Laser Raman spectroscopic study of ferroelastic LiCsSO4

Lithium caesium sulphate has been reported to undergo a phase transition from the room temperature orthorhombic phase with space groupP cmn to a final phase with space groupP 22/n. Though a sharp anomaly in its physical properties has been found at 202.0;K, it was found that there was a need for careful investigations in the vicinity of 240 and 210.0;K. Since the changes in the crystal structure involve primarily a rotation of the SO4 tetrahedron about thec-axis and as this may be reflected both in the intensity and polarisation of the internal as well as external phonon modes, the laser Raman spectra of oriented single crystals of LiCsSO4 at different temperatures were investigated. For correlation and definite identification of the spectral features, its infrared absorption spectrum was also studied. An analysis of the intensities and polarizations of the internal modes of the sulphate ions reveals the change in symmetry of the crystal. The integrated intensity and peak height of thev 1 line, plotted against temperature show anomalous peaks in the region of the phase transition. Differential scanning calorimetric study gives the enthalpy change ΔH across the phase transition to be 0.213 kJ/mol.

Thermal degradation of polystyrene

The importance of the study of thermal degradation of polymeric fuels arises from their role in the combustion of solid propellants. Estimation of the condensed-phase heat release during combustion can be facilitated by the knowledge of the enthalpy change associated with the polymer degradation process. Differential scanning calorimetry has been used to obtain enthalpy data. Kinetic studies on the polymeric degradation process have been carried out with the following objectives. The literature values of activation energies are quite diverse and differ from author to author. The present study has tried to locate possible reasons for the divergence in the reported activation energy values. A value of 30 kcal has been obtained and found to be independent of the technique employed. The present data on the kinetics support to chain-end initiation and unzipping process. The activation energies are further found to be independent of the atmosphere in which the degradation of polymer fuel is carried out. The degradation in air, N2, and O2 all yield a value of 30 kcal/mole for the activation energies.

Evidence of an intermediate phase in ternary Ge7Se93-xSbx glasses

The compositional dependence of thermal properties, such as glass transition temperature (T-g), non-reversing enthalpy change (Delta H-NR) and the specific heat capacity change (Delta C-p) of melt quenched Ge7Se93-xSbx (21 a parts per thousand currency sign x a parts per thousand currency sign 31) glasses, has been studied using alternating differential scanning calorimetry (ADSC) which is analogous to modulated differential scanning calorimetry (MDSC). The glass transition temperature, T-g, which is a measure of global connectivity of the glass, has been found to increase with the addition of Sb. In addition, a change in slope has been observed in the composition dependence of T-g at an average coordination aOE (c) r > = 2.40. The experimentally observed compositional variation of glass transition temperature, has been compared with the theoretical predictions from the stochastic agglomeration theory (SAT) and has been found to be consistent. Further, a narrow thermally reversing window is seen in the compositional variation of the relaxation enthalpy (Delta H-NR), which is centered around aOE (c) r > = 2.40. The change in specific heat capacity (Delta C-p) at T-g is also found to exhibit a distinct minima at aOE (c) r > = 2.40, suggesting that the structural rearrangements for the liquid in the glass transition region are minimized around aOE (c) r > = 2.4.

Melting of an Anchored Bilayer: Phase Transitions in the Organic-Inorganic Hybrid Pervoskite (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n=11, 13, 15, 17)

The conformation, organization, and phase transitions of alkyl chains in organic-inorganic hybrids based on the double pervoskite-slab lead iodides, (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 (n = 11, 13, 15, 17) have been investigated by X-ray diffraction, calorimetry, and infrared vibrational spectroscopy. In these hybrid solids, double pervoskite (CH3NH3)Pb2I7 slabs are interleaved with alkyl ammonium chains with the anchored alkyl chains arranged as tilted bilayers and adopting a planar all-trans conformation at room temperature. The (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 compounds exhibit a single reversible phase transition above room temperature with the associated enthalpy change varying linearly with alkyl chain length. This transition corresponds to the melting in two-dimensions of the alkyl chains of the anchored bilayer and is characterized by increased conformational disorder of the methylene units of the chain and loss of tilt angle coherence leading to an increase in the interslab spacing. By monitoring features in the infrared spectra that are characteristic of the global conformation of the alkyl chains, a quantitative relation between conformational disorder and melting of the anchored bilayer is established. It is found that, irrespective of the alkyl chain length, melting occurs when at least 60% of the chains in the anchored bilayer of (CH3NH3)(CH3(CH2)(n)NH3)(2)Pb2I7 have one or more gauche defects. This concentration is determined by the underlying lattice to which the alkyl chains are anchored.

