N A S A C O N T R A C T O R N A S A CR-2622

R E P O R T

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EXPLOSIVE AND PYROTECHNIC

AGING DEMONSTRATION

Lnzoreme L. Rouch, Jr., and J . Nornzan Maycock

Prelicr red by
MARTIN MARIETTA CORI'ORATION
Baltimore, Md. 2 1 2 27
for Laiigley Research Ceiiter

N A T I O N A L AERONAUTICS A N D SPACE A D M l N l S T l l A T l O N * W A S H I N G T O N , D. C. FEBRUARY 1976

 ERRATA
I

NASA CONTRACTOR REPORT

NASA CR-2622

F e b r u a r y 1976

EXPLOSIVE AND PYROTECHNIC

AGING DEMONSTRATION

By Lawrence L. Rouch, Jr., and J. Norman Maycock

Martin Marietta Corporation
Baltimore, Maryland 21227

F o r Langley R e s e a r c h Center

P a g e 17: The attached corrected Thermograph on page 17,

F i g u r e 4. - Initial Thermograph f o r HNS-IIA,
should b e i n s e r t e d in the above referenced r e p o r t ,
and none of t h e data presented elsewhere r e q u i r e
correction.

Issued March 1977

f
\

17
1. Report No. 2. Government Accoion No. 3. Recipient's Catalog No
NASA CR-2622 I ._
4. Title m d Subtitle 5. R m Date
February 1976
EXPLOSIVE AND PYROTECHNIC AGING DEMONSTRATION 6. Performing Orgnizatiar code

--
7. Author(s1 8. Performing Orgmization R e p a t No.
.awrence L. Rouch, J r . and J. Norman Maycock
~
10. Work Unit No.
9. Rrfaming Organization Name and Address 506-21 -31
11. Contrxt or Grant No.
l a r t in M a r i e t t a C o r p o r a t i o n
l a r t i n Marietta Laboratories NASl -1 2280
450 South R o l l i n g Road, B a l t i m o r e , Maryland 21227 13. Type of Rcpon and P ~ i Coverec
d
L2. Sponsoring Agency and Address: C o n t r a c t Rept. 4/18/73 t o
lnll 7 A -.
l a t i o n a l A e r o n a u t i c s and Space A d m i n i s t r a t i o n 14. &%r$/&&cy Code
ashington. D. C . 20546
-e-tary NO~-

Technical monitor - Laurence J. Bement

Final report
6. Absaact
An 18-month s t u d y was conducted t o e x p e r i m e n t a l l y v e r i f y t h e s u r v i v a b i l i t y o f f i v e

hermal c h a r a c t e r i s t i c s . The a c c e l e r a t e d a g i n g t e s t s i n d i c a t e d t h a t u n s t e r i l i z e d
N S - I I A and Zr/KC104 can w i t h s t a n d t h e 10 y e a r , e l e v a t e d temperature exposure,
u r e PbN6 and KDNBF e x h i b i t small w e i g h t l o s s e s ( l e s s than 2 p e r c e n t ) and B/KC104
x h i b i t s s i g n i f i c a n t changes i n i t s thermal c h a r a c t e r i s t i c s . A c c e l e r a t e d a g i n g
ests a f t e r s t e r i l i z a t i o n indicated t h a t only HNS-IIA exhibited high s t a b i l i t y .
_I__.___

17. K~~ wor& ( s u w t & by Author(s)) (STAR category underlined) 18. Distribution Statement

Unclassified - Unlimited
Space p r o p u l s i o n and power, p r o p e l l a n t :
and f u e l s , p y r o t e c h n i c s ana expIosiveS, !
I
s t e r i I i z a t i o n , deep-space a g i n g I
Subject Category 20 I:
- I

20. Security Clanif. (of this ppel 21, No. of Pegs 22. Rice'
19. Scuritv O i o i f . (of this reoortl
Unclassified Unclassified i2 $4.25
--
 CONTENTS

LIST O F FIGURES ................................................. iv

LIST O F TABLES ................................................. v i
SUMMARY ........................................................ 1
INTRODUCTION ................................................... Z
EXPERIMENTAL SECTION ......................................... 5
Materials ..................................................... 5
Equipment .................................................... 7
P r o c e d u r e s ................................................... 9
RESULTS AND DISCUSSIONS ....................................... 16
HNS-IIA ...................................................... 16
PbN6 ........................................................ 28
KDNBF ...................................................... 39
Z r / K C 1 0 4 ....................................................48
B / K C ~ O ....................................................
~ 53
CONCLUSIONS .................................................... 64
REFERENCES rn e . . e e . a .. 66

iii
 LIST O F FIGURES

NUMBER wrLE PAGE

1. Mettler Thermoanalyzer .. .. ... .. . . . . 0 e - 0 e e
8
2. Quartz Spring Balance Apparatus . . . 0 9 e a 0
10
3. Accelerated Aging Apparatus . .. . ... .. ... -... . .... .. . . e..
11
4. Initial Thermograph f o r €INS-IIA e 0 - 17
5. Thermograph of HNS-IIA After Two Sterilization Cycles 18
6. SEM Photograph of HNS-IIA Before Sterilization --- - * 19
7. SEM Photograph of HNS-IIA After Sterilization e * 0 0 * 19
8. Sublimation Data Plot f o r HNS-IIA e 0 0 9 21
9. Fractional Decomposition of HNS-IIA 22
10. Plot of f ( a ) V e r s u s T i m e f o r HNS-HA * * 0
23
11. Arrhenius Plot f o r “S-IIA 0 . . 0 . . - - - -
* e J I - - 24
12. Accelerated Aging Weight Loss f o r HNS-IIA 0 0 ,. 0 26
13. Thermograph of HNS-IIA After 183 Days Accelerated Aging 27
14. Thermograph of Sterilized HNS-IIA After 94 Days
Accelerated Aging 0 . e . 0 0 . e . .. .. e D . e.. .. 29
15. Initial Thermograph f o r Dextrinated PbN6 ,. e e
30
16. Thermograph of Dextrinated PbN6 After Two Sterilization
Cycles .... o . o . . . . . . . . . . . . . . . . . . . . . . . . . . . ~ . . . . . . . . . . . . . . .
31
17. S E M Photograph of Dextrinated P b N 6 Before Sterilization o 32
18. SEM Photograph of Dextrinated PbN6 After Sterilization 0 0 32
19. Sublimation Data Plot f o r Dextrinated P b N 6 0 0 33
20. Initial Thermograph f o r P u r e PbN6 . .. . . o 0 - 36
21. Thermograph of P u r e P b N 6 After Two Sterilization Cycles 37
22. SEM Photograph of P u r e PbN6 Before Sterilization o 0 . 38
23. SEM Photograph of P u r e PbN After Sterilization - 0 0 . o 38
24. Accelerated Aging Weight L o s s f o r P u r e PbN6 40
25. Thermograph of P u r e PbN6 After 183 Days of Accelerated
Aging . 0 . . . . . . . . . 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~ . . . 41
.
26. Thermograph of Sterilized P u r e PbN6 After 66 Days
Accelerated Aging *. o.. e e . . . ... ........ *..... . . e 42
27. Initial Thermograph f o r KDNBF . . . . .. . . 0 43
28. Thermograph of KDNBF After Two Sterilization Cycles 44

iv
 LIST O F FIGURES - Continued

29. SEM Photograph of KDNBF Before Sterilization ........ .. 46

30. SEM Photograph of KDNBF After Two Sterilization Cycles .-. 46
31. Accelerated Aging Weight L o s s f o r KDNBF ... ... . . . 47 e

32. Thermograph of KDNBF After 183 Days Accelerated Aging 49

33. Initial Thermograph f o r Z r / KC104 ..-.... .... 50 e . . - 0

34. Thermograph of Z r / KC104 After Two Sterilization Cycles 51

35. SEM Photograph of Z r / KC104 Before Sterilization . 52
36. SEM Photograph of Z r / KC104 After Two Sterilization
Cycles . . 0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0 . . . . ~ . . . . . ~ .52
.......
37. Accelerated Aging Weight L o s s f o r Z r / KC104 .. . .. e .. 54
38. Thermograph of Z r / KC104 After 183 Days Accelerated
Aging . . . . . . . . . . . 0 . . . . . . 0 . . . . . . . ~ ~ . * . ~ . . . . ~ . . . . . . .55
.......
39. Thermograph of Sterilized Z r / KC104 After 94 Days
A c c e l e r a t e d Aging .....-....................... . 56
..
e e *.. e.

40. Initial Thermograph f o r B / KC104 . . .. - . -. 57

e e e

41; Thermograph of B / KC104 After Two Sterilization Cycles 58

42. SEM Photograph of B! KC104 Before Sterilization e 62
43. SEM Photograph of B / KC104 After Sterilization .... . .... 62
44. Thermograph of B / KC104 After 183 Days Accelerated Aging 63

V
 LIST O F TABLES

NUMBER TITLE PAGE

I. Sublimation Results f o r HNS-IIA ......................... 20

11. Isothermal Decomposition Results f o r HNS-IIA ............ 25
111. Sublimation Results f o r Dextrinated PbN6e .................34
IV . Isothermal Decomposition Results f o r Dextrinated PbN6- 34
V. Accelerated Aging P a r a m e t e r s f o r P u r e P b N 6 e e 0 39
VI. Isothermal Decomposition Results f o r KDNBF- * e 45
VII. Isothermal Decomposition Results f o r Z r / KC104 e 48
T h e r m a l Events of Sterilized and Unsterilized B / KC104
VIII.
Propellant .............................................59
IX.
Sterilization o ..
Weight L o s s ( as fractional Decomposition, a ) During
. e .. ..
e .
0 . e ..e . .. 59
0 0 0 e

X. Sublimation Results f o r B / KC104 0 * 61

vi
 EXPLOSIVE AND PYROTECHNIC AGING

DEMONSTRATION

Lawrence L. Rouch, Jr. and J. Norman Maycock

Martin Marietta L a b o r a t o r i e s

SUMMARY

An 18-month study was conducted to experimentally verify the

survivability of five selected explosive and pyrotechnic propellant m a t e r i a l s
(two p r i m a r y explosives, one secondary explosive, and two pyrotechnic pro-
pellants) when subjected to s t e r i l i z a t ' o n and prolonged exposure to space
environments (up to ten y e a r s at l o - & t o r r vacuum a t 66OC).

