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Formation and Properties of Thermosetting and High TG
Formation and Properties of Thermosetting and High TG
7, 67-74 (1987)
FORMATION AND PROPERTIES OF THERMOSETTING AND HIGH Tg
POLYMERIC MATERIALS
John K. G i l l h a m
Polymer M a t e r i a l s Program, Department o f Chemical Engineering,
P r i n c e t o n U n i v e r s i t y , Princeton, New Jersey 08544, USA
A b s t r a c t - I n t e r r e l a t i o n s h i p s between r e a c t i o n c o n d i t i o n s
and m a t e r i a l p r o p e r t i e s o f t h e r m o s e t t i n g and h i g h Tg
polymers a r e discussed from t h e p o i n t o f view o f a
g e n e r a l i z e d time-temperature-transformation (TTT) diagram.
INTRODUCTION
T h i s a r t i c l e p e r t a i n s p r i n c i p a l l y t o t h e f o r m a t i o n and p r o p e r t i e s o f h i g h
Tg polymeric glasses which are made by t h e t r a n s f o r m a t i o n o f l i q u i d t o
The area i s o f p a r t i c u l a r imporamorphous s o l i d by chemical r e a c t i o n .
tance i n t h e making o f composites, coatings, and adhesives by thermos e t t i n g "cure" r e a c t i o n s i n which m u l t i f u n c t i o n a l molecules o f low
molecular weight a r e converted i n t o network macromolecules.
An attempt
has been made t o produce a g e n e r a l i z e d model f o r t h e f o r m a t i o n and propert i e s o f thermosetting systems which a l s o i n c o r p o r a t e s l i n e a r systems:
an
example o f t h e former i s t h e c u r e o f a neat epoxy r e s i n ; an example o f t h e
l a t t e r i s t h e p o l y m e r i z a t i o n o f neat s t y r e n e monomer below t h e g l a s s t r a n s i t i o n o f polystyrene.
T h i s a r t i c l e w i l l t h e r e f o r e emphasize t h e r mosetting systems w i t h some r e f e r e n c e t o l i n e a r systems.
The s i m p l e s t
model f o r chemical s e t t i n g assumes a s i n g l e r e a c t i o n mechanism and no
phase separation.
THE
TIME-TEMPERATURE-TRANSFORMATION
67
68
reactions. These states include liquid, sol/gel rubber, gel rubber
(elastomer), ungelled (sol) glass, gelled glass, and char. The gelled
glass region in the TTT cure diagram is divided into two parts by the fullcure line; in the absence of degradation (Fig. 1 , devitrification and
char), the top and lower parts can be designated fully cured gel glass and
undercured sol/gel glass regions, respectively. The technological terms,
A - , B- and C-stage resins correspond to sol glass, sol/gel glass, and fully
cured gel glass, respectively. The illustration also displays the critical
temperatures Tgm, elTg, and Tgo, which are the glass-transition temperature of the fuyly cured system, the temperature at which gelation and
vitrification occur simultaneously, and the glass-transition temperature of
the reactants, respectively.
LOG TIME
Fig.
1.
69
The isothermal TTT cure diagram i s more l i m i t e d f o r t h e c u r i n g o f l i n e a r
rubber systems than f o r t h e r m o s e t t i n g systems because i n p r a c t i c e o n l y t h e
Gelation i n the vulcanization
r e g i o n above Tgm i s r e l e v a n t f o r t h e former.
o f rubbers occurs a t low conversions i n comparison w i t h t y p i c a l thermos e t t i n g systems.
The u n g e l l e d g l a s s y s t a t e i s t h e b a s i s o f commercial molding m a t e r i a l s
since, upon h e a t i n g , t h e u n g e l l e d ( s o l ) m a t e r i a l f l o w s b e f o r e g e l l i n g
through f u r t h e r r e a c t i o n .
Formulations can be processed as s o l i d s (eg,
> ambient temperature; they can be processed
molding compositions) when T
as l i q u i d s (eg, as c a s t i n g f j u i d s ) when Tgo < ambient temperature.
