Heat Capacity and Other Thermodynamic Properties of Linear Macromolecules. VIII. Polyesters and Polyamides

Heat Capacity and Other Thermodynamic Properties of Linear
Macromolecules. VIII. Polyesters and Polyamides

Umesh Gaur, Suk-fai Lau, Brent B. Wunderlich, and Bernhard Wunderlich
Department o/Chemistry, Rensselaer Polytechnic Institute, Troy, New York 12181
Heat capacity of polyglycolide, polY(E-caprolactone), poly(ethylene terephthalate),

poly(ethylene sebacate), polyglycine, poly(L-alanine), poly(L-valine),nylon 6, nylon 6.6,
~~LnY!9!1§J~j~x~~~\V_~__ ontheQ~sis Qfmeasurern~ntR on 35 samples_reported in the-
literature. All heat capacity data are compiled and a set of recommended data have been
derived for each polymer. Crystallinity dependence is critically evaluated for poly(ethyl-
ene terephthalate). Enthalpy and entropy functions are calculated for amorphous poly-
(ethylene terephthalate). This is the eighth paper in a series of publications which will
ultimately cover all heat capacity measurements of linear macromolecules.
Key words: amorphous; crystal; enthalpy; entropy; fusion; glass transiton; heat capacity; polyester;
polyamide; polypeptide; nylon; thermodynamic properties.
Contents
Page
1. Introduction ........................................................ 66 Table 4. Recommended heat capacity data for semi-

-2-;-HeatCeapacity-of-Polyesters~ .............. , 66- crystalline(wc--=-O; 67)poly-glyooIioe ...... -69--
2.1. Introduction ........ .......... .............. ............... 66 Table 5. Recommended heat capacity data for mol-
2.2. Literature data on heat capacity of polyes- ten polyglycolide ......................................... 69
ters .............................................................. 67 Table 6. Heat capacity measurements of polY(E-ca-
2.3. Recommended data on heat capacity and prolactone) .................................................. 70
thermodynamic functions of polyesters...... 68 Table 7. Recommended heat capacity data for semi-
2.3.1. Polyglycolide.................................... 68 crystalline (we = 0.76) polY(E-caprolactone}.. 70
2.3.2. PolY-(E-caprolactone) ....................... 70 Table 8. Recommended heat capacity data for mol-
2.3.3. Poly(ethylene terephthalate) ............ 71 ten polY{E-caprolactone) .............................. 71
2.3.4. Poly{ethylene sebacate) .................... 74 Table 9. Heat capacity measurements of poly(ethyl-
3. Heat Capacity ofPolyamides ...................... ~...... 77 ene terephthalate) ........................................ 72
3.1. Introduction ............................................... 77 Table 10. Recommended thermodynamic data for
3.2. Heat capacity of polypeptides..................... 78 amorphous poly(ethylene terephthalate) ..... 75
3.3. Heat capacity of nylons .............................. 83 Table 11. Heat capacity vs crystallinity. Results of
3.3.1. Literature data on heat capacity of 'curve fitting data into 'the equation
nylons............................................... 83 Cp = wCCp c + (1 + wC)C~ ........................ 76
3.3.2. Recommended data on heat capacity Table 12. Heat capacity measurements of poly(ethyl-
of nylons ......................... ........ .......... 83 ene sebacate) ............................................... 76
4. Conclusions ........................................................ 88 Table 13. Heat capacity data for poly(ethylene seba-,
5. References ~.......................................................... 88 cate) ............................................................. 76
Table 14. Crystal structures of polypeptides .............. 77
Table 15. Crystal structures and thermal properties of
List of Tables nylons .......................................................... 77
Table 1. Crystal structures and'thermal properties of Table 16. Heat capacity measurements ofpolyglycine 78
polyesters .... ............ .............. ......... ............. 67 Table 17. Heat capacity of polyglycine I .................... 78
Table 2. Heal capacity investigations on polyesters Table 18. Heat capacity of polyglycine II ....... ........... 79
not included in this study ........... ~............... 68 Table 19. Heat capacity measurements of poly(L-
Table 3. Heat capacity measurements of poly(glyco- alanine) ... ........ ........... .............. .................... 80
lide) ............................................................. 68 Table 20. Heat capacity of random poly(L-alanine) ... 80
Table 21. Heat capacity of alpha poly(L-alanine) ... ~ ... 81
Table 22. Heat capacity of beta poly(L-alanine) ......... 81
@) 1983 by the U.S. Secretary of Commerce on behalf of the United States.
Table 23. Heat capacity measurements of poly(L-va-
'This copyright is assigned to the American Institute of Physics and the
American Chemical Society. line) ............................................................. 81
Reprints available from ACS; see Reprint List at back of issue. Table 24. Heat capacity of poly(L-valine) ................... 82
0047-2689/83/010065-25/$06.00 65 J. Phvs. Chern. Ref. Data. Vol. 12. No.1. 1983
Downloaded 01 Jun 2013 to 171.67.34.69. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://jpcrd.aip.org/about/rights_and_permissions
66 GAUR ETAL.
Table 25. Heat capacity investigations on nylons not Table AS. Heat capacity data for various poly(ethyl-
included in this study.......... .......... .............. 82 ene terephthalate)s between glass transi-
Table 26. Heat capacity measurements of nylon 6 ..... 83 tion and melting
Table 27. Recommended heat capacity data for nylon Table A6. Heat capacity of various molten poly(eth-
6 below the glass transition ...... ................... 84 ylene terephthalate)s
Table 28. Recommended heat capacity data for mol- Table A 7. Heat capacity of various nylon 6 samples
ten nylon 6 .................................................. 84 below the glass transition
Table 29. Heat capacity measurements of nylon 6.6 .. 85 Table A8. Heat capacity of vanous semicrystalline
Table 30. Recommended heat capacity for semicrys- nylon 6 samples above the glass transition
talline nylon 6.6 .......................................... 85 Table A9. Heat canacitv of various molten nylon 6
Table 31. Recommended heatcapaclty chltafor nylon samples
6.6 below the glass transition temperature. 86 Table i}10. Heat capacity of various nylon 6.6 sam-
Table 32. Recommended heat capacity data for mol- ples at low temperature
ten nylon 6.6 ............................................... 86 Table All. Heat capacity of various nylon 6.6 sam-
Table 33. Heat capacity measurements of nylon 6.12 87 ples below the glass transition
Table 34. Recommended heat capacity data for nylon Table A12. Heat capacity of various nylon 6.6 sam-
6.12 below the glass transition .................... 87 ples above the glass transition
Table 35. Recommended heat capacity for molten ny- Table AI3. Heat capacity of molten nylon 6.6
lon 6.12 ....................................................... 88
Table 36. Heat capacity change at the glass transition. 88 List of Figures Page
Figure I. Recommended heat capacity data for poly-
glycolide, polY(E-caprolactone), and poly-
List of Tables Deposited in PAPSa (ethylene terephthalate) ............................... 69
Figure 2. Heat capacity of poly(ethylene terephtha-
T-able--A-I ~--Heat-capacitydata-for-polyglycolide ---- ------------------late) as a fUnction: of-crystalUmty--at vanom.
fable A2. Heat capacity of polY(E-caprolactone) temperatures ............................................... 75
Table A3. Heat capacity data for various poly(ethyl- Figure 3: Heat capacity of polyglycine I, polyglycine
ene terephthalate)s at low temperature II, a-poly(L-alanine), p-poly(L-alanine), and
Table A4. Heat capacity data for various poly(ethyl- poly(L-valine) ............................................... 82
ene terephthalate)s below the glass transi- Figure 4. Recommended heat capacity data for nylon
tion 6, nylon 6.6, and nylon 6.12 ..... ................... 84
1. Introduction 2. Heat Capacity of Polyesters

This is the eighth paper in a series of discussions on the
2.1. Introduction
heat capacity of linear macromolecules. In the earlier pa-
pers,I-7 the heat capacity of selenium, polyethylene, poly- .Polyesters derive from all-carbon backbone polymers
propylene. polystyrene and various types of polyoxides. by occasional substitution of the ester group --COO in the
acrylic polymers, and other carbon backbone polymers have backbone chain. The repeating units, formula weight, crys-
been analyzed. In this paper polyesters and polyamides for tal structure, density, melting temperature, heat of fusion,
which heat capacity data are available have been analyzed. and glass transition temperature of all polyesters analyzed in
These are polyglycolide, polY{E-caprolactone}, poly(ethylene this paper are listed in Table 1.9 ,47,48
terephthalate), poly(ethylene sebacate), polyglycine, poly- The ester group is directional, and successive units can
(L-alanine), poly(L-valine), nylon 6, nylon 6.6, and nylon be introduced into the polymer so that all point in one direc-
6.12. In the last paper in this series the analysis of heat capa- tion or, in alternating directions. The first type of polymer is
cities of aromatic and inorganic polymers will be reported. polar and can be obtained on polymerization of a hydroxy
acid or the corresponding lactone. The second polyester is
nonpolar and the polymerization can be thought of as in-
volving the reaction of a diacid with a glycol.
The first and the fifth members of the series of polar,
a See AlP document no. PAPS JPCRD-12-OO65-19 for 19 pages of data unsubstituted aliphatic polyesters are polyglycolide and
tables. Order by PAPS number and journal reference from the American polY-E-caprolactone. Chatani et aZ. 8 ,47 have reported crystal
Institute of Physics, Physics Auxiliary Publication Service, 335 East 45th stuctures of both, polyglycolide and polY-E-caprolactone.
Street, New York, N.Y. 10017. The price is $1.50 for a microfiche or $5.00
Polyglycolide crystals contain planar zig-zag chains in an
for photocopies. Airmail is additional. This material also appears in Cur-
rent Physics Microform, the monthly microfilm edition ofthe complete set arrangement different from all three polyethylene struc-
of journals published by AlP on frames following this journal article. tures. 47 Increasing the number of CH2 groups per ester
. t Phv-,=. ChAm_ RAf nld~ Vnl 1~ Nn 1 1QA~
THERMODYNAMIC PROPERTIES OF POLYESTERS AND POLYAMIDES 67
Table l. CrYstal structures and thermal. proEcrties of polyesters
Polvester Crystal syst. Uni t cell No. of "c Crys~<tl TIll(K) l~lIf P Amorph. Tg (K)
space group axes and uni ts. a
Ng 111- 3 ~:~~~~;
(Forllluia Ht.) k.J mole- 1 ~Ig m- 3 packing
Structure of mol. helix anglcs dens'i t}'
rel2ea t uni t
I'0ly(ethylene TRIC 0.448 1. SIS O.7B 553 26.9 1. 336 0.74 342
te reph tha la te) PI O.5B5
[192.16] 12* 1/1 1.075*
-(CllZ)ZO-CO- 99,5
118.4
C l!4-CO-0-
6 112.2
Poly(ethylene ~IONO O. SS2 1. 247 0.73 356 32.0 1. (l85 0.64

