Brief ReviewNo Access

GELATION MECHANISMS

ÖNDER PEKCAN

Kadir Has University, Cibali, Fatih, 34083 Istanbul, Turkey

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and

SELIM KARA

Trakya University, Faculty of Science, Department of Physics, 22030 Edirne, Turkey

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https://doi.org/10.1142/S0217984912300190Cited by:19 (Source: Crossref)

Abstract

In this paper, we survey the gelation mechanisms for various polymeric systems which are classified by the type and the strength of the cross-linkages. These are the "irreversible" gels that are cross-linked chemically by covalent bonds and the "reversible" gels that are cross-linked physically by hydrogen or ionic bonds and by the physical entanglement of polymer chains. Some of the natural polymer gels fall into the class of physical gels, among which the red algae that has attracted attention for various applications is discussed in detail. Various composite gels, formed from mixture of physical and chemical gels are also discussed in the last section of the article. Theoretical models describe the gelation as a process of random linking of subunits to larger and larger molecules by formation of an infinite network, where no matter what type of objects are linked, there is always a critical "gel point" at which the system behaves neither as a liquid nor as a solid on any length scale. The Flory–Stockmayer theory and percolation theory provide bases for modeling this sol–gel phase transition. The experimental techniques for measuring the critical exponents for sol–gel phase transitions in different polymeric systems are introduced and the validation of various theoretical predictions are surveyed.