T o accomplish t h i s , each m a t e r i a l was:

1. t h e r m a l l y c h a r a c t e r i z e d by simultaneous differential
t h e r m a l analysis and t h e r m o g r a v i m e t r i c analysis
(DTA/ E A ) ;

2. t e s t e d f o r the ability to withstand two sterilization

cycles of 64 h o u r s each at 125OC;

3. t e s t e d to m e a s u r e its sublimation c h a r a c t e r i s t i c s ;

4. subjected to i s o t h e r m a l decomposition m e a s u r e m e n t
t e s t s to determine kinetic data, and;

5. aged at a p r e s e l e c t e d elevated t e m p e r a t u r e to obtain

definitive a c c e l e r a t e d - aging data.

The initial thermograph r e c o r d e d f o r each m a t e r i a l served a s

both a r e f e r e h c e standard f o r the comparison of the t h e r m a l c h a r a c t e r i s t i c s
a f t e r sterilization and a c c e l e r a t e d aging, and a s a guide for the selection of the
t e m p e r a t u r e r a n g e s used in sublimation and i s o t h e r m a l decomposition m e a -
s u r e m e n t tests. T e m p e r a t u r e s chosen w e r e believed to b e those i n which the
decomposition p r o c e s s e s o c c u r r i n g would b e the s a m e a s those taking p l a c e i n
r e a l - t i m e aging. The elevated t e m p e r a t u r e selected (84OC) f o r a c c e l e r a t e d
aging was based upon the p a r a m e t e r s calculated f r o m the kinetic data obtained
i n the i s o t h e r m a l m e a s u r e m e n t t e s t s and was such that one month of accele8-
a t e d aging in the laboratory approximated one y e a r of r e a l - t i m e aging at 66 C.

Results of the study indicate that two of the m a t e r i a l s (one

s e c o n d a r y explosive and one pyrotechnic propellant) appear to be capable of
withstanding s t e r i l i z a t i o n a n d / o r a c c e l e r a t e d aging, hence should be capable
of surviving polonged exposure to s p a c e environments.
 INTRODUCTION

F u t u r e l o n g - t e r m m i s s i o n s , such as deep space p r o b e s , plane-

t a r y explorations and l o n g - t e r m E a r t h - o r b i t a l m i s s i o n s , will r e q u i r e s p a c e -
c r a f t pre-launch s t e r i l i z a t i o n heat cycling and exposure to deep space e n v i r -
onments f o r periods up to 10 y e a r s . Explosive- and propellant-actuated
devices used to p e r f o r m in-flight mechanical functions m u s t survive t h e s e
exposures and still p e r f o r m reliably. More specifically, the chemical com-
ponents (i. e . , the explosive and pyrotechnic propellant m a t e r i a l s ) in the
devices m u s t maintain t h e i r initial p e r f o r m a n c e c h a r a c t e r i s t i c s throughout
t h e mission.

When subjected t o relatively high s t e r i l i z a t i o n t e m p e r a t u r e s

0
(two 64-hour cycles a t 125 C) and on prolonged exposure to space environ-
m e n t s (10 y e a r s a t 66OC* under t o r r ) , t h e s e chemical components could
undergo s e v e r a l physical changes. F o r example, m a t e r i a l s having relatively
high vapor p r e s s u r e s could sublime away f r o m initiating i n t e r f a c e s , thus
creating voids and possible functional f a i l u r e s ; i n p a r t i c u l a r , exposed m a t e r i -
al at the open ends of mild detonating fuse l e a d s (MDF) might evaporate o r
sublime, creating voids and the possibility of failure. O r , a f t e r inflight
s t o r a g e at an elevated s p a c e c r a f t t e m p e r a t u r e f o r p e r i o d s of up to 10 y e a r s ,
sufficient t h e r m a l decomposition of the m a t e r i a l s could o c c u r to affect p e r -
formance of the device. F u r t h e r , many ordnance devices contain s e v e r a l
explosives, and any m a t e r i a l that would m e l t during s t e r i l i z a t i o n o r flight
could be subjected t o eutectic mixing during cooling, t h e r e b y affecting p e r -
formance.

To d e t e r m i n e whether such d e l e t e r i o u s affects will occur i n

l o n g - t e r m , deep space m i s s i o n s , e a c h m a t e r i a l had t o b e tested. Since h e a t
s t e r i l i z a t i o n i s accomplished i n a few days, l a b o r a t o r y t e s t s duplicating the
s t e r i l i z a t i o n r e q u i r e m e n t s can be p e r f o r m e d quite easily1 -6. However,
since it i s not p r a c t i c a l t o conduct r e a l - t i m e aging and p e r f o r m a n c e testing of
devices o r analytical ( c h e m i c a l ) testing of components to d e t e r m i n e t h e i r
survivability and reliability a f t e r s e v e r a l y e a r s ; a n a c c e l e r a t e d aging testing
technique m u s t be used.
, P r e v i o u s and r e c e n t stud' s being conducted on the " a c c e l e r a t e d
aging'' of explosives and p r o p e l l a n t s7-i8 have been d i r e c t e d at determining
t h e effects of a g e on t h e p e r f o r m a n c e of devices o r propellants and at e s t a -
blishing t h e m a x i m u m s a f e s t o r a g e life. However, i n t h e s e s t u d i e s , "accel-
e r a t e d aging'' is the s t o r a g e of a n explosive- o r propellant-actuated d e v i c . at
s o m e r a t h e r a r b i t r a r i l y chosen t e m p e r a t u r e above ambient (typically, 50 t o
0
80 C) under ambient p r e s s u r e , f o r p e r i o d s ranging f r o m 1 t o 3 y e a r s . T h e
philosophy of such a n approach i s t h a t since h e a t i s a p r i m a r y contributor t o
c h e m i c a l decomposition, than i f t h e i t e m s survive s t o r a g e a t a n elevated
t e m p e r a t u r e f o r a p a r t i c u l a r length of t i m e , they will s u r v i v e f o r longer
p e r i o d s of t i m e at lower t e m p e r a t u r e s .
The authors gratefully acknowledge the valuable a s s i s t a n c e of
Mr. G. Fair of Martin Marietta L a b o r a t o r i e s f o r experimental work during
t h i s investigation.
I
*Caused by s o l a r radiation o r onboard radioisotope t h e r m o e l e c t r i c
g e n e r a t o r s (RTGs).
2
 The m o s t quantitative accelerated aging method proposed thus far
is based on a modification of the Arrhenius reaction rate equationll. This
method a s s u m e s that i f a m a t e r i a l survives a c e r t a i n length of time at some
elevated t e m p e r s t u r e , survival t i m e i n c r e a s e s by a factor of between 2.7 and
2.9 f o r every 10 C d e c r e a s e in temperature. Conversely, it is assumed that
t h e reastion r a t e f o r a l l m a t e r i a l s i n c r e a s e s by a factor between 2 and 3 f o r
each 10 C r i s e i n temperature.

But neither the modified-Arrhenius approach nor any other c u r -

r e n t accelerated aging method considers the possibility that a change may
o c c u r in the activation energy of the c r i t i c a l degradation p r o c e s s with t e m p e r -
a t u r e change.

An a c c e l e r a t e d aging procedure can be valid only if the c r i t i c a l

degradation p r o c e s s occurring a t the elevated t e s t t e m p e r a t u r e is exactly the
s a m e p r o c e s s that o c c u r s under actual conditions. The relationship between
the r a t e of a degradation p r o c e s s and t e m p e r a t u r e may not b e a single linear
relationship; r a t h e r , two o r even m o r e linear relationships may develop. An
example is the c a s e of PETN, where the plot of log (70weight l o s s ) against
r e c i p r o c a l t e m p e r a t u r e r e s u l t s i n two straight l i n e s with the b r e a k occurring
at the melting point12. In such a c a s e , any accelerated aging above the melt-
ing point would be meaningless because the t e s t would be monitoring a r e a c -
tion completely different f r o m the one actually occurring in aging. Another
example is s e e n in the t h g r m a l decomposition of ammonium p e r c h l o r a t e (AP).
Below approximately 300 C, A P undergoes deco%position such that only 30%
of the starting m a t e r i a l is decomposed; above 300 C, the reaction goes t o
completion (100%) with a different activation energy. T h e r e f o r e , it is ex-
t r e m e l y important that the t e m p e r a t u r e selected f o r the a c c e l e r a t e d aging
t e s t s be within the t e m p e r a t u r e range applicable to the chemical reaction
occurring i n r e a l - t i m e aging.

The p r o c e s s e s involved in aging can be described i n t e r m s of

s o l i d - s t a t e kinetics. It i s possible to deduce a meaningful and c o r r e c t aging
mechanism f r o m data on the p a r a m e t e r s relating to the physicochemical p r o -
p e r t i e s of the m a t e r i a l s (e. g. , thermal-decomposition kinetics , sublimation
kinetics , phase-change c h a r a c t e r i s t i c s , change-of- state phenomena, etc. ).
T h e s e decomposition and sublimation data can be used to predict m a t e r i a l
l o s s e s f o r deep space exposure periods up to ten years. When t h e s e kinetic
data a r e not available, an analytical approach can be used t o determine t h e s e
p a r a m e t e r s . Since explosive and propellant m a t e r i a l s s t o r e d f o r y e a r s i n a
vacuum at some elevated t e m p e r a t u r e will undergo degradation through sub-
limation a n d / o r t h e r m a l decomposition, the r a t e s of t h e s e two p r o c e s s e s
constitute the p a r a m e t e r s of m a j o r interest.

The r a t e a t which a m a t e r i a l decomposes thermally is designa-

t e d by the r a t e constant, k , the t h e r m a l dependence of which i s given by:

k = A exp ( - E / R T )

3
w h e r e k is e x p r e s s e d i n units p e r second, E is the activation energy i n kcal
p e r mole, T is the absolute t e m p e r a t u r e , and A is an experimentally d e t e r -
mined frequency factor. If the fractional decomposition, a , under isother-
m a l conditions, can be determined a s a function of time, t, then k can be
evaluated. Several equations have been derived to describe the complete a t -
curves1 such that accurate linear plots can be obtained up to a - 0.99. F o r
our purposes, we a r e interested in a values of 0. l o m a x i m u m decomposition
o r less, permitting u s e of the simple expression:

t = l n ( l - a ) /k

f o r a l l cases.

