Abstract
The phase behavior of semicrystalline, aliphatic nylons is analyzed on the basis of differential scanning calorimetry, DSC, and quasi-isothermal, temperature-modulated DSC, TMDSC. The data of main interest are the apparent heat capacities, C p, in the temperature range from below the glass transitions to above the isotropization. Based on the contributions of the vibrational motion to C p, as is available from measurements in our laboratory, the ATHAS Data Bank, and multifaceted new TMDSC results, as well as on information on the crystal structures, NMR, molecular dynamics simulation of paraffin crystals, and quasi-elastic neutron scattering, the following observations are made: (a) In semicrystalline nylons the glass transition of the mobile-amorphous phase is broadened to higher temperature. The additionally present rigid-amorphous phase, RAF, undergoes a separate, broad glass transition at somewhat higher temperature. (b) The transition of the RAF, in turn, overlaps usually with an increase in large-amplitude motion of the CH2-groups within the crystals and latent heat effects due to melting, recrystallization, and crystal annealing. (c) Above the glass transitions of the two non-crystalline phases, C p of the crystals approaches and exceeds that of the melt. This effect is due to additional entropy contributions (disordering) within the crystals, which may for some nylons lead to a mesophase. In case a mesophase is formed, the C p drops to the level of the melt as is common for mesophases. (d) Some locally reversible melting is present on the crystal surfaces, but seems to be minimal for the mesophase. (e) The increasing amount of large-amplitude motion in the crystals is described as a third glass transition, occurring over a broad temperature range below the melting or disordering transition from crystal to mesophase.
The assumption of a separate glass transition in ordered phases was previously discovered on analyzing aliphatic poly(oxide)s such as poly(oxyethylene), POE, and in the broad class of mesophase-forming small and large molecules. To attain a full description of the globally-metastable, semicrystalline phase-structure of nylons and to understand its properties, one needs quantitative information about the glass transitions of the two non-crystalline phases and that of the crystal, as well as the various irreversible and locally reversible order/disorder transitions and their kinetics. Finally, with different substitutions in the α-position of the backbone structure of nylon 2, one describes poly(amino acid)s which on proper copolymerization yield proteins. This links the present study to the earlier thermal analyses of all naturally occurring poly(amino acid)s, a number of copoly(amino acid)s, and globular proteins in their dehydrated states. It will be of importance to check by quantitative thermal analysis if similar glass transitions and phase structures as seen in the aliphatic nylons are also present in the poly(amino acid)s to possibly gain new information about the nanophase structure of proteins.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
M. I. Kohan (Ed.), Nylon Plastics Handbook, Hanser Gardener: Cincinnati, 1995; see in particular: Chapter 5 on Physical Structure by A. Xenopoulos and E. Clark, pp. 107–138 and Chapter 6 on Transitions and Relaxations by H. W. Starkweather, Jr., 139–150.
H. Mark and G. E. Whitby, Collected Papers of Wallace H. Carothers on Polymerization. Interscience, New York 1940.
B. Wunderlich, Thermal Analysis of Polymeric Materials, Springer-Verlag, Berlin 2005.
W. P. Slichter, J. Polym. Sci., 35 (1958) 77.
J. Hirschinger, H. Miura, K. H. Gardner and A. D. English, Macromolecules, 23 (1990) 2153.
H. Miura, J. Hirschinger and A. D. English, Macromolecules, 23 (1990) 2169.
J. Wendoloski, K. H. Gardner, J. Hirschinger, H. Miura and A. D. English, Science, 247 (1990) 431.
A. Xenopoulos, B. Wunderlich and A. H. Narten, Macromolecules, 26 (1993) 1576.
R. Brill, J. Prakt. Chem., 161 (1942) 49.
D. Garcia and H. W. Starkweather, Jr., J. Polym. Sci., Polym. Phys. Ed., 23 (1985) 537.
H. W. Starkweather, Jr., P. Zoller, G. A. Jones and A. Glover, J. Polym. Sci., Polym. Phys. Ed., 22 (1984) 1615.
H. W. Starkweather, Jr., G. A. Jones and A. Glover, J. Polym. Sci., Polym. Phys. Ed., 19 (1981) 467.
H. W. Starkweather, Jr., and J. R. Barkley, Polym. Phys. Ed., 19 (1981) 1211.
H. W. Starkweather, Jr., J. F. Whitney and D. R. Johnson, J. Polym. Sci., Pt. A, 1 (1963) 715.
H. W. Starkweather, Jr. and R. E. Moynihan, J. Polym. Sci., 22 (1956) 363.
H. W. Starkweather, Jr., G. E. Moore, J. E. Hansen, T. M. Roder and R. E. Brooks, J. Polym. Sci., 21 (1956) 1892.
H. W. Starkweather, Jr. and R. E. Brooks, J. Appl. Polym. Sci., 1 (1959) 236.
H. W. Starkweather, Jr., J. Appl. Polym. Sci., 2 (1959) 129.
W. Qiu, A. Habenschuss and B. Wunderlich, Polymer, 48 (2007) 1641.
H. Haberkorn, K.-H. Illers and O. Simak, Colloid Polym. Sci., 257 (1979) 820.
J. H. Magill, M. Girolamo and A. Keller, Polymer, 22 (1981) 43.
A. Xenopoulos, ’Thermal Analysis and Studies of Conformational Disorder in Aliphatic Polyamides.’ Thesis, Rensselaer Polytechnic Institute, Chemistry, Troy, NY 1990.
