100 ADVANCED BINDERS FOR SOLID PROPELLANTS by M u r r a y S.

Cohen Thiokol C h e m i c a l C o r p o r a t i o n , Reaction M o t o r s Division, Denville, New J e r s e y

- A REVLEW

r o c k e t s i n the 13th Century. F r o m t h a t period up until r e l a t i v e l y r e c e n t t i m e s t h e cornposition of s o l i d propellants r e m a i n e d e s s e n t i a l l y constant, t h a t i s , a m i x t u r e of loose powder containing s u l f u r , n i t r a t e s a l t s and c a r b o n ( c h a r c o a l ) . A composition of t h i s type could n e v e r be developed f o r a m a j o r r o l e in propulsion because by i t s v e r y nature i t could not give r e l i a b l e b a l l i s t i c p r o p e r t i e s nor could i t be used i n l a r g e d i a m e t e r (high powder w a s adapted t o propelling rockets. H e r e again loose powder m i x t u r e s w e r e f i r s t used with many of the previously mentioned limitations. Consolidation of t h e loose powd e r s into homogeneous f o r m s o r g r a i n s w a s a m a j o r development i n double b a s e technology. T h e colloidal solution of t h e p o l y m e r , nitrocellulose, - in the p l a s t i c i z e r , n i t r o -

>

I)

A m a j o r advance i n p r o p e l l a n t technology o c c u r r e d when i t was d i s c o v e r e d t h a t m e t a l l i c f u e l s could be i n c o r p o r a t e d into the binder-oxidizer m i x t u r e t o give higher energy as w e l l as higher density p r o p e l l a n t s without affecting the mechanical p r o p e r t i e s of the s y s t e m (i. e. without lowering t h e allowable binder l e v e l ) . This paradoxical situation Can be understood if i t i s r e a l i z e d t h a t a hydrocarbon-oxidizer s y s t e m i s balanced t o give c a r b o n monoxide, c a r b o n dioxide and s t e a m a s combustion products. The m e t a l l i c

_-

101

additive i s oxidized by the s t e a m and t h e r e f o r e does not r e q u i r e additional oxidant. In the c a s e where aluminum i s added t o a hydrocarbon-ammonium p e r c h l o r a t e s y s t e m , the combustion p r o c e e d s in t h e following m a n n e r : NH4C104 t (CH,), t 2A1

> 1/2 N, t CO t 5/2 H, t A1203 t HC1

The f o r m a t i o n of hydrogen g a s a s a combustion product i s v e r y d e s i r a b l e because p e r f o r m a n c e of a s y s t e m i s proportional to the factor

w h e r e AH i s the h e a t r e l e a s e d in combustion and =is the m e a n molecular weight of the combustion products. F i g u r e 2 i l l u s t r a t e s the p e r f o r m a n c e i m p r o v e m e n t found i n t h e s e m e t a l l i z e d s y s t e m s and s h o w s , a s w e l l , the f a c t t h a t the binder l e v e l f o r optimum p e r f o r m a n c e s t a y s the s a m e as it would be i n a m e t a l - f r e e s y s t e m . The example shown is f o r a typical hydrocarbon-aluminum-ammonium p e r c h l o r a t e s y s t e m . With the foregoing background it i s now p o s s i b l e to p r o c e e d with a d i s c u s s i o n of the d i r e c t i o n s that r e s e a r c h h a s t a k e n in the development of new and i m p r o v e d binder s y s t e m s . Two m a j o r e f f o r t s c a n be c a t e g o r i z e d i n this review. The f i r s t w a s motivated by a t t e m p t s t o i m p r o v e the physical p r o p e r t i e s of propellants while maintaining t h e i r e n e r g e t i c s . The second e f f o r t i s a s t r a i g h t f o r w a r d a t t e m p t t o i n c r e a s e e n e r g e t i c s while maintaining acceptable m e c h a n i c a l p r o p e r t i e s . F o r a t r e a t m e n t of binder developments leading to the i m p r o v e m e n t of physical p r o p e r t i e s one m u s t r e c o g n i z e t h a t a l l hydrocarbon b i n d e r s a r e equal i n energetics. N e v e r t h e l e s s the binding capability of a h y d r o c a r b o n polymer w i l l v a r y with s m a l l changes i n i t s g e o m e t r i c a l s t r u c t u r e . Although t h e r e w a s enough scientific information available e a r l y i n the development of solid propellants t o aid i n t h e s e l e c t i o n of the best- p o l y m e r i c s t r u c t u r e s , the actual developments followed a typical evolutionary route. T h e e a r l i e s t c a s t , composite binder to be used w a s molten asphalt. This m a t e r i a l w a s heated until i t f o r m e d a fluid m e l t , w a s mixed with oxidant and the heated m i x t u r e c a s t into a motor cavity and allowed to cool. This s y s t e m w a s a poor one because of the limited t e m p e r a t u r e r a n g e , the low solids content which could be f o r m u l a t e d , and the poor m e c h a n i c a l p r o p e r t i e s of highly loaded asphalt. A chemically c u r e d s y s t e m w a s then introduced when a c r y l a t e m o n o m e r s w e r e mixed with oxidizer and curative. The m i x t u r e could be c a s t , h e a t e d t o c u r e t e m p e r a t u r e and the a c r y l a t e polymerized t o give a well consolidated g r a i n . T h e b a s i c deficiencies encountered i n t h i s type of s y s t e m w e r e the e x o t h e r m , a t t i m e s uncontrollable, during c u r e and the s h r i n k a g e of the solid due to the f a c t that the polymer h a d an appreciably higher density than t h e monomer. F u r t h e r m o r e , the a c r y l a t e s used w e r e not p a r t i c u l a r l y r u b b e r y s o that t h e i r mechanical p r o p e r t i e s w e r e only suitable for s m a l l g r a i n s . The addition of a polyfunctional u n s a t u r a t e , such a s divinyl benzene, t o t h e a c r y l a t e acted a s a c r o s s - l i n k i n g agent i n t h i s s y s t e m . The next advance i n s o l i d p r o p e l l a n t binders c a m e f r o m the u s e of partially polym e r i z e d liquids which r e t a i n e d functionality f o r subsequent curing. The best example of such a s y s t e m i s t h e controlled m o l e c u l a r weight p o l y m e r s obtained f r o m butadiene and a c r y l i c acid. T h i s s y s t e m is s t i l l a liquid of 200 t o 300 poise v i s c o s i t y a t 25OC at 2000 to 3000 molecular weight. It is sufficiently fluid a t p r o c e s s i n g t e m p e r a t u r e s (50 t o 60C) to allow f o r m u l a t i o n with 80 t o 85 p e r c e n t by weight of s o l i d s and s t i l l give a c a s t a b l e mix. C u r a t i v e s of the epoxy o r i m i n e type a r e added t o the m i x and the s y s t e m is

