Thermodynamic and lamella models relationship for the eutectic system benzoic acid – cinnamic acid

The present investigation reveals the relationship between excess thermodynamic functions and the growth habits of the eutectic phases from the melt by continuous melt‐growth technique. Excess thermodynamic functions computed for different compositions of the benzoic acid – cinnamic acid eutectic system have been found consistent with the criteria of spontaneity and Planck formulation, and their reliability has been ascertained by the application of Guggenheim lattice theory. The results on the kinetics of anisotropic growth of the eutectic phases from the melt, evidentially evince the dislocation mechanism. Evidences have been obtained for a parabolic variation of mechanical strength with growth velocity of the eutectic material grown anisotropically from the melt at different intervals, which offer supporting complement to the dislocation mechanism governing the dependence of growth velocity on supercooling ΔT in the solidus – liquidus interface in a form : V = k(ΔT)². A moderate anisotropic growth region has been explored by unique results of strength properties and microscopic results as well, to growing a layer of lamellae in a unidirectional lamina. An anisotropic eutectic composite lamellae lamina developed by moderate growth velocity (7.3 × 10^‐8m³s^‐1), is of greater interest offering optimum hardness, approximately varying between three‐and eight fold average increase in different modes of the mechanical strength in comparison to its isotropic growth carried out in an ice‐bath (∼273K), and manifold superior to its constituent phases irrespective of the growth mode. The directional lamina of uniform microstructural parameter lamellae, indicates that there is a perfect lamella‐ matrix equilibrium for which excess thermodynamic functions do vanish. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemistry of organic eutectics (III). α-Naphthol-naphthalene system

Relative supercooling, linear velocity of crystallization and microstructure for the α-naphthol-naphthalene eutectic system have been investigated in order to understand the mechanism of eutectic solidification. Heat of fusion measurements indicate the possibility of molecular association in the liquid melt. The effective distribution coefficient, direction of solute transference, and separation efficiency have also been determined using zone melting technique.     

Chemistry of organic eutectics (IV). α-Naphthol-β-naphthol eutectic system

The detailed methods of investigating the phase diagram, supercooling, crystallization velocity, microstructure, and diffusion coefficient for the α-naphthol-β-naphthol eutectic system have been discussed. The results are discussed in the light of existing theories describing morphology, nucleation, crystallization kinetics, and diffusion phenomena.     

Characteristics of the binary faceted eutectic: benzoic acid – salicylic acid system

The consistent symmetry relations computed from the heterogeneous nucleation data of the non‐ideal benzoic acid – salicylic acid eutectic system verifies the validity of nucleation theory. The kinetics of crystal growth from the molten state of the system follows the dislocation mechanism. Anomalous behaviour of both viscosity and activation energy for the eutectic melt confirms the essence of specific interactions animating molecular clusters rich in predominating eutectic phase. Micromorphology of the system obeys the Hunt‐Jackson model. The plot between a mechanical property and variable anisotropic growth velocity for the eutectic composite evidentially complies with the Weibull probability distribution curve. The curve is perused with two cut‐off points corresponding to a lower strength limit in the slow and fast growth regions and an upper strength limit in the moderate growth region. The latter aspect reveals the theoretical strength of the eutectic crystallites. The strength‐growth relationship explicated thereby is linear, optimum and linear respectively in the slow, moderate and fast growth regions of solidification. The moderate anisotropic growth (∼2.96 X 10^‐7m³s^‐1) is of greater interest by virtue of its attribute to unifying and organizing the crystallites parallel to each other in the growth direction. The eutectic composite material obtained by this process attains remarkable superiority in the mechanical properties over its isotropic growth in an ice bath (∼273 K), and its constituent phases. The co‐relation between excess thermodynamic functions indeed predicting the liquidus character and the microstructural parameters inevitably structuring the morphology is presented. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Heat of fusion and excess thermodynamic functions of organic eutectics

Phase diagrams and heats of fusion of some organic eutectics have been studied. An empirical equation is proposed for the determination of heats of fusion of eutectics. Excess thermodynamic functions such as h^E, S^E and g^E have been calculated. The heats of fusion of various organic eutectics have been compared with values obtained from the mixture law. The results have been explained on the basis of the fact that clusters are formed during melting. The cluster formation tendency is greater in systems in which hydroxyl groups are present.     

