21

Advanced Thermal Analysis System (ATHAS)

Polymer Heat Capacity Data Bank
1
UMESHGAUR and BERNHARD WUNDERLICH
Rensselaer Polytechnic Institute, Department of Chemistry, Troy NY 12181
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Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

Heat capacity is the key thermodynamic property of a

material. It is well enough understood to permit, when deter-
mined over a wide range of temperature, the connection between
macroscopic thermodynamic properties and microscopic structure
and motion. Through the knowledge of heat capacity the other
thermodynamic functions, namely enthalpy, entropy, and Gibbs
energy can be derived.

H-H 0 = ∫ CpdT+ΔH + ∫ CpdT+ ΔH ...(1)

0
T1
1 T1
T2
2

S =∫ 0
T1
Cp/T dT + ΔH /T + ∫
1 1 T1
T2
Cp/T + ΔH /T ... (2)
2 2

G-H 0 = H - TS (3)

In these equations T , T ... represent equilibrium f i r s t

1 2

order transition temperatures and ΔH , ΔH ... the corres- 1 2

ponding equilibrium transition enthalpies. H is the enthalpy 0

of the material analyzed at 0 K.

Heat capacity theory permits a correlation with the chemical

structure of the repeating unit (1-3). In the solid state, only
vibrational contributions need to be considered (skeletal and
group vibrations). For an approximate discussion of the
skeletal vibrations, the molecule is considered to be a string
of structureless beads of the given formula weight. For linear
macromolecules with similar backbones, the geometry and force
constants are similar so that intramolecular skeletal vibrations
are fixed by the mass of the structureless bead. The inter-
molecular vibrations of linear macromolecules have quite low

1
Current address: Personal Products, Division of Johnson & Johnson, Milltown, NJ 08850

0097-6156/82/0197-0355$06.00/0
© 1982 American Chemical Society

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 356 COMPUTER APPLICATIONS IN APPLIED POLYMER SCIENCE

f r e q u e n c i e s and a r e few i n n u m b e r . They a r e u s u a l l y e x c i t e d

a l r e a d y b e l o w 50 K so t h a t t h e i r d e t a i l e d f r e q u e n c i e s must be
known o n l y f o r t h e h e a t c a p a c i t i e s b e l o w 50 K . Due t o t h e l a r g e
d i f f e r e n c e s i n f r e q u e n c y and g e o m e t r y o f t h e g r o u p and s k e l e t a l
v i b r a t i o n s , t h e g r o u p v i b r a t i o n s c a n be c o n s i d e r e d l a r g e l y
u n c o u p l e d f r o m t h e s k e l e t a l v i b r a t i o n s , and t h u s a r e o n l y
chemical s t r u c t u r e dependent. The same g r o u p w i l l g i v e t h e same
h e a t c a p a c i t y c o n t r i b u t i o n i n any m o l e c u l e . T h u s , a l l c o n t r i b u -
t i o n s t o heat c a p a c i t i e s o f l i n e a r m a c r o m o l e c u l e s , except t h e
i n t e r m o l e c u l a r s k e l e t a l v i b r a t i o n s , a r e dependent on t h e chem-
i c a l s t r u c t u r e o n l y , and a r e a d d i t i v e . Based upon t h e a b o v e
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h y p o t h e s i s , a c h e m i c a l s t r u c t u r e based heat c a p a c i t y p r e d i c t i o n
scheme f o r p o l y m e r s and c o p o l y m e r s was d e v e l o p e d i n o u r l a b o r a -
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

t o r y (2). To t e s t t h e a d d i t i o n scheme a h e a t c a p a c i t y d a t a b a s e
was e s t a b l i s h e d i n 1967. The h e a t c a p a c i t y a d d i t i o n scheme
c o u l d p r e d i c t t h e h e a t c a p a c i t y o f c a r b o n b a c k b o n e p o l y m e r s and
c o p o l y m e r s w i t h i n $% (2). H o w e v e r , t o f u r t h e r e x t e n d t h e a d d i -
t i o n scheme t o more c o m p l i c a t e d p o l y m e r s c o n t a i n i n g h e t e r o c h a i n
atoms and l a r g e s i d e g r o u p s , and t o r i g i d b a c k b o n e p o l y m e r s i n
t h e s o l i d s t a t e as w e l l as i n t h e l i q u i d s t a t e , a much l a r g e r
h e a t c a p a c i t y d a t a b a s e r e p r e s e n t i n g v e r y many t y p e s o f r e p e a t
u n i t was n e e d e d .

Heat c a p a c i t i e s o f p o l y m e r a r e c o m p l i c a t e d b y p h y s i c a l and
c h e m i c a l s t r u c t u r a l c h a n g e s , namely b y c h a n g e s i n c r y s t a l 1 i n i t y ,
c r y s t a l s t r u c t u r e , m o r p h o l o g y , t a c t i c i t y , m o l e c u l a r w e i g h t and
copolymer u n i t c o n t e n t . F u r t h e r m o r e t h e p i c t u r e c a n be c o m p l i -
c a t e d by c h a n g e s i n m e c h a n i c a l , t h e r m a l and p o s s i b l y e l e c t r i c a l
h i s t o r y of the polymer.

