Abstract
The morphological orders of spherulitic crystal patterns in a Belousov-Zhabotinsky-type oscillatory reaction system were studied. The experiments showed that the morphology of crystal patterns were highly dependent on the reaction temperature. The reaction was initially carried out at 30 °C, leading to the growth of multi-centred spherulitic patterns. The single-centred spherulitic patterns with fairly large crystal fibrils were obtained at 35°C. A number of undersized crystal assemblies with fractal geometry were also investigated at 25°C. The gross morphology of the crystal patterns was examined using optical microscopy and a scanning electron microscope which revealed the fibrous organisations. A particle-mediated self-assembly scheme was proposed for the growth of the spherulitic patterns. The insight into the nucleation mechanism, growth behaviour, and morphological orders of the growing patterns is discussed in detail. The crystal phases, ordering of textures, and composition of the crystals were characterised by thermal and X-ray diffraction techniques.
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References
Beck, R., & Andreassen, J. P. (2010). Spherulitic growth of calcium carbonate. Crystal Growth & Design, 10, 2934–2947. DOI: 10.1021/cg901460g.
Chow, P.S., Liu, X. Y., Zhang, J., & Tan, R.B.H. (2002). Spherulitic growth kinetics of protein crystals. Applied Physics Letter, 81, 1975–1977. DOI: 10.1063/1.1506208.
Das, I., Goel, N., Agarwal, N. R., & Gupta, S. K. (2010). Growth patterns of dendrimers and electric potential oscillations during electropolymerization of pyrrole using mono-and mixed surfactants. The Journal of Physical Chemistry B, 114, 12888–12896. DOI: 10.1021/jp105183q.
Ferreiro, V., Douglas, J. F., Warren, J., & Karim, A. (2002). Growth pulsations in symmetric dendritic crystallization in thin polymer blend films. Physical Review E, 65, 051606. DOI: 10.1103/PhysRevE.65.051606.
Gan, Z. H., Abe, H., & Doi, Y. (2001). Crystallization, melting, and enzymatic degradation of biodegradable poly(butylene succinate-co-14 mol % ethylene succinate) copolyester. Biomacromolecules, 2, 313–321. DOI: 10.1021/bm0056557.
Goldenfeld, N. (1987). Theory of spherulitic crystallization. Journal of Crystal Growth, 84, 601–608. DOI: 10.1016/0022-0248(87)90051-0.
Gómez, A., Luque, J. J., & Córdoba, A. (2005). Fractal structures for a catalysed reaction on homogenous and fractal surfaces. Chaos, Solitons & Fractals, 24, 151–156. DOI: 10.1016/j.chaos.2003.12.106.
Gránásy, L., Pusztai, T., Börzsönyi, T., Warren, J. A., & Douglas, J. F. (2004). A general mechanism of polycrystalline growth. Nature Materials, 3, 645–650. DOI: 10.1038/nmat1190.
Gránásy, L., Pusztai, T., Tegze, G., Warren, J. A., & Douglas, J. F. (2005). Growth and form of spherulites. Physical Review E, 72, 011605. DOI: 10.1103/PhysRevE.72.011605.
Gránásy, L., Pusztai, T., Börzsönyi, T., Tóth, G. I., Tegze, G., Warren, J. A., & Douglas, J. F. (2006). Polycrystalline patterns in far-from-equilibrium freezing: a phase field study. Philosophical Magazine, 86, 3757–3778. DOI: 10.1080/14786430500198569.
He, Z., & Olley, R. H. (2000). On spherulitic forms in an aromatic polyesteramide. Polymers, 41, 1157–1165. DOI: 10.1016/s0032-3861(99)00253-0.
Hoffman, J. D., & Miller, R. L. (1989). Surface nucleation theory for chain-folded systems with lattice strain: curved edges. Macromolecules, 22, 3038–3054. DOI: 10.1021/ma00197a027.
Hoffman, J. D., & Miller, R. L. (1997). Kinetic of crystallization from the melt and chain folding in polyethylene fractions revisited: theory and experiment. Polymer, 38, 3151–3212. DOI: 10.1016/s0032-3861(97)00071-2.
Hutter, J. L., & Bechhoefer, J. (1997). Many modes of rapid solidification in a liquid crystal. Physica A: Statistical Mechanics and its Applications, 239, 103–110. DOI: 10.1016/s0378-4371(97)00024-1.
Hutter, J. L., & Bechhoefer, J. (1999). Morphology transitions in diffusion- and kinetics-limited solidification of a liquid crystal. Physical Review E, 59, 4342–4352. DOI: 10.1103/PhysRevE.59.4342.
Hutter, J. L., & Bechhoefer, J. (2000). Banded spherulitic growth in a liquid crystals. Journal of Crystal Growth, 217, 332–343. DOI: 10.1016/s0022-0248(00)00479-6.
Keith, H. D., & Padden, F. J., Jr. (1963). A phenomenological theory of spherulitic crystallization. Journal of Applied Physics, 34, 2409–2421. DOI: 10.1063/1.1702757.
Kyu, T., Chiu, H. W., Guenthner, A. J., Okabe, Y., Saito, H., & Inoue, T. (1999). Rhythmic growth of target and spiral spherulites of crystalline polymer blends. Physical Review Letter, 83, 2749–2752. DOI: 10.1103/PhysRevLett.83.2749.