sehacate) P21/a 0.730
[228.28] 1.665
14*1/1
-(CH ) 20-CO- 13"115.0
Z
(Cll )g-CO-O-
Z
polygl)"colide ORTH 0.522 1.700 0.81 506 11. 1 1. 450 0.69 313
[58.04 J Pemn 0.619
-CI12-CO-0- 3*2/1 7.02""
poly l£- ORTIl (). 747 1.195 0.70 337 16.2 1. 096 0.64 209
caprolactone) P2 2 2 0.498
1 1 1
[114.15J 17.05*
7*2/1
- (CHZ)S-CO-O-
group must naturally lead to crystal structures similar to ments have been reported in poly(ethylene sebacate). Its
polyethylene. Poly-c-caprolactone already comes close to crystal structure and related properties are listed in Table 1.
the polyethylene structure. 8 Equilibrium melting param-
etersofpolyglycolide and poly-c-caprolactone have been es- 2.2. Literature Data on Heat Capacity of Polyesters
tablished by Wunderlich. 9 Their crystal structures and relat- Twenty investigations have been reported in the litera-
ed properties are listed in Table 1. ture on the heat capacity of various types of polyesters. Heat
Poly(ethylene terephthalate) is the simplest polyester capacities of over 40 samples have been measured over wide
with a phenylene group within its backbone. Its crystal ranges of temperature.
-struct-ure-is-practically-fully extende<t---The--ester-groups are- All·investigations-were-criticallyevaluated-in-terms "of
tilted about 12° out of the plane of the benzene rings and the sample characterization, experimental technique used, error
CH2-CH2 sequence is rotated about 20° out of the trans- limits. and accuracy of representation of data. It was found
conformation, less than in the aliphatic polyesters of suffi- that only 9 of the 20 investigations met our standards of
ciently long CH2 sequences. Fakirov et al. 10 have recently acceptable data (discussed in Ref. I). These investigations
redetermined the complete unit cell parameters. These are are discussed in the following Sec. 2.3. Heat capacity data on
listed in Table 1. Equilibrium melting parameters, recently 25 samples of four types of polyesters are treated. Eleven
established in our laboratory from calorimetric data on var- investigations which did not contain acceptable data were
ious semicrystalline samples are also listed in Table 1. The not included in further analysis. These are listed in Table 2,
glass transition is reasonably well established at 342 K.ll along with brief commets on the reasonS for exclusion from
The last polyester for which heat capacity measure- this study.
J. Phys. Chern. Ref. Data, Vol. 12, No.1, 1983
68 GAURETAL
Table 2. Heat capacity investigations on polyesters
=:===========-.-==n:::o:::t=i=nc::l::u::ded in_ this study.
Refere:.::n:::::ce~_ _ Reason(s) [or exclusion

Stee re (1966) [12] Hea t capaci ties per unit volume reported
for poly(ethylene terephthalate). These
values are not directly comparable to
the <lata presented here.
Yoshimoto and Miyagi lieat capacity data on poIy(ethylene
(1966) [13] terephthalate) could not be read
accurately from too small graphs.
Goetze andlHnkler tleat capacity data reported for poly-
(1967) [14] (ethylene terephthalate) fibers in
various humidity conditions.
Haly and Snaith Heat capacity, data reported from 200 to
(1969) [IS] 400 K for poly(ethylene terephthalate)-
water system (water concentration
0.72-2.34 g/lOO g of polymer). Heat
.capacity_ of poly-(ethy~ene ..:tereph.thalateJ.
was found to be insensitive to the
water content.
Privalko et al. Heat capacity reported for filled
(1970) [16] .2.ligomeric poly(ethylene glycol adipate).
Mn = 2000 in the crystallization and
and mel ting regions.
lIager (1972) [17] lieat capacity of poly(ethylene terephtha-
late) was measured using high speed
thin foil calorimetry (Heating rate
30,000 deg/min). The data are associated
with large error limits.
Mikhal 'chenko et al. Heat capacity data reported for a com-
(1972) [18] mercial sample of crumbled aluminized
poly(ethylene terepht!"talate).
Philips et al. (1975) Heat capacities reported for oligomeric
[19] poly(hexamethylene sebacate) (DP = l,2,3).
Yagfarov Heat capacity data reported for

(1975) [20] oligomeric poly(butylene adipate)
Mn = 1770 in the crystallization and
melting regions.
Bair et al. (1976) Heat capacity reported for poly(butylene
--{-21-:1 -te.r.e.ph tha1at:.e-)--s em icr.y.s.tal..l-ine---fw.L.i'-O-.-3 I.}.
from 290 to 515 K in the glass transition
and melting regions.
Ito et al. (1978) Heat capacity reported for amorphous
[22] poly(ethylene terephtha1ate} at 320 K
as a fUnction of annealing below the
glass transition temperature.
2.3. Recommended Data on Heat Capacity and Publication Service of the American Institute of Ph; 'Q,
Thermodynamic Functions of Polyesters Since only one set of heat capacity data for a sample Wlm
2.3.1. Polyglycolide
crystallinity 0.67 is available, only the recommended data
for the heat capacity of semicrystalline polyglycolide
(W = 0.67) from 0 K to the glass transition temperature (318
C
Only one investigation23 .24 has been reported in the li- K) and of molten polyglyeolide from 318 to 550 K have been
terature which deals with the heat capacity of polyglycolide. derived.
Details' of this investigation are given in Table 3. The heat To determine the recommended data for semicrystal-
capacity of this samp1e ha.~ been measured over the tempera- line polyglycolide (W = 0.67) from 0 to 250 K. the authors'
C
ture range from 13 to 550 K. The data are given in Table Al. data were interpolated using the spline function technique to
Table Al has been deposited with the Physics Auxiliary obtain heat capacity values are every 10° interval. These rec-
Table 3. ileat capacity measurements of Polyglycolide
Investigator Sample no., Temperature Experimental Source of

characterization range (K) technique data
(claimed uncertainty)
Lebedev 16. Mv=3S,OOO 13-550 Adiabatic S-10K: Equation a

ct al. (1978) 1
20-SS0K: Tab1e b
(1%)
all =lS.7 kJ mol-
f
[23, 24] C
w =0.67
b Data I,crc intcrpolateu u,;ing tht' ,;"lillt' rUII.:tloll tl'.:lllli.liuc to gh'c heat
capacities at every ten degree interval.
J. Phys. Chem. Ref. Data, Vol. 12, No.1, 1983
Table 4. Recommended heat capacity data for Table 5. Recommended heat capacity data for mol ten po1yg1yco1ide a
c a
semicrystalline (w = 0.67) polyg1ycolide .
T(l() C
T(K) Cp P -1 -1
------- (J mol K )
(J m01- 1 K- 1 ) 318. 0 (T ) 226.5
g
0.0 0.0
320.0 226.6
5.0 0.1990
330.0 227.4
10.0 1. 547 340.0 228.1
15.0 4.36,8 350.0 228.8
20.0 7.973 360.0 229.6
25.0 11:92 370.0 230.3
30.0 16.00 380.0 231. 0
40.0 74.22 390.0 231. 7
50.0 :SZ.07 400.0 232.5
60.0 39.12 410.0 233.2
70.0 45.39 420.0 233.9
80.0 51. 02 430.0 234.7

90.0 56.16 440.0 235.4
100.0 60.94 450.0 236.1
110.0 65.48 460.0 236.9
120.0 69.80 470.0 237.6
130.0 73.90 480.0 238.3
140.0 77.78 490.0 239.1
1 50.0 81.44 500.0 Z:53.8
160.0 84.88 510.0 240.5
170.0 88.10 520.0 241. 3

530.0 242.0
180.0 91.10
540.0 242. Z
190.0 93.87
550.0 243.4
ZOO.O 96 . .:13
210.0 98.78
220.0 101.1 ~he table may contain more significant figures than
230.0 103.5 justified by both source of data and data treatment. The extra
240.0 100. :3 significant figures are included only for the purpose of smooth
representa tion.
250.0 109.5
260.0 111.6
270.0 114.2 The rms deviation was 0.3%. Equation (1) was used to evalu-
273.15 115.0 ate the recommended heat capacity of semicrystalline poly-
280.0 116.7 glycolide from 260 to 318 K. These values are listed in Table
290.0 119.3 4 and plotted in Fig. 1.
298.15 121.4 The recommended data on the heat capacity of molten
300.0 121. !l polyglycolide were determined by curve fitting the data on
310.0 124.4 sample 26 at 501 and 550 K into the equation
126.5
Cp = 0.07315 T + 203.2 J mol- 1 K- 1• (2)
~he table may contain more significant figures than
justified by both source of data and data treatment. The extra
450~--~--~----~---T----r---~
si2.nificant fieures are included onl y for. th" 1'"'1'I'OSP of smooth
representation. __ ~_ _ _ _+ -__~_ j PEll,---I

