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Phase diagram, optical, nonlinear optical, and physicochemical studies of the organic monotectic system: Pentachloropyridine–succinonitrile

Published online by Cambridge University Press:  03 March 2011

R.N. Rai
R.N. Rai*
Affiliation:
Department of Chemistry, Birla Institute of Technology and Science, Pilani, Rajasthan 333031, India
*
a)Address all correspondence to this author. e-mail: rn_rai@yahoo.co.in
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Abstract

The two immiscible liquid phases in equilibrium with a single liquid phase have been observed during the phase diagram study of an organic analog of a metal–nonmetal system involving pentachloropyridine (PCP)–succinonitrile (SCN). The phase equilibrium shows the formation of a monotectic and a eutectic, with large miscibility gap in the system, containing 0.0456 and 0.9658 mole fractions of SCN, respectively, and the consolute temperature being 99.0 °C above the monotectic horizontal line. The heat of mixing, entropy of fusion, roughness parameter, interfacial energy, and excess thermodynamic functions were calculated based on enthalpy of fusion data determined via the differential scanning calorimetry method. The effects of solid–liquid interfacial energy on morphology of monotectic structure as well as the variation of interfacial energies with temperature have been discussed. The microstructures of monotectic and eutectic show peculiar characteristic features. The material properties of PCP and PCP doped with SCN crystals, grown by the Bridgman–Stockbarger method, have been studied via studying second harmonic generation efficiency, transparency range, and mechanical hardness.

Keywords

Phase equilibriaMicrostructureThermochemical studies
Type
Articles
Information
Journal of Materials Research , Volume 19 , Issue 5 , May 2004 , pp. 1348 - 1355
Copyright
Copyright © Materials Research Society 2004