Langer, J. S. (1980). Instabilities and pattern formation in crystal growth. Reviews on Modern Physics, 52, 1–28. DOI: 10.1103/RevModPhys.52.1.
Liu, X. Y., & Sawant, P. D. (2002). Mechanism of the formation of self-organized microstructures in soft functional materials. Advanced Materials, 14, 421–426. DOI: 10.1002/1521-4095(20020318)14:6<421::AID-ADMA421>3.0.CO;2-7.
Magill, J. H. (2001). Review spherulites: A personal perspective. Journal of Material Science, 36, 3143–3163. DOI: 10.1023/a:1017974016928.
Mullins, W. W., & Sekerka, R. F. (1963). Morphological stability of a particle growing by diffusion or heat flow. Journal of Applied Physics, 34, 323–329. DOI: 10.1063/1.1702607.
Murray, S. B., & Neville, A. C. (1998). The role of pH, temperature and nucleation in the formation of cholesteric liquid crystal spherulites from chitin and chitosan. International Journal of Biological Macromolecules, 22, 137–144. DOI: 10.1016/s0141-8130(98)00002-6.
Noyes, R. M., (1990). Mechanisms of some chemical oscillators. The Journal of Physical Chemistry, 94, 4404–4412. DOI: 10.1021/j100374a010.
Okabe, Y., Kyu, T., Sato, H., & Inoue, T. (1998). Spiral crystal growth in blends of poly(vinylidene fluoride) and poly(vinyl acetate). Macromolecules, 31, 5823–5829. DOI: 10.1021/ma980668m.
Okada, T., Saito, H., & Inoue, T. (1994). Kinetic studies of crystallization in mixtures of isotactic polystyrene and atactic polystyrene. Polymer, 35, 5699–5705. DOI: 10.1016/s0032-3861(05)80044-8.
Ruoff, P. (1984). Oscillation inhibition by bromide-removing reagents near the transition to the excitable steady state in the closed stirred Belousov-Zhabotinsky reaction. The Journal of Physical Chemistry, 88, 1058–1060. DOI: 10.1021/j150650a004.
Salter, L. F., & Sheppard, J. G. (1982). A dual-frequency Belousov Zhabotinskii oscillating reaction with ethyl acetoacetate as organic substrate. International Journal of Chemical Kinetics, 14, 815–821. DOI: 10.1002/kin.550140802.
Singfield, K. L., Klass, J. M., & Brown, G. R. (1995). Optically active polyethers. 2. Atomic force microscopy of melt-crystallized poly(epichlorohydrin) enantiomers and their equimolar blend. Macromolecules, 28, 8006–8015. DOI: 10.1021/ma00128a006.
Sunde, M., & Blake, C. (1997). The structure of amyloid fibrils by electron microscopy and X-ray diffraction. Advance in Protein Chemistry, 50, 123–159. DOI: 10.1016/s0065-3233(08)60320-4.
Tegze, G., Gránásy, L., Tóth, G. I., Douglas, J. F., & Pusztai, T. (2011). Tuning the structure of non-equilibrium soft materials by varying the thermodynamic driving force for crystal ordering. Soft Matter, 7, 1789–1799. DOI: 10.1039/c0sm00944j.
Mareau, V. H., & Prud’homme, R. P. (2002). Dual growth rates and morphologies of isothermally crystallized miscible polymer blends. Macromolecules, 35, 5338–5341. DOI: 10.1021/ma011989s.
Wang, R. Y., Liu, X. Y., Xiong, J. Y., & Li, J. L. (2006). Realtime observation of fiber network formation in molecular organogel: Supersaturation-dependent microstructure and its related rheological property. The Journal of Physical Chemistry B, 110, 7275–7280. DOI: 10.1021/jp054531r.
Yadav, N., & Srivastava, P. K. (2011). Growth of spherulitic crystal patterns in a Belousov-Zhabotinski type reaction system. New Journal of Chemistry, 35, 1080–1087. DOI: 10.1039/c0nj00798f.
Yadav, N., Majhi, S. S., & Srivastava, P. K. (2012). Growth mechanism and crystal ordering of spherulitic patterns in a Belousov-Zhabotinsky type reaction system. Bulletin of the Korean Chemical Society, 33, 3397–3406. DOI: 10.5012/bkcs.2012.33.10.3397.
Yen, K. C., Woo, E. M., & Tashiro, K. (2010). Six types of spherulite morphologies with polymorphic crystals in poly(heptamethylene terephthalate). Polymer, 51, 5592–5603. DOI: 10.1016/j.polymer.2010.09.031.
Yu, L. (2003). Growth rings in D-sorbitol spherulites: Connection to concomitant polymorphs and growth kinetics. Crystal Growth & Design, 3, 967–971. DOI: 10.1021/cg034062n.
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Yadav, N., Majhi, S.S., Saw, S.K. et al. Morphological orders of spherulitic crystal textures in Belousov-Zhabotinsky-type oscillatory reaction system. Chem. Pap. 69, 604–615 (2015). https://doi.org/10.1515/chempap-2015-0059
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DOI: https://doi.org/10.1515/chempap-2015-0059