Abstract
Thermodynamics of heat- and strain-induced crystallization of networks is presented which allows the description of both crystallization modes. The network is treated as a eutectoid copolymer. Chains of different length are components representing crystallizable “c-sequences”. For thermodynamic reasons, extended c-sequence crystals are formed in any case. It is the essential step to combine the van der Waals theory of networks and the theory of eutectoid copolymers. The solubility in the solid seems to be increased in presence of a mechanical field. The typical hysteresis in stress-strain cycles is then understandable only if “quasi-static constraints” are introduced. These constraints are responsible for the observation that strain-induced crystallization is enforced under large overdrawings. Melting during retraction seems to run under invariant constraints. With the aid of this approach, it is possible to describe the work and the heat exchanged during stress-strain cycles of natural rubber measured in a stretching micro-calorimeter. The origins of the constraints are discussed.
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References
Flory PJ (1947) Chem Phys 15:3976
Treloar LRG (1974) The Physics of Rubber Elasticity, 3rd Ed., Clarendon Press, Oxford
Mandelkern L (1964) Crystallization of Polymers, McGraw, New York
Göritz D, Müller FH, Sietz W (1977) Prog Coll Polym Sci 62:114
Mitchell JC, Meyer DJ (1968) J Polym Sci A-2 6:1689
Kawai H, Oda T, Tomita S, Furata I (1968) 5th Int Congr Rheology, Kyoto
Yamamoto M, White J (1971) J Polym Sci A2 9:1399
Kim Hg, Mandelkern L (1968) I Polym Sci A2 16:181
Krigbaum WR, Dawkins JV, Via HG, Balta YG (1966) J Polym Sci A 2:475
Oth JF, Flory PJ (1958) J Am Chem Soc 80:1297
Gent AN (1954) Trans Farad Soc 50:521
Holl B, Kilian HG, Yeh GSY (1985) Coll Polym Sci 263:313
Mukherji S, Woodward AC (1984) J Polym Sci Polym Phys Ed 22:793
Pei-guo Wang, Woodward C (1987) Macromol 20:1818
Gavish M, Corrigan J, Woodward AC (1988) Macromol 21:2079
Candia T, Romano G, Russo R (1987) J Appl Polym Sci, 34:211
Allegra G, Bruzzone M (1983) Macromol 16:1167
Siesler H, Perl W (1988) Mikrochim Acta I:323
Smith KJ (1974) Polym Eng Sci 16:168
Burfield D, Tanaka Y (1985) Proc Int Rubber Conf 140
Kilian HG (1986) Progr Coll Polym Sci 72:60
Kilian HG, Unseld K, Jäger E, Müller J, Jungnickel B (1985) Coll Polym Sci 263:607
Glenz W, Kilian HG, Klattenhoff D, Stracke F, (1977) Polymer 18:685
Rosenberger R, Asbach GI, Kilian HG, Wilke W, Rodriguéz M (1988) Macromol Chem 189:2627
Heise B, Kilian HG, Schmidt H (1981) Coll Polym Sci 259:611
Kilian HG (1988) Progr Coll Polym Sci 78:161
Kilian HG (1981) Polymer 22:209
Kilian HG (1987) Progr Coll Polym Sci 75:55
Vilgis T, Kilian HG (1986) Coll Polym Sci 264:137
Eisele K, Heise B, Kilian HG, Pietralla M (1981) Angew Makromol Chem, 100 (1981), 67
Kilian HG (1989) Macromol Chem, Macromol Symp 26:411
Holl B, Thesis, University Ulm, 1987
Hosemann R, Baggchi SN (1962) Direct Analysis of Diffraction b Matter, North-Holland Publ Comp, Amsterdam
Wilke W, Martis K, Coll Polym Sci, 252(1974), 718
Kilian HG, Unseld K, Jaeger E, Jungnickel B (1985) Coll Polym Sci 263:607
Enderle HF, Kilian HG (1987) Prog Coll Polym Sci 75:55
Ambacher H, Enderle HF, Kilian HG, Sauter A (1989) Prog Coll Polym Sci, 80:209
Kilian HG, Unseld K (1986) Coll Polym Sci 264:9.
Kilian HG, Enderle HF, Unseld K, (1986) Coll Polym Sci 264:866
Kilian HG (1989) Makrom Chem, in press
Green AG, Atkins JC (1970) Large Elastic Deformations, Claredon Press, Oxford
Vilgis T, Kilian HG (1986) Coll Polym Sci 264:137
Zrinyi M, Kilian HG, Horkay F (1989) Coll Polym Sci 267:311
Callen HB (1960) Thermodynamics, Wiley and Sons, New York-London-Sydney
Keller JU (1977) Thermodynamik der irreversiblen Prozesse, Teil 1, Thermostatik und Grundbegriffe, Walter de Gruyter, Berlin-New York
Guggenheim EA (1967) Thermodynamics, North-Holland Pub Comp, Amsterdam
Flory PJ (1969) Statistical Mechanics of Chain Molecules, Interscience, New York
Volkenstein MV (1963) Configurational statistics of Polymeric Chains, Interscience Publ, John Wiley, New York-London
Dusek K, Prins W (1969) Adv Polym Sci 6:1
Müller FH, Engelter A (1957) Koll-Z u Z Polym, 152:15
Engelter A, Müller FH (1958) Koll-Z u Z Polym 157:89
Göritz D, Müller FH (1973) Koll-Z u Z Polym 251:892
Kilian HG, Höhne G, Trögerle P, Ambacher H (1984) J Polym Sci Polym Symp, 77:221
Ambacher H (1985) Diplomarbeit, Universität Ulm
Göritz D, (1982) Coll Polym Sci 26:193
Godovsky YK (1977) Vysokomol Soed A19:2359
Godovsky YK (1986) Adv Polym Sci 76:31
Kilian HG (1981) Coll Polym Sci 259:75
Kraus G (1971) Adv Polym Sci 8:155
Kraus G (1971) Rubber Chem Tech 44:99
Mullins L, Tobin NR (1965) J Appl Polym Sci 9:2993
Rigbi Z (1980) Adv polym Sci 36:21
Ambacher H, Enderle FH, Kilian HG, Sauter A (1989) Prog Coll Polym Sci, in press
Treloar LRG (1947) Trans Faraday Soc 43:277
Stein RS, Wilkes GL in (1975) “Structure and Properties of Oriented Polymers” ed by Ward IM, Appl Sci Publ, London, page 57
Pietralla M, Kilian HG (1980) J Polym Sci, Phys Ed 18:285
Folkes MJ, Keller A (1971) Polymer 12:222
Hoshino S, Powers J, LeGrand DG, Kawai H, Stein RS (1962) J Polym Sci 58:185
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Holl, B., Kilian, H.G. & Schenk, H. Crystallization in unstretched and in stretched rubber and its thermodynamic description. Colloid & Polymer Sci 268, 205–221 (1990). https://doi.org/10.1007/BF01490245
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DOI: https://doi.org/10.1007/BF01490245