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References

P. G. De Gennes , Scaling Concepts in Polymer Physics ( Cornell University Press , Ithaca , 1979 ) . Google Scholar
D. De Rossi et al. , Polymer Gels ( Plenum Press , New York , 1991 ) . Crossref, Google Scholar
W. H. Carothers, Trans. Faraday. Soc. 32, 39 (1936), DOI: 10.1039/tf9363200039. Crossref, Google Scholar
J. Qin, W. Guo and Z. Zhang, Polymer 43, 1163 (2002), DOI: 10.1016/S0032-3861(01)00715-7. Crossref, Web of Science, Google Scholar
R. G. W. Norrish and R. R. Smith, Nature 150, 336 (1942), DOI: 10.1038/150336a0. Crossref, ADS, Google Scholar
M. D. Ediger, C. A. Angell and S. R. Nagel, J. Phys. Chem. 100, 13200 (1996), DOI: 10.1021/jp953538d. Crossref, Web of Science, Google Scholar
C. Webb , G. M. Black and B. Atkinson , Process Engineering Aspects of Immobilized Cell Systems ( Institution of Chemical Engineers , Warwicksshire , 1986 ) . Google Scholar
C. Rochas and S. Landry, Carbohydr. Polym. 17, 435 (1987). Google Scholar
E. E. Brando, Food Hydrocoll. 6, 25 (1992). Web of Science, Google Scholar
R. P. Millaneet al., Carbohydr. Res. 182, 1 (1988), DOI: 10.1016/0008-6215(88)84087-4. Crossref, Web of Science, Google Scholar
R. P. Millane, E. U. Nzewi and S. Arnott, Frontiers in Carbohydrate Research: Food Applications, eds. R. P. Millane, J. N. BeMiller and R. Chandrasekaran (Elsevier, London, 1989) p. 104. Google Scholar
P. J. Flory, J. Am. Chem. Soc. 63, 3083 (1941), DOI: 10.1021/ja01856a061. Crossref, Google Scholar
W. H. Stockmayer, J. Chem. Phys. 11, 45 (1943), DOI: 10.1063/1.1723803. Crossref, ADS, Google Scholar
D. Stauffer, A. Coniglio and M. Adam, Adv. Polym. Sci. 44, 103 (1982), DOI: 10.1007/3-540-11471-8_4. Crossref, Web of Science, Google Scholar
D. Stauffer , Introduction to Percolation Theory ( Taylor and Francis , London , 1985 ) . Crossref, Google Scholar
H. Herrmann, J. Phys. Rep. 136, 153 (1986), DOI: 10.1016/0370-1573(86)90047-5. Crossref, Web of Science, ADS, Google Scholar
D. Stauffer and A. Aharony , Introduction to Percolation Theory ( Taylor and Francis , London , 1992 ) . Google Scholar
M. Gordon, Proc. R. Soc. Lond. A 268, 240 (1962). Crossref, Web of Science, ADS, Google Scholar
C. W. Macosko and D. R. Miller, Macromolecules 9, 199 (1976), DOI: 10.1021/ma60050a003. Crossref, Web of Science, ADS, Google Scholar
D. S. Pearson and W. W. Graessley, Macromolecules 11, 528 (1978), DOI: 10.1021/ma60063a021. Crossref, Web of Science, ADS, Google Scholar
D. Durand and C.-M. Bruneau, J. Polym. Sci. Polym. Phys. Ed. 17, 273 (1979), DOI: 10.1002/pol.1979.180170207. Crossref, Web of Science, Google Scholar
G. M. Barrow , Introduction to Molecular Spectroscopy ( McGraw-Hill , New York , 1962 ) . Google Scholar
J. B. Birks , Photophysics of Aromatic Molecules ( Wiley-Interscience , London , 1965 ) . Google Scholar
D. M. Hercules , Fluorescence and Phosphorescence Analysis , ed. D. M. Hercules ( Wiley-Interscience , New York , 1966 ) . Google Scholar
M. D. Galanin , Luminescence of Molecules and Crystals ( Cambridge International Science Publishing , Cambridge , 1995 ) . Google Scholar
W. F. Jager, A. A. Volkers and D. C. Neckers, Macromolecules 28, 8153 (1995), DOI: 10.1021/ma00128a027. Crossref, Web of Science, ADS, Google Scholar
T. C. Schaeken and J. M. Warman, J. Phys. Chem. 99, 6145 (1995), DOI: 10.1021/j100016a059. Crossref, Web of Science, Google Scholar
J. S. Royal and J. M. Torkelson, Macromolecules 26, 5331 (1993), DOI: 10.1021/ma00072a009. Crossref, Web of Science, ADS, Google Scholar
K. E. Miller, R. H. Krueger and J. M. Torkelson, J. Polym. Sci. B, Polym. Phys. 33, 2343 (1995), DOI: 10.1002/polb.1995.090331705. Crossref, Web of Science, ADS, Google Scholar
R. Vatanparastet al., Macromolecules 33, 438 (2000), DOI: 10.1021/ma991414j. Crossref, Web of Science, ADS, Google Scholar
J. M. Warmanet al., J. Phys. Chem. B 101, 4913 (1997), DOI: 10.1021/jp970642h. Crossref, Web of Science, Google Scholar
S. Ercelen, A. S. Klymchenko and A. P. Demchenko, Anal. Chim. Acta 464, 273 (2002), DOI: 10.1016/S0003-2670(02)00493-2. Crossref, Web of Science, Google Scholar