The g l a s s - t r a n s i t i o n temperature o f t h e m a t e r i a l a t t h e composition
corresponding t o g e l a t i o n i s gelTg, s i n c e g e l a t i o n occurs as t h e m a t e r i a l
v i t r i f i e s when t h e temperature o f cure i s gelTg ( 4 ) . The g e l a t i o n curve
( F i g . 1 ) t h e r e f o r e corresponds t o Tg = gelTg.
Temperature gelTg i s c r i t i c a l i n d e t e r m i n i n g t h e upper temperature f o r s t o r i n g r e a c t i v e m a t e r i a l s
However, c u r e below g e l T g
t o a v o i d g e l a t i o n (which r e l a t e s t o "pot l i f e " ) .
e v e n t u a l l y leads t o g e l a t i o n .
The morphology developed i n two-phase systems, f o r example, those i n which
r u b b e r - r i c h domains n u c l e a t e and grow as a dispersed phase, depends on
t h e temperature o f cure.
The r e a c t i o n temperature determines t h e comp e t i t i o n between thermodynamic and k i n e t i c ( i e , t r a n s p o r t ) f a c t o r s which
a f f e c t s t h e amount, t h e composition, and t h e d i s t r i b u t i o n o f dimensions o f
t h e dispersed phase. As an example, r e a c t i o n a t i n t e r m e d i a t e temperatures
can r e s u l t i n a maximum i n t h e amount o f p r e c i p i t a t e d phase which may g i v e
r i s e t o a minimum i n t h e t i m e t o t h e onset o f phase s e p a r a t i o n (as shown
i n F i g . 1 ) . For optimum mechanical p r o p e r t i e s , a two-phase system i s
cured f i r s t a t one temperature t o p r o v i d e a p a r t i c u l a r morphology, and
subsequently a t a h i g h e r temperature t o complete t h e r e a c t i o n s o f t h e
m a t r i x ( 5 , 6 ) . The Tga, o f t h e m a t r i x w i l l be determined by t h e e x t e n t o f
phase separation.
I n composite systems, shrinkage stresses due t o volume c o n t r a c t i o n o f t h e
r e s i n on i s o t h e r m a l cure b e g i n t o develop w i t h adhesion o f t h e c u r i n g
r e s i n t o a r i g i d inclusion.
T h i s occurs a f t e r g e l a t i o n above gelTg and
b e f o r e v i t r i f i c a t i o n below g e l T
The t e n s i l e s t r e s s e s i n t h e r e s i n and
t h e corresponding compressive s?resses on an i n c l u s i o n a f f e c t composite
behavior,
One consequence i s f i b e r - b u c k l i n g i n r e s i n / f i b e r composites.
A
r e l a t e d consequence o f the shrinkage due t o cure and t h e d i f f e r e n t coeff i c i e n t s o f expansion and c o n t r a c t i o n o f t h e c o n s t i t u e n t s i n b r i t t l e
r e s i n / f i b e r composites i s t h e f o r m a t i o n o f s p i r a l and h e l i c a l cracks i n
Their l a r g e surface
t h e r e s i n around i s o l a t e d f i l a m e n t s and yarns ( 7 , 8 ) .
areas per u n i t volume o f m a t r i x may c o n t r i b u t e t o t h e toughening o f
f i b e r / r e s i n composites.
The l i m i t i n g v i s c o s i t y i n t h e f l u i d s t a t e i s c o n t r o l l e d by g e l a t i o n above
gelTg, and by v i t r i f i c a t i o n below e l T g .
A t g e l a t i o n , t h e weight-average
molecular weight and zero shear-raqe v i s c o s i t y become i n f i n i t e , although
t h e number-average molecular weight i s very low. V i s c o s i t y i n t h e v i c i n i t y o f v i t r i f i c a t i o n below g e l T g , i ~ described by t h e
Williams-Landel-Ferry (WLF) equation ( 1 3 ) .
