Small-angle neutron scattering on polymer gels: Phase behavior, inhomogeneities and deformation mechanisms

Polymer Journal

Volumn 43, Issue 1, 2011, Pages 18-34

  Shibayama, Mitsuhiro ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

inhomogeneities; N isopropylacrylamide; polymer gels; small angle neutron scattering; tetra PEG gel; tough gel; volume phase transition

Indexed keywords

INHOMOGENEITIES; N-ISOPROPYLACRYLAMIDES; POLYMER GELS; SMALL-ANGLE NEUTRON SCATTERING; TETRA-PEG GEL; TOUGH GEL; VOLUME PHASE TRANSITION;

ACRYLIC MONOMERS; AMIDES; DEFORMATION; GELS; HYDROPHOBICITY; INCOHERENT SCATTERING; MICROPHASE SEPARATION; NEUTRONS; PHASE BEHAVIOR; POLYMERS; SINGULAR VALUE DECOMPOSITION;

NEUTRON SCATTERING;

EID: 78651063202     PISSN: 00323896     EISSN: 13490540     Source Type: Journal    
DOI: 10.1038/pj.2010.110     Document Type: Review

References (101)

1. Doty, P. M., Zimm, B. H. & Stein, R. S. Classical theory of ligbt scattering from solutions\A review. Polym. Bull. 1, 90 (1945).
2. Zimm, B. H. The scattering of light and the radial distribution function of high polymer solutions. J. Chem. Phys. 16, 1093-1099 (1948).
3. Chu, B. Laser Light Scattering 2nd edn (Academic Press, New York, 1991).
4. Berry, G. C. in Soft-Matter Characterization Vol. 1 (eds Borsali, R. & Pecora, R.) 41-132 (Springer, Würzburg, 2008).
5. Chu, B. Laser light scattering. Annu. Rev. Phys. Chem. 21, 145-174 (1970).
6. Ezquerra, T. A., Garcia-Gutierrez, M. C., Nogales, A. & Gomez, M. Applications of Synchrotron Light to Scattering and Diffraction in Materials and Life Sciences (Springer, Berlin and Heidelberg, 2009).
7. Squires, G. L. Introduction to The Theory of Thermal Neutron Scattering (Cambridge University Press, Cambridge, 1978).
8. Higgins, J. S. & Benoit, H. C. Polymers and Neutron Scattering (Clarendon Press, Oxford, 1994).
9. Guinier, A. & Fournet, G. Small-Angle Scattering of X-rays (John Wiley & Sons, New York, 1955).
10. Borsali, R. in Light Scattering: Principles and Development (ed Brown, W.) (Oxford Univ. Press, Oxford, 1996).
11. Kirste, R. G., Kruse, W. A. & Schelten, J. Die bestimmung des tragheitsradius von polymethylmethacrylat im glaszustand durch neutronenbeugung. Makromol. Chem. 162, 299-303 (1973).
12. Schelten, J., Wignall, G. D. & Ballard, D. G. H Chain conformation in molten polyethylene by low angle neutron scattering. Polymer 15, 682-685 (1974).
13. Shibayama, M. in Soft Matter Characterization, Vol. 2 (eds Pecora, P. & Borsali, R.) Ch. 14, 783-832 (Springer-Verlag, Würzburg, 2008).
14. Shibayama, M., Tanaka, T. & Han, C. C. Small angle neutron scattering study on Poly(N-isopropyl acrylamide) gels near their volume-phase transition temperature. J. Chem. Phys. 97, 6829-6841 (1992).
15. Shibayama, M., Tanaka, T. & Han, C. C. Small-angle neutron scattering study on weakly charged temperature sensitive polymer gels. J. Chem. Phys. 97, 6842-6854 (1992).
16. Shibayama, M. Spatial inhomogeneity and dynamic fluctuations of polymer gels. Macromol. Chem. Phys. 199, 1-30 (1998).
17. Shibayama, M., Isono, K., Okabe, S., Karino, T. & Nagao, M. SANS study on pressure-induced phase separation of Poly(N-isoproptylacylamide) aqueous solutions and gels. Macromolecules 37, 2909-2918 (2004).
18. Nasimova, I. R., Karino, T., Okabe, S., Nagao, M. & Shibayama, M. Small-angle neutron scattering investigation of pressure influence on the structure of weakly charged Poly(N-isopropyl acrylamide) solutions and gels. Macromolecules 37, 8721-8729 (2004).