360 I - ~II
PGL
ommended data are listed in Table 4. 1801----t----t-""":"

The measured heat capacity values from 260 to 300 K
are somewhat higher, because they are associated with the
beginning of the glass transition. The data from 260 K up to
Tg (318 K) were determined by linearly extrapolating the 100 200 300 400 500 600
data below 250 K. The heat capacity values from 200 to 250 Temperature (K )
K were curve fitted into the equation
FIG. 1. Recommended heat capacity data for polyglycolide (PGL), polY-E-
Cp = 0.2570 T + 44.78 J mol- 1 K- 1• (1) caprolactone (peL). and poly(ethylene terephthalate) (PET).
J. Phys. Chem. Ref. Data, Vol. 12, NO.1, 1983
70 GAUR ETAL.
Equation {2} was used to evaluate the heat capacity of molten To determine the recommended data for semicrystal-
polyglycolide from 318 to 550 K. These values are listed in line polY(E-caprolactone) (WC = 0.16) from 0 to 200 K, the
Table 5 and plotted in Fig. 1. authors' data were interpolated using the spline function
technique to obtain heat capacity values at every 10° interval.
2.3.2. POIY(E-caprolactone) These recommended data are lisied in Table 7 and are plot-
Only one investigation25 has been reported in the litera- ted in Fig. 1.
ture which deals with the heat capacity of polY(E-caprol~lC The recommended data on the heat capacity of semi-
tone). Details of this investigation are given in Table 6. The crystalline polY(E-caprolactone) at the glass transition tem-
heat capacity o( one sample has been measured over the temperature were determined by curve fitting the data on sample
IX'raturc range from 10 to 350 K. The data on this samplc arc 27 froxp. 150 to 200 K irito the equation
given in Table A2. Table A2 has been deposited with the
(3)
Physics Auxiliary Publication Service of the American Insti-
-ttiteof Physics. -Since oiilyone se:Cofheafcapacity data of The fillS deviation was 0.1 %. Equation (3) was used to evalu-
polY{E-caprolactone). with crystallinity of 0.16 is available, ate the heat capacity of semicrystalline· polY(E-caprolactone)
only the recommended data for the heat capacity of semi- at 209 K. ThiS value is listed in Table 7.
crystalline poIY(E-caprolactone)(wC = 0.76) from 10 K to The recommended data 'on the heat capacity of molten
the glass tr~sition temperature (209. K) .and of molten polY(E-caprolactone) were determined by curve fitting the
polY(E-caprolactone) from 209 to 350 K have been derived. data on sample 21 at 342 and 350 K into the equation
Table 6. Heat capacity measurements of poly (e; -caprolactone)
Investigator Sample no., Temperature Experimental Source of data

characteriza tion range (K) technique
(claimoJ. un-cortainty)
Lebeuev et a1. 27. Melt Crysta1- 10-350 Adiabatic Table

(1974) [25] lized
Mw = 29,000 (1%)
~Hf = 12. 27 kJ mo 1 - 1
- wC_=--O'~7o-
Table 7. Recommended heat capacity data for semicrystal1ine'
===========(w:::c=== 0.76) ~~-CaprQlactone)a _ _ _.

T(K) C
p
(J mOl- 1K- 1 )
0.0 0.0
10.0 2.42
20.0 10.72
30.0 20.66
40.0 30.17
50.0 38.36
60.0 45.74
70.0 52.88
80.0 59.61
90.0 65.67
100.0 71.18
110.0 76.14
120_ ° RO_ Q7
130.0 85.43
140.0 89.82
150.0 94.19
160.0 98.62
170.0 103.1
180.0 107.7
190.0 112.2
200.0 116.8
209.0(T g ) 120.9
aThe table may contain more significant figures than
justified by both source of data treatment. The extra significant

fig,ures: 2.ro in.clu']g,J. only for thG purpoG'G of :;;lnooth rGpr9£9ntation.
Table 8. Recommended heat capac i ty data for mol ten
poly (E -capro1actone) a
T(K) Cp
(J mo1- 1 K- 1 )
209.0( T
g
l 181.1
210.0 181. 4
220.0 184.2
230.0 187.1
240.0 190.0
250.0 192.9
260.0 195.7
270; 0 198;6 .
273.15 199.5
280.0 201. 5
290.0 204.4
298.1S 206.7
300.0 207.2
310.0 210.1
320.0 213.0
330.0 215.9
340.0 218.7
350.0 221.6
a,:he table may contain more significant figures than

justified by both source of data and data treatment. The
extra significant figures are included only for the purpose of
SmOJ;LtJLr_epI.e.s e.nt.a.t. ion
(4) heat capacity data for poly(ethylene terephthalate).

Equation (4) was used to evaluate the heat capacity of molten To determine the recommended values of heat capacity
polY(E-caprolactone) from 209 to 350 K. These values are of amorphous poiy(ethylene terephthalate) below 10 K, the
listed in Table 8 and are plotted in Fig. 1. data on samples 8, 9, and 15 were averaged at each tempera-
ture and cu~e fitted into the equation
2.3.3. Poly(ethylene terephthalate)
Cp = exp[ - 0.112238(ln T)3 + 0.458274(ln T)2
Six acceptable investigations26-31 have been reported in
the literature which deal with the heat capacity of poly(ethyl-
+ 2.51758(lnT) - 4.33633] J mol- l K- 1• (5)
ene terephthalate). Details of these investigations are given The rms deviation was 2.0%. Equation (5) was used to calcu-
in Table 9. The heat capacities of25 samples have been mea- late the recommended values of heat capacity of amorphous
sured over the temperature range from 1.2 to 590 K. The poly(ethylene terephthalate) from 1.2 to 10 K. These values
data on these samples are given in Tables A3 to A6. These are listed in Table 10.
tables have been deposited with the Physics Auxiliary Publi- An attempt was made to calculate the heat capacity of
cation Sel·vicc:: of thc:: AlIlc::rican Institute of Physics. The heat crystalline poly(ethylene terepbthalate) below 10 K by extra-
capacity of various poly(ethylene terephthalate) samples at polating the data in Table A3 with respect to crystallinity. It
temperatures below 10 K are given in Table A3. The data on was found that the heat capacity of semicrystalline samples
samples below and above the glass transition are given in does not vary linearly with crysta11inity. This situation seems
Tables A4 and A5, respectively. Finally, the data on molten to indicate that heat capacity of semicrystalline poly(ethyl-
poly(ethylene terephthalate) are given in Table A6. All mea- ene terephthalate) does not depend only on the crystallinity.
surements are either on semicrystalline samples with low Only two samples (sample 23 and 24) were available to
crystallinity (samples 1,2, 10--14, 16-:22, and 24) or comple- give the heat capacity data between 12 to 25 K. Since these
tely amorphous samples (samples 6, 8, 9, 15, 23, and 25). reported data had to be retrieved from too small graph, they
Thus, the calculation of the heat capacity of completely crys- are not very reliable.
talline poly(ethylene terephthalate) from crystallinity ex- From 30 to 120 K, Roinishvili'sdata27 on amorphous
trapolationsusing the two phase model cannot be made safe- sample were used as recommended data for this region be-
ly. cause no other data were available.
The heat capacity of three drawn poly(ethylene ter- To determine the heat capacity of completely amor-
ephthalate) (samples 3, 4, and 5) have also been reported by phous poly(ethylene terephthalate) above 130 K and up to
Smith et al. 26 These samples give higher heat capacity values Tg (342 K) the data at each temperature from 240 to 330 K
than those that have not been under any strain. Therefore, from samples 1, 2, 6, 19-25 were plotted as a function of
these three samples are not included in the analysis of the crystallinity. Plots of we vs C" at several temperatures are
72 GAUR ETAL.
Table 9. Heat capacity measurements of poly(ethylene terephthalate)
a
characterization range (K) technique
( claimed uncertainty)
Smi th and Dole 1. Melt annealed b 270-470 Adiabatic 270-320K: Equation

(1956) [26] p =1.423 Mg m-3 (1%) 380-470K: Equation
6H£=l7.2l kJ mol - 1
C
w " 0.52
2. Premelt annealed 260-470 Adiabatic 260-3S0K: Equation
fiber b (1%) 370-470K: Equation
p " 1.404 Mg m-
3
1111£=14.;'9 II.J moi- 1
C
w =0.41
3. F1akeb 250-330 Adiabatic Equation 5

- p- '=1";3'11 Mg-in- 3 (1%)
6H =14.23 kJ mol- 1
f
C
w =O.03
4. Drawn
b 260-330 Adiabatic Equation 6
3
p =1.374 Mg m- (1%)
1
... H =14.39 kJ mo1-
f
C
w =O.23
b Adiabatic Equation 7
5. Cold-drawn 270-310
p s1.349 Mg m~3 (1%)
"'H£,"13.91 kJ mol- l
C
w =0.08
6. Undrawn
P "'1. ;';HI Ng m-" (H)
l
... H£=12.70 kJ mol-
C
w =0.01
·7. Melt
(1%)
. Rainishvili, et ai. d . Amorphous 11-280 Adiaba dc Graph

(1967) [27] p "1.338 ~Ig m- 3 (unreported)
wCz O.01
24. Semicrysta11ine 11-280 Adiabatic Graph
p =1.401 Hg m- 3 (unreported)
C
w "0.39
Assfalg (1975) [28] 8. Amorphous c , 1. 2-10 Transient ~1ethod Equation 10
p =1.335 Mg m- 3 (15%)
wC=O.O
9. Annealed c 1.2-10 Transient Method Equatio'n 11