102 allowed t o c u r e over a p e r i o d of 3 to 2 4 h o u r s to a r e s i l i e n t solid. r e p r e s e n t e d i n the following m a n n e r : The s y s t e m c a n be 0 $0

nn/Ln*vI

I COOH

.dy w t curative COOH

COOH

> n N y w J ? GO
0

60
b

F r o m a t h e o r e t i c a l point of view t h e mechanical p r o p e r t i e s of a p o l y m e r i c s y s t e m c a n be optimized if the c r o s s - l i n k s a r e introduced in a r e g u l a r m a n n e r and not in a r a n d o m f a s h i o n as shown i n t h e p r e v i o u s equation. It w a s t h e r e f o r e c o n s i d e r e d a d e s i r a b l e development when c o n t r o l l e d m o l e c u l a r weight s y s t e m s w e r e m a d e available which h a d t h e i r functional groups only at the ends of chains. T h e s e s y s t e m s w e r e c u r e d with t r i and polyfunctional c u r i n g a g e n t s of the t r i s i m i n e type. The following equation i l l u s t r a t e s t h e c u r i n g r e a c t i o n of a c a r b o x y t e r m l n a t e d h y d r o c a r b o n polymer.

V a r i o u s a t t e m p t s h a v e been m a d e t o r e d u c e t h e s o l i d s loading of b i n d e r s by i n c o r p o r a t i n g oxygen into t h e p o l y m e r i c s t r u c t u r e . In o r d e r t o m a i n t a i n the oxidizing potent i a l of the binder oxygen, g r o u p s s u c h a s the n i t r a t o a n d n i t r o w e r e first used. Actually t h e e a r l i e s t solid p r o p e l l a n t b i n d e r w a s cellulose n i t r a t e plasticized with t h e n i t r a t e ' e s t e r nitroglycerin. T h i s s y s t e m h o w e v e r , w a s not c a s t a b l e i n the conventional s e n s e in Other nitrate that u n w a r r a n t e d extenslve development w o r k would be r e q u i r e d . e s t e r system:; w e r e s t u d i e d such as t h a t d e r i v e d f r o m glycidyl n i t r a t e and p e t r i n acrylate.'
6

T h e s e n i t r a t e s y s t e m s w e r e found to suffer f r o m ths s a m e ihsrrndl instability c h a r a c t e r is tics enco..mtered i n t h e double b a s e s y s t e m s s o that i n c o r p o r a t i o n of oxygen a s the m o r e

s t a b l e n i t r o groups a p p e a r e d a t t r a c t i v e . Both addition and condensation n i t r o p o l y m e r s w e r e p r e p a r e d a s i l l u s t r a t e d i n t h e following equations: CH,=CH COOCHzC(NO,), NO2 HOCHzCCH20H t OCNCHzCHzNCHzCH2NC0 .> f.Hz-YH+x C03CHz(NOz) 3

]
1

i
I
I
/

>

NO2

NO2
r

'

103

Another e n e r g e t i c oxygen r i c h binder w a s pregar-ed which i n c o r p o r a t e s the p e r c h l o r a t e 'group a s an a m i n e s a l t .

