Abstract
The recent development of a microscopic theory of the equilibrium properties of polymer solutions, melts and alloys based on off-lattice Polymer Reference Interaction Site Model (PRISM) integral equation methods is reviewed. Analytical and numerical predictions for the intermolecular structure and collective density scattering patterns of both coarse-grained and atomistic models of polymer melts are presented and found to be in good agreement with large scale computer simulations and diffraction measurements. The general issues and difficulties involved in the use of the structural information to compute thermodynamic properties are reviewed. Detailed application of a hybrid PRISM approach to calculate the equation-of-state of hydrocarbon fluids is presented and found to reproduce accurately experimental PVT data on polyethylene. The development of a first principles off-lattice theory of polymer crystallization based on a novel generalization of modern thermodynamic density functional methods is discussed. Numerical calculations for polyethylene and polytetrafluoroethylene are in good agreement with the experimental melting temperatures and liquid freezing densities. Generalization of the PRISM approach to treat phase separating polymer blends is also discussed in depth. The general role of compressibility effects in determining small angle scattering patterns, the effective chi-parameter, and spinodal instability curves are presented. New theoretical concepts and closure approximations have been developed in order to describe correctly long wavelength concentration fluctuations in macromolecular alloys. Detailed numerical and analytical applications of the PRISM theory to model athermal and symmetric blends are presented, and the role of nonmean field fluctuation processes are established. Good agreement between the theory and computer simulations of simple symmetric polymer blends has been demonstrated. Strong, nonadditive compressibility effects are found for structurally and/or interaction asymmetric blends which have significant implications for controlling miscibility in polymer alloys. Recent generalizations of PRISM theory to treat block copolymer melts, and nonideal conformational perturbations, are briefly described. The paper concludes with a brief summary of ongoing work and fertile directions for future research.
Preview
Unable to display preview. Download preview PDF.
References
Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca
Dudowicz J, Freed MS, Freed KF (1991) Macromolecules 24: 5096; Freed KF, Dudowicz J (1992) Theoretica, Chimica Acta 82; Dudowicz J, Freed KF (1993) Macromolecules, 26: 213; Freed K, Dudowicz J (1992) J Chem Phys 97: 2105
For polymer solutions: Doi M, Edwards SF (1986) Theory of polymer dynamics. Oxford Press, Oxford
For block copolymers: Bates FS, Fredrickson GH (1990) Ann Rev Phys Chem 41: 525
Roe RJ (ed) (1991) Computer simulations of polymers. Prentice Hall, Englewood Cliffs, N.J.; Colburn EA (ed) (1992) Computer simulations of polymers. Longman, Harlow; Binder K (1993) Advances in Polymer Science, in press
Hansen JP, McDonald IR (1986) Theory of simple liquids, 2nd edn. Academic, London