A similar approach h a s been used by Green, et. all4. In a n

effort to make long-term predictions of propellant compatibility based on
accurate s h o r t - t e r m data, the r a t e of m e t a l ion concentration buildup i n the
propellant was measured. F r o m this data, \he kinetic r a t e expression was
established and an Arrhenius plot (log k vs / T ) was used to determine the
t e m p e r a t u r e dependence of the r a t e constant. Using this information, Green
w a s able to predict the concentration of m e t a l buildup over a given period of
t i m e o r the time required f o r the m e t a l buildup concentration to reach a given
level. F u r t h e r m o r e , they showed that the maximum storage t e m p e r a t u r e to
limit the m e t a l buildup to a specified concentration over a given duration could
be calculated, thus, the maximum allowable storage t e m p e r a t u r e could b e
projected.

The d e g r e e of sublimation exhibited by a m a t e r i a l can be d e t e r -

mined by the Langmuir method15 using the expression:
7

G =
17.14

2
w h e r e G is the r a t e of sublimation i n g m p e r c m p e r s e c , P is the vapor
p r e s s u r e in t o r r , M is the molecular weight, and T is the absolute tem-
perature. If the vapor p r e s s u r e of a m a t e r i a l cannot be extracted f r o m ex-
p e r i m e n t a l data, it can be derived f r o m the vapor p r e s s u r e eyuation16 ex-
p r e s s e d as:

log P = A t E/4.576T

w h e r e A and E a r e experimentally determined constants (A the frequency

factor and E the activation energy associated with the p r o c e s s ) and T is the
a b solute t e m p e r atu r e.

By using data available f r o m the l i t e r a t u r e and these analytical

expressions on explosive and pyrotechnic propellant m a t e r i a l s , a selection of

4
 candidate m a t e r i a l s m o s t likely to survive sterilization and l o n g - t e r m deep
space aging has been made by Gorzynski and Maycock18 under contract to
NASA Langley R e s e a r c h Center (Contract No. NAS1-10698). Their study con-
tained a list of those chemicals considered most likely to m e e t a l l m i s s i o n
requirements. The objective of the Martin Marietta L a b o r a t o r i e s ' p r o g r a m ,
then, was to verify experimentally the survivability of these materials. To
achieve this objective, the t h e r m a l decomposition and sublimation c h a r a c t e r -
i s t i c s of each of these m a t e r i a l s was determined i n the first p a r t af the p r o -
g r a m so that a meaningful elevated t e m p e r a t u r e could be chosen for the
accelerated-aging studies. Using this approach, we obtained definitive accel-
erated-aging data pertaining to a 10-year flight t i m e i n a laboratory time span
of about 10 months.

EXPERIMENTAL SECTION

Materials

The m a t e r i a l s selected f o r testing under this p r o g r a m w e r e

chosen f i s m l i s t s of candidate m a t e r i a l s recommended by Gorzynski and
Maycock .
F r o m these l i s t s m a t e r i a l s w e r e selected for each of the
functional categories of compounds - p r i m a r y explosives, secondary explo-
s i v e s and pyrotechnic propellants. The specific selections for each category
are:

- - P r i m a r y explosives: lead azide and potassium

dinitrobenzofuroxan

- -Secondary explo sive s : hexanitr o stilb ene

--Pyrotechnic propellants: Z r / KC104 and B / KC1O4.

To a s s u r e validity of the r e s u l t s , an effort was made to obtain

samples f r o m well- characterized, high-quality lots of materials. Specific de-
t a i l s f o r each s a m p l e m a t e r i a l a r e given below.

Lead azide (PbN6). - a sample of dextrinated lead azide (contain-

ing 5% dextrin) was obtained f r o m Picatinny A r s e n a l , N. J. The sample was
f r o m Lot No. 52-127 manufactured by du Pont in 1952 and was purchased
under military s ecification MIL-L-3055. This batch of m a t e r i a l has been ex-
tensively tested r19, 20) and characterized by Picatinny Arsenal.

Pure lead azide was p r e p a r e d in-house for sterilization and

accelerated-aging m e a s u r e m e n t s t o replace the dextrinated PbN6. This was
p r e p a r e d f r o m "CP" g r a d e lead acetate and sodium azide according to the re-
action:

I 5
 P b .(C2H302)2 t 2 NaN3 -. PbN6

t 2 N a (C2H302)

The PbNb, was then filtered, washed, vacuum dried and characterized by
t h e r m a l analysis.

P o t a s s i u m dinitrobenzofuroxan (KDNBF). - The KDNBF sam-

ple was a l s o obtained f r o m Picatinny Arsenal, N. J. and is f r o m SMUPA lot
1 B7172. Manufactured in 1966 , t h i s m a t e r i a l was purchased under Military
Specification MIL-P-50486 (MU). This material Lot h a s been used i n s e v e r a l
studiesl9, 20, and i t therefore, is well characterized.

Hexanitrostilbene (HNS). - A sample of high purity commercial-

ly p r e p a r e d HNS-IIA was obtained f r o m the Naval Ordnance L a b o r a t o r i e s ,
W h i t e Oak. The sample was f r o m L o t X-773 (NOL), manufactured by G e m -
t r o n i c s , Inc. (Lot No. 36-45) i n October, 1971, using the Shipp and Kap1an2l
process. The "IIA" designation indicates that the material has been r e c r y s t -
allized to a controlled bulk density from a mixed solvent refluxed o v e r HNS-I.

Other p r o p e r t i e s are:

Bulk Density 0.55 g / c c

W a t e r Soluble Materials 0.02%

Surf a c e Volatile s 0.01%

Insoluble Mate r i a l s 0.02%

P a r t i c l e Size 8070 between 50 and 100 m i c r o n s

by coulter counter.

Impurities High purity, possible trace

NaCl as r e s u l t of manufacturing
process.

Zirconium - potassium perchlorate ( Z r / KC104). - P r i m a r i l y

a 50 / 50 m i x t u r e of powdered zirconium metal and potassium p e r c h l o r a t e
with a small percentage of Viton binder, this pyrotechnic propellant was ob-
tained f r o m the Hi-Shear Corporation. The sample is f r o m Lot No. 021,

6
manufactured J a n u a r y 6 , 1972. Exact details of the composition and manu-
facturing p r o c e s s a r e p r o p r i e t a r y information of the manufacturer.

Boron - potassium perchlorate (B/KClO ). - A sample of

B / KC104 propellant was supplied by the Hi-Shear torporation. The m a t e r i a l
w a s f r o m Lot No. 055, manufactured April 23, 1973. The composition was
approximately 2 0 / 80 proportion of B and KC104 with a s m a l l percentage of
f e r r i c oxide and Viton binder. Exact details of composition and method of
manufacture p r o c e s s a r e p r o p r i e t a r y information of the manufacturer.

Equipment

Thermoanalyzer - m a s s spectrometer. - P r e l i m i n a r y s c r e e n -
ing and i s o t h e r m a l decomposition m e a s u r e m e n t s of the sample m a t e r i a l s
w e r e conducted using a Mettler TA-1 Thermoanalyzer (Figure 1) capable of
p e r f o r m i n g simultaneous differential t h e r m a l analysis (DTA) and t h e r m o -
g r a v i m e t r i c analysis (TGA). In differential t h e r m a l analysis (DTA), the
s a m p l e under evaluation and an appropriate reference m a t e r i a l a r e heated o r
cooled at a l i n e a r r a t e , and the t e m p e r a t u r e difference between t h e m i s m e a -
sured. Since a l l of the phenomena that can occur to a sample a s it is heated
a r e accompanied by energy changes, then the resulting DTA t h e r m o g r a m s
may be used t o c h a r a c t e r i z e o r identify the m a t e r i a l under study i n t e r m s of
its physical and chemical t h e r m a l reactions. DTA, therefore, can be used to
o b s e r v e changes i n the t h e r m a l behavior of a m a t e r i a l resulting f r o m a l t e r a -
tions t o its physical o r chemical p r o p e r t i e s p r i o r to testing.

T h e r m o g r a v i m e t r i c analysis (TGA) is the study of m a t e r i a l

weight changes, m e a s u r e d either a s a function of t i m e under i s o t h e r m a l con-
ditions (static method) o r a s a function of t e m p e r a t u r e while the sample i s
heated a t a linear r a t e (dynamic method). Since t h e r m a l decomposition and
sublimation a r e both weight-loss p r o c e s s e s the extent of decomposition o r
sublimation of a m a t e r i a l and i t s dependence on t i m e , t e m p e r a t u r e , a t m o s -
p h e r e , and p r e s s u r e thus can be determined.

The thermoanalyzer is capable of testing samples f r o m one to

500 mg. In this c a s e , 5 mg s a m p l e s w e r e used for HNS, Zr/KC104,
and B/KC10 while 2 mg s a m p l e s w e r e used for PbN6 and 3 mg s a m p l e s
f o r KDNBF. 4’Samples may be tested in vacuum o r any gaseous a t m o s p h e r e ,
s t a t i c o r flowing, up to one a t m o s p h e r e p r e s s u r e . Heating may be i s o t h e r -
mally controlled o r a t a p r o g r a m m e d r a t e (0.2 to 100oC/Min) up to 16OOOC.
A 10oC/Min heating r a t e was used for a l l m a t e r i a l s except KDNRF which w a s
60C/Min. Maximum sensitivity of the TGA is 1Opg of weight change, while
f o r the DTA it is 0.2OC /in. The maximum TGA sensitivity was used f o r all
s a m p l e s , but the DTA sensitivity used was 1. O°C/in. All s a m p l e s w e r e
vibrated t o achieve optimum packing of the s a m p l e i n the crucible.

7
 Figure 1 . - Mettler Thermoanalyzer

8
 Coupled t o the thermoanalyzer is a B a l e e r s QMG lOlA Quadru-
pole Mass Spectrometer which is used for EGA (evolved gas analysis) identi-
fication of decomposition products. The B a l z e r s i s mounted directly i n the
Mettler thermoanalyzer , so that immediate identification of evolved products
can be obtained. EGA of the effluent gases was performed during the highest
and lowest isothermal decompositions for each of the four t e s t environments
to p r o d e a comparison t o identify differences in decomposition mechanisms
attributable to different t e s t t e m p e r a t u r e s and atmospheres. It was found,how-
e v e r , that the concentration of the decomposition products was so s m a l l as t o
be beyond the detection limits of m a s s spectrometer.

Quartz spring balances. -

Measurements of the sublimation
r a t e s w e r e made using quartz spring balances a s shown i n Figure 2. The
quartz springs w e r e calibrated f o r dimensional length change i n t e r m s of
weight change p e r unit of length change (e. g. , m g / mm ). A s m a l l fused quartz
bucket containing the sample was hung on each spring, These quartz buckets
w e r e suspended within an electronically regulated furnace. Five such set-ups
w e r e used so that the sublimation r a t e of each m a t e r i a l , with the exception of
KDNBF, could be m e a s u r e d simultaneously at five different temperatures.