19. Nasimova, I. R., Karino, T., Okabe, S., Nagao, M. & Shibayama, M. Effect of ionization on the temperature and Pressure-induced phase transitions of poly(N-isopropylacryl-amide) gels and solutions. J. Chem. Phys. 121, 9708-9715 (2004).
20. Osaka, N. & Shibayama, M. Pressure-induced phase transitions of hydrophobically solvated block copolymer solutions. Phys. Rev. Lett. 96, 048303 (2006).
21. Osaka, N., Miyazaki, S., Okabe, S., Endo, H., Sasai, A., Seno, K., Aoshima, S. & Shibayama, M. Pressure-induced reentrant micellization of amphiphilic block copo-lymers in dilute aqueous solutions. J. Chem. Phys. 127, 094905 (2007).
22. Osaka, N., Shibayama, M., Kikuchi, T. & Yamamuro, O. Micro-and macrophase separations of hydrophobically solvated block copolymer aqueous solutions induced by pressure and temperature. Macromolecules 39, 5875-5884 (2006).
23. Tanaka, T. Collapse of gels and the critical endpoint. Phys. Rev. Lett. 40, 820-823 (1978).
24. Tanaka, T. Gels. Sci. Am. 244, 110-138 (1981).
25. Shibayama, M. & Tanaka, T. Volume phase transition and related phenomena of polymer gels. Adv. Polym. Sci. 109, 1-62 (1993).
26. Hirokawa, Y. & Tanaka, T. Volume phase transition in a nonionic gel. J. Chem. Phys. 81, 6379-6380 (1984).
27. Pelton, R. H. & Chibante, P. Preparation of aqueous latices with N-isopropylacryla-mide. Colloids Surf. A Physicochem. Eng. Asp. 20, 247-256 (1986)
28. Schild, H. G. Poly(N-isopropylacrylamide): experiment, theory and application. Prog. Polym. Sci. 17, 163-249 (1992).
29. Hirotsu, S., Hirokawa, Y. & Tanaka, T. Volume-phase transitions of ionized N-isopropylacrylamide gels. J. Chem. Phys. 87, 1392-1395 (1987).
30. Li, Y. & Tanaka, T. Study of the universality class of the gel network system. J. Chem. Phys. 90, 5161-5166 (1989).
31. Hirotsu, S. Elastic anomaly near the critical point of volume phase transition in polymer gels. Macromolecules 23, 903 (1990).
32. Hirotsu, S. Coexistence of phases and the nature of first-order phase transition in Poly-N-isopropylacrylamide gels. Adv. Polym. Sci. 110, 1-26 (1993).
33. Bates, F. S. & Fredrickson, G. H. Block copolymer thermodynamics: theory and experiment. Annu. Rev. Phys. Chem. 41, 525-557 (1990).
34. Shibayama, M., Ikkai, F., Inamoto, S., Nomura, S. & Han, C. C. pH and salt concentration dependence of the microstructure of Poly(N- isopropylacrylamide-co-acrylic acid) gels. J. Chem. Phys. 105, 4358-4366 (1996).
35. Ikkai, F., Iritani, O., Shibayama, M. & Han, C. C. Effect of degree of cross-linking on spatial inhomogeneity in charged gels. 3. Ionized effect. Macromolecules 31, 8526-8530 (1998). (Pubitemid 128565552)
36. Dusek, K. & Prins, W. Structure and elasticity of non-crystalline polymer networks. Adv. Polym. Sci. 6, 1-102 (1969).
37. Candau, S., Bastide, J. & Delsanti, M. Structural, elastic, and dynamic properties of swollen polymer networks. Adv. Polym. Sci. 44, 27 (1982).
38. Bastide, J. & Leibler, L. Large-scale heterogeneities in randomly cross-linked networks. Macromolecules 21, 2647 (1988).
39. Panyukov, S. & Rabin, Y. Statistical physics of polymer gels. Phys. Rep. 269, 1-132 (1996).
40. Panyukov, S. & Rabin, Y. Polymer gels: frozen inhomogeneities and density fluctuations. Macromolecules 29, 7960 (1996).
41. Rabin, Y. & Panyukov, S. Scattering profiles of charged gels: frozen inhomogeneities, thermal fluctuaitons, and microphase separation. Macromolecules 30, 301-312 (1997).