393 K. 10 min (15%)
p =1.338 Mg m-
3
wC =0.013 .
10. Annealed c 1.2-10 Transient r.lethod· Equation 12

(15%)
393 K, 15 min
p =1. 349 Mg m- 3
wC =0.082
Table 9. Heat capacity measurements of poly(ethylene terephthalate)--Continueu
Investigator Sample no., Temperature Experimental Source of data a

11. Annealed
c 1. 2-10 Trans ient Method Equation 13
393 K, 30 min (15%)
p =1.362 ~fg m-
3
wC =0.16
12. Annea1ed c 1.2-10 Transient Method Equation 14
493 K, 30 min (15%)
p . =1. 382 "Ig m- 3
wC =0.28
1.2-10
13. Annealed c Transient "Iethod Equati0;z:t 15
(15%)
533 K, 3 h
p =1.405 Mg m- 3
;c~-O:-4-Z
c 1.2-10 Transient ~Iethod Equation 16

14. Annealed
(15%)
533 K, 24 h
p =1. 4 21 Mg m- 3
C
w :0.51
Choy ct a1. 15. Quenched 1.2-4.2 Heat pulse Graph
(1975) [29) p =1.337 Mg m- 3 (10%)
wC"'O.OO
16. Annealed 1.2-4.2 H"at pill "p
373 K,70 min (10%)
p =1.354 Mg m-
3
wC"'O .11
17. AnnealeJ 1.2-4.2 lie at Dulse Graph
403 K, 30 min (10%)
p =1.382, Mg m-
3
C
w =O.28
18. Annealed 1.2-4.2 Heat pulse Graph

483 K, 20 h (10%)
p =1.403 Mg
in- 3-
wC=O.40
Droscher (1979) 19. Annealed 280-520 DSe Table
(30] 527 K, 10 min (Unreported)
t.H =9.68 kJ mol- l
f
wC=0.36
20. Annealed 280-520 DoSe Table
527 K, 46 min (Unreported)
r.Jo1- 1
lIH f =12.53 kJ
wC =0.47
21. Annealed 280-560 DSC Table
527 K, ,260 min (Unreported)
lIlI =12.49 kJ mol- l
f
C
w "'O.46
zaO-57U D::iL: Table
22. Annealed
527 K, 886 min (UnreporteJ)
lIH =12.9l kJ mol- l
f
wC =0.48
Menczel and 25. Amorphous 240-59p DSC Table
Wunderlich (1980) (H)
[31] wC=O.O
aUquations cited as sources of data are tabulated separately in table 9a.
iii
w = !'In '"
bCVUllItt:: I .... 1(11 ::,aUlplt::; D""l'UII (DuPullt.). Z3,000, 15,400
C
Mn : 22,100
J. Phys. Chem. R~f. Data, Vol. 12, NO.1, 1983
74 GAUR ET AL.
a
Table 9a 0 Source of data
Eqo 1 C = 0.2399 + 9.22 x 10- 4 ('I-273) <::al g-lK- 1 (Av. Devo=O.60~)

p
4
liq. 2 C = 0.2628 + 8.62 x 10- (T-273) cal g-l K-1 (Av. Dev.=0.20%)
p
4
eq',3 C 0.2431 + 9'.23 )( 10- (T-273) cal g-l1\-l (Av. Dev."'O.lS%)
p
Eq. 4 C 0.2502 + 9.:n x 10- 4 (T-273) cal g-IK- I (Av. Dev.=0.06%)
p
4
E4. 5 C 0.2502 + 9.40 x 10- (T-273) cal (Av. ,Dev.=0.32%)
p
Eq. 6 C "0.2482 + 9.89 x 10- 4 (T-273) cal g-1;;:-1 (Av. Dev.=0.20%)
p .
Eq. 7 C = 0.2525 + 9.42 x 10- 4 (T-273)' cal g-l[-l (Av. Dev.=0.26%)
p
E4. 8 C = 0.2469 + 1.007 x 10- 3 (1-273) cal g-l K-1 (Av. Dev.=0.47%)
p
(T-.27..3). caLg_~lK-l (Av ... Dev_-"'-O_.7-%).

4
Eq •. 9.... C ."'0.32A3_L5.6LL10-
p
Eq. 10 C 6.26 x 10- 5 T3 J g -l K-1
p
Eq. 11 C 6.82 x 10- 5 T3 J g-1 K-1

p
Eq. 12 Cp = 5.80 )( 10- 5 T3 J g-I K-1
5 g -I - 1
Eq. 13 C 5.39 x 10- T3 J K
P
g -l -1
Eq. 14 ep = 3.76 x 10- 5 T3 J K
bq. 15 C '" (i.05 x 10- 5 r3 J

g-l K -l
P
Eg. 16 C = 7084 x 10- 5 T3 J
g-1 K-1
p
aEquation numbers correspond to the equations jn tahle 9.
giv.~n inF!g~.7..:Th~_~~!l1!~_9fth<? cry:s.~~lli~!~y_ ~JC!!:.~QlatiQns T.herms deviatiQUWas 0.9%-Lliqua.tion(7) was used_to_e~alu~_

to obtain heat capacity of amorphous poly(ethylene ter- ate the heat capacity of molten poly(ethylene terephthalate)
ephthalate) are given in Table 11. The heat capacity of amor- from 350 to 590 K. These values are listed in Table JO and
phuus puly(t::thylt::nt:: tt::n:phthalatt::) frum 240 to 330 K, ub- plotted in Fig. 1.
tained from crystallinity extrapolation, and the heat Enthalpy and entropy of amorphous poly(ethylene ter-
capacity data on sample 23 from 130 to 230 K were then ephthalate) were calculated by numerically integrating the
further smoothed by curve fitted into the following equation: heat capacity data. These thermodynamic functions are list-
Cp = 6.6153.104 T- 2 + 0.72042T + 8.3776 J mol- 1 K- 1• ed in Table 10.
(6)
The rms deviation was 0.'%. Equation (6) was used to evalu-
ate the heat capacity of amorphous poly(ethylene terephtha- 2.3.4. Poly(ethylene sebacate)
late) from 130 ~o 340 K. These recommended values are list- Only one investigation 32 has been reported in the litera-
ed in Table 10 and plotted in Fig. 1. t.urt:: which ut::als wit.h t.ht:: ht::at. capacity of poly(t::t.hylc:::m: se-
The recommended data on the heat capacity of molten bacate}. Details of this investigation are given in Table 1l.
poly(ethylene terephthalate) above Tg (342 K) were deter.. The heat capacity of one semicrystalline sample has been
mined by curve fitting the data on sample 7 from 540 to 560 measured over the temperature range of 250 to 410 K. The
K, on samples 21 and 22 from 550 to 570 K, and on sample data on this sample are given in Table 13.
25 from 360 to 400 K and from 540 to 590 K into the equa- Since only one set of heat capacity data are available
tion over a limited temperature, no further analysis of heat capac-
Cp =0.282 T+236.95 Jmol- t K- 1• (7) ity data were made.
J.Phys. Chern. Ref. Data, Vol. 12, No.1, 1983
THERMODYNAMIC PROPERTIES OF POLYESTERS AND POLYAMI DES 75
Table 10. Recommended thermodynamic data for amorphous Table 10. Recommended thermodynamic data for amorphous
poly(ethy1ene terephthalate) a poly(ethylene tereph thaI a tel a - -Continued
T(K)
0.0 0.0 0.0 0.0 400.0 349.8 65258 327.8
1.2 0.02101 0.0126 0.0105 410.0 352.6 68770 336.5

1.4 0.03201 0.0179 0.0145 420.0 3 S5. 4 72310 345.0
1.6 0.04672 0.0258 0.0197 430.0 358.2 75878 353.4
1.8 0.06581 0.0370 0.0263 440.0 361. 0 79474 361.7

2.0 0.08995 0.0526 0.0345 450.0 363.9 83099 369.9
3.0 0.3115 0.2533 0.1089 460.0 366.7 86752 377.9
4.0 0.7676 0.7929 0.2567 470.0 369.5 90433 385.8

-5.0- 1. 545 1":949 0.-5072 480.0 372."3 94142 393.6
6.0 2.719 4.081 0.8883 490.0 375.1 97879 401.3
7.0 4.353 7.617 1.426 500.0 378.0 101644 408.9
8.0 6.496 13.04 2.143 510.0 380.8 105438 416.4
9.0 9.18Z 20.88 3.059 520.0 383.6 109260 423.9
10.0 12.43 31.69 4.190 530.0 386.4 113110 431. 2
30.0 Z2.91 385.1 24.26 540.0 389.2 116988 438.4

40.0 36.18 "680.5 32.60 550.0 392.1 120895 445.6
50.0 48.24 1103 41.94 560.0 394.9 124830 4S2.7
60.0 56.68 1627 51. 49 570.0 397.7 128793 459.7

70.0 ZZ30 60.78 560.0 400.5 13<:764 46(;.7
80.0 69.95 2900 69.72 590.0 403.3 136803" 473.5
90.0 77.18 3635 78.38
100.0 84.42 4443 86.89

110.0 91. 70 5321 95.28
jus-ti-fied "by both-"5ource of data-and-data--t-reatment~ The
120. U 100.1 6283 103.6
extra significant figures are included only for the purpose
130.0 105.9 7313 111.9
of smooth representation.
140.0 llZ.6 8405 120.0
150.0 119.4 9565 128.0
160.0 126. Z 10793 135.9