All of the samples w e r e maintained under high vacuum through

continuous pumping with a Varian Vac Ion pump, after initial evacuation with a
Varian cryogenic absorption pump. The u s e of this pumping system, r a t h e r
than the conventional mechanical pump and oil diffusion pump system, elirni-
nated the possibility of oil vapors entering the s y s t e m and any consequent oil-
sample reactions.

The quartz spring balance apparatus w a s also used f o r a c c e l e r a -

ted-aging m e a s u r e m e n t s on s a m p l e s of unsterilized m a t e r i a l s since it pro-
vided a method of continuously monitoring the weight of a sample.

Oil bath. - Accelerated aging of the samples for thermoanaly-

sis was performed by suspending pyrex tubes contoaining the s a m p l e s i n a c i r -
culating oil bath thermostatically controlled at 84 C. The pyrex tubes w e r e
connected t o a v a c u u m manifold and w e r e evacuated using the s a m e pumping
s y s t e m used with the quartz spring balance apparatus. See Figure 3.

Miscellaneous equipment. - Sterilization of the sample m a t e r i -

als was performed i n a i r in a conventional laboratory oven capable of main-
taining i25 -
t 3OC. Sample weighings w e r e performed using a- Mettler H-16
balance.

Procedure s

P r e l i m i n a r y screening. - An initial simultaneous DTA !TGA

test was conducted on each m a t e r i a l t o provide a c h a r a c t e r i s t i c control t h e r m o -
graph to be used a s a reference standard for evaluating the effects of s t e r i l i z a -
tion and aging upon the individual m a t e r i a l s , By comparision of peak shape,
height and t e m p e r a t u r e , changes i n the m a t e r i a l s can be detected. These
m e a s u r e m e n t s w e r e conducted i n a flowing a t m o s p h e r e of d r y nitrogen with
calcined aluminum oxide being used a s the DTA reference material. To

9
 3-
-
A-
.............
:::::::::::::
.............
.............
-ELECTR IC
FURNACE

THERMOCOUPLE

10
Figure 3. - Accelerated Aging Apparatus

11
provide an i n t e r n a l t e m p e r a t u r e standard, s e v e r a l tin pellets (A DTA t e m p e r -
a t u r e standard i s s u e d and certified by the National Bureau of Standards i n
cooperation with the International Confederation f o r T h e r m a l Analysis. ) w e r e
placed i n the r e f e r e n c e cup. The melting t i n p e l l e t s ' r e s u l t in a s m a l l exoo
t h e r m i c peak on the DTA t r a c e with an onset t e m p e r a t u r e known to be 230 C.

In addition, t h e s e thermographs w e r e used to s e l e c t the t e m p e r a -

t u r e a t which the i s o t h e r m a l decomposition and sublimation m e a s u r e m e n t s
would be performed.

Sterilization. - Each m a t e r i a l was subjected to twoo64-hour heat

sterilization cycles i n a conventional laboratory oven at 125 t 3 C in a i r .
Following each cycle, a simultaneous DTA/TGA t e s t was performed on a sample of
each material. The r e s u l t s of t h e s e t e s t s w e r e compared with those obtained
during the p r e l i m i n a r y screening.

Additionally, the morphology, of each m a t e r i a l before and a f t e r

each sterilization cycle was examined through the u s e of a scanning electron
m i c r o s cope.

Sublimation. - Measurements of the sublimation r a t e s w e r e

made on each of the m a t e r i a l s , with the exception of K D N B F , using the quartz
spring balances. The s y s t e m was designed to m e a s u r e the sublimation r a t e of
e a c h m a t e r i a l at five different t e m p e r a t u r e s simultaneously. A small fused
quartz bucket containing a known amount of s a m p l e with a known exposed s u r -
face a r e a was suspended f r o m each of the five quartz spring balances into -6
five electronically regulated furnaces. The s a m p l e s w e r e evacuated to "10
t o r r and then r a i s e d to and maintained at the t e s t t e m p e r a t u r e by the regula-
t e d furnaces.

T e s t t e m p e r a t u r e s w e r e selected a f t e r examination of the t h e r m -

ographs obtained during the p r e l i m i n a r y screening of the m a t e r i a l s . C r i t e r i o n
f o r selection was to choose the maximum sublimation t e m p e r a t u r e such that the
amount of t h e r m a l decomposition taking place would be negligible. T h e s e
t e m p e r a t u r e s ranged between looo and 200°C. P e r i o d i c reading w e r e taken to
m e a s u r e the dimensional changes of the quartz s p r i n g s a s a r e s u l t of the
weight change of the sample. The r e s u l t s of t h e s e m e a s u r e m e n t s w e r e plot-
t e d against t i m e and the r a t e of sublimation was calculated.

F o r m a t e r i a l s composed of a single chemical compound, the

vapor p r e s s u r e was calculated using the Langmuir expression:

G ; - -P
\ / M
17.14 T

Additionally, the heats of sublimation w e r e determined f o r t h e s e m a t e r i a l s

whose vapor p r e s s u r e could be calculated using the vapor p r e s s u r e equation:

12
 log P = A t E/4.576T

and curves of log P vs reciprocal temperature.

Isothermal decomposition. - Initial DTA/ TGA analyses of each

m a t e r i a l provided characteristic thermographs to be used a s reference stan-
dards. Any changes i n the chemical o r physical properties of a m a t e r i a l pro-
duced (for example, by sterilization) would be detected a s changes in the
thermographs when compared to the standards. The standard thermographs
a l s o w e r e used to select the t e m p e r a t u r e s f o r the isothermal TGA studies.
This approach to t e m p e r a t u r e selection ensured that the t e m p e r a t u r e s chosen
could be reached with a n appropriate heating r a m p before any significant de-
composition took place. Following the initial t e s t at the first selected tem-
p e r a t u r e , f o r each successive t e s t , the t e m p e r a t u r e was adjusted to provide
the m o s t meaningful isothermal data.

The isothermal decompositions of each m a t e r i a l a l s o w e r e per-

f o r m e d in the Mettler Thermoanalyzer 1. Each m a t e r i a l was tested at five
different t e m p e r a t u r e s for each of the four specified t e s t environments: (1)
closed volume vacuum, (2) continuously pumped vacuum, (3) closed volume
air, and (4) open to the atmosphere. These four conditions simulate the en-
vironmental exposures possible with both occluded and vented systems.

Isothermal decomposition data is i n the f o r m of a s e t of curves

depicting weight l o s s a s a function of time a t different temperatures. T h e s e
curves first a r e normalized i n t e r m s of fractional decomposition ( a ) a s a
-
function of t i m e , t. F o r each t e m p e r a t u r e , the a t data i s analyzed accord-
ing to the equation:

t = In ( l - a ) / k

whereby l i n e a r plots a r e obtained i f In (1 - a ) is plotted against t. The

slopes of these lines are equal t o k, the r a t e constant f o r the respective t e m -
perature. The k values a r e plotted as In k vs reciprocal t e m p e r a t u r e ,
since

In k = In A - E/RT

The slope of the resultant line will be equal t o E / R, where E is the activa-
tion energy of the decomposition process. This analytical analysis a s s u m e s
that the topochemistry of the decomposition i s known. If not, a m o r e general
analytical model should be used. This is possible if the r a t e equation can be
e x p r e s s e d i n the general form:

f ( a ) = kt

13
when k is the r a t e constant and a n , a n a r e values of the fractional de-
l
composition a a t t i m e s t and tn *espectively. Thus,
n

F o r a different t e m p e r a t u r e , but f o r the s a m e values of a :

A lot sf In ( t n + - t n ) against T - I shsuld be linear and have a slope qf

E R. P
To i l l u s t r a t e the u s e of t h e s e t h e s e techniques, the analysis of
the kinetics data f o r the i s o t h e r m a l decomposition of HNS-IIA under continu-
ously pumped vacuum i s described below. (Curves a r e shown on pages 20-24.)
3
F r o m the Arrhenius plot (In k VS. 10 / T ) for HNS-IIA under
these t e s t conditions, the slope of the line i s m e a s u r e d to be 16.7. Using this
value we obtain the activation energy :

-1
Ea = slope (R) = 16.7 (1.99) = 33.2 kcal.mole

F r o m the function a VS. t i m e plot (in this c a s e , 1 -

VS. t), the r a t e constant a t 23OoC is determined to be 4.225 x lO-"s;c-
~ ) 3~ l /

Using this value and t h e slope of the Arrhenius plot, it is possible to calculate
.
t h e r a t e constant at 66OC by:
1 1
slope ( L
k2 = kl e thus
T1

K660 = 4.225 X 10
-5 16.7 (1.937 - 2.949) 12 1
e = 4.454 x 10 sec

T h e r e f o r e , the fractional decomposition ( a ) f o r one y e a r at 66OC is:

7
a = 1 - e -kt , where t = one y e a r = 3.15 x 10 s e c ,

if k t << 1 then a = kt and,

a = 4.45 1 0 - l (~ 3.15 lo7 = 1.40

14
 F o r one month accelerated aging t o be equivalent to one y e a r
at 66'C, the r a t e constant m u s t be

--a , where t = one month = 2.59 6

x 10
kA t

then
- 1.40
= 5.40 x sec- 1
kA - 2.59 x 10

The accelerated aging t e m p e r a t u r e (TA) i s then calculated

thusly ,

-
1
TA
= 2.949 1
slope In -
k A
k66°
1 5.40 x lo-''
= 2.949 -'= In
4.45 x 10-l2

= 2.799

= 357Ok o r 84OC
TA

Decomposition reaction r a t e s and activation energies have

been tabulated over the t e m p e r a t u r e range studied f o r each t e s t environment
and compared to d e t e r m i n e whether the s a m e reaction i s occurring over the
t e m p e r a t u r e range of i n t e r e s t for the accelerated-aging studies.

