Abstract
The influence of untreated glass beads (GB) and Aerosil (A), as well as glass beads treated with aminosilanes (GBA) on the melting behavior of nylon 6 was studied with the aid of differential scanning calorimeter (DSC-1). It was found that glass beads with low surface energy (GBA) exerted no appreciable influence on the melting characteristics of a polymer, while in filled samples of the GB and A series, heats of crystallization and melting linearly decreased with a total solid surface area, the slope being numerically equal to the heat of the wetting of A by nylon 6 melt. Equilibrium melting temperature in the samples of these series abruptly dropped from 511 K to 499 K after interparticle separation decreased below about x=10×10−6 m, and remained thereafter approximately constant at Tm0=501±3 K down to x=50×10−6 m. At x=30×10−6 m, no crystallization was observed above 440 K, and the melting temperature of this sample when cooled to room temperature was independent of the crystallization temperature in the range below 440 K. Annealing of these samples at 300 K resulted in the appearance of relaxation endotherms on the heat capacity curves above the glass-transition interval, the strength of said endotherms smoothly increasing with the filler content. The experimental data were discussed in terms of changes in the initial melt structure of nylon 6 and competition between surface forces tending to increase the filler coverage and opposing its bulk driving force for polymer crystallization tending to pull segments from filler surface onto growing crystal face.
Similar content being viewed by others
Article PDF
References
Yu. S. Lipatov and G. M. Pavlyuchenko, Vysokomol. Soedin., Ser. A, 2, 1564 (1960).
C. Kumins and J. Roteman, J. Polym. Sci., A, 1, 527 (1963).
T. K. Kwei, J. Polym. Sci., A, 3, 3229 (1965).
D. Droste and A. T. Dibenedetto, J. Appl. Polym. Sci., 13, 2149 (1969).
V. F. Babich and Yu. S. Lipatov, Mekh. Polim., 3, 548 (1969).
T. Kajiyama, T. Yoshinaga, and M. Takayanagi, J. Polym. Sci., Polym. Phys. Ed., 15, 1557 (1977).
V. P. Privalko, Yu. D. Besklubenko, Yu. S. Lipatov, S. S. Demchenko, and G. I. Khmelenko, Vysokomol. Soedin., Ser. A, 19, 1744 (1977).
K. Iisaka and K. Shibayama, J. Appl. Polym. Sci., 22, 1321 (1978).
Yu. S. Lipatov, “Physical Chemistry of Filled Polymers,” Izdvestbo Khimia, Moscow, 1977 (in Russian).
Yu. S. Lipatov and V. P. Privalko, Vysokomol. Soedin., Ser. A, 14, 1643 (1972).
Yu. M. Malinskii, Usp. Khim., 39, 1511 (1970).
Yu. S. Lipatov and F. G. Fabulyak, J. Appl. Polym. Sci., 10, 2131 (1972).
Yu. S. Lipatov, V. P. Privalko, Yu. D. Besklubenko, and S. S. Demchenko, Vysokomol. Soedin., Ser. A, 19, 1756 (1977).
Yu. S. Lipatov, Adv. Polym. Sci., 22, 1 (1977).
S. S. Krafchik, Yu. Yu. Kercha, and Yu. S. Lipatov, Sintez Fiz. Khim. Polimerov, No. 8, 103 (1971).
G. J. Howard, Kolloid Z. Z. Polym., 244, 213 (1971).
V. P. Privalko, G. I. Khmelenko, and Yu. S. Lipatov, Sintez Fiz. Khim. Polimerov, No. 16, 107 (1975).
V. A. Kargin, T. I. Sogolova, and I. I. Kurbanova, Dokl. Akad. Nauk USSR, 162, 1092 (1965).
H. N. Beck and H. D. Ledbetter, J. Appl. Polym. Sci., 9, 2131 (1965).
M. Inoue, J. Polym. Sci., A, 1, 2013 (1963).
F. L. Binsbergen, Polymer, 11, 253 (1970).
G. Groeninckx, H. Bergmans, N. Overbergh, and G. Smets, J. Polym. Sci., Polym. Phys. Ed., 12, 303 (1974).
I. Gutzov, V. Dochev, E. Pancheva, and K. Dimov, J. Polym. Sci., Polym. Phys. Ed., 16, 1155 (1978).
G. Gurato, D. Gaidano, and R. Zannetti, Makromol. Chem., 179, 231 (1978).
E. P. Chang, R. O. Kirsten, and E. L. Slagowski, Polym. Eng. Sci., 18, 932 (1978).
S. Gogolewski and A. J. Pennings, Polymer, 16, 673 (1975).
P. Engler and S. H. Carr, Polym. Eng. Sci., 18, 450 (1978).
DSC-1 Instruction Manual, Perkin-Elmer Corp., Norwalk, Conn., 1969.
V. Bares and B. Wunderlich, J. Polym. Sci., Polym. Phys. Ed., 11, 861 (1973).
D. R. Gee and T. P. Melia, Polymer, 11, 192 (1970).
K.-H. Illers and H. Haberkorn, Makromol. Chem., 142, 31 (1971).
G. Gurato, A. Fichera, F. Z. Grandi, R. Zannetti, and P. Canal, Makromol. Chem., 175, 953 (1974).
B. Valenti, G. Greppi, A. Tealdi, and A. Ciferri, J. Phys. Chem., 77, 389 (1973).
J. D. Hoffman, SPE Trans., 4, 315 (1964).
M. Gopalan and L. Mandelkern, J. Phys. Chem., 71, 3833 (1967).
V. P. Privalko, T. Kawai and Yu. S. Lipatov, Colloid Polym. Sci. (Part II, submitted for publication).
G. I. Tsereteli, Thesis, Leningrad State University, Leningrad, 1975.
B. Wunderlich, “Macromolecular Physics”, Academic Press, New York, 1976, Vol. II.
R. Chujo and T. Kawai, “Physical Chemistry of Polymers”, Kyoritsu Shuppan Publ. Co., Tokyo, 1973 (in Japanese).
F. Danusso, Polymer, 8, 281 (1967).
T. Arakawa, F. Nagatoshi, and N. Arai, J. Polym. Sci., A-2, 7, 1461 (1969).
M. Kyotani and S. Mitsuhashi, J. Polym. Sci., A-2, 10, 1497 (1972).
T. Matsumoto, N. Ikegami, K. Ehara, T. Kawai, and H. Maeda, Kogyo Kagaku Zasshi, 73, 2441 (1970).
M. M. Egorov, K. G. Krasil’nikov, and E. A. Sysoev, Dokl. Akad. Nauk USSR, 108, 103 (1956).
A. C. Zettlemoyer, J. J. Chessick, and C. M. Hollabaugh, J. Phys. Chem., 62, 489 (1958).
A. C. Makrides and N. Hackerman, J. Phys. Chem., 63, 594 (1959).
H. Utsugi and S. Nishimura, Nihon Kagaku Zasshi, 92, 759 (1971).
S. K. Rhee, Mater. Sci. Eng., 19, 151 (1975).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Privalko, V., Kawai, T. & Lipatov, Y. Crystallization of Filled Nylon 6. I. Heat Capacities and Melting Behavior. Polym J 11, 699–709 (1979). https://doi.org/10.1295/polymj.11.699
Issue Date:
DOI: https://doi.org/10.1295/polymj.11.699