170.0 13:>.1 12009 14::'.7
180.0 140.1 13455 151.5
1"90.0 147.1 14891 159.3

270
ZOO.O 154.1 16397 167.0 PET
Z10.0 161. 2 17974 174.7
220.0 168.2 19621 182.4
230.0 175.3 21338 190.0
240.0 182.4 23127 197.6
Z50.0 189.5 24986 205.2
260.0 196.7 26917 212. B
270.0 203.8 28920 220. :5
273.15 206.1 29576 " 22.2.8
280.0 210.9 30994 227.9

290_0 218.1 33139 235.4
298.15 223.8 34950 241. 6
300.0 225.2 35354 242.9
310.0 232.4 37642 250.4

320.0 239.6 40002 2S 7.9
330.0 246.7 42434 265.4
340.0 253.9 44937 272.9
342.0(T ) 255.6 45446 274.4

g
34Z.0(T ) 333.4 45446 274.4
g
350.0 335.7 48123 282.1 170 '--_-'--_--I.-_---'-_----'-_~
360.0 338.5 51494 291.6 o 0.2 0.4 0.6 0.8 1.0
370.0 341.3 54893 300.9 Crystallinity
380.0 344.1 58320 310.1
390.0 346.9 61775 319.0 FIG. 2. Heat capacity of poly(ethylene terephthalate) as a function of crystal.
linity "l vwiuul) ('CIUIX'l"tUH;l),
76 GAUR ET AL.
Table 11. Heat capacity vs. crystallinity: Results of curve
fitting data into the equation C "c_c~ + {l-"Wc}C/

p
T(K} C ~IS
p
(amorphous) aeviation
(J mo1- 1 K-l) (%)
240 183.6
250 188.5
260 196.5 1.2
270 202.2 1.5
280 209.6 3.0
290 218.3 3.4
300 225.2 3.3
310 233.3 3.5
320 238.4 3.7

330 248.2 3.0
Source of
data
Wunderlich and 28. Semicry s tall inc 250 - 410 Adiabatic 250-310K:
Dole (1958) p = 1.167 Mg m- 3
(1%) Equation a
[32] 350-4l0K:
llH f 17.4 cal/g Equation b
C
w 0.54
a cp = 0.159 + 1.26 x 10-8 T 3 cal g-lC- 1 (Authors' curve-fitteu equation')
bC 0.444 + 5.81 x 10- 4 T cal g-l C-1 (Authors' curve-fitted equation)

p
Table 13. Heat capacity Jata for po1y(ethy1ene sebacate)

l 1
in J mo1- K-
T(K) 28 a
250 340.2
260 363.7
270 389.0
280 416.4
290 445.7
300 477 .. Z
310 510.0
320 546.7
lIle 1 ti ng
350 467.1
360 472.7
370 478.2
380 483.9
390 489.4
400 494.9
410 500.5
aSample number corresponds to the sample described in

table 12.
+Phys. Chem. Ref. Data, Vol. 12, No.1, 1983

3. Heat Capacity of Polyamides The repeating units, formula weight, and crystal struc-
3.1. Introduction ture of p()lyglycineand poly-(L-alanine) are listed in Table
14.47 Reliable crystal structure data on poly(L-valine) are not
Polyamides derive from, all-carbon backbone polymers available. Also, reliable melting and glass transition data are
by occasional substitution of the amide group NHCO into not available for any of the polypeptides. The crystal struc-
the backbone chains. The polyamides derived from the first tures of simple polypeptides are characterized by the a-helix
member of the series, having the general formula CHR- and the pleated sheet (with parallel or antiparallel chains).
NHCO-, are referred to as polypeptides. Higher members of Polyglycine I is a P structure or pleated structure and the
the series are referred to as nylons crystal form II is 3*3/1 helix with intermolecular'hydrogen
o bonds. a-poly-(L-alanine) is made up of a statistical distribu- ,
II
Nylon a (CH2-)a _ 1 C-NH- tion of right-handed helices pointing up and down, and the
p-crystal form consists of sheets of almost planar zig-zag
o 0 riioleciiles.-Tlie slieets are-parallel to tlieac plariewifli liydro:
II II
Nylon a.b NH -(CH2-1a NH-C-(CH2-)b _ 2 C- gen bonds along the a-axis.
The crystal structure of all the nylons contains two-
Two other related types of polymers are polyurethanes and dimensional layers of fully or almost fully extended poly-
polyureas. Both derive from polycarbonates by substitution mers linked together by hydrogen bonds as in the pleated
of one or both of the ester oxygen atom by NH groups,re- sheet structures. Crystal structures for all the nylons for
spectively. which heat capacity' measurements have been reported are
Heat (,;apa(,;ity uata have been J'eporteu for a number of listed in Table 15. Also listed in the table are equilibrium
polypeptides and nylons over a wide range of temperature. melting data for nylon 6 and nylon 6.6 9 and nonequilibrium
However, the heat capacity measurements on polyurethanes melting data for nylon 6.12.9 Glass transition temperatures
and polyurea.~ have heen on poorly characterized samples for nylons are not well established. Preferred values taken
over only limited temperature ranges. 33-46 from Ref. 48 are listed in Table 15.
,.T~b~.e U, , --L,ry..s.taL..s.iruc.tu.r.es_oL.p.o~*peptides., ---------_.
Polypeptide Crystal syst. Unit Cell No. of Pc Crystal

-3
(formula wt.) space group axes (nm) and units f.-Igm packing
structure of 11101. helix angles density
repeat uni t
Polyg1ytine J 0.477 1. 30
(57.05) o. ~77
CIlZ-CO-NII- 0.70
y=66
Polyglycine II TRIG 0.48 1. 53 0.79

(57.05) P31(P32) 0.48
CII -CO-NH- 3*3/1 0.93
2
a- Poly (L- alani ne) TRIG 0.855 47 1.246 0.69

(71.08) ( P3 1) 0.855
CIiCII -CO-NII- 3*47/13 7.03
3
B- Poly(L- alanine) ORTII 0.4734 1. 374 0.76