The t i m e t o reach a s p e c i f i e d v i s c o s i t y ( F i g . 1) i s o f t e n used as a pract i c a l method f o r measuring g e l a t i o n times. Although t h i s i s o v i s c o s i t y
approach i s i n c o n s i s t e n t w i t h the isoconversion t h e o r y o f g e l a t i o n , above
temperature gelTg, t h e apparent a c t i v a t i o n energies obtained from t h e temp e r a t u r e dependence o f the t i m e t o reach a s p e c i f i e d v i s c o s i t y approach
t h e t r u e a c t i v a t i o n energy f o r t h e chemical r e a c t i o n s l e a d i n g t o g e l a t i o n
w i t h increase o f t h e s p e c i f i e d v i s c o s i t y ( 1 ) .
The t i m e t o g e l a t i o n can be computed from t h e r e a c t i o n k i n e t i c s and the
conversion a t g e l a t i o n , which i s constant according t o F l o r y ' s t h e o r y o f
gelation.
The t i m e t o v i t r i f i c a t i o n can be computed from t h e r e a c t i o n
k i n e t i c s and t h e conversion a t v i t r i f i c a t i o n (14.15.16). which increases
w i t h Tcure.
Since v i t r i f i c a t i o n occurs when t h e g l a s s - t r a n s i t i o n temp e r a t u r e reaches t h e temperature o f cure, computation o f t h e time t o
v i t r i f y r e q u i r e s knowledge o f t h e r e l a t i o n s h i p between Tg and conversion.
F i g u r e 2 shows t h a t T increases w i t h conversion a t an i n c r e a s i n g r a t e .
I n t h e absence o f d i f q u s i o n c o n t r o l , t h e general k i n e t i c equation
describing the r e a c t i o n is:
71
dX/dt = A - e x p [ - E A / (RTq f ( X )
where X i s t h e e x t e n t o f r e a c t i o n , EA t h e a c t i v a t i o n energy, and t h e o t h e r
c h a r a c t e r s have t h e i r usual s i g n i f i c a n c e .
The times t o g e l a t i o n and t o
v i t r i f i c a t i o n can be computed versus temperature u s i n g t h i s equation when
X e l ( f o r g e l a t i o n ) , a r e l a t i o n s h i p between X and T g . ( f o r v i t r i f i c a t i o n )
( 2 i g . 2 ) , and t h e r e a c t i o n k i n e t i c s a r e known. The i n f l u e n c e o f d i f f u s i o n
c o n t r o l on t h e r e a c t i o n r a t e can be deduced i n p r i n c i p l e from t h e d i f ferences between t h e e x p e r i m e n t a l l y measured and t h e computed g e l a t i o n and
v i t r i f i c a t i o n curves.
Xgel
I
I
I
I
F i g . 2.
CONVERSION ( X )
Tg vs conversion a t v i t r i f i c a t i o n f o r r e a c t a n t s d i f f e r i n g i n
f u n c t i o n a l i t y (101 > 011). The conversions a t g e l a t i o n a r e also
included.
The diagram can be used to demonstrate t h e e f f e c t of
i n c r e a s i n g f u n c t i o n a l i t y of t h e r e a c t a n t s on g e l a t i o n , v i t r i f i c a t i o n , and t h e temperatures gelTg. Tgo, and Tgm.
72
approached.
Knowledge o f t h e minimum time and t h e corresponding temp e r a t u r e i s u s e f u l i n molding technology.
Cure of f i n i t e specimens a t temperatures below t h a t f o r the minimum t i m e
f o r v i t r i f i c a t i o n ( F i g . 1 ) w i l l lead t o t h e h o t t e r i n s i d e v i t r i f y i n g
b e f o r e t h e o u t s i d e when t h e r e a c t i o n i s exothermic. Conversely, cure a t
higher temperatures would l e a d i n p r i n c i p l e t o t h e o u t s i d e v i t r i f y i n g
before the inside:
i n t h i s case i n t e r n a l stresses develop as t h e i n s i d e
c o n t r a c t s r e l a t i v e t o t h e v i t r i f i e d o u t s i d e due t o t h e volume c o n t r a c t i o n
o f p o l y m e r i z a t i o n . S i m i l a r l y , c o o l i n g cured m a t e r i a l from above Tgm w i l l
lead t o t h e o u t s i d e v i t r i f y i n g b e f o r e t h e i n s i d e ; i n t e r n a l s t r e s s e s i n
t h i s case w i l l be minimized by c o o l i n g v e r y s l o w l y ( i . e . , annealing).