Accelerated aging. -
E a r l y in the i s o t h e r m a l decomposi-
tion m e a s u r e m e n t s , it bscameoapparent that many of accelerated aging tem-
p e r a t u r e s w e r e in the 75 - 90 C range. This i s not unusual considering that
a l l of the m a t e r i a l s a r e of the metastable type, which decompose rapidly after
initiation. Since the accelerated aging t e m p e r a t u r e s f a l l within the s a m e
g e n e r a l range and the u s e of a single aging t e m p e r a t u r e would greatly simplify
the experimental apparatus set-up and operation, it was decided t o test a l l of
the m a t e r i a l s a t the s a m e accelerated aging temperature. T h e r e f o r e , each
of the unsterilized specified explosive and pyrotechnic matoerials was aged in
a vacuum of l e s s than 1 x 10'6 t o r r a t a t e m p e r a t u r e of 84 C . The 84OC
t e m p e r a t u r e was chosen because the degradation p r o c e s s r a t e of each m a t e r i -
a l a t that t e m p e r a t u r e is accelerated t o the extent that approximately one
month of accelerated aging equaled one y e a r of r e a l - t i m e aging. Four of the
m a t e r i a l s (the exception being B/KC104) w e r e s e t up i n the quartz spring
balances so the weight change could be continuously monitored during aging

15
while the samples w e r e held a t aging t e m p e r a t u r e by the electronically con-
trolled furnaces.

In addition, samples of each of the m a t e r i a l s w e r e stored in

pyrex tubes to provide s a m p l e s f o r periodic t h e r m a l analysis. These samples
w e r e maintained a t the aging t e m p e r a t u r e by i m m e r s i o n in an oil bath. Both
sets of samples w e r e maintained under vacuum by a VacIonpump t o eliminate
the possibility of pump oil- sample interaction. At each appropriate test-time
point (as determined by the continously monitored quartz spring balance m e a -
surements), a simultaneous DTA/ TGA test was performed on the aged materi-
al. These w e r e compared with the control thermograph to observe the changes.

After the unsterilized accelerated aging t e s t s w e r e in p r o g r e s s

and preliminary data was obtained, one m a t e r i a l was selected f r o m each of the
functional categories (1, e. , p r i m a r y explosive, secondary explosive, pyro-
technic propellant) f o r limited sterilized accelerated aging. The m a t e r i a l s
selected w e r e pure PbN6, HNS and Zr/KClO4. Samples of each 8f these
m a t e r i a l s w e r e sterilized (two heat soaks of 64 hours each a t 125 C) then aged
under vacuum in the oil bath with the unsterilized samples for simultaneous
DTA/ TGA testing.

RESULTS AND DISCUSSIONS

Hexanit r o stilbene (HNS-1IA)

P r e l i m i n a r y screening of HNS-IZA (hexanitrostilbene) was con-

ducted and the r e s u l t s a r e s h o w n i n Figure 4 , the initial t h e r m o g r a h f o r
HNS-UA. Important features of the thermograph a r e the peak a t 230% C which
is the r e s u l t of melting of the tin in the reference cup, the melting of the
HNS-IIA a t 322OC just p r i o r to decomposition, and the main decomposition ex-
t h e r m t e m p e r a t u r e occurring a t 344OC. This thermograph was used a s the
control standard f o r comparison with thermographs taken a f t e r sterilization
and aging.

Following each of two sterilization cycles (125OC f o r 64 h o u r s

each) simultaneous DTA/ TGA t e s t s w e r e repeated. The t h e r m o g r a p h after
two sterilization cycles is shown in Figure 5. This figure is essentially iden-
t i c a l t o the control thermograph with the melting point of HNS-IIA occurring at
323OC and the main decomposition e x o t h e r m t e m p e r a t u r e occurring at 342OC.
Apparently, no significant change has taken place i n the HNS-IIA a s a r e s u l t of
sterilization.

SEM m i c r o g r a p h s taken before and a f t e r sterilization t o deter-

mine morphology changes a r e shown in F i g u r e s 6 and 7, respectively. No
morphological change is apparent upon examination of the micrographs.

Sublimation m e a s u r e m e n t s of HNS-IIA w e r e conducted at tem-

p e r a t u r e s f r o m 82OC to 15OoC f o r a test period of 216 hours. No m e a s u r e -
able weight l o s s o c c u r r e d at the lower t e m p e r a t u r e s , however, a t 132OC,

16
 1000 2000 3000 4000
I I I I I I
TEMPERATURE - OC

Figure 4. - Initial Thermograph for HNS-IIA

17
 --\
EX0

END0
, I
1ooO 2000 3000 I
I

18
 SCANNING ELECTRON MICROSCOPE PHOTOGRAPHS

Figure 6. - HNS-IIA-Before Sterilization (300X)

-
Figure 7. HNS-IIA-After Sterilization (2X, 64 hr, 125O C) (300X)

19
139OC and 15OOC weight l o s s data was obtained. These data a r e shown in
Figure 8. Weight l o s s r a t e s , sublimation rates, and vapor p r e s s u r e s calcula-
t e d f r o m these data a r e given in Table I .

TABLE I. - SUBLIMATION RESULTS FOR HNS-IIA

-
G P
Temp. Wt. L o s s Rate Sublimation Vapor P r e s s
OC mg/hr. gm/ cm2/ sec torr.

132 6.24 x l o m 4 2.63 x 10-l' 4.28 x

139 2.75 x 1.02 x 1.67
150 3.75 x 1.41 x 2.34

Isothermal decomposition measurements w e r e conducted f o r

HNS-IIA over the t e m p e r a t u r e range of 230° to 3OO0C using the four t e s t envi-
ronments : (1) continuously pumped vacuum, (2) closed volume vacuum, (3)
closed volume a i r , and (4) open t o the atmosphere.

Analysis of the i s o t h e r m a l decomposition data f o r HNS-IIA

t e s t e d i n a continuously pumped vacuum t e s t environment is described below.

First, the weight l o s s as a function of t i m e w a s normalized by

expressing it i n terms of the fractional decomposition, Q .
A plot of Q v s
time (t) as a function of t e m p e r a t u r e is shown in Figure 9.
1
Next, a function of Q ( L e . In (1- a ) , ( l - ~ )1~- ,( l - ~ ) ," etc.)
~
was selected which would produce linear plots when plotted against t. A s e t of
curves f o r HNS-IIA t e s t e d i n a continuously pumped vacuum envi ment i s
shown i n F i g u r e 10. The function of Q i n t h i s c a s e was l - ( l - a p 9 ? Since
t h e s e lines f i t the equation:

f ( a ) = kt

the slope of these lines equals the rate constant (k) at each temperature.

Finally, a n Arrhenius plot of In k v e r s u s the reciprocal t e m -

p e r a t u r e ( 1 0 3 / T ) (Figure 11) was prepared. The slope of this line according
t o the Arrhenius equation, k = A exp ( E / RT), equals E / R , where E is the
activation energy of the decomposition p r o c e s s and R is the international gas
constant .

20
1 I I I 1
I
I I

21
 I

22
23
24
 Using the r a t e constants and activation energy thus determined,
the accelerated-aging p a r a m e t e r s can be calculated by the method outlined i n
t h e P r o c e d u r e s section.

A s u m m a r y of the experimental r e s u l t s obtained f o r HNS-IIA

a r e given i n Table II.

TABLE 11. - ISOTHERMAL DECOMPOSITION RESULTS FOR HNS-IIA

Activation a
=A
Conditions Energy k @ 66OC One Year Accel. Aging
-1 T e m p OC
K c a l / mole sec

Cont. Pumped 33.2 4.45 x 1.40 84O

Vac.

Closed Vol. 48.6 1.34 10-l~ 4.22 x 7 So

Vac.

Open A i r 39.2 1.71 10-l~ 5.39 x 81°

Closed Vol. 11.8 1.10 x - 123'

Air
-
The r e s u l t s obtained f o r the closed volume air environment a r e
somewhat confusing F o r example, the rate of weight loss at 23OoC was
g r e a t e r than a t 240 C. During the first s e v e r a l hours of testing, however
weight i n c r e a s e s w e r e observed. It was a l s o l e a r n e d that i f the vent to the
thermoanalyzer was closed completely, gas p r e s s u r e changes within the instru-
ment would produce corresponding weight changes in the TGA curve. More-
o v e r , the possibility of reaction of the decomposition products with the HNS-
IIA f u r t h e r complicates the p r o c e s s .

0
Accelerated aging m e a s u r e m e n t s w e r e conducted i n vacuum at
84 C on unsterilized HNS-IIA using the quartz spring balance apparatus. This
d a t a is shown i n F i g u r e 12. Excluding the cyclic variation of the data (due t o
vibrations, etc. ) , no significant change i n weight o c c u r s over the t e s t period,
297 d a y s (equivalent t o 9.9 y e a r s a t 66OC).

Additionally, a t h e r m o g r a p h of a s a m p l e of unsterilized HNS-

IIA after 183 days of a c c e l e r a t e d aging (equivalent t o 6.1 y e a r s ) is shown in
F i g u r e 13. When compared with the initial thermograph, this figure shows no
significant change i n the t h e r m a l c h a r a c t e r i s t i c s of the material.

25
 0
0

0
0
0
0
0
0
0

0
0
0

0
0
0

0
0
0
0
0
0
0
0 8
0 I 8
0 0
0 t
0 0
0 a
c
2
0 w
0

' 2
a
0
0 3

0
0 2
$
0 v)

0
a
0
0 5
t >
0 0

00

0
0 0
3
00 O

04

0
0 0
0
N
800

a8
0 0 :

II c

26
 f
TGA 1 mg

EX0

lo00
END0
2000 300'
'I
I I I I 1
TEMPERATURE - O C

Figure 13. - Thermograph of HNS-IIA After 183 Days Accelerated Aging

21
 F i g u r e 14 is a thermograph of s t e r i l i z e d HNS-IIA a f t e r 94 days
of a c c e l e r a t e d aging equivalent to 3.1 y e a r s . Again, no significant change i s
observed.

L e a d azide (PbN6)

A v e r y sensitive p r i m a r y explosive, lead azide, can easily be

detonated by impact, friction, heat o r s t a t i c discharge, Therefore, initially,
dextrinated lead azide was selected a s the t e s t m a t e r i a l because the dextrin
r e d u c e s the initiation sensitivity of the PbN6 t h e r e b y reducing the h a z a r d s in-
volved i n handling it.

P r e l i m i n a r y screening of the dextrinated PbN6 produced the

thermograph shown i n F i g u r e 15. Important f e a t u r e s of this figure a r e the
s h a r p exothermic decomposition peak o c c u r r i n g at 317OC with the accompany-
ing precipitous weight loss in the TGA curve.