W. F. Jager, A. M. Sarker and D. C. Neckers, Macromolecules 32, 8791 (1999), DOI: 10.1021/ma9907688. Crossref, Web of Science, ADS, Google Scholar
Ö. Pekcan, Y. Yılmaz and O. Okay, Polymer 38, 1693 (1997), DOI: 10.1016/S0032-3861(96)00683-0. Crossref, Web of Science, Google Scholar
Ö. Pekcan, Y. Yılmaz and O. Okay, Chem. Phys. Lett. 229, 537 (1994), DOI: 10.1016/0009-2614(94)01112-5. Crossref, Web of Science, ADS, Google Scholar
Y. Yılmaz, A. Erzan and Ö. Pekcan, Eur. Phys. J. E 9, 135 (2002), DOI: 10.1140/epje/i2002-10069-1. Crossref, Web of Science, Google Scholar
A. Hugerth, S. Nilsson and L. O. Sundelöf, Int. J. Biol. Macromol. 26, 69 (1999), DOI: 10.1016/S0141-8130(99)00065-3. Crossref, Web of Science, Google Scholar
S. Karaet al., Int. J. Biol. Macromol. 31, 177 (2003), DOI: 10.1016/S0141-8130(02)00080-6. Crossref, Web of Science, Google Scholar
Ö. Pekcan and S. Kara, J. Biomater. Sci. Polym. Ed. 16, 317 (2005), DOI: 10.1163/1568562053654086. Crossref, Web of Science, Google Scholar
S. Kara and Ö. Pekcan, Polymer 41, 3093 (2000), DOI: 10.1016/S0032-3861(99)00416-4. Crossref, Web of Science, Google Scholar
S. Kara, O. Okay and Ö. Pekcan, J. Appl. Polym. Sci. 86, 3589 (2002), DOI: 10.1002/app.11173. Crossref, Web of Science, Google Scholar
P. J. Flory, J. Am. Chem. Soc. 63, 3083 (1941), DOI: 10.1021/ja01856a061. Crossref, Google Scholar
W. Stockmayer, J. Chem. Phys. 11, 45 (1943), DOI: 10.1063/1.1723803. Crossref, ADS, Google Scholar
W. Stockmayer, J. Chem. Phys. 12, 125 (1944), DOI: 10.1063/1.1723922. Crossref, ADS, Google Scholar
M. Sahimi , Application of Percolation Theory ( Taylor and Francis , London , 1994 ) . Crossref, Google Scholar
A. Aharony, Phys. Rev. B 22, 400 (1980), DOI: 10.1103/PhysRevB.22.400. Crossref, Web of Science, ADS, Google Scholar
R. H. Colby, J. R. Gilmor and M. Rubinstein, Phys. Rev. E 48, 3712 (1993), DOI: 10.1103/PhysRevE.48.3712. Crossref, Web of Science, ADS, Google Scholar
C. P. Lusignanet al., Phys. Rev. E 60, 5657 (1999), DOI: 10.1103/PhysRevE.60.5657. Crossref, Web of Science, ADS, Google Scholar
Y. Liu and R. B. Pandey, J. Chem. Phys. 105, 825 (1996), DOI: 10.1063/1.471891. Crossref, Web of Science, ADS, Google Scholar
R. B. Pandey and Y. Liu, J. Sol-Gel Sci. Technol. 15, 147 (1999), DOI: 10.1023/A:1008739505899. Crossref, Web of Science, Google Scholar
S. B. Ross-Murphy, J. Macromol. Sci. B, Phys. 44, 1007 (2005). Crossref, Web of Science, Google Scholar
K. te Nijenhuis , Thermoreversible Networks: Viscoelastic Properties and Structure of Gels , Advances in Polymer Science 130 ( Springer , Berlin , 1997 ) . Crossref, Google Scholar
L. J. Kropp and R. W. Dawson , Fluorescence and Phosphorescence of Aromatic Hydrocarbons in Polymethylmethacrylate , ed. E. C. Lim ( International Conference on Molecular Luminescence , New York , 1969 ) . Google Scholar
M. Bixon and J. Jortner, J. Chem. Phys. 48, 715 (1968), DOI: 10.1063/1.1668703. Crossref, Web of Science, ADS, Google Scholar
J. B. Birks, M. D. Lumb and I. H. Munro, Proc. R. Soc. Lond. A 277, 289 (1964). Web of Science, Google Scholar
P. F. Jones and S. Siegel, J. Chem. Phys. 50, 1134 (1969), DOI: 10.1063/1.1671168. Crossref, Web of Science, ADS, Google Scholar
Ö. Pekcan, J. Appl. Polym. Sci. 57, 25 (1995), DOI: 10.1002/app.1995.070570103. Crossref, Web of Science, Google Scholar
R. O. Loutfy, Macromolecules 14, 270 (1981), DOI: 10.1021/ma50003a009. Crossref, Web of Science, ADS, Google Scholar
R. O. Loutfy, Pure Appl. Chem. 58, 1239 (1986), DOI: 10.1351/pac198658091239. Crossref, Web of Science, Google Scholar
R. O. Loutfy and K. Y. Law, J. Phys. Chem. 84, 2803 (1980), DOI: 10.1021/j100458a027. Crossref, Web of Science, Google Scholar
W. F. Jager, A. A. Volkers and D. C. Neckers, Macromolecules 28, 8153 (1995), DOI: 10.1021/ma00128a027. Crossref, Web of Science, ADS, Google Scholar
T. C. Schaeken and J. M. Warman, J. Phys. Chem. 99, 6145 (1995), DOI: 10.1021/j100016a059. Crossref, Web of Science, Google Scholar
J. S. Royal and J. M. Torkelson, Macromolecules 26, 5331 (1993), DOI: 10.1021/ma00072a009. Crossref, Web of Science, ADS, Google Scholar
K. E. Miller, R. H. Krueger and J. M. Torkelson, J. Polym. Sci. B, Polym. Phys. 33, 2343 (1995), DOI: 10.1002/polb.1995.090331705. Crossref, Web of Science, ADS, Google Scholar
