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21.
Thermal lens detection with a 325.0 nm He-Cd excitation laser is used for thermooptical indirect detection in combination with the capillary electrophoretic separation of organic anions. The optimization of indirect thermooptical detection is discussed. With Mordant Yellow 7 (an azo dye) chosen as a probe ion limits of detection for 1-heptane-, 1-pentane-, 1-butane-, 1-propanesulfonic, and acetic acid at a level of n × 10−7 M were achieved with a separation electrolyte containing 50 μM of the probe ion and 5 mM Tris pH 9.90. A further increase in the detection sensitivity (twofold decrease in the limit of detection ) was obtained with a separation electrolyte containing a volume fraction of 20% acetonitrile. 相似文献
22.
The thermal decomposition of 4,4′-diaminodiphenylsulphone (DDS) was studied by thermogravimetry, differential scanning calorimetry and thermal volatilisation analysis. Solid residues, high-boiling and gaseous products of degradation were collected at each step of thermal decomposition and analysed by infrared spectroscopy and gas chromatography/mass spectrometry.
On programmed heating at normal pressure, DDS starts to evaporate at 250°C. Thermal decomposition, which probably proceeds through homolytic scission of the S-C bond is simultaneously observed. The resulting sulphonyl radicals provoke polymerisation and cross-linking of the solid residue which undergoes a limited degradation at 350°C with elimination of heteroatoms N and S as volatile moieties. Above 400°C, the residue undergoes a complex charring process leading to an aromatic char typical of carbonised aromatic polymers. 相似文献
23.
A. Marongiu T. Faravelli G. Bozzano M. Dente E. Ranzi 《Journal of Analytical and Applied Pyrolysis》2003,70(2):519-553
This paper presents an initial attempt at describing poly(vinyl chloride) (PVC) thermal degradation through a semi-detailed and lumped kinetic model. A mechanism of 40 species and pseudocomponents (molecules and radicals) involved in about 250 reactions permits quite a good reproduction of the main characteristics of PVC degradation and volatilization. The presence of the two step mechanism—the first step of which corresponds to dehydrochlorination and the second to the tar release and residue char formation—are correctly predicted both in quantitative terms and in the temperature ranges. The model was validated by comparison with several thermo gravimetric analyses, both dynamic at different heating rates, and isothermal. When compared with the typical one step global apparent degradation models, the approach proposed here spans quite large operative ranges, especially when it comes to predicting product distributions. The initial results of these product predictions, even though quite preliminary, are encouraging and confirm the validity of the model. 相似文献
24.
25.
Solubility of lanthanum oxide was measured by thermal analysis. The solubility in alkali cryolites is rather high, because of chemical reactions between lanthanum oxide and cryolites. In Li3AlF6-La2O3, alumina precipitates, in the other systems the mixed oxide LaAlO3 is formed. In La2O3-Li3AlF6 the eutectic point is at 9.5 mol% La2O3 and 755 °C. The eutectic points in La2O3-Na3AlF6 and La2O3-K3AlF6 are at 11.5 mol% La2O3, and at 937 and 934 °C, respectively. 相似文献
26.
F. Gugumus 《Polymer Degradation and Stability》2006,91(9):2079-2092
There are many potential reactions for trans-vinylene groups in oxidizing polyethylene melts. The main possibilities are reactions with peroxy radicals, molecular oxygen, hydroperoxides and peracids. These different reactions can all contribute to the removal of trans-vinylene groups to some extent. This is especially so, for the reactions with hydroperoxides that have been found to be the dominant reactions with vinylidene and vinyl groups in the low temperature range. The reaction with peroxy radicals is thought to be as important relatively as with vinylidene groups. Therefore, the importance of the reaction is decreasing with increasing temperature. However, the most characteristic reaction for trans-vinylene groups can be detected without any doubt only in the advanced stages of processing. It is mechanical stress induced oxygen addition to the double bond. The discussion shows that the reaction should be important from the beginning of processing. The reaction cannot operate with vinyl and vinylidene groups, which are not part of the polyethylene main chain. After oxygen addition to the trans-vinylene group, the “ene” reaction yields an allylic hydroperoxide so that the double bond is not immediately removed. It is acid catalyzed hydroperoxide decomposition that leads to chain scission with aldehyde formation at the new chain ends. 相似文献
27.