Solidification behaviour of organic eutectics and 1:1 addition compound: p-Phenylenediamine-resorcinol system

The phase diagram of p-phenylenediamine-resorcinol system, determined by thaw-melt method, shows the formation of a 1:1 molecular compound and two eutectics. The linear velocity of crystallization, determined by measuring the rate of movement of growth front in a capillary, indicates that crystallization data obey Hillig-Turnbull equation: Where u and n are constants and ΔT is undercooling. X-ray diffraction data of the molecular compound, eutectics and pure components infer that these eutectics are not simply the mechanical mixture of the two components and there is preferential ordering of atomic planes during their formation. The infrared studies carried out on this system reveal the intermolecular hydrogen bonding between two components forming the molecular compound. Using experimental values of heats of fusion, entropy of fusion and excess thermodynamic functions were also calculated.     

Study on the Phase equilibrium in the Systems Sodium Selenate — Cadmium Selenate — Water and Sodium Selenate — Manganese Selenate — Water at 25 °C

The phase equilibrium in the systems Na₂SeO₄ CdSeO₄ H₂O and Na₂SeO₄ MnSeO₄ H₂O were studied and it was established that new phases were obtained — double salts with a composition: Na₂Cd(SeO₄)₂ · 2 H₂O and Na₂Mn(SeO₄)₂ · 2 H₂O. The fields of phase equilibrium of the double salts in the triple systems were determined. The composition of the new phases and the number of the water molecules of crystallization were investigated, respectively by the Schreinemackers' method of physico-chemical analysis and thermogravimetrical analysis. An X-ray diffraction analysis of the new phases obtained was done.     

Positron annihilation study of defects and microheterogeneity of chalcogenide glassy semiconductors — chemical bonding in ge—se and some AVBVI systems

Recently developed ideas on the mechanisms of positron annihilation in chalcogenide glassy semiconductors are used in studying chemical bonding of the A^VB^VI structures (A = As, B = S, Se, Te) and Ge Se.     

Thick LPE Layers of InAs1—xSbx for 3—5 μm Optoelectronic Applications

N-InAs_1—xSb_x/n, p-InAs heterostructures were grown by liquid phase epitaxy on (100) oriented substrates. The layer composition was varied in the interval 0 < x < 0.1, the corresponding lattice mismatch being not greater than 0.5%. The layer composition was studied by microprobe analysis on the surface of the structure cross-section. Microhardness profiles were investigated using Vickers and Knoop indentors. Raman scattering was also studied.     

Neutronographical investigations of the age hardening behaviour on Iron — Manganese — Nickel alloys

Age hardenable martensitic Iron—Manganese—Nickel alloys were neutronographically investigated in order to explain the age hardening effect occurring during the heat treatment. The formation of coherent precipitations of an ordering phase within the matrix proved to be the reason for the occurring hardness increase.     

The Crystal and Molecular Structure of 11,12‐dibromo‐ 7,8—benzo‐1,5‐di(p—tolylsulphonyl)‐1,5‐diazacyclononan

The crystal structure of the title compound, C₂₅H₂₆Br₂N₂O₄S₂ was determined by single crystal X‐ray diffraction technique. The crystals are monoclinic, space group C 2/c, with a=20.7142(2) Å b=11.7910(2) Å, c= 10.6735(3) Å, β=98.549(2)°, V=2577.94(9) ų, Z=4. The structure was solved by direct methods and refined by least‐squares methods to a final R=0.046 for 1866 observed reflections with I>2sigma(I). The title compound, displays disordered geometry around the C1 atom located almost on twofold axis. The nine‐membered heterocylic ring is close to the half‐chair conformation. The dihedral angle between phenyl rings is 34.2(1)°.     

Synthesis and Characterisation of Bulk Textured Phases in the Bi(Pb)—Sr—Ca—Cu—O System

Growth of lead-doped textured Bi-cuprate, using an immersed heater floating zone (TSFZ) apparatus, from a narrow supercooled melt created an essentially dense structure consisting of locally aligned long platelet crystal grains. The extended grains have their long axes parallel to the growth axis with a low angle misorientation. The effect of gas bubbles and the pulling rates on the microstructure and superconducting transition temperature of the textured boules have been studied. The decomposing nature of the 2223 phase on melting leads to form the energetically favourable low T_c 2212 phase.     

