Abstract
This study characterizes the rheological behavior of the HPC/H2O/H3PO4 tertiary system based on the 3-D phase diagram that was obtained in our earlier work. The effects of frequency, temperature, HPC concentration, liquid composition (H2O/H3PO4 ratio), and phase status on the rheological parameters were thoroughly investigated. The most useful parameter for distinguishing the isotropic (I) and liquid crystalline (LC) phases was tanδ. Agglomeration in the cloudy suspension (CS) phase at high temperature was too severe to allow a smooth flow, so the tanδ and η* represented significant damping, which is a good indicator of the presence of the CS phase. With an increase in temperature, the viscosity of the flow with a single homogeneous phase—either the I phase or the LC phase—or a combination of two homogeneous phases in sequence, obeyed the Arrhenius model. In contrast, once the temperature rose to that of the formation of heterogeneous CS phase, the Arrhenius model was no longer valid. The activation energy E of the I phase was greater, and more sensitive to the HPC concentration, than the LC phase. Finally, the concentration of the sol/gel transition (SGT) declined as temperature increased but increased as the H3PO4 content increased. Furthermore, this tertiary system exhibited no clear order of the onsets of the formations of SGT phase, the LC phase, and the CS phase as HPC concentration was varied.
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References
Aharoni SM (1980) Rigid backbone polymers, xiii: effects of the nature of the solvent on the lyotropic mesomorphicity of cellulose acetate. Mol Cryst Liq Cryst 56:237–241. doi:https://doi.org/10.1080/01406568008070497
Aharoni SM (1981) Rigid backbone polymers. Xxiii. Thermotropic and lyotropic trifluoroacetoxypropyl cellulose. J Polym Sci Polym Lett Ed 19:495–496. doi:https://doi.org/10.1002/pol.1981.130191004
Aharoni SM (1982) Rigid backbone polymers—25. Solvent effects in phase behavior of solutions of cellulose derivatives. J Macromol Sci, Phys B21:287–298. doi:https://doi.org/10.1080/01406568008070497
Budgell DR (1989) Liquid crystalline properties of ethyl cellulose. PhD Thesis, McGill University, Canada
Carotenuto C, Grizzuti N (2006) Thermoreversible gelation of hydroxypropylcellulose aqueous solutions. Rheol Acta 45:468–473. doi:https://doi.org/10.1007/s00397-005-0075-x
Chang SA, Gray DG (1978) The surface tension of aqueous hydroxypropyl cellulose solutions. J Colloid Interface Sci 67:255–265. doi:https://doi.org/10.1016/0021-9797(78)90010-3
Clasen C, Kulicke WM (2001) Determination of viscoelastic and rheo-optical material functions of water-soluble cellulose derivatives. Prog Polym Sci (Oxford) 26:1839–1919
Conio G, Bianchi E, Ciferri A, Tealdi A, Aden MA (1983) Mesophase formation and chain rigidity in cellulose and derivatives. 1. (hydroxypropyl)cellulose in dimethylacetamide. Macromolecules 16:1264–1270. doi:https://doi.org/10.1021/ma00242a004
Desbrières J, Hirrien M, Ross-Murphy SB (2000) Thermogelation of methylcellulose: rheological considerations. Polymer 41:2451–2461
Flory PJ (1956) Statistical thermodynamics of semi-flexible chain molecules. Proc R Soc Lond A 234:60–73. doi:https://doi.org/10.1098/rspa.1956.0015
Flory PJ (1978) Statistical thermodynamics of mixtures of rodlike particles. 6. Rods connected by flexible joints. Macromolecules 11:1141–1144. doi:https://doi.org/10.1021/ma60066a016
Fortin S, Charlet G (1989) Phase diagram of aqueous solutions of (hydroxypropyl)cellulose. Macromolecules 22:2286–2292. doi:https://doi.org/10.1021/ma00195a050