(71.08)
CHCH -CO-NIl-
3
~~Uil ) 1.0535
0.689
Table [5. Crystal structures and thermal properties of nylons
Nylon Cr)'sta1 ~yst. Unit cell No. of ,Pc Crys~al Tm(K) Illi f Amorp. T (K)
~~~~)~~~;\:\~~[) ~~~~eh~~'~~P ~~~~ (nm) units (\I~ m- 3
) t~~;~i~~, (k,1 Ino1 1) eM!) m-3) packing g
dens 1 ty
repeat uni t ~l1g1C'''
Nylon 6, ,~ t·10;-) 0 0.956' 1.235 0.75 543 26.0 1.090 0.66 313-360
( 113.16) P2 1. 724
1 O. SOl
(CIIZ-)5CO-XI1-
7*2/1 B=67.S
~Jyl on (" y ~IQNO 0.933 1.163 0.7i

(113.16) P2/a 1. 688
(Cli Z-) 5CO - Nll - 0.478
7*2/1
6=121
Nylon 6.6, C! TRIC 0.49 1. 24 0.75 553 67.9 1.091 0.66 "'323
(226.31) 1'1 O.Sq
(C1I2-)6NIl-CO- 14*1/1 1.P
48.5
(CII -) 4CO- Nil 77
Z
(i3.5
Nylon 6.l2 319

(310.5)
(CII -)6 NHCO -
2
(CII Z-) lOCO- NIl-
78 GAUR ET AL.
Table 16. Heat capacity measurements of polyglycine
laves tiga tor Sample no., Tempera ture Experimental Source of

characterization range (K) technique data
Fanconi and 10. Polyglycine II 2.0-20 Adiabatic Equation a

Finegold (1975) (Unreported)
[49, 50]
Finegold and 11. Polyglycine I 150-375 DSC Equation b

Kumar (8%)
[51] Equation c
12. Polyglygine II 150-375 DSC
(8%)
a Cp = (exp[-0.218472(lnT)3 + 0.993217(lnT)2 - 1.33988(lnT + 3.13432])T 3 IlJ g.-l
(authors'. tabulated data curv~_~~~t_~c!. .int? the .equat.ion)

2 l
b Cp = 7.592 + 0.401T - 2.505.10- 4 T 1
J mol- K- (authors' curve fitted equation)
2 el
C = 34.19 + O.177T + 8.927.10- 5r J mo1- l K (authors' curve fitted equation)
cp
1
Table 17. Heat capacity of polyg1ycine la in J mo1- K- 1
T(K) 11
150 62.11
160 65.34
170 68.52
180 71. 66
190 74.74
200 77.77
210 80.75
220 83.69
230 86.57
240 89.40
250 92.19
260 94.92
270 97.60
280 100.2
290 102.8
300 105.4
310 107.8
320 1l0.3
330 112.6
340 115.0
350 117.3
360 119.5
a
Description of sample 11 is given ill tahle 16.
3.2. Heat Capacity of Polypeptides measurements meet our standards of acceptable datab (dis-
cussed in Ref. 1).
Since all the measurements were made on polypeptides
of different crystal forms and their mixtures, and only a few
measurements are available, no recommendations are made
for the heat capacity of polypeptides. Acceptable data on
Nine investigations49- 57 have been reported in the liter-
various types of polypeptides are presented in Tables 17, 18,
ature which deal with the heat capacity of various types of
20-22, and 24. The acceptable data are summarized in Fig.
polypeptides. Heat capacity data have been reported for var-
3.
ious crystal forms of polyglycine, poly(L-alanine), and po-
b The data on polyglycine (samples 11 and 12) are associated with large error
ly(L-valine). The heat capacities of 10 samples have been limits (claimed uncertainty 8%). Since there are the only data available for
measured over a wide temperature range.· Details of these polyglycine, these measurements were included in the discussion, but
investigations are given in Tables 16, 19, and 23. All the should be considered preliminary.
THERMODYNAMIC PROPERTIES OF POLYESTERS AND POL YAMIDES 79
a in J mo1- 1 K- 1
Table 18. Heat caEacitz of Eo1l~lZcine II
T~K) 10 12
1.4 0.002542
1.6 0.003482
1.8 0.004688
2.0 0.006207
3.0 0.02015
4.0 0.04933
5.0 0.09991
6.0 0.1771
7.0 0.2849
8.0 0.4253
9.0 0.599
10 0.B056
12 1. 30B
14 1.907
16 2.570
18 3.265
20 3.959
150 62.75
160 64.80
170 66.86
1BO 68.94
190 71. 04
200 73.16
210 75.30
_.22.0 77. •.45
230 79.62
240 81. 81
250 84.02
260 86.24
270 88.49
280 90.75
290 93.03
300 9S.32
:no 97.04
320 99.97
330 .102.3
340 104.7
350 107.1
360 109.5
370 111.9
aSample numbers correspond to the samples described
in table 16.
80 GAUR ET AL.
Table 19. Heat capacity measurements of polY(L-alanine)

Finegolad and' 1. Random form; 1.5-10 Heat pulse Graph
Cude (1972) Mw = 19,000 (Unreported)
[52,53,54]
a
7. a-helix; 1. 5 - 20 Heat pulse Equation
Mw = 106,000 (Unreported)
b
8. a-sheet; 1.5-20 Heat pulse Equation
Mw = 5,650 (unreported)
Delhaes 4. Mixture of a-helix 1.5-4.0 Adiabatic

et a!.· (85%) and a-sheet f:)%) Graph
(1972) [55] (15%)
Mv = 35,000
Daurel et al. 5. a-helix (85%) 2.0-300 Adiabatic Graph c

(1975) (3%)
[56] 6.--fl-sheec(85%) - 2. 0:::300 --Adi-aoaHc-- Graph c -
(3%)
aAuthors' tabulated data curve fitted into the equation
'C
p
= exp[-O.0434849(lnT)3 - O.0728239(lnT)2 + 3.09478(lnT) - 3.11191J mJ i- 1 K- 1
(RMS deviation 1.4%)
bAuthors' tabulated data curve titted lnto the equatlon
C " exp[-0.089740l(lnT)3 + 0.198371(lnT)2 + 2.78085(lnT) - 3.32327] mJ g-I K-l
p
(RMS deviation 1.4%)
CHeat capacity data presented on a logarithmic plot. Retrieving data from a logarithmic
plot increases the error by 2 - 5%.
Table 20. Heat capacity of random poly{L-alanine)a in J mol- 1 K- 1 "

T(K) 1
1.8 0.01700
2.0 0.02337
3.0 0.07811
4,0 0.1733
5.0 0.3119
6.0 0.4836
7. ° 0.6948
8.0 0.9426
9.0 1. 218
10 1. 521
aSample number corresponds to the sample described in

table 19.
Table 21. Heat capacity of alpha poly(L-alanine)a in.J mo1- l K- 1 Table 22. Heat capacity of beta poly (L- alanine) a
T(K) in J mo1- 1 K- 1
1.6 0.007573 0.01328 T(K)
1.8 0.01270 0.01886 1.6 0.009793
2.0 0.01507 0.01841 0.02573 1.8 0.01381
3.0 0.05806 0.05945 0.08194 2.0 0.01260 0.01879
4.0 0.1460 o 1397 0.1788 3.0 0.03729 0.06131
5.0 0.2577 0.3102 4.0 0.09033 0.1394
b.O 0.4084 0.4992 5.0 0.1780 0.2587
7.0 0.5598 0.7192 6.0 0.Z891 0.4215
8.0 0.7351 0.9737 7.0 0.4184 0.6274
9.0 P.·977g 1. 260 8.0 0.6280 0.8749
10 1. 025 1. 573 9.0 0.8657 1.160
12 1. 548 2.264 10 1. 096 1. 480
14 2.200 3.019 12 1. 682 2.205
16 2.620 3.811 14 2.322 3.015
H 3.724 4.621 16 3.033 3.877
20 4.439 5.433 18 3.757 4.762
30 8.004 20 4.912 5.646
40 12.53 30 8.920
50 16.96 40 13.31
60 21.48 so 17.80
70 25.46 6U tl.4tl
80 30.34 70 25.92
90 34.26 80 31.10
100 36.84 90 37.07

110 ---40.4.8 JoQ9. 41. 84.
120 44.48 110 46.85
130 48.99 120 52.34
140 53.35 130 58.71
150 57.10 140 65.90
160 61.30 150 73.62
170 66.98 160 81.00
180 73.51 170 87.40
190 79.98 180 93.68
200 86.02 190 100.8
210 91. 71 200 108.3
220 98.32 210 116.0
230 106.9 220 125.3
240 116.5 230 137.3
250· 126.0 240 149.4
260 135.6 250 159.1
270 146.1 260 168.6
280 158.7 270 179.8
290 174.2 280 190.3
300 191. 5 200 197.4
300 202.2
aSample numbers correspond to the samples described in
aSample numbers correspond to the samples described
Table 19.
in table 19.
Table 23. Heat capacity measurements of poly(L-valine)
Investigator Sample no., Temperature Experimental Source of

characteriza tion range (K) technique da ta
Daure1 9. Beta sheet 2.0-300 Adiabatic Graph a
et a1. (3%)
(1976) [57)
aHeat capacity data presented on a logarithmic plot. Retrieving data from a
logarithmic plot increased the error by 2- 5%.
82 GAUR ET AL~
Table 2.t. Heat capacity of poly(L-valine)'" 500r-----~------~----~~----__
PLVB
400F--------+-------+-----.~-4_------~
2.0 0.02.727 Cp
3.0 0.08688 (Jmor' Kt) t------+--------4__
4.0 0.2157
5.0 0.4296
200r-----~-----
6.0 0.6671
7.0 0.9348
1001-:------+--/
8.0 1.349
9.0 1.680
10 2..082
12 2.875
14 3.965 FIG. 3. Heat capacity of polyglycine I (POI). polyglycine II (POll), a·po-
16 5.254 ly(L-alanine) (PLAA), p-poly(L-alanine) (PLAB), and p-poly(L-va·
18 6.642
line) (PLVB).
20 8.327
30 13.90
40 21. 57
50 32.04
60 37.65
Table 2S. Heat capacity investigations on nylons
70 47.61
not included in this study
80 57.61
Reference Reason(s) for exclusion
90 65.75
Allen (1952) [58] ~ndirectmeasurement of heat capacity
100 78.40
of nylon 6 and nylon 6.6. Data
110 89.46 associated with large error limits.
·~130 -1-1-5-;"2- WiTKOTtiinuDole (1952) Heat capacItydatareporte;rfor
140 131. 0 (59] nylon 6.10. Very limited number of
data points to establish heat capa-
150 145.5
city variation below the glass tran-
160 160.9 sition and in the molten state
170 180.0 (acceptable data).
180 200.3 Hellwege et aL (1959) Nylon, type not reported

(60)
190 220.6
Mikhailov et al. Heat capacity data on various nylons,
200 239.0
(1959) [61) could not be read accurately from
210 255.1 too small graphs.
710 177 _ 7 Kole50v et al. (1962.) Heat capacity data reported for
230 295.3 [621 nylon 6 and 7. _ Based upon additivity
of heat capacity, values on nylon 7
240 320.,
are large. Since no characterization
250 345.1 of nylon 7 is reported, the sample
260 371. 0 characterization is questionable.
27{) 399.1 Tautz ct al. Data could not be read accurately

(1963, 1964) from too small graphs.
280 423.5 [63, 64]
290 439.1
Jones and Porter (1965) Heat capacity data reported for
300 449.1 [65] nylon 6.6 yarn containing moisture.
as ample number corresponds to the sample described in Reese and Tucker (1905) Nylon, type not reported
[66]
table 23.
Yoshimoto and Miyagi Heat capacity data on nylon 6,
(1966) [13] could not be read accurately from
too small graphs.
Egorov and Kilesov Indirect measurer.tent of heat

(1970) [68] capacity from thermal diffusivity:
Sample characterization not reported
for nylon 6.