Recently, the d i s c o v e r y of organic compounds which p o s s e s s t h e difluoramino g r o u p (RNF,) h a s p r o m p t e d study of p o l y m e r s which have high concentrations of NF,.

y ; C H

?;
COOCHz
I

In addition, fluorocarbon p o l y m e r s , which c a n be c o n s i d e r e d as low energy oxidizing b i n d e r s have b e e n investigated b e c a u s e they a r e compatible with r e a c t i v e oxid a n t s and a r e of high density. E x a m p l e s of such s y s t e m s a r e t h e fluoroalkyl a c r y l a t e s and fluoropolyesters. CHz=CH COOCHZ
I

> kHz-yHfx,

H O C H z ( C F , ) , ~ , O H t HOOC(CF,),COOH HO CH2(CFz)3CHzOOC(CF2),C00 CH2(CFz),CHzOH

P a r a l l e l i n g the oxidizer binder developments h a s been w o r k o n e n e r g e t i c f u e l binders. In t h i s way t h e binder c a n be looked upon not only f o r its mechanical p r o p e r t i e s but a l s o f o r its t r u l y e n e r g e t i c contributions t o the s o l i d propellant. One example of such a n approach w a s w o r k c a r r i e d out t o i n c o r p o r a t e t h e high h e a t of f o r m a t i o n acetylenic group into t h e polymer s t r u c t u r e . A c a s t a b l e s y s t e m w a s p r e p a r e d b a s e d upon t h e r e a d i l y available acetylenic m o n o m e r butynediol and its r e a c t i o n with f o r m a l dehyde. HOCH,CCCHzOH t CHzO

>

- > HO

A l s o , p o l y m e r s w e r e p r e p a r e d by t h e oxidative coupling of d i p r o p a r g y l e t h e r

HCZCCHZOCHZCFCH t 0 2

cut

>

~C~CCH,OCH,C~C+~+H,O

and t h e vinyl polymerization of isopropenylacetylene.

104
A s u c c e s s f u l e f f o r t w a s m a d e in i n c o r p o r a t i n g b o r o n h y d r i d e s into polymer s y s t e m s . The early s t u d i e s m a d e u s e of d e c a b o r a n e and its s i m p l e alkyl d e r i v a t i v e s . The difunctionality of d e c a b o r a n e t o w a r d s L e w i s b a s e s allowed t h e f o r m a t i o n of coor dination p o l y m e r s of t h e following type:

T h e s e p o l y m e r s tended to b e r e s i n o u s and w e r e also still s t r o n g reducing agents. T h e r e f o r e they could not b e s a f e l y f o r m u l a t e d with oxidants. A m a j o r development took p l a c e when the dicarbaclovododecaborane ( c a r b o r a n e s ) compounds w e r e d i s c o v e r e d b e c a u s e t h e s e m a t e r i a l s w e r e e x t r e m e l y s t a b l e a n d w e r e organophilic i n c h a r a c t e r . The b a s i c r e a c t i o n for c a r b o r a n e f o r m a t i o n is d e s c r i b e d i n t h e following equation.

.BI0H,, t R,C='CR2

Lewis Base

I
4
'

A wide r a n g e of m o n o m e r s and p o l y m c r s w e r e synthesized; of t h e s e the polyester

s y s t e m , shown in the following equations, w a s m o s t intensively developed.

HOCHzC

\ 01

> - CCH20H t HOOC( CH2)qCOOH -

HO CH2C

BI&H,4
A 4 By adjusting t h e r a t i o s of m o n o m e r s it w a s possibie to p r e p a r e OH, COOH and mixed t e r m i n a l groups. T h e p o l y m e r s w e r e chain extended and c r o s s - l i n k e d with i s o c y a n a t e s II , 1 to give r e s i l i e n t r u b b e r y p r o d u c r s .

O t h e r c a r b o r a n e s y s t e m s which w e r e studied included t h e copolymer of isopropenyl c a r b o r a n e with butadiene a n d a c a r b o r a n y l a c r y l a t e , both of which a r e shown i n the following equations.

CH3 CH2=C t CH,=CH-CH=CH, I C-CH

\O/
BIOHIO

CHz=CH I COOCH2C-CH

. > {CH-i%

\o/
BloHIO

COOCH2C-CH

It c a n be seen f r o m a r e v i e w of t h e pertinent synthetic c h e m i s t r y u s e d f o r binder r e s e a r c h t h a t significant s c i e n t i f i c contributions fell out of t h i s work. Most of the advanced s y s t e m s developed, h o w e v e r , have found v e r y l i m i t e d application t o solid propulsion due to s u c h f a c t o r s a s t h e r m a l and shock sensitivity, l o w e r e n e r g y than originally calculated, high c o s t a n d l a c k of availability of c h e m i c a l s , the physical p r o p e r t i e s of the p o l y m e r s p r e p a r e d .

/'

'5

._
1

105 I s p vs. $ Binder f o r a -&H,)-/AP

Propellant

270

2 60

2 50

0;

a .
v)

230

220

210

200

I
5

1
10

I
15

I
LO

I
25

$ CH, Binder
Figure 1

106

Isp

VS.

$ B i n d e r at 3 A 1 L e v e l s f o r a X H , k - A l - A P P r o p e l l a n t

27f

26(

,16% A 1

' /
i ,

'

"Ir

L3C

22 C

L1C

200

10

15

20

25

$ CH, B i n d e r

Figure L