The m i c r o s c o p i c s t r u c t u r e o f p o l y m e r s i s p r i m a r i l y i d e n t i -
f i e d b y t h e c r y s t a l s t r u c t u r e and t h e c r y s t a l 1 i n i t y o f t h e
sample. It can produce s i g n i f i c a n t changes i n t h e heat c a p a c i t y
( e s p e c i a l l y a t v e r y low t e m p e r a t u r e and i n t h e t e m p e r a t u r e
r e g i o n between t h e g l a s s t r a n s i t i o n and t h e m e l t i n g t e m p e r a -
ture). Most h e a t c a p a c i t y s t u d i e s do n o t c o n t a i n d a t a on t h e
v a r i a t i o n in macroscopic s t r u c t u r e . For t h i s type o f a n a l y s i s ,
m e a s u r e m e n t s a r e needed on a l a r g e number o f s a m p l e s o f d i f f e r -
ing c r y s t a l 1 i n i t i e s . T h u s , t h e r e e x i s t s b e s i d e s e x t e n s i v e new
m e a s u r e m e n t s , a need f o r t h e c o l l e c t i o n o f a l l m e a s u r e d d a t a i n
a d a t a bank t o most e f f i c i e n t l y c o r r e l a t e h e a t c a p a c i t i e s w i t h
t h e m i c r o s c o p i c s t r u c t u r e and t o e x t r a p o l a t e t h e h e a t c a p a c i t y
data to the l i m i t i n g s t r u c t u r e s o f the m o l e c u l e s . O n l y on t h e
b a s i s o f a l a r g e volume o f c r i t i c a l y a n a l y z e d d a t a can t h e
d e t a i l e d s t r u c t u r e d e p e n d e n c e be d e r i v e d .

The g l a s s t r a n s i t i o n o f p o l y m e r s i s e a s i l y c h a r a c t e r i z e d by
thermal a n a l y s i s . A s h a r p i n c r e a s e i n h e a t c a p a c i t y on
u n f r e e z i n g over a narrow temperature r e g i o n i s o b s e r v e d . At

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 21. GAUR AND WUNDERLICH A THAS Polymer Heat Capacity Data Bank 357

p r e s e n t two e m p i r i c a l rules exist for estimation of this heat

c a p a c i t y change:
Wunderlich's rule (4) AC - 11.3 JK" 1
(mol b e a d ) ' 1
(4)
P
and B o y e r ' s r u l e (5) AC T = 15 + 0.04 T c a l g" 1
K"
1
(5)
P 9 9
where a bead i s d e f i n e d a s a m o l e c u l a r g r o u p i n g w h i c h c a n b e
c o n s i d e r e d a r i g i d bead i n t h e m o l e c u l e . In t h e r e c e n t p a s t
we have f o u n d many e x c e p t i o n s t o b o t h t h e r u l e s ( 3 . 6 ) . Most
o f t h e d e v i a t i o n s were f o r p o l y m e r s c o n t a i n i n g l a r g e a r o m a t i c
g r o u p s , w h i c h c o n t r i b u t e a l m o s t t w i c e a s much t o t h e h e a t
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c a p a c i t y i n c r e a s e a s s m a l l e r b e a d s s u c h a s CH - . T h i s c r e a t e s
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

t h e need f o r a l a r g e , c r i t i c a l l y e v a l u a t e d d a t a b a s e f o r h e a t
c a p a c i t y changes at t h e g l a s s t r a n s i t i o n . As f o r t h e h e a t
c a p a c i t y i t s e l f , c o n s i d e r a b l e changes i n g l a s s t r a n s i t i o n
t e m p e r a t u r e , t e m p e r a t u r e r a n g e , and d e t a i l e d h e a t c a p a c i t y
v a l u e s ( h y s t e r e s i s ) a r e observed f o r samples f o r n o n - s t a n d a r d
t h e r m a l and m e c h a n i c a l h i s t o r i e s .

The f i r s t o r d e r p h a s e t r a n s i t i o n s , p r i m a r i l y i d e n t i f i e d
w i t h t h e m e l t i n g t r a n s i t i o n , make up t h e f i n a l t h e r m a l c h a r a c -
terization of a material. E q u i l i b r i u m h e a t s o f t r a n s i t i o n and
t r a n s i t i o n t e m p e r a t u r e s a r e needed t o u s e e q s . 1-3 f o r a f u l l -
range thermal c h a r a c t e r i z a t i o n . A larger discussion of the
i n t e r p r e t a t i o n and p r e d i c t i o n o f m e l t i n g t e m p e r a t u r e s h a s been
g i v e n r e c e n t l y (7). In b r i e f , q u i t e f r e q u e n t l y t h e h e a t o f
f u s i o n p e r l a r g e atom i n a macomodecule ( s u c h a s C, 0, N , b u t
e x c l u d e H) i s 2.4 (+0.3) kJ/mol and t h e e n t r o p y o f f u s i o n p e r
f l e x i b l e m a i n c h a i n segment ( s u c h a s CH - , 0 - , C , H , , CH=CH-,
C0-NH-, e t c . ) i s 9-5 (+1.4) J / ( K m o l ) . These + q u a n t i t i e s a r e
l i n k e d by t h e m e l t i n g t e m p e r a t u r e .