Thermogravimetric analysis of hydroxyl terminated polybutadiene (HTPB) and its fractions of different molecular weights separated by preparative GPC shows two major stages of weight loss of different nature in a nitrogen atmosphere. The first stage is primarily depolymerisation, cyclisation and crosslinking of molecules and the second stage is mainly the decomposition of the residue from the first stage. The kinetic parameters, viz. activation energy E and pre-exponential factor A using four different non-isothermal integral equations show a systematic increase with increase in molecular weight for the first stage, whereas for the second stage, the effect of molecular weight on E and A values is not prominent. The increase in E and A values for the first stage is attributed to the formation of greater number of cyclised and crosslinked products from molecules of higher dimensions. Quantitative correlations between the kinetic constants and the molecular weight parameters were derived for the first stage as a quadratic curve following the equation: E or ln A = K1 − K2/M (where K1 and K2 are empirical constants whose values are different for the different molecular weight averages, viz. Mn, Mw and Mz and for the different equations). 相似文献
28.
Simultaneous thermogravimetry–differential thermal analysis (TG–DTA) and gas and liquid chromatography with mass spectrometry detection have been used to study the kinetics and decomposition of 2-hydroxybenzoic acid, 2-carboxyphenyl ester, commercially known as salsalate. Samples of salsalate were heated in the TG–DTA apparatus in an inert atmosphere (100 ml min−1 nitrogen) in the temperature range 30–500 °C. The data indicated that the decomposition of salsalate is a two-stage process. The first decomposition stage (150–250 °C) had a best fit with second-order kinetics with Ea=191–198 kJ/mol. The second decomposition stage (300–400 °C) is described as a zero-order process with Ea=72–80 kJ/mol. The products of the decomposition were investigated in two ways:
- (a)Salsalate was heated in a gas chromatograph at various isothermal temperatures in the range 150–280 °C, and the exit gas stream analyzed by mass spectrometry (GC–MS). This approach suggested that salsalate decomposes with the formation of salicylic acid, phenol, phenyl salicylate, and cyclic oligomers of salicylic acid di- and tri-salicylides.
- (b)One gram samples of salsalate were heated in a vessel under nitrogen to 150 °C, and the residues were analyzed by liquid chromatography–mass spectrometry (LC–MS). The major compound detected was a linear tetrameric salicylate ester.
29.
利用双光束电子散斑干涉法(ESPI)对试件受热变形进行了实时观测,针对一次实验过程中得到的图片较多(300~500幅)的特点,在图像处理时摒弃了以往的手动识别等位移线的办法,用MATLAB语言编写了批处理程序,能够在采集的大量散斑图片中自动快速准确地标定等位移线,得到相应的位移和应变,并结合实时测量的温度值,获得了45钢和LY12铝合金在不同温升率下的热膨胀系数及其随温度的变化。实验结果表明,在涉及的温升率范围内,温升率的改变对材料热膨胀系数的影响不明显,材料的热膨胀系数随温度的升高略有上升。 相似文献
30.
通过仿真计算分析了激光在光束控制系统通道内传输所产生的热效应及其对远场光束质量的影响。激光传播由近轴波方程描述,用快速傅里叶变换技术求解;激光热效应引起的流场密度变化采用完全Navier-Stokes方程计算。计算给出了不同波长、不同吸收系数条件下的远场光斑情况。计算结果表明,在典型的工作条件和状态下,较高能量激光在光束控制系统通道内产生的热效应影响不容忽视,它会明显降低远场目标处的能量集中度,增大光斑的发散。 相似文献