Structural and physical properties of Mg3−xZnxSb2 (x=0-1.34)

The Mg_3−xZn_xSb₂ phases with x=0-1.34 were prepared by direct reactions of the elements in tantalum tubes. According to the X-ray single crystal and powder diffraction, the Mg_3−xZn_xSb₂ phases crystallize in the same P3¯m1 space group as the parent Mg₃Sb₂ phase. The Mg_3−xZn_xSb₂ structure is different from the other substituted structures of Mg₃Sb₂, such as (Ca, Sr, Ba) Mg₂Sb₂ or Mg_5.23Sm_0.77Sb₄, in a way that in Mg_3−xZn_xSb₂ the Mg atoms on the tetrahedral sites are replaced, while in the other structures Mg on the octahedral sites is replaced. Thermoelectric performance for the two members of the series, Mg₃Sb₂ and Mg_2.36Zn_0.64Sb₂, was evaluated from low to room temperatures through resistivity, Seebeck coefficient and thermal conductivity measurements. In contrast to Mg₃Sb₂ which is a semiconductor, Mg_2.36Zn_0.64Sb₂ is metallic and exhibits an 18-times larger dimensionless figure-of-merit, ZT, at room temperature. However, thermoelectric performance of Mg_2.36Zn_0.64Sb₂ is still poor and it is mostly due to its large electrical resistivity.     

Modeling high-pressure densities at wide temperature range with volume scaling: Cyclohexane + n-hexadecane mixtures

High-pressure density data for cyclohexane + n-hexadecane mixtures at a wide temperature range was modeled with several classical equations of state (EOS) and correlative models. A modification for softening the co-volume and another for a volume scaling of the Peng–Robinson EOS (VS-PR) were proposed. The VS-PR model is able to correlate the pure component experimental data employing only five adjustable parameters, with root-mean-square deviation (RMSD) between calculated and experimental densities essentially within the experimental error. This result is superior to widely used approaches, i.e., a six parameter Tait model and six parameter volume translations (temperature and pressure dependent) for Peng–Robinson and Patel–Teja EOS. The VS-PR model also represents well the isobaric thermal expansion and the isothermal compressibility coefficients of the pure cyclohexane, a small naphthenic substance as well as a long chain n-alkane hydrocarbon, n-hexadecane. When modeling the mixture data, the use of VS-PR model of pure components along with the Redlich–Kister expansion, truncated at the first term, the density was correlated within a RMSD only 60% greater than the experimental error. The proposed model is able to accurately represent all the tested mixture data with a relatively small number of parameters.     

Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties

Poly(methyl methacrylate) (PMMA)/silica/titania ternary nanocomposites with covalent bonding interaction between polymer and inorganic phases have been prepared using a novel non-hydrolytic sol-gel method. Transmission electron microscope (TEM) image of silica/titania binary inorganic component indicates a core-shell-like structure. Scanning electron microscope (SEM) images suggest that the well dispersed silica/titania particles in the hybrid are on the nanometer-scale. The transparencies of nanocomposites are maintained in visible region while the absorption band in ultraviolet (UV) region is red shifted with increasing inorganic content. The thermogravimetric analysis (TGA) results show that the thermal stability of PMMA copolymer increases dramatically with the addition of silica/titania moieties both in nitrogen and in air.     

Depolymerization and ionic conductivity of enzymatically deproteinized natural rubber having epoxy group

Preparation of liquid epoxidized natural rubber (ENR) was made by oxidative depolymerization of ENR in latex stage without loss of epoxy group. Epoxidation of fresh natural rubber latex, which was purified by deproteinization with proteolytic enzyme and surfactant, was carried out with freshly prepared peracetic acid. The glass transition temperature (T_g) and gel content of the rubbers increased after the epoxidation, both of which were dependent upon an amount of peracetic acid. The gel content was significantly reduced by oxidative depolymerization of the rubber with (NH₄)₂S₂O₈ in the presence of propanal. The resulting liquid epoxidized rubber (M_n≈10⁴) was found to have well-defined terminal groups, i.e. aldehyde groups and α-β unsaturated carbonyl groups. The novel rubber was applied to transport Li⁺ as an ionic conducting medium, that is, solid polymer electrolyte.     

First radical cation salts of 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions: β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4

New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)₄Cu₂Cl₆ and (BDA-TTP)₂CuCl₄, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting BDA-TTP layers alternate with the [Cu₂Cl₆]²⁻ or [CuCl₄]²⁻ anions. Both salts show the semiconductor-type temperature dependence of the conductivity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007.     

