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31.
Fei Xu Xiangli Shi Qingzhu Zhang Wenxing Wang 《International journal of molecular sciences》2015,16(8):18714-18731
The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH. 相似文献
32.
Rock joints infilled with sediments can strongly influence the strength of rock mass. As infilled joints often exist under unsaturated condition, this study investigated the influence of matric suction of infill on the overall joint shear strength. A novel technique that allows direct measurement of matric suction of infill using high capacity tensiometers (HCTs) during direct shear of infilled joints under constant normal stiffness (CNS) is described. The CNS apparatus was modified to accommodate the HCT and the procedure is explained in detail. Joint specimens were simulated by gypsum plaster using three-dimensional (3D) printed surface moulds, and filled with kaolin and sand mixture prepared at different water contents. Shear behaviours of both planar infilled joints and rough joints having joint roughness coefficients (JRCs) of 8–10 and 18–20 with the ratios of infill thickness to asperity height (t/a) equal to 0.5 were investigated. Matric suction shows predominantly unimodal behaviour during shearing of both planar and rough joints, which is closely associated with the variation of unloading rate and volumetric changes of the infill material. As expected, two-peak behaviour was observed for the rough joints and both peaks increased with the increase of infill matric suction. The results suggest that the contribution of matric suction of infill on the joint peak normalised shear stress is relatively independent of the joint roughness. 相似文献
33.
This study aims to evaluate the tribological behaviour of 3Y-TZP/Ta (20 vol%) ceramic-metal composites and 3Y-TZP monolithic ceramic prepared by spark plasma sintering (SPS) against ultrahigh molecular weight polyethylene (UHMWPE). According to the results of pin (UHMWPE)-on-flat wear test under dry conditions, the UHMWPE – 3Y-TZP/Ta system exhibited lower volume loss and friction coefficient than the UHMWPE – monolithic ceramic combination due to the presence of an autolubricating layer that provides sufficient lubrication for reducing the friction. Owing to the lubrication of the liquid media, under wet conditions obtained using simulated body fluid (SBF), similar behaviour is observed in both cases. Additionally, the ceramic and biocomposite materials were subjected to a low temperature degradation (LTD) process (often referred to as “ageing”) to evaluate the changes in the tribological behaviour after this treatment. In this particular case, the wear properties of the UHMWPE-biocomposite system were found to be less influenced by ageing in contrast to the case of the UHMWPE-zirconia monolithic material. In addition to their exceptional mechanical performance, 3Y-TZP/Ta composites also showed high resistance to low temperature degradation and good tribological properties, making them promising candidates for biomedical applications, especially for orthopaedic implants. 相似文献
34.
Crossover designs are an extremely useful tool to investigators, and group sequential methods have proven highly proficient at improving the efficiency of parallel group trials. Yet, group sequential methods and crossover designs have rarely been paired together. One possible explanation for this could be the absence of a formal proof of how to strongly control the familywise error rate in the case when multiple comparisons will be made. Here, we provide this proof, valid for any number of initial experimental treatments and any number of stages, when results are analyzed using a linear mixed model. We then establish formulae for the expected sample size and expected number of observations of such a trial, given any choice of stopping boundaries. Finally, utilizing the four-treatment, four-period TOMADO trial as an example, we demonstrate that group sequential methods in this setting could have reduced the trials expected number of observations under the global null hypothesis by over 33%. 相似文献
35.
The effect of biochar substituted for anthracite as reductant on magnetizing-roasting pyrite cinder was investigated.The key of magnetizing-roasting is the gasification reaction between reductants and CO2.Since biochar could react with CO2 more rapidly at lower temperature,the reactivity of biochar is better than that of anthracite.The gasification of biochar could produce reducing condition ofφCO/(φCO+φCO2)about 10%-20% between 700-800 ℃,which is in accord with the atmosphere and temperature of Fe2O3 reduction.So it is beneficial to the reduction of iron mineral of pyrite cinder.Compared with anthracite,biochar could decrease the roasting temperature from825 to 750 ℃ and roasting time from 20 to 15min,which shows that a better effect of magnetization could be obtained in the condition of lower temperature and shorter time.Using biochar as reductant,iron concentrate extracted from pyrite cinder as about 64%iron grade could be produced,and the recovery is over 90% under the condition of above 90% grinding particle less than 0.045 mm and magnetic intensity of 0.124-0.194 T. 相似文献
36.
Fresh and frozen-thawed (F-T) pork meats were classified by Vis–NIR hyperspectral imaging. Eight optimal wavelengths (624, 673, 460, 588, 583, 448, 552 and 609 nm) were selected by successive projections algorithm (SPA). The first three principal components (PCs) obtained by principal component analysis (PCA) accounted for over 99.98% of variance. Gray-level-gradient co-occurrence matrix (GLGCM) was applied to extract 45 textural features from the PC images. The correct classification rate (CCR) was employed to evaluate the performance of the partial least squares-discriminate analysis (PLS-DA) models, by using (A) the reflected spectra at full wavelengths and (B) those at the optimal wavelengths, (C) the extracted textures based on the PC images, and (D) the fused variables combining spectra at the optimal wavelengths and textures. The results showed that the best CCR of 97.73% was achieved by applying (D), confirming the high potential of textures for fresh and F-T meat discrimination. 相似文献
37.
本文主要研究随机环境中配对依赖人口数两性 Galton-Watson 分枝过程的条件均值增长率的极限性质.利用上可加函数的性质,得到配对单元平均增长率的极限性质和该过程条件均值的上界和下界.文中给出了关于过程条件均值增长率的两个序列,利用配对单元平均增长率的性质,获得了这两个序列的极限性质.随机环境中配对依赖人口数两性分枝过程比较复杂,本文的结论推广了现有的研究成果. 相似文献
38.
The present study was carried out to evaluate the effects of ozone on rice grains for the following three conditions: saturation time, decay rate, and half-life of ozone. Experiments were performed in different bed thicknesses (5 and 10 cm) and moisture content (11.4 and 14.2% wb) at atmospheric conditions. The lowest saturation time of ozone was 119 min, with the concentration of 516 ppm for rice grains ozonated at 5-cm bed thickness with 11.4% (wb) moisture content. The decay rate kinetics of ozone obtained were consistent with a first-order model. Regarding the half-life of ozone, the lowest value obtained was 6.78 min for rice grains ozonated at 10-cm bed thickness with 14.2% (wb) moisture content. 相似文献
39.
40.
A system is frequently represented by transfer functions in an input–output characterization. However, such a system (under mild assumptions) can also be represented by transfer functions in a port characterization, frequently referred to as a chain-scattering representation. Due to its cascade properties, the chain-scattering representation is used throughout many fields of engineering. This paper studies the relationship between poles and zeros of input–output and chain-scattering representations of the same system. 相似文献