Chandler D (1982) In: Montroll EW, Lebowitz L (eds) Studies in statistical mechanics, vol. VIII. North-Holland, Amsterdam, p. 274 and references cited therein
Percus JK (1964) In: Frisch HL, Lebowitz KL (eds) Classical fluids. Wiley, New York
Chandler D, Andersen HC (1972) J Chem Phys 57: 1930
Lowden LJ, Chandler D (1974) J Chem Phys 61: 5228; (1973) 59: 6587; (1975) 62: 4246
Chandler D, Hsu CS, Streett WB (1977) J Chem Phys 66: 5231; Sandler SI, Narten AH (1976) Mol Phys 32: 1543; Narten AH (1977) J Chem Phys 67: 2102; Hsu CS, Chandler D (1978) Mol Phys 36: 215; Mol Phys 37: 299 (1979)
Schweizer KS, Curro JG (1987) Phys Rev Lett 58: 246
Curro JG, Schweizer KS (1987) Macromolecules 20: 1928
Curro JG, Schweizer KS (1987) J Chem Phys 87: 1842
Schweizer KS, Curro JG (1988) Macromolecules 21: 3070
Schweizer KS, Curro JG (1988) Macromolecules 21: 3082
Volkenstein MV (1963) Configurational statistics of polymer chains. Interscience, New York; Flory PJ (1969) Statistical mechanics of chain molecules. Interscience, New York
Flory PJ (1949) J Chem Phys 17: 203
Curro JG (1976) J Chem Phys 64: 2496; (1979) Macromolecules 12: 463; Vacatello M, Avitabile G, Corradini P, Tuzi A (1980) J Chem Phys 73: 543
Ballard DG, Schelton J, Wignall GD (1973) Eur. Polymer Journal, 9: 965; Cotton JP, Decker D, Benoit H, Farnoux B, Higgins J, Jannick G, Ober R, Picot C, des Cloizeaux J (1974) Macromolecules 7: 863
Lue, L, Blanckschtein D (1992) J Phys Chem 96: 8582
Elliot JR, Kanetar US (1990) Mol Phys 71: 871 and 883
deGennes PG (1979) Scaling concepts in polymer physics. Cornell University Press, Ithaca
Schweizer KS, Curro JG (1990) Chemical Physics, 149: 105; Schweizer KS, Curro JG (1991) J Chem Phys 94: 3986
Honnell KG, Curro JG, Schweizer KS (1990) Macromolecules, 23: 3496
Koyama R (1973) J Phys Soc Japan, 22: 1029; Mansfield ML (1986) Macromolecules, 19: 854
Chandler D, Silbey RS, Ladanyi BM (1982) Mol Phys 46: 1335; Richardson DM, Chandler D (1984) J Chem Phys 80: 4484
Curro JG, Schweizer KS, Grest GS, Kremer K (1989) J Chem Phys 91: 1357; Kremer K, Grest GS (1990) J Chem Phys 92: 5057
Andersen HC, Weeks JD, Chandler D (1971) Phys Rev A 4: 1597; Weeks JD, Chandler D, Andersen HC (1971) J Chem Phys 54: 5237
Yethiraj A, Hall CK (1991) J Chem Phys 93: 4453; (1992) 96: 797
Yethiraj A, Schweizer KS (1992) J Chem Phys 97: 1455
McCoy JD, Honnell KG, Curro JG, Schweizer KS, Honeycutt JD, Macromolecules (1992) 25: 4905
Honnell KG, McCoy JD, Curro JG, Schweizer KS, Narten AH, Habenschuss A (1991) J Chem Phys 94: 4659
Narten AH, Habenschuss A, Honnell KG, McCoy JD, Schweizer KS (1992) J Chem Soc Faraday Trans 88: 1791
Honnell KG, McCoy JD, Curro JG, Schweizer KS, Narten AH, Habenshuss A (1991) Bull Am Phys Soc 36(3): 481, and paper in preparation
Barker JA, Henderson D (1967) Chem Phys 47: 4714; (1972); Ann Rev Phys Chem 23: 439; (1976) Rev. Mod Phys 48: 587
Dickman R, Hall CK (1988) J Chem Phys 89: 3168
Yethiraj A, Hall CK (1991) J Chem Phys 95: 3749
Yethiraj A, Curro JG, Schweizer KS, McCoy JD (1993) J Chem Phys 98: 1635
Curro JG, Yethiraj A, Schweizer KS, McCoy JD, Honnell KG (1993) Macromolecules 26: 2655
Dickman R, Hall CK (1986) J Chem Phys 85: 4108; Honnell KG, Hall CK (1989) J Chem Phys 90: 1841
Olabisi O, Simha R (1975) Macromolecules 8: 206