R. Vatanparastet al., Macromolecules 33, 438 (2000), DOI: 10.1021/ma991414j. Crossref, Web of Science, ADS, Google Scholar
D. K. Aktas, G. A. Evingur and Ö. Pekcan, J. Biomol. Struct. Dyn. 24, 83 (2006). Crossref, Web of Science, Google Scholar
G. A. Evingur, D. K. Aktas and Ö. Pekcan, Phase Transit. 82, 53 (2009). Crossref, Web of Science, Google Scholar
D. K. Aktas, G. A. Evingur and Ö. Pekcan, Compos. Interf. 17, 301 (2010). Crossref, Web of Science, ADS, Google Scholar
Z. Dogruyolet al., Phase Transit. 81, 935 (2008). Crossref, Web of Science, Google Scholar
X. Liuet al., Polymer 44, 407 (2003), DOI: 10.1016/S0032-3861(02)00771-1. Crossref, Web of Science, Google Scholar
T. Norisuyeet al., Macromol. Symp. 242, 208 (2006), DOI: 10.1002/masy.200651029. Crossref, Web of Science, Google Scholar
Ö. Pekcan, Y. Yilmaz and O. Okay, Polymer 37, 2049 (1996), DOI: 10.1016/0032-3861(96)85848-4. Crossref, Web of Science, Google Scholar
Ö. Pekcan and D. Kaya, Compos. Interf. 12, 501 (2005), DOI: 10.1163/1568554054915192. Crossref, Web of Science, ADS, Google Scholar
Z. Dogruyol, N. Arsu and Ö. Pekcan, J. Macromol. Sci. B, Phys. 48, 745 (2009). Crossref, Web of Science, Google Scholar
D. Kaya, Ö. Pekcan and Y. Yilmaz, Phys. Rev. E 69, 016117 (2004), DOI: 10.1103/PhysRevE.69.016117. Crossref, Web of Science, Google Scholar
P. Polanowski, J. K. Jeszka and K. Matyjaszewski, Polymer 51, 6084 (2010), DOI: 10.1016/j.polymer.2010.10.006. Crossref, Web of Science, Google Scholar
A. Malekiet al., Polym. Int. 55, 365 (2006), DOI: 10.1002/pi.1978. Crossref, Web of Science, Google Scholar
A. L. Kjoniksen and B. Nystro, Macromolecules 29, 5215 (1996). Crossref, Web of Science, ADS, Google Scholar
H. Özbek and Ö. Pekcan, J. Mol. Struc.-Theochem. 676, 19 (2004), DOI: 10.1016/j.theochem.2004.01.033. Crossref, Web of Science, Google Scholar
Ö. Tari, S. Kara and Ö. Pekcan, J. Macromol. Sci. B, Phys. 48, 812 (2009). Crossref, Web of Science, Google Scholar
Ö. Tari, S. Kara and Ö. Pekcan, J. Appl. Polym. Sci. 121, 2652 (2011), DOI: 10.1002/app.31233. Crossref, Web of Science, Google Scholar
M. T. Nickerson and A. T. Paulson, Carbohydr. Polym. 58, 15 (2004), DOI: 10.1016/j.carbpol.2004.06.016. Crossref, Web of Science, Google Scholar
T. Fujiiet al., Food Hydrocolloid. 14, 359 (2000), DOI: 10.1016/S0268-005X(00)00012-6. Crossref, Web of Science, Google Scholar
D. J. McHugh, A Guide To the Seaweed Industry (FAO Fisheries, Rome, 2003) p. 39. Google Scholar
L. Luet al., Biomacromolecules 6, 2150 (2005), DOI: 10.1021/bm050126u. Crossref, Web of Science, Google Scholar
T. Tripathyet al., Eur. Polym. J. 35, 2057 (1999), DOI: 10.1016/S0014-3057(98)00284-5. Crossref, Web of Science, Google Scholar
M. G. Neumann, C. C. Schmitt and E. T. Iamazaki, Carbohydr. Res. 338, 1109 (2003), DOI: 10.1016/S0008-6215(03)00051-X. Crossref, Web of Science, Google Scholar
D. Solpan and M. Torun, Colloid Surf. A 268, 12 (2005). Crossref, Web of Science, Google Scholar
L. Luet al., J. Phys. Chem. B 110, 25013 (2006), DOI: 10.1021/jp060155e. Crossref, Web of Science, Google Scholar
D. Solpan and M. Torun, J. Appl. Polym. Sci. 100, 335 (2006). Crossref, Web of Science, Google Scholar
H. Omidian, J. G. Rocca and K. Park, Macromol. Biosci 6, 703 (2006), DOI: 10.1002/mabi.200600062. Crossref, Web of Science, Google Scholar
D. Solpan, M. Torun and O. Guven, J. Appl. Polym. Sci. 108, 3787 (2008). Crossref, Web of Science, Google Scholar
G. A. Evinguret al., Phase Transit. 85, 530 (2012). Crossref, Web of Science, Google Scholar
V. H. V. Sarmentoet al., J. Non-Cryst. Solids 304, 134 (2002), DOI: 10.1016/S0022-3093(02)01015-3. Crossref, Web of Science, ADS, Google Scholar
A. Kelarakiset al., Polymer 46, 11591 (2005), DOI: 10.1016/j.polymer.2005.10.009. Crossref, Web of Science, Google Scholar

Vol. 26, No. 27

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History

Received 22 June 2012

Accepted 27 July 2012

Published: 21 September 2012

Keywords

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GELATION MECHANISMS

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