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101.
102.
低密度聚乙烯光引发交联机理——Ⅱ.BNB自旋捕捉ESR研究 总被引:6,自引:4,他引:2
在光引发剂二苯甲酮(BP)存在下,紫外光辐照低密度聚乙烯(LDPE)所形成的自由基中间体已被自旋捕捉剂2,4,6-三特丁基亚硝基苯(BNB)所捕捉,其自旋加合物自由基已为电子自旋共振(ESR)所特征。现已检测和鉴定到二种自旋加合物:一种是叔碳自由基;另一种是仲碳自由基。它们分别是由BP的激发三重态从LDPE链的支化点和亚甲基团上夺氢所形成的自由基中间体同自旋捕捉剂BNB反应生成的。上述的证据表明:LDPE的光引发交联点主要发生在叔碳和仲碳原子上,且H-型交联点占主导地位。 相似文献
103.
The pressure dependence of the direct and indirect bandgap of epitaxial In0.52Al0.48As on InP(001) substrate has been measured using photoluminescence up to 92 kbar hydrostatic pressure. The bandgap changes
from Γ toX at an applied pressure of ∼ 43 kbar. Hydrostatic deformation potentials for both the Γ andX bandgaps are deduced, after correcting for the elastic constant (bulk modulus) mismatch between the epilayer and the substrate.
For the epilayer we obtain
and+(2.81±0.15)eV for the Γ andX bandgaps respectively. From the pressure dependence of the normalized Γ-bandgap photoluminescence intensity a Γ-X lifetime ratio, (τΓ/τ
X
), of 4.1×10−3 is deduced. 相似文献
104.
Yuichiro Tada Masakatsu Ueno Noriaki Tsuchihashi Kiyoshi Shimizu 《Journal of solution chemistry》1992,21(9):971-985
The limiting molar conductances ° of deuterium chloride DCl in D2O were determined as a function of pressure and temperature in order to examine the proton-jump mechanism in detail. The excess deuteron conductances °E(D
+), as estimated by the equation [°E(D
+) = °(DCl/D
2
O) – °(KCl/D
2
O)], increases with an increase in the pressure and temperature as well as the excess proton conductance [°E(H
+) = °(HCl/H
2
O) – °(KCl/H
2
O)]. The isotope effect on the excess conductances, however, depends on the pressure and temperature contrary to the model proposed by Conway et al.: °E(H
+)/°E(D
+) decreases with increasing pressure and temperature. The magnitude of the decrease with pressure becomes more prominent at lower temperature. These results are discussed in terms of the pre-rotation of adjacent water molecules, the bending of hydrogen bonds with pressure, and the difference in strength of hydrogen bonds between D2O and H2O. 相似文献
105.
The solubilities of o-, m- and p-xylene in water were measured at 25.0°C up to 250, 385, and 50 MPa, respectively. The solubility increased with increasing pressure up to 120 MPa (50 MPa for p-xylene) and then decreased. The reaction volumes, Vo accompanying the dissolution at 0.1 MPa were estimated as –3.6±0.5, –3.4±0.5, and –4.1±0.5 cm3-mol–1 for o-, m-, and p-xylene, respectively, from the pressure dependences of the solubilities. The limiting partial molar volumes, of p- and o-xylene in water under high pressure were estimated from Vo and the molar volume of the xylene. The partial molar volumes decreased with increasing pressure. The reaction volume for the formation of intra-molecular pairwise hydrophobic interaction between the methyl groups, as proposed by Ben-Naim, is discussed for the Vo of p- and o-xylene at 0.1 MPa. 相似文献
106.
Yu. A. Dyadin F. V. Zhurko I. V. Bondaryuk G. O. Zhurko 《Journal of inclusion phenomena and macrocyclic chemistry》1991,10(1):39-56
Experimental data on the investigation of the water-trimethyleneoxide system,P, t, x phase diagram (up to 6 kbar) are presented. The results are compared with those on water systems with ethyleneoxide, 1,3- and 1,4-dioxane, 1,3-dioxolane and tetrahydrofuran, on the basis of which a summarizedP, t, x diagram is plotted for water-cyclic ether systems. It is shown that in all the systems in which a cubic structure II hydrate forms at 1 bar, it eventually turns to cubic structure I under pressure. The nature of high pressure hydrates is discussed.Dedicated to the memory of D. W. Davidson. 相似文献
107.
Hubert HuppertzRolf-Dieter Hoffmann Rainer Pöttgen 《Journal of solid state chemistry》2002,169(2):155-159
EuPd0.72In1.28 and EuPt0.56In1.44 were prepared under multianvil high-pressure (10.5 GPa) high-temperature (1500 and 1400 K) conditions from the precursor compounds EuPdIn and EuPtIn. They were investigated by X-ray diffraction on both powders and single crystals: MgZn2-type, space group P63/mmc, a=578.7(1) pm, c=944.9(3) pm, wR2=0.0734, 263 F2 values for EuPd0.72In1.28 and a=591.1(2) pm, c=933.8(2) pm, wR2=0.0853, 151 F2 values for EuPt0.56In1.44 with 13 variable parameters per refinement. Both structures are built up from face- and corner-sharing tetrahedra of palladium (platinum) and indium atoms. The europium cations are located in cavities within the three-dimensional [Pd0.72In1.28] and [Pt0.56In1.44] networks. The 2a and 6 h positions of the tetrahedral networks show mixed Pd/In and Pt/In occupancy in EuPd0.72In1.28 and EuPt0.56In1.44, respectively. The crystal chemistry of these indides is briefly discussed. 相似文献
108.
A. Hazra K. Alexander D. Dollimore A. Riga 《Journal of Thermal Analysis and Calorimetry》2004,75(1):317-330
The present study was aimed at determining the kinetics of evaporation and establishing vapor pressure curves for both single and multi-component systems by thermogravimetry (TG) and differential scanning calorimetry (DSC). Essential oils (e.g. lavender oil, orange oil, clove oil and eucalyptus oil, etc.) are typically multi-component systems consisting of various volatile pure components (e.g. linalyl acetate, limonene, cinnamaldehyde, etc.) which resemble single component systems. In this study linalyl acetate was taken as the calibration compound for TG. The vapor pressure curves for the pure substances were plotted using TG and vapor pressure plots for clove oil and eucalyptus oil were constructed using DSC. The thermodynamic and kinetic parameters of the pure compounds were compared to that of the multi-component systems to quantitatively and qualitatively measure the influence of different compounds on each other. The k-value from the vapor pressure data for linalyl acetate was calculated as 112006 Pa kg0.5mol0.5s-1 m-2 K-0.5. The vapor pressure values were used to determine the Antoine constants using the SPSS 10.0 software.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
109.
采用分子量500万的聚氧化乙烯和无水溴化铜,通过混溶蒸发法制备成高聚物固体电解质P(EO)n-CuBr2薄膜,并在0.1~300MPa范围不同的流体静水压下详细测量其复平面阻抗谱,分别得到在不同压力下离子电导率和介电常数与测量频率的关系.进一步解谱准确地求出P(EO)n-CuBr2(n=12、16)薄膜离子电导率和介电常数的静水压效应,并结合X-光物相分析,根据离子迁移通道的物理图象和高聚物的极化机构进行了初步的讨论.添加20%的增塑剂碳酸丙烯酯,较大改进了压力下的导电性.120~300MPa的离子电导率提高一个数量级 相似文献
110.
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