Lopez-Rodriguez A, Vega C, Freire JJ, Lago S (1991) Mol Phys 73: 691
Martynov GA, Vompe AG (1993) Phys Rev E 47: 1012
Flory PJ (1956) Proc Roy Soc A 234: 60
Nagle JF, Gujrati PD, Goldstein M (1984) J Phys Chem 88: 4599
Ramakrishnan TV, Yussouff M (1979) Phys Rev B 19: 2775
Haymet ADJ, Oxtoby DW (1981) J Chem Phys 74: 2559; Laird BB, McCoy JD, Haymet ADJ (1987) J Chem Phys 87: 5451
Chandler D, McCoy JD, Singer SJ (1986) J Chem Phys 85: 5977; McCoy JD, Singer SJ, Chandler D (1987) J Chem Phys 87: 4953
McCoy JD, Rick SW, Haymet ADJ (1989) J Chem Phys 90: 4622; (1990) 92: 3034; Rick SW, McCoy JD, Haymet ADJ (1990) J Chem Phys 92: 3040
Ding K, Chandler D, Smithline SJ, Haymet ADJ (1987) Phys Rev Lett 59: 1698
McMullen WE, Freed KF (1990) J Chem Phys 92: 1413
McCoy JD, Honnell KG, Schweizer KS, Curro JG (1991) Chem Phys Lett 179: 374; J Chem Phys 95: 9348
Wunderlich B, Czornj G (1977) Macromolecules 10, 906
Starkweather HW, Zoller P, Jones GA, Vega AJ (1982) J Polym Sci., Polym Phys 20: 751
See, for example, Bates FS (1991) Science 251: 898; Sanchez IC (1983) Ann Rev Mater Sci 13: 387; Solc K (ed) (1981) Polymer compatibility and incompatibility. Midland, Michigan
Wignall GD (1987) in Encyclopedia of polymer science and engineering, second edition. Wiley, New York, vol. 12, p. 112
See, for e.g., Jung WG, Fischer EW (1988) Makromol, Chem Makromol Symp 16: 281; Brereton MG, Fischer EW, Herkt-Maetzky C, Mortensen K (1987) J Chem Phys 87: 6114; Han CC, Bauer BJ, Clark JC, Moroga Y, Matsushita Y, Okada M, Tran-cong Q, Chang T, Sanchez IC (1988) Polymer 29: 2002; Bates FS, Muthukumar M, Wignall GD, Fetters LJ (1988) J Chem Phys 89: 535
Marie P, Selb J, Rameau A, Gallot Y (1988) Makromol Chem Makromol Symp 16: 301; Jung WG, Fischer EW (1988) ibid 16: 281; Hashimoto T, Ijichi Y, Fetters LJ (1988) J Chem Phys 89: 2463; Ijichi Y, Hashimoto T, Fetters LJ (1989) Macromolecules 22: 2817; Tanaka H, Hashimoto T (1991) Macromolecules 24: 5398
Schweizer KS, Curro JG (1988) Phys Rev Lett 60: 809
Curro JG, Schweizer KS (1988) J Chem Phys 88: 7242
Schweizer KS, Curro JG (1989) J Chem Phys 91: 5059
Curro JG, Schweizer KS (1990) Macromolecules 23: 1402
Curro JG, Schweizer KS (1991) Macromolecules 24: 6736
Kirkwood JG, Buff FP (1951) J Chem Phys 19: 774
Chen XS, Forstmann F (1992) J Chem Phys 97: 3696; Malescio G (1992) J Chem Phys 96: 648, and references cited therein; Arrieta E, Jedrzejek C, Marsh KN (1991) ibid 95: 6806 and 6838
Sanchez IC (1991) Macromolecules 24: 908
Schweizer KS (1993) Macromolecules 26: 6033 and 6050
Schweizer KS, Yethiraj A (1993) J Chem Phys 98: 9053
Yethiraj A, Schweizer KS (1992) J Chem Phys 97: 5927
Yethiraj A, Schweizer KS (1993) J Chem Phys 98: 9080
Singh C, Schweizer KS, Yethiraj A (1994) J Chem Phys, submitted
Honeycutt JD (1992) ACS Polymer Preprints 33(1): 529; (1992) Proc. of CAMSE'92, Yokohama, Japan, in press; private communication
Singh C, Schweizer KS (1994) J Chem Phys, submitted
Deutsch H-P, Binder K (1992) Europhysics Lett 17: 697; (1993) Macromolecules 25: 6214; (1993) J Phys II France 3: 1049, see also, Sariban A, Binder K (1988) Macromolecules 21: 711
Gehlsen MP, Rosedale JH, Bates FS, Wignall GD, Hansen L, Almdal K (1992) Phys Rev Lett 68: 2452