Phase transition and mixed oxide-proton conductivity in germanium oxy-apatites

La_9.75□_0.25(Ge₆O₂₄)O_2.62 oxy-apatite shows a phase transition from triclinic to hexagonal symmetry at approximately 1020 K that has been characterised by high-temperature synchrotron X-ray and neutron powder diffraction, and ionic conductivity measurements. The crystal structure at 1073 K has been determined from joint Rietveld refinements of synchrotron X-ray and neutron powder diffraction data. The study shows that hexagonal-La_9.75□_0.25(Ge₆O₂₄)O_2.62 contains interstitial oxygen at the position previously reported for other oxy-germanates. Changes in the oxide conductivity associated with this structural transition are discussed. The thermal analyses showed a weight loss on heating close to 600 K very likely due to water release. The synchrotron thermodiffractometric study shows an anomaly in the cell parameters evolution at that temperature, which indicates that this residual water is located into the apatite channels. The electrical characterisation under different atmospheres (dry and wet synthetic air) indicates that there is a significant proton contribution to the overall conductivity below 600 K, mainly under wet atmosphere.     

Thermal and mechanical properties of UV irradiated collagen/chitosan thin films

The thermal and mechanical properties of collagen/chitosan blends before and after UV irradiation have been investigated using thermal analysis and mechanical (Instron) techniques. Comparisons were made with the thermal and mechanical properties of both collagen and chitosan films. Air-dried collagen, chitosan and collagen/chitosan films were exposed to UV irradiation (wavelength 254 nm) for different time intervals. Thermal properties of collagen/chitosan blends depend on the composition of the blend and are not significantly altered by UV irradiation.Mechanical properties such as ultimate tensile strength and ultimate percentage of elongation were much better for collagen films than for collagen/chitosan films. The results have shown that the mechanical properties of the blends were greatly affected by the duration of UV irradiation. Ultimate tensile strength and ultimate percentage elongation decreased after UV irradiation of the blend. Increasing UV irradiation leads to an increase in Young's modulus of the collagen/chitosan blend.     

Synthesis, characterization and thermal studies on cellulose acetate membranes with additive

Cellulose acetate (CA) membranes are used in ultrafiltration applications, although they show low chemical, mechanical and thermal resistance. In order to prepare membranes with improved properties, modification of cellulose acetate with polyethelene glycol (PEG 600) has been attempted. In this study, CA has been mixed with PEG 600 as an additive in a polar solvent. The effects of CA composition and additive concentration given by a mixture design of experiments on membrane compaction, pure water flux, water content and membrane hydraulic resistance have been studied and discussed. The efficiency of protein separation by the developed CA membranes have been quantified using model proteins such as pepsin, egg albumin (EA) and bovine serum albumin (BSA). The thermal stability of the developed membranes prepared with PEG 600 additive has also been investigated using thermogravimetric analysis and differential scanning calorimetry.     

Aspects of thermal conductivity relative to heat flow

Summary The various techniques and methodologies of thermal conductivity measurement have been conventionally based on the determination of the rate of directional heat flow through a material having a unit temperature differential between its opposing faces. The constancy of this rate depends on the material density, its thermal resistance and the heat flow path itself. The last of these variables contributes most significantly to the true value of steady-state axial and radial heat dissipation depending on the magnitude of transient thermal diffusivity along these directions. The purpose of this paper is to exemplify the above features by defined parameters of heat flow measurement by existing methodologies. No new method is proposed here. Importantly, the relationship between the rate of heat transfer, total heat transferred and thermal conductivity at a given temperature under steady-state conditions for a fixed heat flow path will be illustrated.     

Crystallization and second harmonic generation in thermally poled niobium borophosphate glasses

Crystallization of glasses with compositions (1−x)(0.95 NaPO₃+0.05 Na₂B₄O₇)+xNb₂O₅, x=0.4, 0.43, 0.45, 0.48 was investigated by differential scanning calorimetry and X-ray powder diffraction. Crystallization of two phases was observed in the glasses with x=0.43-0.48. First phase is a sodium niobate with the structure of tetragonal tungsten bronze () and second phase is Na₄Nb₈P₄O₃₂ (). The crystallization of sodium niobate is correlated with increasing of nonlinear optical efficiency reported for thermally poled glasses with x>0.4. The results of Raman spectroscopy show the formation of three-dimensional (3D) niobium oxide framework in the glasses with increase of niobium concentration. This framework is supposed to have tetragonal tungsten bronze structure and to be responsible for nonlinear optical properties of the glass. Second harmonic generation signals of as prepared and crystallized glass after thermal poling are compared. The nucleation and crystallization do not improve the NLO properties of the glasses under study.