(6)
H
T = A f

The e r r o r l i m i t s g i v e n i n A H - and AS^ a r e d e r i v e d f r o m a

c r i t i c a l e v a l u a t i o n o f a b o u t 4o d i f f e r e n t m a c r o m o l e c u l e s ( ] ) •
As i n h e a t c a p a c i t i e s and g l a s s t r a n s i t i o n s , e x t e n s i o n o f t h e
d e s c r i p t i o n o f m a c r o m o l e c u l e s i s p o s s i b l e ( n e c e s s a r y ) when
considering the normally present n o n - e q u i l i b r i u m s t a t e s .
P a r t i a l c r y s t a l l i z a t i o n , s m a l l c r y s t a l s i z e s , i m p u r i t y and
c o p o l y m e r c o n t e n t , and s t r a i n i n g o f m o l e c u l e s f r o m t h e random
c o i l c o n f o r m a t i o n a r e t h e major e f f e c t s t o be c o n s i d e r e d . The
c h a n g e s o f h e a t s o f t r a n s i t i o n and t e m p e r a t u r e s o f t r a n s i t i o n
and t h e i r u s e t o c h a r a c t e r i z e t h e n o n - e q u i l i b r i u m s t a t e have
been g i v e n an i n i t i a l c r i t i c a l s u r v e y ( j O .

In t h i s p a p e r o u r e f f o r t s a r e d i r e c t e d t o w a r d s t h e e s t a b -
1 i s h m e n t o f a h e a t c a p a c i t y d a t a bank w h i c h a r e d e t a i l e d . Of
n e c e s s i t y , t h e i n i t i a l s t e p s a r e d i r e c t e d towards t h e e q u i l i -
brium p r o p e r t i e s . Extensions to include glass t r a n s i t i o n s ,

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 358 COMPUTER APPLICATIONS IN APPLIED POLYMER SCIENCE

m e l t i n g t r a n s i t i o n s * and u l t i m a t e l y a l s o s o l i d - s o l i d and
mesophase t r a n s i t i o n s a r e i n v a r i o u s s t a g e s o f p l a n n i n g . A
f i n a l s t e p must be t h e e x t e n s i o n o f t h e d a t a bank t o n o n -
equilibrium properties.

The P o l y m e r Heat C a p a c i t y D a t a Bank

To a d d r e s s o u r e f f o r t s t o w a r d s c o r r e l a t i n g t h e m a c r o s c o p i c -
a l l y measured heat c a p a c i t y d a t a t o t h e i r m i c r o s c o p i c o r i g i n ,
t h e d a t a b a s e s t a r t e d i n t h e 1960's was u p d a t e d and c o m p u t e r i z e d
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a b o u t f i v e y e a r s ago ( 8 J . The d a t a bank i s now i n c o r p o r a t e d

w i t h i n ATHAS, A d v a n c e d T h e r m a l A n a l y s i s * a l a b o r a t o r y f o r
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

r e s e a r c h and i n s t r u c t i o n . The d a t a b a n k m a i n t a i n s a c o l l e c t i o n
o f more t h a n 500 p u b l i c a t i o n s o n h e a t c a p a c i t i e s o f p o l y m e r s
w h i c h i n c l u d e s a l l measurements e v e r r e p o r t e d . The p u b l i c a t i o n
l i s t i s updated e v e r y s i x months. From e a c h p u b l i c a t i o n t h e
following information is retrieved:

1. polymers studied
2. temperature range s t u d i e d
3. t h e r m a l h i s t o r y and s a m p l e c h a r a c t e r i z a t i o n
4. e x p e r i m e n t a l t e c h n i q u e used and c l a i m e d u n c e r t a i n t y
5. accuracy of representation of data.

Based upon t h e above i n f o r m a t i o n * t h e p u b l i c a t i o n i s t h e n c r i t i -

c a l l y a s s e s s e d f o r q u a l i t y and r e l i a b i l i t y o f t h e h e a t c a p a c i t y
data. Judgments f o r e v a l u a t i n g t h e q u a l i t y o f h e a t c a p a c i t y
d a t a a r e b a s e d upon t h e f o l l o w i n g :

a) c h a r a c t e r i z a t i o n o f t h e s a m p l e s used f o r h e a t c a p a c i t y
measurements
b ) e x p e r i m e n t a l t e c h n i q u e used and r e p o r t e d u n c e r t a i n t y
c ) r e p r e s e n t a t i o n o f d a t a , and
d) v i s u a l c o m p a r i s o n o f d a t a w i t h o t h e r i n v e s t i g a t i o n s .