One s t e r i l i z a t i o n cycle of 64 h o u r s a t 125OC caused the s h a r p

exothermic decomposition peak to broaden and d e c r e a s e in height, indicating
t h a t t h e r a t e of decomposition h a s decreased. The TGA curve showed a de-
c r e a s e i n the r a t e of weight l o s s and the total weight l o s s was significantly
s m a l l e r also.

Results following the second s t e r i l i z a t i o n cycle (shown i n

F i g u r e 16) a r e a f u r t h e r broadening and d e c r e a s e i n height of the decomposi-
tion peak. A f u r t h e r d e c r e a s e i n the r a t e and amount of weight l o s t i s indica-
~ TGA curve. T h e s e r e s u l t s indicate a change h a s o c c u r r e d i n the
t e d . 5 the
dextrinated PbN6 as a r e s u l t of sterilization.

Scanning e l e c t r o n m i c r o g r a p h s taken of dextrinated PbN6 before

and a f t e r two sterilization cycle a r e shown i n F i g u r e s 17 and 18. F i g u r e 17
shows the m a t e r i a l i n the "as received" condition at 2000X magnification;
F i g u r e 18 shows a s a m p l e of the m a t e r i a l at the s a m e magnification a f t e r two
sterilization cycles. F r o m comparison of t h e s e m i c r o g r a p h s , no change is
apparent i n the inorphology of the dextrinated lead azide a s a r e s u l t of s t e r i l i -
zation.
I F o r m e a s u r e m e n t of the sublimation r a t e of dextrinated PbN6,
~

t e m p e r a t u r e s frcjm 120°C to 18OoC w e r e selected f o r testing. The data f o r

t h e weight l o s s as a function of t i m e a t various t e m p e r a t u r e s a r e shown i n
F i g u r e 19. At 120° and 14OoC, the r a t e s of weight l o s s r e m a i n relatively
constant. However, a t 160° and 18OoC, the initial r a t e s of weight l o s s de-
crease markedly a f t e r approximately 40 h r s . then i n c r e a s e again a f t e r appro-
ximately 110 h r s . P r i o r experience indicates that p u r e PbN6 would not
 TGA 1 rng

_+__

END0
1000 2000 w
I I I I

Figure 14. - Thermograph of Sterilized HNS-IIA After 94 Days Accelerated Aging

29
 f

I
1000
I
2000 1
m I I
TEMPERATURE - OC

Figure 15. - Initial Thermograph for Dextrinated PbN6

30
 DTA 1OpV
-0

1000 2000 3ocP 4Ooo

I I I I I I I I
TEMPERATURE- OC

-
Figure 16. Thermograph of Dextrinated PbN6 After Two Sterilization Cycles

31
 SCANNING ELECTRON MICROSCOPE PHOTOGRAPHS

Figure 17. - Dext. PbNg-Before Sterilization (200x)

Figure 18. - Dext. PbNg-After Sterilization (2X, 64 hr, 125OC) (2000X)

32
 I 1 I I
I 1
1 1 1
1 I I I

0
3

6UJ -SSOl'lM

33
exhibit this stepwise decomposition and should be relatively stable at these
temperatures. Therefore, it is probable that the dextrin i s decomposing,
possibly by a dehydration reaction which could proceed in a stepwise fashion.

Weight l o s s r a t e s and sublimation r a t e s calculated f r o m the data

shown i n Figure 190 a r e given i n Table 111 below. The r a t e s at the higher two
t e m p e r a t u r e s (160 and 180OC) a r e based on the data taken during the first 20
h o u r s of testing,

TABLE 111. - SUBLIMATION RESULTS FOR DEXTRINATED PbN6

9

T e q p e raturc Wt, L o s s Rate Sublimati n Rate

C mg/hr gm/cm /sec?

120 1.43 6-02 x

140 2.0 7.42 x 10-l'
160 5.0 x (a) 2.10 x (a)
180 7.5 x (a) 2.78 x (a)

Isothermal decomposition m e a s u r e m e n t s w e r e made on dextri-

nated PbN6 i n the open-to-atmosphere (OA) t e s t environment over the t e m p e r -
a t u r e range of 15OoC to 20OoC. These data w e r e analyzed in a manner simi-
lar t o that shown f o r HNS, and the r e s u l t s a r e given i n Table IV. Listed in the
tabole a r e the measured activation energy (Ea), the calculated r a t e constant at
66 C (k), the accelerated-aging r a t e constant (K ) required f o r one months
aging t o equal one year a t 66OC, and the calculat& accelerated-aging t e m p e r -
a t u r e (Ta) n e c e s s a r y t o obtain kA.

TABLE IV. - ISOTHERMAL DECOMPOSITION DATA FOR DEXT. PbN6

Activation KA TA
Conditions Energy k 63 66OC One Year Accel. Aging
K c a l / mole sec-1 63 66OC Temp. OC

Open A i r 21.7 2.28 x 2.7 x 94.7

34
 At this point, based upon the r e s u l t s obtained, the decision was
made t o change f r o m dextrinated lead azide to pure lead azide. The dextrinat-
ed m a t e r i a l did not appear capable of withstanding sterilization and t h e acti-
vation energy m e a s u r e d was significantly lower than the value f o r pure lead
azide i n the l i t e r a t u r e . It was decided that pure lead azide would be p r e p a r e d
as described under the Materials section and tested for sterilization and a c c e b
erated-aging m e a s u r e m e n t s ,

Results of the sterilization t e s t of pure lead azide a r e shown in

F i g u r e s 20 and 21. F i g u r e 20 is the thermograph f o r pure PbN6 before steri-
lization; F i g u r e 27 is the r e s u l t following two sterilization cycles. Compari-
son of the thermographs shows that the only change is a n upward ghift of the
main decomposition exotherm peak t e m p e r a t u r e f r o m 302O to 328 C. This
would indicate a slightly g r e a t e r degree of stability, but the r a t e of decompo-
sition and weight l o s s did not change.

SEM photographs before and a f t e r sterilization a r e shown by

F i g u r e s 22 and 23, respectively. These micrographs indicate no apparent
change i n t h e morphology of pure PbN6 due to sterilization.

Since p u r e PbN6 h a s been the subject of considerable r e s e a r c h ,

l i t e r a t u r e values of t h e r a t e constant and activation energy w e r e used to cal-
culate the accelerated-aging p a r a m e t e r s , thus minimizing the delay i n begin-
ning the accelerated-aging - - m e a s u r e m e n t s of this alternate material. The
values obtained a r e :
Source
Evans, Yoffe and Gray (22)
Hutchinson, et al. (23)
Activation energy Griffths and Groocock (24)
36 kcal / mole
e
J a c h (25)
P a i Verneker and Maycock (26)

Rate Constant
-1
5.95 x sec Kleinberg and Stein (27)
@ 21oOc

Based upon t h e s e values, the values i n Table V w e r e calcula-

ted for the aging p a r a m e t e r s :

35
 TGA 1 mg

4
END0

lo00 2000 3ooo

1 I I I
TEMPERATURE - O C
I
Figure 20. - Initial Thermograph for Pure PbN6

36
 T
TGA lmg

END0

1000 2000
TEMPERATURE -0c

Figure 2 1. - Thermograph of Pure PbN6 After Two Sterilization Cycles

37
 SCANNING ELECTRON MICROSCOPE PHOTOGRAPHS

Figure 22. - Pure PbN6-Before Sterilization (600X)

Figure 23. -Pure PbNg-After Sterilization (2x,64 hr, 125' c) (600X)

38
 TABLE V. - ACCELERATED AGING PARAMETERS FOR PURE PbN6

Activation a Ta
Conditions Energy k @ 66OC One Year 'Accel. Aging
-1
I
Kcal/ mole sec @ 66OC Temp OC
I
I
I
Closed Vol. 36 3.32 x 1.05 x 81.9O

Accelerated aging of the pure lead azide was performed a t 84OC

1 i n vacuum. Data obtained f r o m the quartz spring balance for the accelerated
aging of unsterilized pure PbN6 a r e presented in Figure 24. Unfortunately,
this balance seemed to be m o r e sensitive to external vibrations, etc. than the
other balances and exhibited a fairly l a r g e cyclic variation. This would tend
to m a s k v e r y s m a l l weight l o s s e s , however, the mean value can be used t o
follow the total weight l o s s , Over the 228 days (equivalent to 7.6 y e a r s at
66OC) duration of the t e s t p u r e PbN6 lost "0.15 mg (0.44%).

T h e r m a l analysis of a sample of PbN6 after 183 days of accel-

erated aging (equivalent to 6 . 1 y e a r s ) shows no significant change in the t h e r -
mograph (Figure 25) after this period.

F o r sterilized pure PbNG, however, the r e s u l t s w e r e different.

The thermograph in Figure 26 was obtained after 66 days of accelerated aging
(equivalent to 2.2 years). Examination of the DTA curve indicates that the
main decomposition exotherm has d e c r e a s e d in size and broadened. These
changes a r e reflected in the TGA curve, also, i n both the amount and r a t e of
weight loss.

It i s noteworthy that unsterilized P b N 6 i s capable of withstand-

ing accelerated aging f o r almost t h r e e t i m e s a s long a s sterilized PbN6.
Possibly the sterilization p r o c e s s , in the p r e s e n c e of a i r , promotes the f o r m -
1 ation of b a s i c lead azide a n d / o r decomposition nuclei which s e r v e a s initiation
s i t e s f o r further decomposition.

P o t a s s i u m dinitrobenzofuroxan (KDNBF)

The initial thermograph obtained during the preliminary s c r e e n -

ing of KDNBF is shown i n Figureo27. The main decomposition exotherm peak
f o r this m a t e r i a l o c c u r r e d a t 203 C.

Following two sterilization cycles, the r e s u l t s i n Figure 28

w e r e obtained. The only change noted i s the shift of the main decomposition
peak to 177OC.

39
 I 1 I

D
w
t-
a
a
3
w 3
A
w
0
0
a
(D
z
n
a.
w (3
K
-
z
2 (3
a
D
0 0 w
0
0
E'?a
0 w
0 A
0 0 w
0
0
OO
0
0
z
L
OO
0
0
0
O0
9
a
8 n
0
0 0
O O
0 0 0
0
0
r
0

\8
0
O 0
0

0 OO

40
 $

TGA 1 mg
z

l0O0 2000 3ooo

1 I J
TEMPE RATU RE - OC

Figure 25. - Thermograph of P u r e P b N 6 After 183 Days Accelerated Aging

41
42
 I
1/20 c

loo0 2000
I I 1
TEMPERATURE - OC

Figure 27. - Initial Thermograph for KDNBF

43
 I
TGA 1mg

EX0

I 1/20 c

END0

lo00
1 I I I I
TEMPERATURE - OC
-
Figure 28. Thermograph of KDNBF After Two Sterilization Cycles

44
 SEM photographs taken before and a f t e r two sterilization cycles
are shown in F i g u r e s 29 and 30, respectively.
Examination of these figures
indicates no change i n the morphology of the m a t e r i a l as a r e s u l t of s t e r i l i z a -
tion.