42. Panyukov, S. & Rabin, Y. Volume transitions, phase separation, and anisotropic surface phases in charged gels. Macromolecules 29, 8530-8537 (1996).
43. Takata, S., Norisuye, T. & Shibayama, M. Small-angle neutron scattering study on preparation temperature dependence of thermosensitive gels. Macromolecules 35, 4779-4784 (2002). (Pubitemid 34630566)
44. Shibayama, M., Takata, S. & Norisuye, T. Static inhomogeneities and dynamic fluctuations of temperature sensitive polymer gels. Physica A 249, 245-252 (1998). (Pubitemid 128427238)
45. Onuki, A. Scattering from deformed swollen gels with heterogeneities. J. Phys. II France 2, 45-61 (1992).
46. Shibayama, M., Kawakubo, K., Ikkai, F. & Imai, M. Small-angle neutron scattering study on charged gels in deformed state. Macromolecules 31, 2586-2592 (1998).
47. Hadziioannou, G., Wang, L. H., Stein, R. S. & Porter, R. S Small-angle neutron scattering studies on amorphous polystyrene oriented by solid-state coextrusion. Macromolecules 15, 880-882 (1982).
48. Mendes, E. J., Lindner, P., Buzier, M., Boue, F. & Bastide, J. Experimental evidence for inhomogeneous swelling and deformation in statistical gels. Phys. Rev. Lett. 66, 1595 (1991).
49. Mendes, E., Oeser, R., Hayes, C., Boue, F. & Bastide, J. Small-angle neutron scattering study of swollen elongated gels: butterfly patterns. Macromolecules 29, 5574 (1996).
50. Mendes, E., Schosseler, F., Isel, F., Boue, F., Bastide, J. & Candau, S. J. A sans study of uniaxially elongated polyelectrolyte gels. Europhys. Lett. 32, 273 (1995).
51. Geissler, E., Duplessix, R. & Hecht, A. M Radius of gyration in anisotropically swollen gels. Macromolecules 16, 712-713 (1983).
52. Shibayama, M., Kawakubo, K. & Norisuye, T. Comparison of the experimental and theoretical structure factors of temperature sensitive polymer gels. Macromolecules 31, 1608-1614 (1998).
53. Shibayama, M., Ikkai, F., Shiwa, Y. & Rabin, Y. Effect of degree of cross-linking on spatial inhomogeneity in charged gels. I. theoretical prediction and light scattering study. J. Chem. Phys. 107, 5227-5235 (1997).
54. Ikkai, F. & Shibayama, M. Anomalous cross-link density dependence of scattering from charged gels. Phys. Rev. E 56, R51-R54 (1997).
55. Ikkai, F. & Shibayama, M. Static inhomogeneities in thermoreversible gels. Phys. Rev. Lett. 82, 4946-4949 (1999).
56. Osaka, N., Takata, S., Suzuki, T., Endo, H. & Shibayama, M. Comparison of heat-and pressure-induced gelation of b-lactoglobulin aqueous solutions studied by small-angle neutron and dynamic light scattering. Polymer 49, 2957-2963 (2008).
57. 2 nanocystallites in methanol and in N,N-dimehtylformamide. Chem. Lett. 29, 938-939 (2000).
58. Otake, K., Karaki, R., Ebina, T., Yokoyama, C. & Takahashi, S. Pressure effects on the aggregation of poly(N-isopropylacrylamide) and poly(N-isopropylacrylamide-co-acrylic acid) in aqueous solutions. Macromolecules 26, 2194-2197 (1993).
59. Kato, E. Volume-phase transition of N-isopropylacrylamide gels induced by hydrostatic pressure. J. Chem. Phys. 106, 3792-3797 (1997).
60. Rebelo, L. P. N., Visak, Z. P., de Sousa, H. C., Szydlowski, J., Gomes de Azevedo, R., Ramos, A. M., Najdanovic-Visak, V., Nunes da Ponte, M. & Klein, J. Double critical phenomena in (water+polyacrylamides) solutions. Macromolecules 35, 1887 (2002).
61. Smeller, L. Pressure-temperature phase diagram of biomolecules. Biochim. Biophys. Acta 1595, 11-29 (2002).
62. Kato, E. Thermodynamic study of a pressure-temperature phase diagram for poly(N-isopropylacrylamide) gels. J. Appl. Polym. Sci. 97, 405-412 (2005).