Giner J, Ibarz A, Garza S, Xhian-Quan S (1996) Rheology of clarified cherry juices. J Food Eng 30:147–154
Guido S, Grizzuti N (1995) Phase separation effects in the rheology of aqueous solutions of hydroxypropylcellulose. Rheol Acta 34:137–146
Haque A, Morris ER (1993) Thermogelation of methylcellulose. Part I: molecular structures and processes. Carbohydr Polym 22:161–173
Haque A, Richardson RK, Morris ER, Gidley MJ, Caswell DC (1993) Thermogelation of methylcellulose. Part II: effect of hydroxypropyl substituents. Carbohydr Polym 22:175–186
Heymann E (1935) Studies on sol-gel transformations. I. The inverse sol-gel transformation of methylcellulose in water. Trans Faraday Soc 31:846–864
Hirrien M, Chevillard C, Desbrières J, Axelos MAV, Rinaudo M (1998) Thermogelation of methylcelluloses: new evidence for understanding the gelation mechanism. Polymers 39:6251–6259
Hussain S, Keary C, Craig DQM (2002) A thermorheological investigation into the gelation and phase separation of hydroxypropyl methylcellulose aqueous systems. Polymer 43:5623–5628
Kaya A, Belibaǧlı KB (2002) Rheology of solid gazıantep pekmez. J Food Eng 54:221–226
Marsano E, Fossati G (2000) Phase diagram of water soluble semirigid polymers as a function of chain hydrophobicity. Polymer 41:4357–4360. doi:https://doi.org/10.1016/S0032-3861(99)00795-8
Rwei S-P, Lyu M-S (2012) 3-d phase diagram of hpc/h2o/h3po4 tertiary system. Cellulose 19:1065–1074. doi:https://doi.org/10.1007/s10570-012-9707-3
Rwei SP, Chen TY, Cheng YY (2005) Sol/gel transition of chitosan solutions. J Biomater Sci Polym Ed 16:1433–1445. doi:https://doi.org/10.1163/156856205774472290
Rwei SP, Lyu MS, Wu PS, Tseng CH, Huang HW (2009) Sol/gel transition and liquid crystal transition of hpc in ionic liquid. Cellulose 16:9–17. doi:https://doi.org/10.1007/s10570-008-9250-4
Saravacos GD (1970) Effect of temperature on viscosity of fruit juices and purees. J Food Sci 35:122–125. doi:https://doi.org/10.1111/j.1365-2621.1970.tb12119.x
Sarkar N (1979) Thermal gelation properties of methyl and hydroxypropyl methylcellulose. J Appl Polym Sci 24:1073–1087. doi:https://doi.org/10.1002/app.1979.070240420
Sarkar N (1995) Kinetics of thermal gelation of methylcellulose and hydroxypropylmethylcellulose in aqueous solutions. Carbohydr Polym 26:195–203
Shukla S, Seal S, Vij R, Bandyopadhyay S, Rahman Z (2002) Effect of nanocrystallite morphology on the metastable tetragonal phase stabilization in zirconia. Nano Lett 2:989–993. doi:https://doi.org/10.1021/nl025660b
Shukla S, Seal S, Vanfleet R (2003) Sol-gel synthesis and phase evolution behavior of sterically stabilized nanocrystalline zirconia. J Sol Gel Sci Technol 27:119–136. doi:https://doi.org/10.1023/a:1023790231892
Werbowyj RS, Gray DG (1976) Liquid crystalline structure in aqueous hydroxypropyl cellulose solutions. Mol Cryst Liq Cryst 34:97–103. doi:https://doi.org/10.1080/15421407608083894
Werbowyj RS, Gray DG (1980) Ordered phase formation in concentrated hydroxpropylcellulose solutions. Macromolecules 13:69–73. doi:https://doi.org/10.1021/ma60073a014
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The authors would like to thank the National Science Council of the Republic of China, Taiwan, for financially supporting this research under Contract No. NSC 101-2623-E-027-005-IT.
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Rwei, SP., Lyu, MS. HPC/H2O/H3PO4 tertiary system: a rheological study. Cellulose 20, 135–147 (2013). https://doi.org/10.1007/s10570-012-9810-5
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DOI: https://doi.org/10.1007/s10570-012-9810-5