F. N. Liberti and B. Wunderlich, J. Polym. Sci., Part A-2, 6 (1968) 833.
P. Weigel, A. Hirte and C. Ruscher, Faserforsch. Textiltechnik, 25 (1974) 129.
K. H. Illers, Prog. Colloid Polymer Sci., 58 (1975) 61.
M. Todoki and T. Kawaguchi, J. Polym. Sci., Polym. Phys. Ed., 15 (1977) 1068, 1507.
H. Suzuki, J. Grebowicz and B. Wunderlich, Br. Polym. J., 17 (1985) 1.
W. Qiu, M. Pyda, E. Nowak-Pyda, A. Habenschuss and B. Wunderlich, Macromolecules, 38 (2005) 8454.
W. Qiu and B. Wunderlich, Thermochim. Acta, 448 (2006) 136.
A. Xenopoulos and B. Wunderlich, J. Polym. Sci., Polym. Phys. Ed., 28 (1990) 2271.
U. Gaur, S.-F. Lau, B. B. Wunderlich and B. Wunderlich, J. Phys. Chem. Ref. Data, 12 (1983) 65. Extended by new measurements in [30]. See also, B. Wunderlich, ‘The Athas Data Base on Heat Capacities of Polymers.’ Pure Applied Chem., 67 (1995) 1019. For a collection of the updated critically analyzed data, see the ATHAS website: http://athas.prz.rzeszow.pl
A. Xenopoulos and B. Wunderlich, Polymer, 31 (1990) 1260.
B. G. Sumpter, D. W. Noid, G. L. Liang and B. Wunderlich, in U. Suter and L. Monnerie, Eds, Atomistic Modeling of Physical Properties of Polymers. pp. 27–72, Springer, Berlin 1994 (Adv. Polymer Sci., Vol. 116).
P. Debye, Ann. Phys., 37 (1912) 789.
V. V. Tarasov, Zh. Fiz. Khim., 24 (1950) 111.
B. Wunderlich and H. Baur, Heat Capacities of Linear High Polymers (transl. into Russian by Yu. Godovsky, Publishing House ‘Mir’, Moscow, 1972, p. 240.) Fortschr. Hochpolymeren Forsch. (Adv. Polymer Sci.), 7 (1970) 151.
K. A. Roles, A. Xenopoulos and B. Wunderlich, Biopolymers, 31 (1991) 477.
K. A. Roles and B. Wunderlich, Biopolymers, 33 (1993) 279.
G. Zhang, S. Gerdes and B. Wunderlich, Macromol. Chem. Phys., 197 (1996) 3791.
G. Zhang and B. Wunderlich, Proc. 25th NATAS Conf. in McLean, Va., Sept. 7–9, R. J. Morgan and R.G. Morgan, Eds, 25 (1997) 540.
B. Wunderlich, Thermochim. Acta, 446 (2006) 128.
B. Wunderlich, J. Appl. Polym. Sci., 105 (2007) 49.
M. Reading and D. J. Hourston, Eds, Modulated Temperature Differential Scanning Calorimetry, Springer, Dordrecht, The Netherlands 2006.
B. Wunderlich, Prog. Polym. Sci., 28 (2003) 383.
A. Xenopoulos and B. Wunderlich, Coll. Polym. Sci., 269 (1991) 375.
A. I. Kitaigorodskii, Organicheskaya Kristallokhimiya, Press of the Acad. Sci. USSR, Moscow 1955. Revised, English Translation by Consultants Bureau, New York 1961.
Y. Jin and B. Wunderlich, J. Phys. Chem., 95 (1991) 9000.
M. N. Sanjeeva, J. Polym. Sci., Part B: Polymer Phys., 44 (2006) 1763.
B. Wunderlich, Macromoleculer Physics, Vol. 3, Crystal Melting, Academic Press, New York 1980 (Section 10.3.2).
C. Ramesh, A. Keller and S. J. E. A. Eltink, Polymer, 35 (1994) 2483.
S. J. Cooper, M. Coogan, N. Everall and I. Priestnall, Polymer, 42 (2001) 10119.
W. Li, Y. Huang, G. Zhang and D. Yan, Polym. Int., 52 (2003) 1905.
H. J. Biangardi, J. Macromol. Sci., Phys., B29 (1990) 139.
Y. Yoshioka and T. Kohji, Polymer, 44 (2003) 6407.
T. Kohji, Chinese J. Polym. Sci., 25 (2007) 73.
Y. Yoshioka and T. Kohji, Polymer, 44 (2003) 7007.
Y. Yoshioka and T. Kohji, Polymer, 44 (2003) 6349.
T. Kohji and Y. Yoshioka, Polymer, 45 (2004) 4337.
B. Wunderlich, J. Thermal Anal., 49 (1997) 513.
W. Chen and B. Wunderlich, Macromol. Chem. Phys., 200 (1999) 283.
B. Wunderlich, Thermochim. Acta, 403 (2003) 1.
B. Wunderlich, Macromol. Rapid Commun., 26 (2005) 1521.
B. Wunderlich, Int. J. Thermophys. Fluid Phase Equilib., 89 (2007) 321.
J. Pak and B. Wunderlich, Thermochim. Acta, 421 (2004) 203.
Y. K. Kwon, A. Boller, M. Pyda and B. Wunderlich, Polymer, 41 (2000) 6237.
M. Pyda, J. Polymer Sci., Part B: Polym. Phys., 39 (2001) 3038.
M. Pyda, Macromolecules, 35 (2002) 4009.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Wunderlich, B. Thermal properties of aliphatic nylons and their link to crystal structure and molecular motion. J Therm Anal Calorim 93, 7–17 (2008). https://doi.org/10.1007/s10973-007-8644-0
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-007-8644-0