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81.
Jörg Teichgräber 《Journal of organometallic chemistry》2005,690(23):5255-5263
The synthesis, characterization, and thermal decomposition behavior of dicopper(I) oxalato complexes L4Cu2(C2O4) (L = CNtBu (2a), CNCMe2CH2tBu (2b), CNC6H3Me2-2,6 (2c)) is reported. 2c can be prepared in a straightforward manner by the reaction of stoichiometric amounts of Cu2O and oxalic acid with four equivalents of CNC6H3Me2-2,6, while those complexes with aliphatic isocyanides are better prepared from a copper(I) oxalato complex with alkine capping ligands (Me3SiCCSiMe3)2Cu2(C2O4) (1) via ligand exchange. Crystallographic and spectroscopic evidence for 2a-c confirms the anticipated dinuclear structure with the oxalate in a μ-1,2,3,4 bridging mode and an essentially σ-character of the terminal isocyanides. In solid form the complexes are stable at room temperature and can be handled in air for some time. Their decomposition was studied by thermal gravimetric analysis coupled with mass spectrometry, and the degradation pathway was shown to depend on the type of isocyanide capping ligand. Decomposition of 2a,b takes place between 150 and 200 °C to give CuCN in a clean process that involves isobutene elimination from the terminal ligands, with elimination of (CN)2 and conversion to elemental copper at higher temperatures. Heating of 2c leads to CuO (and then to Cu2O) via release of the intact isocyanide, CO2, and CO in a well-behaved thermal process around 200-280 °C. 相似文献
82.
N. Bouad 《Journal of solid state chemistry》2004,177(1):221-226
We report in this paper a study of the mechanical alloying (MA) process for the Pb0.65Sn0.35Te alloy. MA has been carried out in a high-energy planetary ball mill. The mechanism of formation has been studied from systematic analyses of mechanically alloyed powders using X-ray diffraction, differential scanning calorimetry and scanning electron microscopy. As it was already observed for the MA of PbTe, this synthesis is associated with an exothermic reaction between the elemental powders. The required time to reach an homogeneous phase Pb0..65Sn0.35Te is 31 h. 相似文献
83.
S Çak?r E Co?kunP Naumov E Biçer? Bulut H ?çbudakO Çak?r 《Journal of Molecular Structure》2002,608(1):101-107
Aspartame adduct of copper(II) chloride Cu(Asp)2Cl2·2H2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions. 相似文献
84.
用AM1方法(采用非限制的Hartree-FockUHF计算)研究乙烯与环己-1,3-二烯的热Diels-Alder反应。结果表明反应是放热的且存在两条竞争的路径;协同反应的活化能以及双自由反应速度控制步骤的活化能分别为112.667kJ/mol和78.406kJ/mol。 相似文献
85.
Medical grade PVC plasticised with polycaprolactone–polycarbonate (PCL–PC) was subjected to aqueous environments at different temperatures. The release profile during ageing was determined by solid phase microextraction (SPME) and GC–MS. At the same time changes in the surface composition due to, for example, migration of PCL–PC from the blend were followed by FTIR. Almost no changes in the material or its surface composition were observed during 98 days at 37 °C in water or phosphate buffer. Only trace amount of 6-hydroxyhexanoic acid the final hydrolysis product of PCL–PC was detected in the GC–MS chromatograms and the weight loss was negligible. Even when the ageing temperature was raised to 70 °C only minor increase in the amount of 6-hydroxyhexanoic acid was observed and the weight loss after 98 days was under 1%. Changes in the FTIR spectra indicating migration of PCL–PC towards the surface of the PVC/PCL–PC tubing were observed first after 70 days at 70 °C. Large increase in the hydrolysis rate of PCL–PC and almost complete depletion of PCL–PC from the blend was observed when the ageing temperature was raised to 100 °C. 相似文献
86.