The p r i n c i p l e s f o l l o w e d i n s e l e c t i n g acceptable data

a r e , b r i e f l y , as f o l l o w s :

a) P u r i t y and m o r p h o l o g i c a l c h a r a c t e r i z a t i o n o f t h e s a m p l e s
are examined. D a t a on u n c h a r a c t e r i z e d , c o m m e c i a l
p l a s t i c s are considered u n r e l i a b l e . The k e y c h a r a c t e r -
i z a t i o n parameter u s e f u l f o r our a n a l y s i s , b e s i d e s
m o l e c u l a r w e i g h t and t h e r m a l h i s t o r y , i s t h e c r y s t a l -
1 i n i t y o f the sample. C r y s t a l 1 i n i t y c a l c u l a t e d from
d e n s i t y measurement i s p r e f e r r e d o v e r i t s d e t e r m i n a t i o n
f r o m t h e h e a t o f f u s i o n , X - r a y and IR s p e c t r o s c o p y .
C r y s t a l 1 i n i t y d e t e r m i n a t i o n f r o m e n t h a l p y and t h e h e a t
c a p a c i t y change at t h e g l a s s t r a n s i t i o n a r e c o n s i d e r e d
least r e l i a b l e .

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 21. GAUR AND WUNDERLICH ATHAS Polymer Heat Capacity Data Bank 359

b ) The e x p e r i m e n t a l a s p e c t s a r e e x a m i n e d f o r e a c h m e a s u r e -
ment. The r e l i a b i l i t y o f t h e m e a s u r i n g t e c h n i q u e , as
d e t e r m i n e d from r e s u l t s on s t a n d a r d c a l i b r a t i o n m a t e -
r i a l s , is considered important. Below 100 K , a d i a b a t i c
c a l o r m e t r i c r e s u l t s a r e i n g e n e r a l c o n s i d e r e d more
r e l i a b l e than d i f f e r e n t i a l scanning c a l o r i m e t r i c
measurements. From 200 t o 350 K , d e p e n d i n g upon t h e
s o p h i s t i c a t i o n o f t h e i n s t r u m e n t and a v e r a g i n g p r o c e d u r e s
u s e d , t h e d i f f e r e n t i a l s c a n n i n g c a l o r i m e t r y and a d i a b a t i c
c a l o r i m e t r y d a t a may be c o n s i d e r e d e q u a l l y g o o d . Above
350 K , i n c e r t a i n c a s e s , due t o m e t a s t a b i 1 i t y o f t h e
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samples, d i f f e r e n t i a l scanning c a l o r i m e t r y r e s u l t s are

often preferred over a d i a b a t i c c a l o r i m e t r y .
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

c) Heat c a p a c i t y d a t a r e p r e s e n t e d o n l y by s m a l l g r a p h s w h i c h
c a n n o t be r e a d a c c u r a t e l y a r e n o t c o n s i d e r e d r e l i a b l e .
T a b u l a t e d d a t a a r e c o n s i d e r e d more r e l i a b l e t h a n
graphical data. I f raw h e a t c a p a c i t y d a t a p o i n t s a r e
r e p o r t e d by i n v e s t i g a t o r s , t h e i r d a t a a r e c u r v e f i t t e d
and t h e h e a t c a p a c i t y f u n c t i o n o b t a i n e d i s p r e f e r r e d o v e r
t h e t a b u l a t e d and g r a p h i c a l v a l u e s .

d) I f any measurement shows o b v i o u s , s i g n i f i c a n t d e v i a t i o n s

from o t h e r d a t a s e t s o f c o m p a r a b l e s a m p l e s , t h e d a t a a r e
questioned. Such d i s c r e p a n c i e s a r e u s u a l l y s e v e r a l
s t a n d a r d d e v i a t i o n s and i n d i c a t e s y s t e m a t i c e r r o r s .

The a c c e p t a b l e h e a t c a p a c i t y d a t a a r e s t o r e d on m a g n e t i c
t a p e i n t e m p e r a t u r e i n t e r v a l s o f 0.1 K up t o 1 K , 0.2 K t o 2 K ,
1 K t o 10 K , 2 K t o 20 K , and 5 K t o 30 K . A t t e m p e r a t u r e s
h i g h e r t h a n 30 K , i n t e r v a l s o f 10 K a r e u s e d . If the data are
n o t r e p o r t e d i n t h e t e m p e r a t u r e i n t e r v a l s d e s i r e d by u s , t h e
data are i n t e r p o l a t e d . The s p l i n e f u n c t i o n t e c h n i q u e i s used t o
d e t e r m i n e t h e i n t e r p o l a t e d heat c a p a c i t y at d e s i r e d t e m p e r a t u r e .
I f unsmoothed d a t a have been r e p o r t e d by t h e a u t h o r s , t h e d a t a
a r e smoothed by c u r v e - f i t t i n g p r i o r t o s t o r a g e .

