N2 co NO co N2 0

Total

0.018 0.031 0.204 0.143 0.017

N7 + 02 0.001 0.005 0.006 0.006 0.008 0.001 0.007 0.010 0.006 0.011 0.008 0.007 0.006 0.005 0.010

CO + NO 0,016 0.012 0.013 0.011 0.021 0.016 0,015 0.016 0.020 0.024 0.014 0.019 0.011 0.015 0.013

0.013 0.011 0.013 0.012 0.015 0.015 0.016 0.016 0.016 0.021 0.015 0.016 0.012 0.015 0.020

TABLE I V . LX-04-1 ( CC-STP)

(3) (41 LLL

0.003

0.003 0.004

- 0.003 0.004 0.005 0.002 - - 0.005 0.002 0.006 0 003 0.007 0.006

0.010 0.013 0.013 - 0.017

TABLE Y. PBX 9404 STANDARD ( CC-STP)

0.019 0.028 0.198 0.143 0.018

0.024 0.022 - 0.039 0.221 0.219 0.171 0.156 0.025 0.024 -

0.412 0.406 0.479 0.460

0.005 0.004 0.005 0.004 0.006 0.005 0.005 0.005 0.005 0.007 0.005 0.005 0.004 0.005 0.007

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TABLE VI. LX-09 VARIATION OF TEMPERATURE

115 C, 22 Hrs. (cc)

(3) (4) X R a n g e

0.003

0.007 0.009 0.002

- 0.002 0.002

0.003 0.007 0.002

- 0.003

0.007 0.011 0,002

- 0.003 0.001

0.005 0.002 0.008 0.002 0.002

- 0.003 0.006 0.002

- 0.013

- 0.023 0.014 0.018 0.004 T o t a l 0 0 021

117 C, 22 Hrs. (cc)

0.006

0.022 0.010 0.004

- 0.014 0.005 0.006

0.018 0.031 0.009 0.018 0.018 0.008 0.003 0.005 0.004

- - c

0.008 0.004

0.020 0.008 0.013 0.004 0.004 0.001

-

Total 0.042 0.053 0.057 0.045 0.011 0.027

123 C, 22 Hrs. (cc )

0.009 0.001 0.002 0.001 0.02 0.003 0.018 0.002 0.006

0.009 0.011 - 0.001

0.024 0.023 0.016 0.021 0.006 0.006

0.007 T

0.016 0.017 0.006

0.009 0.003 0.022 0.017 0.006 - 0.057 Total 0.055 0.062 0.046 0.055 0.006

125 C, 22 Hrs. (cc)

0.007 0.001 0.035 0.025 0.009

0.007 0.001 0.036 0.026 0.009

0.008 0.001 0.029 0.024 0.007

0.019 0.002 0.061 0.032 0.010

0.012 0.005 0.001 0.001 0.080 0.012 0.027 0.003 0.009 0.001

T o t a l 0.076 0.124 0.089 0.020 0.078 0.079

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TABLE VII. PBX 9404 VARIATION WITH PRESSURE ( CC-STP)

50 p s i g 50 p s i g 1 0 p s i g 10 p s i g

N2 0.016 0.010 0.011 0.012 co 0.029 0.027 0.027 0.027 NO 0.188 0.183 0.187 0.184 co2 0.138 0.130 0.134 0.129 Np 0 0.016 0.016 0.016 0.013

- T o t a l 0.387 0.366 0.375 0.365

REFERENCES

1, 2 . Thermal S t a b i l i t y of LX-09, October, 1970. 3,

I n t e r i m Progress Report, Process Development Report No. 0012,

RM 251808 issue G . , Chemical Reac t iv i ty T e s t .

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