Computer simulation, thermodynamic and microstructural studies of benzamide–benzoic acid eutectic system

Phase diagram of benzamide–benzoic acid system has been studied by the thaw–melt method. Linear velocities of crystallization of the components and the eutectic mixture were determined at different undercoolings. Values of the heat of fusion were obtained from DSC studies. Excess Gibbs free energy, excess enthalpy and excess entropy of mixing were calculated. In order to know the nature of interaction between the two components, FT-IR spectral analyses were done. In addition to these studies, computer simulation has been done to obtain an idea about the interaction energy and the optimized geometry of the eutectic mixture. Microstructural studies showed the formation of an irregular structure in the eutectic mixture, which changed with aging and on addition of impurities.     

Synthetic Diamond — Basic Research and Applications

Non-equilibrium growth of synthetic diamond layers by chemical vapour deposition (CVD) techniques on heterosubstrates has largely been improved over the past decade. On silicon substrates highly textured and oriented diamond films can be grown with optical transparencies and thermal conductivities suitable for broad-band optical windows and heat spreaders. Boron pulse-doping of homoepitaxial diamond layers leads to high p-conductivity at room temperature allowing the fabrication of Schottky diodes and field effect transistors operating at temperatures up to 1000 K. Other devices such as sensors and detectors are being successfully fabricated. At the same time many basic questions remain to be solved including efficient n-type doping.     

Physical chemistry of binary organic eutectic and monotectic alloys; 1,2,4,5-tetrachlorobenzene−β-naphthol and 1,2,4,5-tetramethylbenzene-succinonitrile systems

Phase diagrams of 1,2,4,5-tetrachlorobenzene–β-naphthol and 1,2,4,5-tetramethylbenzene–succinonitrile systems which are organic analogues of a nonmetal–nonmetal and a nonmetal–metal system, respectively, show the formation of a simple eutectic (melting point 103.7°C) with 0.71 mole fraction of β-naphthol in the former case and a monotectic (melting point 76.0°C) with 0.07 mole fraction of succinonitrile and a eutectic (melting point 52.5°C) with 0.97 mole fraction of succinonitrile in the latter case. The growth behaviour of the pure components, the eutectics and the monotectic studied by measuring the rate of movement of the solid–liquid interface in a capillary, suggests that the data obey the Hillig–Turnbull equation, v=u(ΔT)ⁿ, where v is the growth velocity, ΔT is the undercooling and u and n are constants depending on the nature of the materials involved. From the values of enthalpy of fusion determined by the DSC method using Mettler DSC-4000 system, entropy of fusion, interfacial energy, enthalpy of mixing and excess thermodynamic functions were calculated. The optical microphotographs of pure components and polyphase materials show their characteristic features.     

Growth and characterization of a novel organic NLO crystal: 4 – ethoxy benzaldehyde – n – methyl 4 – stilbazolium tosylate

The organic material 4‐Ethoxybenzaldehyde‐N‐methyl 4‐Stilbazolium Tosylate (EBST) is a new NLO material and new derivative in Stilbazolium Tosylate family. In this work we synthesized the EBST, the derivative of DAST. By slow evaporation method, we have grown the EBST crystal. Powder XRD confirms the crystalline property, the lattice parameters are calculated from single crystal XRD data and the molecular structure also revealed. The crystal system is found as monoclinic. The crystalline perfection is assessed by the high‐resolution X‐ray diffractometry. A single and reasonably sharp peak observed in the diffraction curve indicates that the quality of the crystal is quite good without having any internal structural grain boundaries. The FTIR and proton NMR study confirm the presence of functional groups. From the UV – Vis Far IR absorption spectra the good transparency is revealed. The Kurtz Perry SHG test confirms the NLO property of the EBST crystal grown and it is 11 times greater than urea. The melting point of the grown crystal is found to be 237°C from the DSC curve. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric Properties of Superionic System AgBr—PbI2—Ag2O—B2O3

Dielectric properties of the system AgBr—PbI₂—Ag₂O—B₂O₃ has been studied for various temperatures and frequencies. Conductivity of the sample has also been measured and it is found that at 160 °C it attains the value 5.9 × 10^—3 (Ohms cm)^—1 and the activation energy calculated from the Arrhenius is found to be 0.16 eV.