A H e w l e t t - P a c k a r d c a l c u l a t o r ( m i n i c o m p u t e r ) o f t y p e 9821A,
e q u i p p e d w i t h m a g n e t i c t a p e d e c k and i n t e r f a c e d w i t h t h e r m a l
l i n e p r i n t e r HP 9866B and p l o t t e r HP 9862A i s t h e d a t a h a n d l i n g
system. Computer p r o g r a m s have been d e v e l o p e d t o g o v e r n i n t e r -
p o l a t i o n , c u r v e f i t t i n g , d a t a s t o r a g e , t a b u l a t i o n and p l o t t i n g
o f the heat c a p a c i t y d a t a . P r o g r a m s have a l s o been d e v e l o p e d
f o r a s s i s t a n c e i n c o m p a r i s o n and c r i t i c a l a s s e s s m e n t o f t h e d a t a
and t o f u r t h e r a n a l y z e t h e d a t a t o d e t e r m i n e t h e b e s t h e a t c a p a -
c i t y values. S u b r o u t i n e s have been w r i t t e n t o c o r r e l a t e t h e
h e a t c a p a c i t y d a t a and t h e m o r p h o l o g i c a l p r o p e r t i e s t o d e t e r m i n e
t h e h e a t c a p a c i t y o f c o m p l e t e l y amorphous and c o m p l e t e l y
c r y s t a l l i n e l i n e a r macromolecules. A d e t a i l e d l i s t i n g of these

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 360 COMPUTER APPLICATIONS IN APPLIED POLYMER SCIENCE

p r o g r a m s and t h e Instructions for their operations are given in

r e f e r e n c e 8.

Results

The d a t a bank c o n t a i n s i n o v e r 800 t a b l e s a l l i n f o r m a t i o n on

the heat c a p a c i t y o f polymers. These a c c e p t a b l e heat c a p a c i t y
d a t a have been c o m p u t e r p r o c e s s e d * t o d e r i v e f o r t h e f i r s t t i m e
a c o m p r e h e n s i v e s e t o f recommended d a t a . At p r e s e n t , recom-
mended d a t a a r e a v a i l a b l e f o r 96 p o l y m e r s . T h e s e recommended
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d a t a are summarized i n t h e t a b l e b e l o w . They a r e b e i n g d i s c u s -

sed i n n i n e s u c c e s s i v e p a p e r s i n t h e J o u r n a l o f P h y s i c a l and
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

C h e m i c a l R e f e r e n c e D a t a (1981/82). The f i r s t two p a p e r s h a v e

a l r e a d y been p u b l i s h e d (9, 10).

No. o f Manuscr i p t
P u b l i c a t ion Polymers Pages

1. Selenium 1 81
2. Polyethylene 1 91
3. Polypropylene 1 62
h. Polystyrene 1 52
5. Polyoxides 12 150
6. A c r y l i c Polymers 15 95
7. Other Carbon Backbone Polymers 2k 170
8. P o l y e s t e r s and P o l yam i d e s 10 120
9. A r o m a t i c and I n o r g a n i c P o l y m e r s 31 103

The recommended d a t a a r e , whenever p o s s i b l e , e x t r a p o l a t e d t o

the l i m i t i n g macroconformation t o determine the heat c a p a c i t y o f
t h e c r y s t a l l i n e and amorphous s t a t e s . In c a s e s where low t e m -
p e r a t u r e d a t a are a v a i l a b l e , t h e thermodynamic f u n c t i o n s ;
e n t r o p y , e n t h a l p y and G i b b s e n e r g y h a v e a l s o been c a l c u l a t e d .

The recommended h e a t c a p a c i t y d a t a a r e c u r r e n t l y b e i n g a n a -
l y z e d in terms o f chemical s t r u c t u r e , s t r u c t u r e o f the polymers
i n t h e g l a s s y , c r y s t a l l i n e and m o l t e n s t a t e s . The d a t a a r e
f u r t h e r being analyzed to study the e f f e c t of branching, mole-
c u l a r w e i g h t and t a c t i c i t y on t h e h e a t c a p a c i t y o f p o l y m e r s .
Comprehensive t a b u l a t i o n o f heat c a p a c i t i e s o f v a r i o u s s t r u c -
t u r a l u n i t s a r e b e i n g p r e p a r e d and w i l l be a v a i l a b l e i n t h e n e a r
future.