Evidence for a thermally reversing window in bulk Ge-Te-Si glasses revealed by alternating differential scanning calorimetry

Experiments on Ge15Tc85-xSix glasses (2 <= x <= 12) using alternating differential scanning calorimetry (ADSC) indicate that these glasses exhibit one glass transition and two crystallization reactions upon heating. The glass transition temperature has been found to increase almost linearly with silicon content, in the entire composition tie-line. The first crystallization temperature (T-cl) exhibits an increase with silicon content for x<5; T-cl remains almost a constant in the composition range 5 < x <= 10 and it increases comparatively more sharply with silicon content thereafter. The specific heat change (Delta C-p) is found to decrease with an increase in silicon content, exhibiting a minimum at x=5 (average coordination number, (r) = 2.4); a continuous increase is seen in Delta C-p with silicon concentration above x = 5. The effects seen in the variation with composition of T-cl and Delta C-p at x=5, are the specific signatures of the mean-field stiffness threshold at (r) = 2.4. Furthermore, a broad trough is seen in the enthalpy change (Delta H-NR), which is indicative of a thermally reversing window in Ge15Te85-xSix glasses in the composition range 2 <= x <= 6 (2.34 <= (r) <= 2.42).

Mixed saturated-unsaturated alkyl-chain assemblies: Solid solutions of zinc stearate and zinc oleate

The linear saturated stearic acid and the bent mono-unsaturated oleic acid do not mix and form solid solutions. However, the zinc salts of these acids can. From X-ray diffraction and DSC measurements we show that the layered zinc stearate and zinc oleate salts form a homogeneous solid solution at all composition ratios. The solid solutions exhibit a single melting endotherm, with the melting temperature varying linearly with composition but with the enthalpy change showing a minimum. By monitoring features in the infrared spectra that are characteristic of the global conformation of the hydrocarbon chain, and hence can distinguish between stearate and oleate chains, it is shown that solid solution formation is realized by the introduction of gauche defects in a fraction of the stearate chains that are then no longer linear. This fraction increases with oleate concentration. It has also been possible from the spectroscopic measurements to establish a quantitative relation between molecular conformational order and the thermodynamic enthalpy of melting of the solid solutions.

Volume effects and associations in liquid alloys

The regular associated solution model for binary systems has been modified by incorporating the size of the complex as an explicit variable. The thermodynamic properties of the liquid alloy and the interactions between theA ?B type of complex and the unassociated atoms in anA-B binary have been evaluated as a function of relative size of the complex using the activity coefficients at infinite dilution and activity data at one other composition in the binary. The computational procedure adopted for determining the concentration of clusters and interaction energies in the associated liquid is similar to that proposed by Lele and Rao. The analysis has been applied to the thermodynamic mixing functions of liquid Al-Ca alloys believed to contain Al2Ca associates. It is found that the size of the cluster significantly affects the interaction energies between the complex and the unassociated atoms, while the equilibrium constant and enthalpy change for the association reaction exhibit only minor variation, when the equations are fitted to experimental data. The interaction energy between unassociated free atoms remains virtually unaltered as the size of the complex is varied between extreme values. Accurate data on free energy, enthalpy, and volume of mixing at the same temperature on alloy systems with compound forming tendency would permit a rigorous test of the proposed model.

Evidence for a thermally reversing window in bulk Ge–Te–Si glasses revealed by alternating differential scanning calorimetry

Experiments on Ge15Te85− x Si x glasses (2 ≤ x ≤ 12) using alternating differential scanning calorimetry (ADSC) indicate that these glasses exhibit one glass transition and two crystallization reactions upon heating. The glass transition temperature has been found to increase almost linearly with silicon content, in the entire composition tie-line. The first crystallization temperature (T c1) exhibits an increase with silicon content for x < 5; T c1 remains almost a constant in the composition range 5 < x ≤ 10 and it increases comparatively more sharply with silicon content thereafter. The specific heat change (ΔC p) is found to decrease with an increase in silicon content, exhibiting a minimum at x = 5 (average coordination number, r = 2.4); a continuous increase is seen in ΔC p with silicon concentration above x = 5. The effects seen in the variation with composition of T c1 and ΔC p at x = 5, are the specific signatures of the mean-field stiffness threshold at r = 2.4. Furthermore, a broad trough is seen in the enthalpy change (ΔH NR), which is indicative of a thermally reversing window in Ge15Te85− x Si x glasses in the composition range 2 ≤ x ≤ 6 (2.34 ≤ r ≤ 2.42).

Synergistic extraction of rare earths(III) from chloride medium with mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and di-(2-ethylhexyl)-2-ethylhexylphosphonate

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP, HA) and di-(2ethylhexyl)-2-ethylhexylphosphonate (DEHEHP, B) in the extraction of rare earths (RE) from chloride solutions has been investigated. Under the experimental conditions used, there was no detectable extraction when DEHEHP was used as a single extractant while the amount of RE(III) extracted by HPMBP alone was also low. But mixtures of the two extractants at a certain ratio had very high extractability for all the RE (III). For example, the synergistic enhancement coefficient was calculated to be 9.35 for Y3+, and taking Yb3+ and Y3+ as examples, RE3+ is extracted as RE(OH)A(2).B. The stoichiometry, extraction constants and thermodynamic functions such as Gibbs free energy change Delta G (-17.06kJmol(-1)), enthalpy change Delta H (-35.08kjmol(-1)) and entropy change Delta S (-60.47JK(-1)mol(-1)) for Y3+ at 298 K were determined. The separation factors (SF) for adjacent pairs of rare earths were calculated. Studies show that the binary extraction system not only enhances the extraction efficiency of RE(III) but also improves the selectivity, especially between La(III) and the other rare earth elements.