Sublimation measurements w e r e not conducted on KDNBF be-

cause they w e r e not within the scope of t h e contract.

As shown by the initial thermograph, this m a t e r i a l detonates at

approximately 2OO0C, therefore to be r e a l i s t i c within the mission r e s t r a i n t s ,
iaothermal decomposition studies w e r e conducted between 90' and 150°, f o r
all four environmental mis sion possibilities. The choice of t h i s t e m p e r a t u r e
range was a l s o dictated by the requirement to have decomposition studies of
the same phenomena which would be expected a t 66OC.

The data obtained f o r these decompositions p r e s e n t a paradox

in that they f a l l into one of two classes: (1) the t i m e required f o r a given
fractional decomposition a s a function of temper a t u r e is relatively constant,
implying a v e r y small activation energy o r that the weight l o s s phenomena is
relatively independent of t e m p e r a t u r e and (2)the time required f o r a given
fractional decomposition i n c r e a s e s . F o r a pure, unsolvated, m a t e r i a l t h e s e
effects would not occur. Thus the implication is that the KDNBF may contain
occluded solvent introduced i n the manufacturing process. (However, a
supplemental mass s p e c t r o m e t r i c analysis failed to detect the p r e s e n c e of any
occluded solvent. )

Only under the continuously pumped vacuum condition could

usable data be obtained and these a r e given in Table VI. P a r a m e t e r s f o r the
other test conditions could not be obtained due t o the inconsistences i n the data.

TABLE VI. - ISOTHERMAL DECOMPOSITION RESULTS FOR KDNBF

Activation Ta
Conditions Energy k @ 66OC One Year Accel. Aging
Kcal/ mole Sec-1 @66OC Temp. OC

Cont. Pumped 30.2 4.37 x - 86. lo

Vac.

Results of the a c c e l e r a t e d aging of unsterilized KDNBF i n t h e

quartz spring balance apparatus a r e shown in F i g u r e 31. This m a t e r i a l ex-
hibited a weight l o s s f r o m the beginning of the test. Over a 255 day test
period (equivalent t o 8.5 y e a r s ) KDNBF l o s t 0.55 mg (1. 32%).

45
 SCANNING ELECTRON MICROSCOPE PHOTOGRAPHS

Figure 29, - KDNBF-Before Sterilization (600X)

Figure 30. - KDNBF-After Sterilization (2X, 6 4 hr, 125O C) (600X)

46
 r

0
0
0

0
0
0
0 c
0
0
0
0
0
0
0 V

0
0
* %
@J
0 0
0
5
0
0
2I-
0 z
0
0 n a4
0 1
0 3
0
0
z
Y
0 0
0 m
(r
0
0
“ e>-
0
0
0
0
0

0 m
0
0
0
0 0

e
0
N
0
00
0

ooo

3
0
0 P

0 0
0

0 :

9
I I I 1 1 I 0
0 T 0” g x z $
0

- SSOl ‘ I M

47
 F u r t h e r accelerated-aging data a r e shown in Figure 32 , a
thermograph f o r unsterilized KDNBF a f t e r 183 days of accelerated aging
(equivalent t o 6 . 1 years). It shows no significant change f r o m the intial ther-
mograph.

Zirconium - potassium perchlorate pyrotechnic propellant ( Z r / KC104)

Results of the preliminary screening test of Z r / KC104 a r e

shown i n Figure 33. The main f e a t u r e s of t h i s figure a r e : the meltin of the
t i n reference at 23OoC, the phase-change endotherm of KC104 at 311%;C, and
the main decomposition exotherm a t 411OC.

Sterilization of the Z r / KC104 produced no significant change

i n t h e r m a l c h a r a c t e r i s t i c s of t h e material, The r e s u l t s following two sterili-
zation cycles a r e shown i n F i g u r e 34.

Additionally, SEM micrographs show no change in the morpho-

logy of the m a t e r i a l as a r e s u l t of sterilization. The m a t e r i a l before s t e r i -
lization is shown i n F i g u r e 35; F i g u r e 36 shows the r e s u l t s following two steri-
lization cycles.

Sublimation m e a s u r e m e n t s w e r e conducted on Z r / KC104 i n

vacuum over the t e m p e r a t u r e range of looo t o 18OoC. No measurable weight
l o s s was observed f o r Zr/KCIOq over a t e s t period of 269 hours.

Results of t h e i s o t h e r m a l decomposition m e a s u r e m e n t s on
Z r / KC104 over the t e m p e r a t u r e range of 250° t o 3OO0C a r e summarized in
Table VII'.

TABLE VII. - ISOTHERMAL DECOMPOSITION RESULTS FOR Z r / KC104

Activation U Ta
Conditions Energy k @ 66;c One Year Accel. Aging
Kcal/ mole Sec- @ 66OC TempOC
1
Cont. Pumped 17. 5 1.01 10-9 2.19 10-2 102.2O
Vac.
Closed Vol. 29. 9 1.21 3.82 86.5O
Vac.

Open A i r 17.2 2.97 x 10- l o 9.36 10-3 94O

Closed Vol. 2.8 2.80 - -

Air
 TGA 1 mg
-
x

EX0

I1/20 c

loo0 2000
I I I
TEMPERATURE - OC

Figure 32. - Thermograph of KDNBF After 183 Days Accelerated Aging

49
 I
TGA 1 mg

I
2000 4Ooo
1 I 1 I I I J
TEMPERATURE - OC 1

Figure 33. - Initial Thermograph for Zr/KC104

50
 f

END0

1
lo00
I

I
2000
I
V
3Ooo
I
so00
I
TEMPERATURE - OC

Figure 34. - Thermograph of Zr / KC104 After Two Sterilization Cycles

51
 SCANNING ELECTRON MICROSCOPE PHOTOGRAPHS

Figure 35. - Zr/KC 104-Before Sterilization (1 OOOX)

Figure 36. - Zr/KClOq-After Sterilization (2X, 6 4 hr, 120' C) (lOOOX)

52
 Based upon the r a t e constant a t 66OC m e a s u r e d under closed
volume a i r t e s t conditions, the a f o r one year would be g r e a t e r than one,
which is not possible. It appears that the t r u e decomposition is being masked
by side effects o r complex interactions under these conditions.

Data f o r the accelerated aging of unsterilized Z r / K C 1 0 in the

quartz spring balance apparatus is shown in Figure 37. No m e a s u r a f l e weight
l o s s was observed during the t e s t period (251 days, equivalent to 8.4 y e a r s at
66OC).

Following 183 days of accelerated aging (equivalent to 6.1 y e a r s )

f o r unsterilized Z r / K C 1 0 4 , the thermograph in Figure 38 was made. It in-
dicates no significant changes i n the chermal properties of the material.

Additionally, a thermograph (Figure 39) of sterilized Z r / KC104

was prepared after 94 days of accelerated aging (equivalent to 3.1 years).
The figure shows a change h a s taken place in the material. The exothermic
peak a t 403OC h a s d e c r e a s e d in size and a new exothermic peak appears at
486OC. This change was not apparent after 39 days of accelerated aging for
the sterilized material. It is possible that some oxidation o c c u r r s during
sterilization creating initiating s i t e s which s e r v e promote the degradation
during accelerated aging (See discussion under B / KC104. )

Boron - potassium perchlorate ( B / KC104)

P r e l i m i n a r y screening t e s t of B /KC104 produces the thermograph

shown i n Figure 40. Major features of the figure a r e the tin reference peak
at 23OoC, the phase change of KC104 at 31loC, and the main decomposition
peak exotherm a t 381OC.

Significant changes w e r e noted in the thermographs following

sterilization. The r e s u l t s following two sterilization a r e shown in Figure 41.
The decomposition exotherm at 381OC has become much s m a l l e r and b r o a d e r
with a new large decomposition exotherm appearing a t 461OC. The results
obtained a f t e r one sterilization cycle w e r e s i m i l a r to those after two cycles
except f o r minor changes i n the exotherm temperatures. It appears that
sterilization has drastically changed the chemical integrity of the B/KCl O4
propellant. Comparison of the a r e a s under the curves suggests that the steri-
lized propellant is m o r e exothermic - this i s an artifact of the measuring
technique and will be discussed later. A compilation of these t h e r m a l events
f o r sterilized and unsterilized propellant i s presented in Table VIII.

Since during sterilization no m e a s u r e of any weight change i n

the sample was recorded, the experiment was repsated with samples i n the
Mettler Thermoanalyzer in a i r for 64 hours a t 125 C so that a d i r e c t m e a s u r e
of weight changes could be made. To account f o r possible reactions with
oxygen in the a i r the experiment was repeated in a flowing nitrogen a t m o s -
sphere. The data show in both c a s e s substantial weight l o s s during the s t e r i -
lization cycles. Typical values a r e listed in Table IX.