From t h e recommended d a t a , a c o m p i l a t i o n o f h e a t c a p a c i t y
c h a n g e s a t t h e g l a s s t r a n s i t i o n has been made. These d a t a are

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 21. GAUR AND WUNDERLICH ATHAS Polymer Heat Capacity Data Bank 361

being analyzed in terms o f the hole theory o f the g l a s s t r a n s i -

t i o n t o p o s s i b l y d e v e l o p an a d d i t i o n scheme f o r A C a t T .
P g

F u t u r e o f t h e P o l y m e r Heat C a p a c i t y D a t a Bank

The p o l y m e r h e a t c a p a c i t y d a t a bank i s , as o u t l i n e d i n t h e
I n t r o d u c t i o n , is o n l y the f i r s t step towards the establishment
o f a c o m p r e h e n s i v e Thermal P r o p e r t i e s D a t a B a n k . P r e s e n t l y we
are expanding our e f f o r t s t o i n c l u d e g l a s s t r a n s i t i o n tempera-
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t u r e s , m e l t i n g t e m p e r a t u r e s and h e a t s o f f u s i o n . In t h e p l a n -
n i n g s t a g e a r e s p e c i f i c v o l u m e , c o m p r e s s i b i l i t y , and t h e r m a l
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

c o n d u c t i v i t y d a t a b a n k s , as w e l l as t h e e x p a n s i o n t o n o n - e q u i l -
ibrium p r o p e r t i e s .

Based on t h e s t r u c t u r e - r e l a t e d a d d i t i o n schemes f o r t h e
t h e r m a l p r o p e r t i e s , i t s h o u l d , f o r e x a m p l e , be p o s s i b l e t o
q u a n t i t a t i v e l y generate d i f f e r e n t i a l scanning c a l o r i m e t r y curves
f o r p o l y m e r s , c o p o l y m e r s and t h e i r m i x t u r e s . With easy access
t o t h e d a t a b a n k , i t s h o u l d be p o s s i b l e f o r t h e r m a l a n a l y s t s t o
compare t h e i r n e w l y measured DSC c u r v e s w i t h t h e c o m p u t e r
generated standard curves f o r o n - l i n e a n a l y s i s o f macro-
molecules.

T h i s improvement o f t h e D a t a Bank t o c o m p u t e r h a n d l i n g i s
p r e s e n t l y b e i n g t e s t e d and d i s c u s s e d . Our g o a l i s t o t r a n s f e r
t h e D a t a Bank t o t h e RPI IBM 3033 c o m p u t e r w h i c h s h o u l d be
a c c e s s i b l e i n t h e f u t u r e t h r o u g h c o m p u t e r n e t w o r k s s u c h as
TELENET. The d a t a management i s p r e s e n t l y e x p l o r e d u s i n g t h e
SPIRES s y s t e m ( S t a n f o r d P u b l i c I n f o r m a t i o n R e t r i e v a l S y s t e m ) . A
b r i e f o u t l i n e o f t h e d e v e l o p m e n t s t a g e s o f t h i s e f f o r t i s as
follows:

1. Input Block

To f i n d t h e needed p o l y m e r we a r e e x p l o r i n g
e x t e n s i v e l i s t s o f s y n o n y m s , s o u r c e and s t r u c t u r e b a s e d
names, and n a m e - s t r u c t u r e c o r r e l a t i o n s so t h a t e n t r y
i n t o t h e d a t a bank i s p o s s i b l e from e v e r y r e c o g n i z a b l e
d e s c r i p t i o n o f the macromolecule. The f i n a l l y c h o s e n
p o l y m e r w i l l be c h a r a c t e r i z e d by i t s r e p e a t i n g u n i t
f o r m u l a ( f o r a d d i t i o n s c h e m e s ) , a s y s t e m number
( a r b i t r a r y f o r d a t a s e a r c h ) , and t h e b e s t name ( f o r
report output).

Out o f t h i s b l o c k t h e u s e r w o u l d e n t e r t h e D a t a
Bank p r o p e r . We e n v i s i o n f o u r i n t e r a c t i n g d a t a b a n k s
o f w h i c h we have c h o s e n t h e Heat C a p a c i t y D a t a Bank f o r

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 362 COMPUTER APPLICATIONS IN APPLIED POLYMER SCIENCE

c l o s e r s c r u t i n y and i n i t i a l d e v e l o p m e n t . The o t h e r
t h r e e d a t a banks are the PVT-Data Bank. T r a n s i t i o n Data
B a n k , and Thermal C o n d u c t i v i t y D a t a B a n k . Their inter-
a c t i o n becomes c l e a r from e g s . 1 t o 3 w h i c h i l l u s t r a t e s
t h e need o f t r a n s i t i o n d a t a . Changes f r o m C t o C
w h i c h a r e needed f o r c o m p a r i s o n o f e x p e r i m e n t a l anci
c a l c u l a t e d d a t a i l l u s t r a t e h e a t c a p a c i t y and P V T - d a t a
bank i n t e r a c t i o n .