Chandler D (1993) Phys Rev E 48: 2898
Melenkevitz J, Curro JG (1994) in preparation
Andersen HC, Chandler D (1972) J Chem Phys 57: 1918, 1930
Lupkowski M, Monson PA (1987) J Chem Phys 87: 3618
Ladanyi BM, Chandler D (1975) J Chem Phys 62: 4308
Dudowicz J, Freed KF (1990) Macromolecules 23: 1519; Tang H, Freed KF (1991) Macromolecules 24: 958
Rowlinson JS, Swinton FL (1982) Liquids and Liquid Mixtures, Butterworth Scientific, London
Hildebrand J, Scott R (1949) The Solubility of Nonelectrolytes, 3rd Edition, Reinhold, New York
Bates FS, Schulz MF, Rosedale JH (1992) Macromolecules 25: 5547
Liu AJ, Fredrickson GH (1992) Macromolecules 25: 5551
Yethiraj A, Schweizer KS (1993) Bull Am Phys Soc 38(1), 485; David EF, Schweizer KS (1994) in preparation
David EF, Schweizer KS (1994) J Chem Phys 100: May 15
Leibler L (1980) Macromolecules 13: 1602
Fried H, Binder K (1991) J Chem Phys 94: 8349
Fredrickson GH, Helfand E (1987) J Chem Phys 87: 697; Brazovski SA (1975) Sov Phys JETP 41: 85
Tang H, Freed KF (1992) J Chem Phys 96: 862
Yethiraj A, Kumar S, Hariharan A, Schweizer KS (1994) J Chem Phys 100: 4691
Yethiraj A, Hall CK, Dickman R (1992) J Colloid and Interface Sci 151: 102
Schweizer KS, Honnell KG, Curro JG (1992) J Chem Phys 96: 3211
Chandler D, Singh Y, Richardson DM (1984) J Chem Phys 81: 1975; Nichols AL, Chandler D, Singh Y, Richardson DM (1984) ibid 81, 5109; Laria D, Wu D, Chandler D (1991) ibid, 95: 4444
Chandler D (1987) Chem Phys Lett 139: 108
Singh Y (1987) J Phys A-Math Gen 20: 3949
Melenkevitz J, Schweizer KS, Curro JG (1993) Macromolecules 26: 6190
Grayce CJ, Schweizer KS (1994) J Chem Phys 100: May 1
Melenkevitz J, Curro JG, Schweizer KS (1993) J Chem Phys 99: 5571
Grayce CJ, Yethiraj A, Schweizer KS (1994) J Chem Phys 100: May 1
Schweizer KS (1986) J Chem Phys 85: 1156, 1176; Synthetic Metals 28: C565 (1989)
Grayce CJ, Schweizer KS (1993) Bull Am Phys Soc 38(1), 485; Macromolecules to be submitted.
Melenkevitz J, Muthukumar M (1991) Macromolecules 24: 4199
Schweizer KS (1989) J Chem Phys 91: 5802 and 5822; J Non-Cryst Sol 131–133, 643 (1991); Physica Scripta (1993) T49: 99
Chiew YC (1990) Mol Phys 70: 129 and 73: 359 (1991); J Chem Phys 93: 5067 (1990).
Lipson JEG (1991) Macromolecules 24: 1334; Lipson JEG, Andrews AA (1992) J Chem Phys 96: 1426
Gan HH, Eu BC (1993) J Chem Phys 99: 4084, 4103
Schweizer KS, Curro JG, Ann Rev Phys Chem, in preparation
Curro JG (1994) Macromolecules, in press
Donley JP, Curro JG, McCoy JD (1994) J Chem Phys, in press; Sen S, Cohen JM, McCoy JD, Curro JG (1994) J Chem Phys, submitted
Author information
Authors and Affiliations
Editor information
Rights and permissions
Copyright information
© 1994 Springer-Verlag
About this chapter
Cite this chapter
Schweizer, K.S., Curro, J.G. (1994). PRISM theory of the structure, thermodynamics, and phase transitions of polymer liquids and alloys. In: Monnerie, L., Suter, U.W. (eds) Atomistic Modeling of Physical Properties. Advances in Polymer Science, vol 116. Springer, Berlin, Heidelberg . https://doi.org/10.1007/BFb0080203
Download citation
DOI: https://doi.org/10.1007/BFb0080203
Received:
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-57827-7
Online ISBN: 978-3-540-48352-6
eBook Packages: Springer Book Archive