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References

REFERENCES

1Gruggel, R.N. and Hellawel, A., Alloys solidification in system containing a liquid missibility gap. Metall. Trans. A 12, 669 (1981).Google Scholar
2Herlach, D.M., Cochrane, R.F., Egry, I., Fecht, H.J. and Greer, A.L., Container less processing of metallic melts. Int. Mater. Rev. 38, 273 (1993).CrossRefGoogle Scholar
3Trivedi, R. and Kurtz, W., Int. Mater. Rev. 32, 49 (1994).CrossRefGoogle Scholar
4Majumdar, B. and Chattopadhyay, K., The rayleigh instability and the origin of rows of droplets in the monotectic microstructure of zinc-bismuth alloys. Metall. Trans. A 27, 2053 (1996).Google Scholar
5Glicksman, M.E., Singh, N.B. and Chopra, M., Manuf. Space 11, 207 (1983).Google Scholar
6Pigon, K. and Krajewska, A., Phase diagram in the binary systems of 2,4,7-trinitrofluorene-9-one with aromatic and hetero-aromatic compound. II. Thermodynamic analysis. Thermochim. Acta 58, 299 (1982).CrossRefGoogle Scholar
7Rastogi, R.P., Singh, N.B. and Dwivedi, K.D., Br. Bunsen-Ges. Phys. Chem. 85, 85 (1981).CrossRefGoogle Scholar
8Farges, J.P., Organic Conductors (Marcel Dekker, New York, 1994).Google Scholar
9Klauk, H. and Jackson, T., Solid State Technol. 43, 63 (2000).Google Scholar
10Thompson, J., Blyth, R.I.R., Mazzeo, M., Anni, M., Gigli, G. and Cingoloni, R., White light emission from blends of blue-emitting organic molecule: A general route to the white organic light emitting diode. Appl. Phys. Lett. 79, 560 (2001).CrossRefGoogle Scholar
11Gunter, P., Nonlinear Optical Effects and Materials (Springer-Verlag, Berlin, Germany 2000).CrossRefGoogle Scholar
12Munn, R.W. and Ironside, C.N., Principles and Applications of Nonlinear Optical Materials (Chapman & Hall, London, U.K., 1993).Google Scholar
13Rai, R.N. and Lan, C.W., Crystal structure and properties of a new organic nonlinear optical material. J. Mater. Res. 17, 1857 (2002).CrossRefGoogle Scholar
14Singh, N.B., Henningsen, T., Hopkins, R.H., Mazelsky, R., Hamacher, R.D., Supertzi, E.P., Hopkins, F.K., Zelmon, D.E. and Singh, O.P., J. Cryst. Growth 128, 976 (1993).Google Scholar
15Rai, R.N., Ramasamy, P. and Lan, C.W., New single crystal of binary organic NLO material. J. Cryst. Growth 235, 499 (2002).CrossRefGoogle Scholar
16Derby, B. and Favier, J.J., A criterion for the determination of monotectic structure. Acta Metall. 31, 1123 (1983).CrossRefGoogle Scholar
17Ecker, A., Frazier, D.O. and Alexander, J.I.D., Metall. Trans. 20A, 2517 (1989).Google Scholar
18Rai, U.S. and Rai, R.N., Physical chemistry of organic eutectic and monotectic: Hexamethylbenzene-succinonitrile system. Chem. Mater. 11, 3031 (1999).CrossRefGoogle Scholar
19Dodd, J.W. and Tonge, K.H., Analytical Chemistry by Open Learning, Thermal Methods, edited by Currel, B.R. (Wiley, New York, 1987), p. 120.Google Scholar
20Rai, R.N. and Rai, U.S., Solid-liquid equilibrium diagram and thermochemical properties of organic eutectic in a monotectic system. Thermochim Acta 363, 23 (2000).CrossRefGoogle Scholar
21Rastogi, R.P. and Rastogi, V.K., Mechanism of eutectic crystallization. II. J. Cryst. Growth 5, 345 (1969).Google Scholar
22Rai, U.S. and Rai, R.N., Physical chemistry of organic analog of metal-metal eutectic and monotectic alloys. J. Cryst. Growth. 191, 234 (1998).Google Scholar
23Kurtz, S.K. and Perry, T.T., Powder technique for the evaluation of nonlinear optical materials. J. Appl. Phys. 39, 3798 (1968).Google Scholar
24Predel, B., Constitution and thermodynamics of monotectic alloys—A survey. J. Phase Equilibria 18, 327 (1997).CrossRefGoogle Scholar
25Rai, U.S. and Rai, R.N., Solidification behaviour of binary organic monotectic alloys. Thermochim Acta 277, 209 (1996).Google Scholar
26Rai, R.N., Rai, U.S. and Varma, K.B.R., Thermal, miscibility gap and microstructural studies of organic analog of metal-nonmetal system: p-dibromobenzene-succinonitrile. Thermochim Acta 387, 101 (2002).CrossRefGoogle Scholar
27Singh, N., Narshingh, B., Rai, U.S. and Singh, O.P., Structure of eutectic melts; binary organic systems. Thermochima Acta 95, 291 (1985).CrossRefGoogle Scholar
28Christian, J.W., The Theory of Phase Transformation in Metals and Alloys (Pergamon Press, Oxford, U.K., 1965).Google Scholar
29Rai, U.S. and Rai, R.N., Physical chemistry of organic eutectics. J. Therm. Anal. 53, 883 (1998).Google Scholar
30Wisnaik, J. and Tamir, A., Mixing and Excess Thermodynamic Properties (Elsevier, Amsterdam, The Netherlands, 1978).Google Scholar
31Chadwick, G.A., Metallography of Phase Transformations (Butterworths, London, U.K., 1972).Google Scholar
32Podolinsky, V.V., Taran, Y.N. and Drykin, V.G., Classification of binary eutectics. J. Cryst. Growth 96, 445 (1989).Google Scholar
33Hunt, J.D. and Jackson, K.A., Trans. Met. Soc. AIME 236, 843 (1966).Google Scholar
34Cahn, J.W., J. Chem. Phys. 66, 667 (1977).Google Scholar
35Cahn, J.W., Monotectic composite growth. Metall. Trans. A 10A, 119 (1979).CrossRefGoogle Scholar
36Good, R., Symposium on chemistry and physics of interface theory for estimation of interfacial energy. Ind. Eng, Chem 62, 54 (1970).CrossRefGoogle Scholar
37Rai, U.S. and Rai, R.N., Studies on physicochemical properties of the eutectic and monotectic in the urea-p.chloronitrobenzene system. J. Cryst. Growth 169, 563 (1996).Google Scholar
38Rossel, H.J. and Scott, H.G., Crystal structure of two forms of pentachloropyridine. J. Cryst. Mol. Struct. 3, 259 (1973).CrossRefGoogle Scholar
39Marder, S.R., Perry, J.W. and Yakymyshyn, C.P., Organic salts with large second-order optical nonlinearity. Chem. Mater. 6, 1137 (1994).CrossRefGoogle Scholar
40Tao, X.T., Yuan, D.R., Zang, N., Jiang, M.H. and Shao, Z.S., Novel organic molecular second harmonic generation crystal: 3-methoxy-4-hydroxybenzaldehyde. Appl. Phys. Lett. 60, 1415 (1992).Google Scholar