2. Heat C a p a c i t y D a t a Bank
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A. Recommended Data
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

The recommended d a t a , as d e v e l o p e d a b o v e , f o r m
s u b b l o c k A o f t h e Heat C a p a c i t y D a t a B a n k . They c a n be
r e t r i e v e d as s u c h , o r t h e y c a n be s e a r c h e d f o r t h e i r
b a s e ( i . e . , d e t a i l e d r e f e r e n c e s and d a t a t a b l e s ) and
a l s o f o r a d d i t i o n a l , non-used d a t a ( d e t a i l e d r e f e r e n c e s
and d a t a t a b l e s as w e l l as r e a s o n s f o r e x c l u s i o n - see,
f o r e x a m p l e R e f s . 9 and 10). I f t h e r e a r e no r e c o m -
mended d a t a , o r o n l y i n s u f f i c i e n t recommended d a t a a r e
a v a i l a b l e o r i f i n f o r m a t i o n on p r e d i c t i o n schemes i s
r e q u e s t e d , b l o c k B o f t h e Heat C a p a c i t y D a t a Bank i s
entered.

B. Prediction Schemes

T h i s s u b b l o c k o f t h e Heat C a p a c i t y D a t a Bank
c o n t a i n s e m p i r i c a l as w e l l as t h e o r e t i c a l prediction
c a l c u l a t i o n s o f the heat c a p a c i t y which are c o n t i n u -
ously updated. Based on t h e c h e m i c a l s t r u c t u r e
( b a c k - b o n e , s i d e - c h a i n ) as w e l l as on t h e p h y s i c a l
s t a t e ( g l a s s , c r y s t a l , mesophase, l i q u i d , semicrystal-
l i n e , e q u i l i b r i u m , h i s t o r y ) , a heat c a p a c i t y i s
retrieved. The P r e d i c t i o n Scheme s u b b l o c k c a n a l s o be
searched f o r i t s base, i . e . , the p r e c i s e assumptions
w h i c h go i n t o t h e p r e d i c t i o n , w i t h d o c u m e n t a t i o n t o t h e
1iterature.

C. Calculation Block

The f i n a l s u b b l o c k o f t h e Heat C a p a c i t y D a t a Bank

i n v o l v e s p r o g r a m s f o r needed c a l c u l a t i o n s in the
thermal a n a l y s i s f i e l d . The s i m p l e s t a g e s i n v o l v e d a t a
t r e a t m e n t f o r i n p u t and o u t p u t , c a l c u l a t i o n o f d e r i v e d
f u n c t i o n s as g i v e n , f o r e x a m p l e , i n e g s . 1 t o 3.
F u r t h e r s t a g e s i n c l u d e t h e d a t a a n a l y s i s i n form o f
Debye and T a r a s o v 8 - t e m p e r a t u r e s and g r o u p v i b r a t i o n
f r e q u e n c i e s , a stage already completed (!!)• Self-

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 21. GAUR AND WUNDERLICH A THAS Polymer Heat Capacity Data Bank 363

a d a p t i v e i n t e g r a t i o n r o u t i n e s and s e l f - g e n e r a t i o n o f
t h e v a r i o u s h e a t c a p a c i t y t a b l e s have been d e v e l o p e d .
C a l c u l a t i o n r o u t i n e s f o r l i q u i d h e a t c a p a c i t i e s and
h i s t o r y e f f e c t s are s i m i l a r l y contemplated.

O v e r a l l t h e n , t h e d a t a bank w o u l d r e p r e s e n t an u p - t o - d a t e know-
ledge o f thermal data o f macromolecules. S i n c e the computer
s t o r a g e p e r m i t s c o n s t a n t u p d a t i n g , i t w i l l always remain
current. N a t u r a l l y , a s e r i e s o f easy e x t e n s i o n s o f such a
system are p o s s i b l e . The e x t e n s i v e r e f e r e n c e l i s t s c o v e r i n g a l l
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a s p e c t s o f t h e r m a l a n a y l y s i s c a n be a c c e s s e d s e p a r a t e l y and used
for l i t e r a t u r e searches. Furthermore, our i n t e r e s t in teaching
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

o f f e r s the i n c o r p o r a t i o n o f i n s t r u c t i o n a l blocks into the data

b a n k s r a n g i n g from s i m p l e "how t o d o " t o b a s i c t h e o r y . Audio
c o u r s e s have a l r e a y d been d e v e l o p e d i n t h e s e a r e a s (1_2) and
p r e s e n t l y computer c o u p l e d t e a c h i n g i s e x p l o r e d .

A l t h o u g h some o f t h e f u t u r e j u s t o u t l i n e d seems t o be f a r
f u t u r e , we f e e l t h a t t h i s c o u r s e o f a c t i o n i s t h e n e x t needed
s t e p i n the development o f thermal a n a l y s i s .

Append i x

A t y p i c a l example o f c o m p u t e r p r o c e s s i n g o f l i t e r a t u r e d a t a
t o y i e l d t h e recommended d a t a . F i g u r e s 1, 2, and 3 a r e c o m p u t e r
p l o t s o f a l l l i t e r a t u r e d a t a on t r i g o n a l , g l a s s y and m o l t e n
selenium. The f i n a l c o m p u t e r r e d u c e d r e c o m m e n d a t i o n d a t a a r e
shown i n f i g u r e 4.