Phase structure and transitions in a poly(methyloctadecylsilane) oligomer

A poly(methyloctadecylsilane) oligomer was synthesized by a typical Wurtz coupling reaction. Upon cooling, three transitions were observed at temperatures of 39.9, 37.5 and 33.9 degreesC at a rate of 2.5 degreesC/min in differential scanning calorimetry (DSC). The first transition, with enthalpy change of 0.47 kT/mol and supercooling of 0.2 degreesC, was characteristic of the conformational change in the Si-Si backbone into an all-trans conformation, which was detected by temperature-dependent Fourier transform infrared (FT-FR) spectroscopy. The second and the third transitions with large supercooling were identified as the formation of two-dimensional hexagonal crystal packing and three-dimensional two-chain orthorhombic crystal packing, respectively. The crystal structure was determined by the combination of WAXD and transmission electron microscopy (TEM) experiments. (C) 2000 Elsevier Science Ltd. All rights reserved.

Synthesis and Characterization of Side-Chain Liquid Crystalline (M6MPP/M6NPAP) Copolymers with NLO Properties

A series of novel thermotropic side-chain liquid crystalline polymer based on polymethacrylate backbone containing electron-accepting 4-(4'-nitrophenylazo)phenoxy as nonlinear optical active group and electron-donating 4(4'-methoxyphenyl) phenoxy group as mesogen attached covalently to the backbone through the flexible spacer was prepared and characterized, respectively. The results from differential scanning calorimetry showed that these series of copolymers were enantiotropic liquid crystal with single mesophase. The melting points and the relative enthalpy change of the copolymers depressed with increasing the molar percent of 4'-nitroazobenzene monomer units over 0 similar to 50mol%, but the enthalpies change of the transition from mesophase to isotropic state increased for the copolymers containing 0 similar to 50mol% 4'-nitroambenzene units. The texture observed under polarized optical microscope identified that the copolymers containing 24molar% or more than 24mol% 4-nitroambenzene monomer units could form smectic mesophase with the focal-conic texture. The results detected by WAXD were in good agreement with the results observed by POM.

Synthesis and thermo-decomposition mechanism of rare earth complexes with phenylacetic acid

Rare earth complexes with phenylacetic acid (LnL(3) . nH(2)O, Ln is Ce, Nd, Pr, Ho, Er, Yb and Y, L is phenylacetate, n = 1-2) were prepared and characterized by elemental analysis, IR spectroscopy, chemical analysis, and X-ray crystal structure. The mechanism of thermal decomposition of the complexes was studied by means of TG-DTG, DTA and DSC. The activation energy and enthalpy change for the dehydration and melting processes were determined.

CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF ERBIUM COMPLEX WITH BENZENE ACETIC ACID

The crystal structure of erbium (III) complex of benzene acetic acid is reported. The complex crystallizes in the monoclinic space group P2(1)/a with a = 0,9008(3)nm, b=1.4242(5) nm, c=1.8437(7) nm, beta=98.80(3)degrees, V = 2.337(1) nm(3), Z = 4. The mechanism of thermal decomposition of complex has been studied by TG-DTG-DTA. The activation energy for dehydration reaction has been calculated by Freeman Carroll method. The enthalpy change for dehydration and phase change process has been determined.

Biosorption of copper(II) from aqueous solutions by green alga Cladophora fascicularis

Biosorption is an effective means of removal of heavy metals from wastewater. In this work the biosorption behavior of Cladophora fascicularis was investigated as a function of pH, amount of biosorbent, initial Cu2+ concentration, temperature, and co-existing ions. Adsorption equilibria were well described by Langmuir isotherm models. The enthalpy change for the biosorption process was found to be 6.86 kJ mol(-1) by use of the Langmuir constant b. The biosorption process was found to be rapid in the first 30 min. The presence of co-existing cations such as Na+, K+, Mg2+, and Ca2+ and anions such as chloride, nitrate, sulfate, and acetate did not significantly affect uptake of Cu2+ whereas EDTA substantially affected adsorption of the metal. When experiments were performed with different desorbents the results indicated that EDTA was an efficient desorbent for the recovery of Cu2+ from biomass. IR spectral analysis suggested amido or hydroxy, C=O, and C-O could combine strongly with Cu2+.

化学冷铁——焓变涂料的研究

焓变涂料是以在一定的温度区间内可发生吸热化学反应的物质为基料配制的,将其涂在砂型(芯)表面,可代替常规冷铁.它对解决难于放置冷铁的串皮芯部位的激冷问题,效果明显.焓变涂料激冷作用的大小,取决于基料物质比焓变的大小以及涂层厚度等因素。