Neduzhi t et al. Heat capacity data reported for
(1971) [69] nylon 6 fibers with various
degrees of drawing.
fllVi111w ",(. .. 1. (1979) Uetlt co.po.city clo.to. roportod for
(70] fi lled nylon 6 over the glass
transition and melting regions
only.
THERMODYNAMIC PROPERTIES OF POLYESTERS AND POLYAMI DES 83
3.3. Heat Capacity of Nylons temperature range from 70 to 600 K. The data on these sam-
3.3.1. Literature Data on Heat Capacity of Nylons ples are given in Table A 7 to A9. These tables have been
Nineteen investigations have been reported in the liter- deposited with the Physics Auxiliary Publication Service of
ature on the heat capacity measurements of various types of the American Institute of Physics. The heat capacities of .
nylons. Heat capacities of 26 samples have been measured various nylon 6 samples below and above the glass transition
over wide ranges of temperature. are given in Tables A7 and A8, respectively. The data on
molten nylon 6 are given in Table A9.
All investigations were critically evaluated in terms of
The heat capacity data on various semicrystalline sam-
sample characterization, experimental technique used, error
ples from 180 K to the glass transition show little or no de-
limits, and accuracy of representation of data. It was found
pendence on the crystallinity (Table A 7). Thus crystallinity
that only 7 of the 19 investigations met our standards of
independent data cannot be derived for nylon 6 below the
acceptable data (discussed in Ref. 1). The investigations are
glass transition.
listed in Sec. 3.-3.2 which contains heat capacity data on 10
.The reconlmended data em the heat capacity of nylon 6
samples of three types of nylons. Fourteen investigations
below the transition was determined by curve fitting the data
which did not contain acceptable data were not included in
on samples 1, 2, 3,4, 5, and 13 from 70 to 300 K into the
further analyses. These are listed in Table 25, along with
equation
blit:f (;OIllIllt:lll~ 011 lht: rt:a:suns fur exclusiun for this study.
Cp = exp[0.174083(ln T)3 - 2.56412(ln T)2
+ 13.3387(ln T) - 19.8298] J mol- 1 K- 1• (8)
3.3.2. Recommended Data on Heat Capacity of Nylons
The rms deviation was 1.3%. Equation (8) was used to evalu-
Nylon 6 ate the heat capacity of nylon 6 from 70 to 313 K. These
Four investigations62 ,71-73 have been reported in the li- values are listed in Table 27 and plotted in Fig. 4.
terature which deal with the heat capacity of nylon 6. netaHs. The re.c.ommended data on the heat capacity of molten
of these investigations are given in Table 26. The heat capac- nylon 6 were determined by curve fitting the data on samples
ity of six semicrystalline samples has been measured over the 4, 5, and 13 from 500 to 600 K into the equation and plotted
Table 20. Heat capacity measurements of nylon 6
Investigator . Sample no., Temperature Experimental Source of

characteriza tion range (K) technique da ta
~larx 1. Undrawn (melt 270-430 Adiabatic Graph
et al. annealed) (0.5%)
(l~SS)
DuPont (1050
[71 J denier, 34 filament)
~l = 18.500
w a
WC = 0.67
270- 450. Adiabatic Graph

2. Drawn
(0.5%)
DuPont (210 denier,
34 filament)
~Iw = 18,500
W
C
= 0.4S
a
Kolesov 3. Highly crys talline b 70- 360 Vacuum Adiabatic Table

<.:1. al. {H)
(1962) [62]
Gee and ~Ielia 4. Film forr.! sample 180-560 DSC 180-310 K:

(1970) [72] p = 1.125 Mg m- 3 (2% ) Equation d
My = 41l,nnn
500-560 K:
Equation'"
wC " 0.27
5. Film (0.5 mm thick) 180-560 DSC 180-310 K:

= 1. 12 5 ~Ig m- 3 Equation d
p (2%)
SOO-S60 K
My = 46,000
Equation f
WC = 0.27
The fi 1m hos been i r-

radiated Id th C 0 60 y-
radiation at 298 K,
total dose 500 ~legrad
hefore DSC analysis.
(~al1 rand 13. Zytel 211; DuPont 230-600 DSC Table
11'tmde1'1 i..:h p = 1.130 ~lg m-
3 (1%)
(1979)
[73] \~c = 0.30e
aEnthalpy measurements
bCrys tall ini ty unreported
c Frolll dens i ty measurements

d cp = 0.179 + 4.27.10- 3 J K-lg- l
e cp = 1.331 + 2.73'10- 3 J K- 1 g- 1
fC = 1. 236 ~2. 73.10- 3T J K- 1 g- 1

P
84 GAURETAL.
Table ::.7. Recommended heat capacity data [or nylon 6 1000
below the glass transition
3
NYIOnlS I I I
*t9
T(K) l1eat Capacity
(J mOl- 1 K- 1 )
800
70.0 49.78
6~m
80· 0 56.40
90.0 62.45
400
100.0
110.0
120.0
68.06
73.34
78.38 200
. ~ -
6
1- 6
130.0
140.0
83.26
88.01
,}---tI
o0----100-- ---200---- - - .--- ---
300 400 500 60d
150.0 92.70
Temperature (K)
160.0 97.35
170.0 102.0
FIG. 4. Recommended heat capacity data for nylon 6, nylon 6.6, and nylon
180.0 106.7 6.12.
190.0 111.4
200.0 116.2
210.0 121.0
220.0 126.0
230 .0 131.0
240.0 136.2 Table 28. Recommended heat capacity data for
250.0 141.4 molter. nylon 6 a
260.0 146.9
T(K) Heat Capacity
270 .0 152.4
(J mol-1K- 1 )
273.15 154.1
?80 .0_ 1.51L~

320. [) 272.&
290.0 164.0
330.0 274.3
298.15 168.8
340. [) 275.8
300.0 170.n
350.0 277.4
310.0 176.2
360.0 278.9
313.0(T ) 178.1
g 370.0 280.4
380.0 281.9
a The table may contain more significant figures than 390.0 283.5
justified by both source of data treatment. The extra 400. [) 285.0
slgnlfl"'''I1L rl~urc" "'-'" included only for tho purpoce of 410.0 286.5
smooth representation. 420.0 288.0
430.0 289.6
440 _ 0 201.1
450.0 292.6
460.0 294.1
470,0 295.7
480.0 297.2
490.0 298.7
in Fig. 4: SOO.O 300.2
Cp = 0.1:526 T + 223.95 J mol- 1 K-t. (9) 510.0 301.8
The rms deviation was 2.2%. Equation (9) was used to evalu- 520.0 303.3
530.0 304.8
ate the heat capacity of molten nylon 6 from 313 to 600 K.
5~O.O 306. :;
These values are listed in Table 28 and plotted in Fig. 4.
550.0 307.9
560.0 309.4
Nylon 6.6 570.0 310.9
580.0 312.4
Four investigationss9,73-7S have been reported in the li-
590.0 314.0
terature which deal with the heat capacity of nylon 6.6. De-
600.0 315.5
tails of these investigations are given in Table 29. Heat ca-
pacity of five semicrystalline samples have been measured ~he tables may contain more significant figures than
over the temperature range of 0.3 to 600 K. The data on these justified by both source of data and data treatment. The
samples are given in Tables AlO to A13. These tables have extra sil!nificant fil!ures are included only for the purpose of
been deposited with the Physics Auxiliary Publication Ser- smooth representation.
vice of the American Institute of Physics. Table AIO con- respect to crystallinity using the two phase model (discussed
tains heat capacity data on nylon 6.6 at low temperatures. in Ref. 2). Since heat capacity data below 5 K are available
Tables All and Al2 contain data on semicrystalline nylon only for two samples (W = 0.36) and these data are in good
C
6.6 below and above the glass transition, respectively. Heat agreement, the recommended heat capacity below 5 K have
capacity data on molten nylon 6.6 are listed in Table A13. been derived only for semicrystalline nylon 6.6 (W = 0.36). C
At low temperatures (below 5 K) -the heat capacity of The recommended data on the heat capacity of semi-
linear macromolecules shows a large dependence upon crys- crystalline nylon 6.6 (we = 0.36) were determined by clirve
tallinity. It is necessary to extrapolate the heat capacity with fitting the data on samples 9 and 10 from 0.3 to 4~O K into the
Table 29. Heat capaci ty measurements of nylon 6.6
I.n)'_e_s_tig~j:J>x_ .. Sample.no., Tempera_ture EXperimental. Source---of·

characteri~ation range (K) technique data
Wilhoit and 6. Annealed 280-510 Adiabatic Table a
Dole (1953) [59J /.In = 11,000 (2%)
C
W = 0.70 (enthalpy)
7. Hot drawn (80 denier; 280-510 Adiabatic
tensile strength = (2%)
6. 5g/ denier elongation
at break = 14.3%)
Mn = 11,000
c
w = 0.58 (enthalpy)
Brewer 9. Commercial sample 1.0-4.0 Heat pulsed Graph

et a1. p = 1.140 Mg m- 3 (3%)
(1966 ) c
w = 0.36
[74 ]
Scott 10. Commercial sample 0.3-1.6 Heat pulsed Graph
et a1. p = 1.140 Mg m- 3 (Unreported)
(1973) [75 J c
w = 0.36
Gaur and 14. Zytel 101; duPont 230-600 DSC Equation

Wunderlich p = 1.140 Hg m- 3 (1%)
(1979) [731 Mn = 11,000
\-Ic. -:-·0·;-36·_·
a Data was interpolated using the spline technique to give heat capacities at every
ten degree interval.
- bAut:hor's curve flt:t:ed equat:lon: Below Tg Z30-5Z0K: C ~ 1.138T-8.10 J JIlul-lK- l
P (RMS dev = 0.4%)
Above Tg 550-600K: C = 0.4683T + 351.14

P (RMS dev. = O. 3 %)
Table 30; Recommended heat capacity data for

semicrystalline nylon 6.6 (w c = O.36)a
T(K) Heat Capacity

(mJ mOl-l[l)
0.3 0.2308
0.4 0.3951
0.5 0.6426
0.6 0.9946
0.7 1.474
0.8 2.107
0.9 2.919
1.0 3.939
1.2 6.714
1.4 10.67
1.6 16.06
1.8 23.13
Z.O 32.13
3.0 114.6
4.0 279.6
aThe tables may contain more significant figures than

justified by both source of data and data treatment. The extra
significant figures are included only for the purpose of smooth
86 GAUR ETAL.
Table 31. ,Recommended heat capacity data for nylon 6.6
below the glass transition
T(K)
230.0 252.1
240. 0 263.4
.Z50· 0 274.7
260.0 286.0