These stresses, which a r e due t o non-isothermal c o n d i t i o n s i n neat
systems, a r e supplemented i n composites by the d i f f e r e n t i a l shrinkage
stresses which were r e f e r r e d t o e a r l i e r i n t h e a r t i c l e .
The conversion a t v i t r i f i c a t i o n can be computed i n p r i n c i p l e by r e l a t i n g
t h e g l a s s - t r a n s i t i o n temperature t o c o n t r i b u t i o n s from t h e molecular
weight and t h e c r o s s - l i n k i n g d e n s i t y , b o t h o f which vary w i t h conversion
(16).
For p o l y m e r i z a t i o n p r i o r t o g e l a t i o n (and f o r l i n e a r
p o l y m e r i z a t i o n ) , t h e computation i s s i m p l i f i e d by t h e absence o f cross1i n k i n g .
The f r a c t i o n a l e x t e n t o f r e a c t i o n a t v i t r i f i c a t i o n and t h e t i m e t o
v i t r i f y , l i k e g e l a t i o n , decrease w i t h i n c r e a s i n g f u n c t i o n a l i t y o f t h e
The e f f e c t o f i n c r e a s i n g f u n c t i o n a l i t y on g e l a t i o n ,
reactants ( 1 2 ) .
can be understood
v i t r i f i c a t i o n , and t h e temperatures gelTg, Tgo, and T
by c o n s i d e r i n g t h e X-vs-T
and the X el
relationships?such
as those i n
For example, t f e f i g u r e S ~ O W Show temperature e l T g f o r t h e
F i g u r e 2.
m a t e r i a l o f lower f u n c t i o n a l i t y can be higher than t h a t
h i g h e r functionality.
03
73
LINEAR POLYMERIZATION AND THE TTT DIAGRAM
T h i s s e c t i o n attempts, i n a general manner, t o i n c o r p o r a t e l i n e a r p o l y m e r i z a t i o n o f neat systems i n t o t h e concept o f t h e TTT diagram.
O i f u n c t i o n a l l i q u i d monomers can be transformed i n t o g l a s s y l i n e a r p o l y meric m a t e r i a l s by r e a c t i o n below t h e maximum g l a s s t r a n s i t i o n temperature
o f t h e polymer, TP.,
The time t o v i t r i f i c a t i o n curve f o r t h e isothermal
f r e e - r a d i c a l p o l y m e r i z a t i o n o f neat s t y r e n e versus t h e isothermal temp e r a t u r e o f r e a c t i o n , Trx, has been computed i n t h e absence o f d i f f u s i o n
control (20).
The c a l c u l a t i o n i n v o l v e d using t h e w e l l e s t a b l i s h e d chemic a l k i n e t i c s from zero conversion t o t h e conversion corresponding t o T -
Trx.
Since t h e neat m i x t u r e a t any t i m e c o n s i s t s o f mostly monomer an8
polymer ( n e g l e c t i n g i n i t i a t o r and a c t i v e c h a i n r a d i c a l s ) , t h e p r o p o r t i o n
o f polymer t o monomer (i.e.,
t h e conversion) was c a l c u l a t e d from t h e g l a s s
t r a n s i t i o n temperatures o f t h e monomer (-100C) and polymer (+lOOC) and
Tg
TCqre.
The computed v i t r i f i c a t i o n curves f o r t h e f r e e - r a d i c a l p o l y m e r i z a t i o n o f s t y r e n e and f o r a l i n e a r - f o r m i n g step-growth p o l y m e r i z a t i o n
were S-shaped.
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