研究了导电聚合物聚(3-丁基噻吩)(PBT)在大气环境下的导电热稳定性。在室温至220℃范围内,测试电导率随时间及温度的变化。TGA分析以及化学分析的结果表明:掺杂态的PBT大约在140℃附近有一转化温度,低于或高于这一转化温度,电导率下降的决定因素各不相同。高于转化温度时,电导率下降的主要原因是反离子和高分子主链的解离,进而发生化学反应,影响了高分子主链的结构。XPS测试结果表明:经热处理后的P 相似文献
87.
The phase analysis of cryolite (Na3AlF6) and sodium metasilicate (Na2SiO3) was performed by thermal analysis. The eutectic system with a region of two immiscible substances at a concentration of Na2SiO3 between 42.8 and 46.3 mol‐% was identified and the eutectic temperature determined to (886±2) °C. Based on the results of mass‐loss measurements, it was assumed that the introduced Na2SiO3 reacts with Na3AlF6 due to the formation of some nonvolatile stable compounds. The stable reaction products were identified by X‐ray diffraction analysis and IR spectroscopy of the spontaneously cooled samples, which established the formation of NaF and stable amorphous aluminosilicate compounds. 相似文献
88.
The compositions in the YBa2−xLaxCu3O7−δ (0x0.2) system were prepared by the solid state reaction, employing a novel high-temperature oxygen sintering route. The modified sintering route yields dense slab like microstructures with large grains. The decomposition (incongruent melting) temperature of the YBa2Cu3O7−δ (Y-123) phase was found to shift to higher temperatures with increasing oxygen partial pressure and lanthanum content. Structure remained orthorhombic up to x=0.2 with a decrease in the orthorhombic strain ((b−a)/b). Iodometric titration indicated a systematic increase in the oxygen content with increasing lanthanum content. Thermo-gravimetric studies in various oxygen partial pressures revealed that the oxygen diffusion in to the YBa2Cu3O7−δ (δ>0.5) lattice is an exothermic event and takes place at temperatures not less than 573 K. High-temperature thermal-expansion measurements in air indicated that the nonlinearity in thermal expansion behaviour was reduced by the substitution of lanthanum. 相似文献
89.
Summary We deal with two diffusion problems: Space-integrated conserved entities characterizing very fast - diffusion - controlled reactions, such as time lags, etc. are universal. They are given by relationships which do not reflect the failure of the mean field hydrodynamic equations. We present another application which does not reflect this failure, for determining the surface flux via a diffusion controlled reaction producing a colored product. Another anomalous diffusion process we considered is transport through cellular materials whose cell sizes are highly nonuniform. We have analyzed the effects of extreme nonuniformity by considering fractal-like models of cellular solids. The diffusion current through these models can exhibit anomalous time-dependencies which are not predicted by the diffusion equation. In particular, it is shown that the initial diffusion current can be characterized by a power-law dependence on the time. Furthermore, the exponent of the power law is given in terms of the distribution of cell sizes in the fractal-like cellular solid. 相似文献
90.
Kolman David Heberlein Joachim Pfender Emil 《Plasma Chemistry and Plasma Processing》1998,18(1):73-89
In this paper, a comprehensive model for thermal plasma chemical vapor deposition (TPCVD) with liquid feedstock injection is documented. The gas flow is assumed to be steady, of a single temperature. Radiation and charged species contributions are excluded, but extensive homogeneous and heterogeneous chemistry is included. The liquid phase is traced by considering individual droplets. Discussion on the model's application to diamond production from acetone in a hydrogen–argon plasma is included. The major conclusions are: (1) Liquid injection possesses a capability to deliver the hydrocarbon precursor directly onto the deposition target. (2) For the case of complete evaporation of the droplet before reaching the substrate, the deposition rate is similar to that obtained with gaseous precursors. (3) The computational results compare well with experimental data. The modeling results can be used to optimize the injection parameters with regard to the deposition rate. 相似文献