T w e n t y - t h r e e i n v e s t i g a t i o n s have been r e p o r t e d i n t h e l i t e r -
a t u r e on t h e h e a t c a p a c i t y o f s e l e n i u m . Although the heat c a p a -
c i t y o f o v e r f o r t y s a m p l e s have been m e a s u r e d , o n l y 13 o f t h e 23
i n v e s t i g a t i o n s c o n t a i n i n g d a t a on 20 s a m p l e s had a c c e p t a b l e
data. U n a c c e p t a b l e d a t a f o r t r i g o n a l s e l e n i u m c o u l d be e a s i l y
e l i m i n a t e d due t o l a r g e s y s t e m a t i c d e v i a t i o n s . For g l a s s y
s e l e n i u m the d a t a c l o s e t o the g l a s s t r a n s i t i o n r e g i o n s showing
d e v i a t i o n s were d i s c a r d e d . In t h e m o l t e n s t a t e , due t o c o m p l i -
c a t i o n s o f r i n g - c h a i n e q u i l i b r i u m , d a t a measured i n o u r l a b o r a -
t o r y on c o o l i n g (shown as a ) and t h e a d i a b a t i c c a l o r i m e t r y
d a t a (shown as +) were p r e f e r r e d o v e r a l l o t h e r measurements
w h i c h were d i f f e r e n t i a l s c a n n i n g c a l o r i m e t r y d a t a o f l e s s e r
precision ( £ ) .

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 364 C O M P U T E R A P P L I C A T I O N S IN A P P L I E D P O L Y M E R S C I E N C E
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Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

120 240 360 600

Temperature ( K )

Figure 1. Computer plot of all literature data on trigonal selenium. Key: •, data
measured in this laboratory and +, adiabatic calorimetry data. See Ref. 9 for fur-
ther explanation.

200

Temperature ( K )

Figure 2. Computer plot of all literature data on vitreous selenium. Key: data
measured in this laboratory and +, adiabatic calorimetry data. See Ref. 9 for fur-
ther explanation.

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 21. GAUR AND WUNDERLICH A THAS Polymer Heat Capacity Data Bank 365

•I I I I'

H I

H0

o 3 3

s 3H
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37
o
OS
P< 3B
Publication Date: September 24, 1982 | doi: 10.1021/bk-1982-0197.ch021

as
O
•+•> 35
aS

w 3H

33

Temperature (K)

Figure 3. Computer plot of all literature data on liquid selenium. Key: • , data
measured in this laboratory and +, adiabatic calorimetry data. See Ref. 9 for fur-
ther explanation.

50

o
a
25

aS
P<
as
O
-<->
as

w
S S 9 S P. i i.
1 I
0^ • I >.

Temperature (K)

Figure 4. Final computer reduced recommendation data on selenium. Key: a,

vitreous; b> trigonal; and c, liquid.

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.
 366 COMPUTER APPLICATIONS IN APPLIED POLYMER SCIENCE

Acknow!edgements

This work has been supported by the Polymers Program of

the National Science Foundation, Grant Number DMR 78—15279.

Literature Cited
1. B. Wunderlich and H. Baur, Adv. Polymer Sci.,7,151
(1970).
2. B. Wunderlich and L. D. Jones, J. Macromol. Sci. B3, 67
Downloaded by MICHIGAN STATE UNIV on February 18, 2015 | http://pubs.acs.org

(1969).
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3. U. Gaur and B. Wunderlich. Polymer Div. Am. Chem. Soc.

Preprints 20, 429 (1979).
4. B. Wunderlich, J. Phys. Chem. 64, 1052 (1960).
5. R. F. Boyer, J. Macromol. Sci.-Phys. B7, 487 (1973).
6. R. C. Bopp, U. Gaur, R. P. Kambour, and B. Wunderlich, to
be published.
7. B. Wunderlich, "Macromolecular Physics, Vol. 3. Crystal
Melting." Academic Press, New York, 1981.
8. U. Gaur, Ph.D. Thesis, Rensselaer Polytechnic Institute
(1979).
9. U. Gaur, H.-C. Shu, A. Mehta, and B. Wunderlich,
J. Phys. Chem. Ref. Data,10,89 (1981).
10. U. Gaur and B. Wunderlich, J. Phys. Chem. Ref. Data, 10,
119 (1981).
11. Yu. V. Cheban, S.-F. Lau, and B. Wunderlich, Colloid
Polymers Sci. to be published 1982.
12. B. Wunderlich, Rensselaer Audio Courses in Thermal
Anaysis and Polymers. For information contact the
author or the Office of Continuing Study, Rensselaer
Polytechnic Institute, Troy, N.Y. 12181;
Telephone (518) 270-6442.
RECEIVED May 17, 1982.

In Computer Applications in Applied Polymer Science; Provder, T.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1982.