53
 n
W
I-
d
a
W
-I
W OW
I 4
0
0
a u
d
2
\
s
0 N
k

Y k
2 0
N rcl

% (3
z
-
0 (3

8 a
O0
n
W
OO I-
a
a
O b0 W
-I
W
\ 0
0
0 a a

i
Q)
U c,
0 cd
8 k
9
a
Q)

0
00 n

Bo
0"
8 0
0 0

0 0 0
6 u - SSOl ' I M

54
 ~- II
T

EX0

END0

100 200 300 400

1 I I I I
TEMPERATURE - OC

Figure 38. - Thermograph of Zr/KClOq After 183 Days Accelerated Aging

55
 i
T G A 1 mg

1000 2000 3Ooo 4oOo 5000

I I I 1 I I I I I
TEMPERATURE - OC

Figure 39. - Thermograph of Sterilized Zr/KC104 After 94 Days Accelerated Aging

56
 DTA

loo0 2000 3000

I I I I I I I I I
TEMPERATURE- OC

Figure 40. - Initial Thermograph f o r B/KC104

57
 T
TGA 1 mg

L
1 I I I 1 1 I I 1
TEMPERATURE - O C

Figure 41. - Thermograph of B/KC104 After Two Sterilization Cycles

58
 ~~~ ~~~

TABLE VIII. - THERMAL EVENTS O F STERILIZED AND UNSTERILIZED

B/KC104 PROPELLANT.

P h a s e Change Decomposition
Endotherm (OC) Exotherms (OC)

Un st e r i liz ed 31 1 382
After 1 heat soak 311 368, 473
After 2 heat soaks 31 1 382, 461

TABLE IX. - WEIGHT LOSS (AS FRACTIONAL DECOMPOSITION a )

DURING STERILIZATION.

F r a c t i o n a l Decomposition ( a ) Air Nitrogen

Sterilization Sterilization

0.1 54 m i n 46 m i n
0.2 2 hrs 12min 12 h r s 2 min
0.3 4 hrs 3 min 22 h r s 54 m i n
0.4 6 hrs 49min 36 h r s
0.5 11 h r s 57 hrs
0.6 18 h r s 12min

It is clear f r o m this data that sterilization i n nitrogen in-

creases the stability of the propellant with r e s p e c t to the obvious degradation
i n air. However, even i n nitrogen t h e degradation is severe.

The c a u s e of the observed degradation is undefined although

we speculate that viton i n t h e propellant environment of oxidizer, metal p a r t i -
cles, i r o n oxide could decompose along a reaction path shown below:

59
 CF3 - C F = C F 2 t CH2=CF2

Polymerize

CH2 - CH2 - CF2ln Viton

initiation by heat, decomposition of

t r a c e amounts of peroxides, catalysis
by metals and m e t a l oxides, etc.
\1/
H B
2
rCF
I
1
- i
CF2 - C - C F 2
1

I or b~-
7

I
C F ~ C - -C F ~1
-l

1 CF3
L
I CF3
L
O2 J
Propagation

FF -
c

1
1
CF2
H
I
- CI - C F 2
1

CF
H
- CF2 - CII - CF2Jn
0
12
t E:;
with polymer unit

CF2
H
- Ci - C F 2
H Propagation
I
Decomposition (continues chain)

The apparent anomaly of the propellant being m o r e exother-

mic after sterilization i s believed t o be due t o the burning of the boron during
propellant combustion. During combustion it i s highly probable that the boron
is reacting i n the gas phase along the following paths

2 B t 02->ZB0

4 BO t 0,-22 B203

60
 and thus the energy of these reactions would not be r e c o r d e d by DTA. During
1 sterilization it is possible that BO can be formed in the solid propellant and

during decomposition whereby the DTA will r e c o r d this energy and exhibit a
higher energy decomposition compared to the unsterilized propellant.

SEM photographs (Figures 42 and 43) indicate no morphology

change in the m a t e r i a l a s a r e s u l t of sterilization.

Sublimation m e a s u r e m e n t s w e r e conductgd o v e r the t e m p e r a -

t u r e range of 100' to 210°C f o r B/KC104. Only a t 200 and 210°C w e r e mea-
surable weight i o s s e s observed. A s u m m a r y of these r e s u l t s appears i n
Table X.

TABLE X. - SUBLIMATION RESULTS FOR B / KC104

Temperature Wt. L o s s Rate G

OC mg/hr Sublimation Rate
I

200° 1.82 7.66 x

210° 8.0 3.37 x 1 0 - l 0

Isothermal decomposition m e a s u r e m e n t s w e r e p e r f o r m e d on
B/KCIOA over the t e m p e r a t u r e range of 255' -33OoC. However, inconsis-
tencies in the data, s i m i l a r to those already discussed, prevented the d e r i -
vation of accel rated-aging t e m p e r a t u r e s and rates. An activation energy o
7.2 kcal mole-' was m e a s u r e d for the open-air condition and 8.9 kcal mole"
w a s m e a s u r e d for the closed-volume a i r condition. But, when these values
w e r e used in conjunction with the rate consoants m e a s u r e d under these two
conditions to calculate r a t e constants a t 66 C, the fractional decomposition (a)
f o r one year a t 66OC exceeded the value of 1. T h e data taken under the con-
tinuously pumped vacuum and closed volume vacuum a r e so confused that no
,
I
r e s u l t s could be obtained.

j Samples of B / KC104 w e r e subjected to accelerated aging i n

I vacuum a t 84OC, the s a m e conditions used f o r the other m a t e r i a l s . After 183

days of accelerated aging, the t h e r m o g r a p h shown in F i g u r e 44 was obtained.
This figure indicates changes s i m i l a r to those observed following sterilization.
T h e s e changes w e r e not observed in the thermograph taken a f t e r 117 days of
accelerated aging.

61
 SCANNING ELECTRON MICROSCOPE PHOTOGRAPHS

Figure 42. - B/KClOq-Before Sterilization (600X)

Figure 43. - B/KC104-After Sterilization (2X, 64 hr, 125' C) (600X)

62
 TGA 1 mg
-

EX0
A
/

END0

I000 2000 4000 5000

I I I 1 I I I I
TEMPERATURE. OC

Figure 44. - Thermograph of B/KC104 After 183 Days Accelerated Aging

63
 CONCLUSIONS

Based upon the r e s u l t s obtained f r o m the sterilization t e s t s , it

would appear that HNS-IIA,pure PbN6, I$,DNBF, and Z r / KClO4 a r e
capable of withstanding two cycles a t 125 C f o r 64 hours each, without causing
m e a s u r a b l e change i n the t h e r m a l c h a r a c t e r i s t i c s of the materials. Dextri-
nated PbN6 and B /KC104 , however, do show significant changes i n t h e i r
t h e r m a l c h a r a c t e r i s t i c s , even after only one sterilization cycle. In the c a s e
of dextrinated lead azide, sterilization appears t o result i n failure of the
m a t e r i a l t o detonate with a corresponding d e c r e a s e in weight loss and energy
release. Whereas, B / KC104 apparently undergoes a mechanism change i n
the m a i n decomposition process. If B/KC104 m u s t be sterilized, i t i s
recommended that functional testing be p e r f o r m e d on the sterilized m a t e r i a l
to a s c e r t a i n that important operational p a r a m e t e r s a r e not affected by s t e r i l i -
zation.

A l l of the m a t e r i a l s (excepting KDNBF which was not tested)

have sufficiently s m a l l sublimation r a t e s and therefore, low vapor p r e s s u r e s
s o a s to not constitute a problem by t h e i r use on extended length misdions.
However, it must be noted that the weight l o s s m e a s u r e d for dextrinated
PbN6 is believed t o be the r e s u l t of decomposition of the dextrin, r a t h e r than
the r e s u l t of sublimation.

Determination of the r e a l i s t i c accelerated aging p a r a m e t e r s of

a m a t e r i a l through the u s e of isothermal decomposition studies is possible.
However, under certain t e s t conditions, the reaction kinetics of the decom-
position may be masked by side effects (e. g. , interaction of the decomposition
products o r back reaction of decomposition products with starting m a t e r i a l ,
etc. )

The u s e of the accelerated aging p a r a m e t e r s to predict the

effect of aging on explosives and propellants has been demonstrated. And the
r e s u l t s of these experiments indicate that HNS-IIA, and Z r / KC104 ,
unsterilized, a r e capable of withstanding up t o ten y e a r s of deep space expo-
s u r e a t 66OC without m e a s u r a b l e change in t h e i r t h e r m a l c h a r a c t e r i s t i c s .
Unsterilized p u r e PbN6. and K D N B F exhibit s m a l l weight l o s s e s ( l e s s than
2%) but do not exhibit significant change in t h e i r thermographs. Unsterilized
B / KClO exhibits significant changes i n i t s t h e r m a l c h a r a c t e r i s t i c s , similar
4
t o those observed a f t e r sterilization, a s a r e s u l t of accelerated aging.

The accelerated aginGof s t e r i l i z e d HNS-IIA o v e r a 94-day

period (equivalent to 3.1 y e a r s a t 66 C ) caused no detectable change i n the
t h e r m o g r a p h of the material. However, sterilized pure PbN6 and Z r / K C 1 0 4
did exhibit changes i n t h e i r t h e r m o g r a p h s after relatively s h o r t accelerated
aging periods of 66 days (2.2 y e a r s ) and 94 days (3.1 y e a r s ) , respectively.
Changes in the sterilized pure PbN.6 a f t e r accelerated aging w e r e s i m i l a r t o
those observed following the sterilization of dextrinated PbN6. Sterilized
Z r / KC104 following aging exhibited changes s i m i l a r t o those observed f o r
B /KC104 (i,e. , a d e c r e a s e i n the size of the m a i n exothermic peak and the
a p p e a r a n c e of a second exothermic peak a t higher t e m p e r a t u r e ) but not t o as

64
g r e a t a degree. One possible explanation f o r this difference i n behavior
between the sterilized and unsterilized m a t e r i a l i s that sterilization in air
c r a t e s initiation s i t e s (by decomposition, oxidation, etc. ) which then enhances
the decomposition during accelerated aging ( s e e discussion under B /KC104
results) .
It should be noted that the objective of this p r o g r a m was t o
evaluate the effect of accelerated aging on the selected m a t e r i a l s and to m e a -
s u r e the changes produced. However, the establishment of c r i t e r i a f o r o r
the determination of the degree of decomposition o r change n e c e s s a r y to
cause failure of a m a t e r i a l in i t s functional performance was not within the
scope of this program. Therefore, p r i o r to the use of one of the m a t e r i a l s
under conditions which caused t h e r m a l c h a r a c t e r i s t i c changes, t e s t s should
be performed to verify that the changes observed do not affect functional p e r -
formance of the material.

65
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66
i 12. Maycock, J. N. and Pai Verneker, V. R , I'Characterization of T h e r m a l
I
and Photosublimation of Organic Explosives by Thermobarogravimetric
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~
.New York, 1955, pp. 18-24, 740-743.

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~

I A Radiation P u l s e Upon P r i m a r y Explosives (U), TR-4230, Picatinny

I
1 Arsenal, N. J., M a y 1971 (Secret - f o r m e r l y Restricted Data).

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21. Shipp, K. G. and Kaplan, L A , "Reactions of (Y - Substituted Poly-

-
nitrotobuenes. II. The Generation and Reactions of 2, 4, 6 T r i n i t r o -
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Inorganic Azides, I ' Chern. Rev. 59 (1959).

67
23. Hutchinson, R W. , Kleinberg, S. and Stein, F., "Effect of Particle-
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-
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Trans. Far. SOC. -

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68 NASA-Langley, 1976 CR-2622