270.0 297. :3
273.15 300.9
280.0 308.6
29C1.0 320.0
298.1S 329.2
300.0 331. 3
310.0 342.6
32 0 .0 354.0
323.0(T g ) 357.4
a The table may contain more significant figure:; than
justified by both source of data treatment. The extra
significant figure" are included only for the purpo"c of
smooth representation.
Table 32. Recommended heat capacity data for
330.0 505.7
340.0 S10.4
350.0 <;,.;, n
360.0 519.7
370.0 524.4
380.0 529.1
390.0) 533.8
400.0 538.5
410.0 543.1
420.0 547.8
430.0 552.5
440.0 557.2
450.0 ~(j1. 9
. 460.0 566.5
470.0 571.2
480.0 575.9
490.0 580.6
500. {) 58S.:k
510.0 590.0
520.0 594.6
530.0 5.99. :5
540.0 604.0
550. () bUlj. I
560.0 613.4
570.0 618.1
580.0 622.7
590.0 627.4
600.0 632.1

justified by bath source of data and data treatment. The
equation Ion 6.6 were obtained from authors' curve fitted equation on
Cp = exp[ - 0.1 I0533(ln Tf + 0.297475(ln T)2 sample 14. These data from 323 to 600 K are listed in Table
+ 2.87493(ln T) + 1.37083] mJ mol- 1 K- 1• 32 and are plotted in Fig. 4.
(10)
The rms deviation was 3.1%. Equation (10) was used to
evaluate the recommended_ data from 0.3 to 4.0 K. These
values are listed in Table 30. Nylon 6.12
The heat capacity data on various semicrystalline sam-
ples from 230 to the glass transition temperature show little Only one investigation 73 has been reported in the litera-
or no dependence on crystallinity (Table All). Thus, crystal- ture which deals with the heat capacity of nylon 6.12. Details -
linity independent data can be derived for nylon 6.6 below of this investigation are given in Table 33. The heat capacity
the glass transition. of a semicrystalline sample has been measured over the tem-
pera~u~~ range fr~m 230 to 6Q9 K.
The recommended data-on the heat-capacity-ofnyloI
6.6 below the glass transition were determined by curve fit- The heat capacity of nylons shows little or no depen-
ting the data on samples 6, 7, and 14 from 230 to 310 K into dence upon crystallinity from about 100 K to the glass tran-
the equation sition (see preceding sections). Thus, crystallinity indepen-
dent, recommended data can be derived for nylon 6.12 below
Cp = l.I32T - 8.28 J mol- l K- 1 • (11)
the glass transition.
The rms deviation was 1.4%. Equation (11) was used to Recommended data for nylon 6.12 below the glass tran-
evaluate the heat capacity of nylon 6.6 from 230 to 323 K. sition and for molten nylon were obtained from the author's
These values are listed in Table 31 and are plotted in Fig. 4. curve fitted equations for heat capacity of sample 15. These
Recommended data on the heat capacity of molten ny- data are listed in Tables 34 and 35 and plotted in Fig. 4.
Table 33. Heat capacity measurements of nylon 6.12

Sample no., Temperature Experimental Source of
-- -Cliafacfen_zation riliige--(lC)- fe-chniqlie--- data ---
Gaur 15. Zytel 15lL:- 230-600 DSC Equation a

and Wunderlich
(1979) [73] ~~i~~~ lofg m- 3
(1%)
aAu thor's curve fitted equation
Below Tg 230-:nO K: 1.628T - 11.96 J mol- 1 K- l (RMS dev. 1.1%)
Above Tm 510-600 K: 0.6038T + 529.81 J mol-lK- l (RMS dey. 0.2%)
Table 34. R.ecommend.ed. hea.t capacity dato. £Qr
nylon 6.12 helow the glass transition&
T(lC} Heat Capacity

(J mol-IX-l)
230.0 362.4
240.0 378.7
250.0 395.0
260.0 411.2
270.0 427.5
273.15 432.7
280.0 443.8
290.0 460.1
298.15 473.4
300.0 476.3
310.0 492.6
319.0(T ) 507.3
g
aThe tables may contain more significant figures than
justified by both source of data and data treatment. The

88 GAUR ET AL.
Table 35. Recommended heat capacity data for Tab Ie 36. Heat capac i ty change a t the gl ass trans i tion
a Polymer lICp
molten nylon 6.lZ
(.1 mol- l K- 1)
T(K) Heat Capacity
(J mol -lK- l ) Polyglycine 318.0 100.0
319.0(T g) 722.1 PolY(E-caprolactone) 209.0 60.2
320.0 723.0 Poly(ethylene terephtha1a.te) 342.0 77.8
330.0 729.1 Nylon 6 313.0 93.6
340.0 735.1 Nylon 6.6 323.0 145.0
350.0 741.1 Nylon 6.12 319.0 214.0
360.0 747.2
370.0 753.2
380.0 759.3
capacity data are availabl~ in their glassy and moiten states
~90:0 -76S;-3-
--are listed-iii Taole1b: These:JCp - fT;rdata areoeing ana-
400.0 771. 3
lyzed, along with L1 Cp (Tg) data for other linear macromole-
410.0 777 .4
cules in terms of the hole theory of the glass transition. 67,75
420.0 783.4
The results of this analysis will also be reported at a later
4JO.O 769.5
date.
440.0 795.5
450.0 801. 5
Acknowledgment
460.0 807.6
470.0 831. 6
This work has been supported by the National Science
480.0 819.6
Foundation Grant No. DMR 78-15279.
490.0 825.7
500.0 831. 7
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510.0 837.8
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520.0 843.8 Data 10,89 (1981).
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540.0 855.9
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580.0 880.0
thermodynamic properties of linear macromolecules. VII. Other carbon
590.0 886.1
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Recommended data on these polymers are being ana-
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lyzed in terms of their chemical structure to derive heat ca- (1978).
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_J. Phys. Chem. Ref. Data, Vol. 12, No.1, 1983
THERMODYNAMIC PROPERTIES OF POLYESTERS AND POL VAMIDES 89
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30M. Droescher, Makromol. Chem.180, 2783 (1979). (1972).
31J. Menczel and B. Wunderlich (unpublished results). s6M. Daurel, P. Delhaes, and E. Dupart, "Yariations thermiques, Entre 1 et
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Heat Capacity and Other Thermodynamic Properties of Linear Macromolecules. VIII. Polyesters and Polyamides

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Heat Capacity and Other Thermodynamic Properties of Linear

Macromolecules. VIII. Polyesters and Polyamides

Department o/Chemistry, Rensselaer Polytechnic Institute, Troy, New York 12181

Heat capacity of polyglycolide, polY(E-caprolactone), poly(ethylene terephthalate),

1. Introduction ........................................................ 66 Table 4. Recommended heat capacity data for semi-

1. Introduction 2. Heat Capacity of Polyesters

Poly(ethylene ~IONO O. SS2 1. 247 0.73 356 32.0 1. (l85 0.64

J. Phys. Chern. Ref. Data, Vol. 12, No.1, 1983

=:===========-.-==n:::o:::t=i=nc::l::u::ded in_ this study.

Refere:.::n:::::ce~_ _ Reason(s) [or exclusion

Yagfarov Heat capacity data reported for

Table 3. ileat capacity measurements of Polyglycolide

Investigator Sample no., Temperature Experimental Source of

Lebedev 16. Mv=3S,OOO 13-550 Adiabatic S-10K: Equation a

J. Phys. Chem. Ref. Data, Vol. 12, No.1, 1983

80.0 51. 02 430.0 234.7

100.0 60.94 450.0 236.1

110.0 65.48 460.0 236.9

120.0 69.80 470.0 237.6

130.0 73.90 480.0 238.3

140.0 77.78 490.0 239.1

1 50.0 81.44 500.0 Z:53.8

160.0 84.88 510.0 240.5

170.0 88.10 520.0 241. 3

representation. __ ~_ _ _ _+ -__~_ j PEll,---I

ommended data are listed in Table 4. 1801----t----t-""":"

J. Phys. Chem. Ref. Data, Vol. 12, NO.1, 1983

Table 6. Heat capacity measurements of poly (e; -caprolactone)

Investigator Sample no., Temperature Experimental Source of data

Lebeuev et a1. 27. Melt Crysta1- 10-350 Adiabatic Table

Table 7. Recommended heat capacity data for semicrystal1ine'

===========(w:::c=== 0.76) ~~-CaprQlactone)a _ _ _.

aThe table may contain more significant figures than

justified by both source of data treatment. The extra significant

J. Phys. Chem. Ref. Data, Vol. 12, No.1, 1983

Table 8. Recommended heat capac i ty data for mol ten

a,:he table may contain more significant figures than

(4) heat capacity data for poly(ethylene terephthalate).

Smi th and Dole 1. Melt annealed b 270-470 Adiabatic 270-320K: Equation

3. F1akeb 250-330 Adiabatic Equation 5

. Rainishvili, et ai. d . Amorphous 11-280 Adiaba dc Graph

9. Annealed c 1.2-10 Transient Method Equatio'n 11

10. Annealed c 1.2-10 Transient r.lethod· Equation 12

J. Phys. Chem. Ref. Data, Vol. 12, No.1, 1983

Investigator Sample no., Temperature Experimental Source of data a

c 1.2-10 Transient ~Iethod Equation 16

18. Annealed 1.2-4.2 Heat pulse Graph

J. Phys. Chem. R~f. Data, Vol. 12, NO.1, 1983

Eqo 1 C = 0.2399 + 9.22 x 10- 4 ('I-273) <::al g-lK- 1 (Av. Devo=O.60~)

(T-.27..3). caLg_~lK-l (Av ... Dev_-"'-O_.7-%).

Eq. 11 C 6.82 x 10- 5 T3 J g-1 K-1

Eq. 12 Cp = 5.80 )( 10- 5 T3 J g-I K-1

bq. 15 C '" (i.05 x 10- 5 r3 J

aEquation numbers correspond to the equations jn tahle 9.

giv.~n inF!g~.7..:Th~_~~!l1!~_9fth<? cry:s.~~lli~!~y_ ~JC!!:.~QlatiQns T.herms deviatiQUWas 0.9%-Lliqua.tion(7) was used_to_e~alu~_

J.Phys. Chern. Ref. Data, Vol. 12, No.1, 1983

0.0 0.0 0.0 0.0 400.0 349.8 65258 327.8

1.2 0.02101 0.0126 0.0105 410.0 352.6 68770 336.5

1.6 0.04672 0.0258 0.0197 430.0 358.2 75878 353.4