63. Okumura, Y. & Ito, K. The polyrotaxane gel: a topological gel by figure-of-eight crosslinks. Adv. Mater. 13, 485-487 (2001).
64. Ball, R. C., Edwards, S. F., Doi, M. & Warner, M. Elasticity of entangled networks. Polymer 22, 1010-1018 (1981).
65. Ito, K. Novel cross-linking concept of polymer network: synthesis, structure, and properties of slide-ring gels with freely movable junctions. Polym. J. 39, 489-499 (2007).
66. Haraguchi, K. & Takehisa, T. Nanocomposite hydrogels: a unique organic-inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties. Adv. Mater. 14, 1120-1124 (2002).
67. Gong, J. P., Katsuyama, Y., Kurokawa, T. & Osada, Y. Double-network hydrogels with extremely high mechanical strength. Adv. Mater. 15, 1155-1158 (2003).
68. Sakai, T., Matsunaga, T., Yamamoto, Y., Ito, C., Yoshida, R., Suzuki, S., Sasaki, N., Shibayama, M. & Chung, U. Design and fabrication of a high-strength hydrogel with ideally homogeneous network structure from tetrahedron-like macromonomers. Macromolecules 41, 5379-5384 (2008).
69. Schmidt, H. in Polymer Based Molecular Composites (eds D. W. Schaefer & J. E. Mark) Mater. Res. Soc. (1990).
70. Novak, B. M Hybrid nanocomposite materials-between inorganic glasses and organic polymers. Adv. Mater. 5, 422-433 (1993).
71. Haraguchi, K., Takehisa, T. & Fan, S. Effects of clay content on the properties of nanocomposite hydrogels composed of poly(N-isopropylacrylamide) and clay. Macro-molecules 35, 10162-10171 (2002).
72. Haraguchi, K., Farnworth, R., Ohbayashi, A. & Takehisa, T. Compositinal effects on mechanical properties of nanocomposite hydrogels composed of poly(N,N-dimthyla-crylamide) and clay. Macromolecules 36, 5732-5741 (2003).
73. Haraguchi, K., Li, H.-J., Matsuda, K., Takehisa, T. & Elliot, E. Mechanism of forming organic/inorganic network structures during in-situ free-radical polymerization in PNIPA-clay nanocomposite hydrogels. Macromolecules 38, 3482-3490 (2005).
74. Shibayama, M., Suda, J., Karino, T., Okabe, S., Takehisa, T. & Haraguchi, K. Structure and dynamics of poly(N-isopropyl acrylamide)-clay nanocomposite gels. Macromole-cules 37, 9606-9612 (2004).
75. Miyazaki, S., Karino, T., Endo, H., Haraguchi, K. & Shibayama, M. Clay concentration dependence of microstructure in deformed poly(N- isopropylacrylamide)-clay nano-composite gels. Macromolecules 39, 8112-8120 (2006).
76. Miyazaki, S., Endo, H., Karino, T., Haraguchi, K. & Shibayama, M. Gelation mechanism of poly(N-isopropylacrylamide)-clay nanocomposite gels. Macromolecules 40, 4287-4295 (2007).
77. Endo, H., Miyazaki, S., Haraguchi, K. & Shibayama, M. Structure of nanocomposite hydrogel investigated by means of contrast variation small angle neutron scattering. Macromolecules 41, 5406-5411 (2008).
78. Shibayama, M., Karino, T., Miyazaki, S., Takehisa, T. & Haraguchi, K. Small-angle neutron scattering study on uniaxially stretched poly(N-isopropylacrylamide)-clay nanocomposite gels. Macromolecules 38, 10772-10781 (2005).
79. Nishida, T., Endo, H., Osaka, N., Li, H. J., Haraguchi, K. & Shibayama, M. Deformation mechanism of nanocomposite gels studied by contrast variation small-angle neutron scattering. Phys. Rev. E 80, 030801 (2009).
80. Karino, T., Okumura, Y., Ito, K. & Shibayama, M. SANS studies on spatial inhomo-geneities of slide-ring gels. Macromolecules 37, 6117-6182 (2004).
81. Haraguchi, K. & Li, H.-J. Mechanical properties and structure of polymer-clay nanocomposite gels with high clay content. Macromolecules 39, 1898-1905 (2006).
82. Shibayama, M., Miyazaki, S., Endo, H., Karino, T. & Haraguchi, K. Deformation studies on polymer-clay nanocomposite gels. Macromol. Symp. 256, 131-136 (2007).
83. Endo, H., Schwahn, D. & Cölfen, J. On the role of block copolymer additives for calcium carbonate crystallization: small angle neutron scattering investigation by applying contrast variation. J. Chem. Phys. 120, 9410-9423 (2004).
84. Osaka, N., Endo, H., Nishida, T., Suzuki, T., Li, H. J., Haraguchi, K. & Shibayama, M. Microphase separation in nanocomposite gels. Phys. Rev. E Rapid Commun. 79, 060801 (2009).
85. Kurakazu, M., Katashima, T., Chijiishi, M., Nishi, N., Akagi, Y., Matsunaga, T., Shibayama, M., Chung, U. & Sakai, T. Evaluation of gelation kinetics of Tetra-PEG gel. Macromolecules 43, 3935-3940 (2010).
86. Matsunaga, T., Sakai, T., Akagi, Y., Chung, U. & Shibayama, M. Structure characterization of Tetra-PEG Gel by small-angle neutron scattering. Macromolecules 42, 1344-1351 (2009).
87. Akagi, Y., Matsunaga, T., Shibayama, M., Chung, U. & Sakai, T. Evaluation of topological defects in Tetra-PEG gels. Macromolecules 43, 488-493 (2010).
88. Akagi, Y. et al. Effect of module size on the network structure of Tetra-PEG gel (in preparation).
89. Bastide, J. & Candau, S. J. in The Physical Properties of Polymer Gels Ch. 9 (ed Cohen Addad, J. P.) 143 (John Wiley, New York, 1996).
90. Mendes, E., Hakiki, A., Herz, J., Boue, F. & Bastide, J. Structure of trifunctional end-link polymer gels studied by SANS. Macromolecules 37, 2643-2649 (2004).
91. Sukumaran, S. K., Beaucage, G., Mark, J. E. & Viers, B. Neutron scattering from equilibrium-swollen networks. Eur. Phys. J. E 18, 29-36 (2005).
92. Sakai, T., Akagi, Y., Matsunaga, T., Kurakazu, M., Chung, U. & Shibayama, M. Highly elastic and deformable hydrogel formed from tetra-arm polymers. Macromol. Rapid Commun. 31, 1954-1959 (2010).
93. Matsunaga, T., Sakai, T., Akagi, Y., Chung, U. & Shibayama, M. SANS and SLS studies on tetra-arm PEG gels in as-prepared and swollen states. Macromolecules 42, 6245-6252 (2009).
94. Hammouda, B., Ho, D. & Kline, S. SANS from poly(ethylene oxide)/water systems. Macrmolecules 35, 8578-8585 (2002).
95. Hammouda, B., Ho, D. L. & Kline, S. Insight into clustering in poly(ethylene oxide) solutions. Macrmolecules 37, 6932-6937 (2004).
96. Haraguchi, K., Xu, Y. & Li, G. Molecular characteristics of poly(N-isopropylacrylamide) separated from nanocomposite gels by removal of clay from the polymer/clay network. Macromol. Rapid Commun. 31, 718-723 (2010).
97. Xu, Y., Li, G. & Haraguchi, K. Gel formation and molecular characteristics of poly(N-isopropylacrylamide) prepared by free-radical redox polymerization in aqueous solution. Macromol. Chem. Phys. 211, 977-987 (2010).
98. Shibayama, M., Matsunaga, T. & Nagao, M. Evaluation of incoherent scattering intensity by transmission and sample thickness. J. Appl. Cryst. 42, 621-628 (2009).
99. Shibayama, M., Takahashi, H. & Nomura, S. Small-angle neutron scattering study on end-linked poly(tetrahydrofuran) networks. Macromolecules 28, 6860-6864 (1995).
100. Villar, M. A. & Valles, E. M Influence of pendant chains on mechanical properties of model poly(dimethylsiloxane) networks.2. Viscoelastic properties. Macromolecules 29, 4081 (1996).
101. Granick, S. & Rubinstein, M. A multitude of macromolecules. Nat. Mater. 3, 586-587 (2004).