Sonolytic degradation of dimethoate: kinetics, mechanisms and toxic intermediates controlling

The sonolytic degradation of aqueous solutions of dimethoate, O,O-dimethyl S-[2-(methylamino)-2-oxoethyl]dithiophosphate, was examined. Optimal degradation rates were obtained at 619 kHz for continuous sonolysis and 406 kHz for pulse sonolysis. The primary pathways for degradation include hydroxyl radical oxidation, hydrolysis and pyrolysis on collapsing cavitation bubble interfaces. Reaction mechanisms coupled with the corresponding kinetic models are proposed to reproduce the observed concentration versus time profiles for dimethoate, omethoate and N-(methyl) mercaptoacetamide during sonolysis. The oxidation and hydrolysis of dimethoate and omethoate occurred at the water-bubble interface was the rate-determining step for sonolytic overall degradation of dimethoate. More than 90% toxicity of dimethoate was reduced within 45 min ultrasonic irradiation. Ferrous ion at micro molar level can significantly enhance the sonolytic degradation of dimethoate and effectively reduce the yields of toxic intermediate omethoate.     

Decay of material properties of degraded MEA caused by repeated cold starts under subzero conditions in polymer electrolyte fuel cells

This study investigated the characteristics of cell performance degradation, decline of component performance, and changes in the properties of membrane electrode assembly materials caused by repeated cold starts under a subzero condition of ?30 °C. It was made clear that functional decay appeared mainly at the cathode due to increased proton conductive impedance and reduction of reactivity of the electrode catalyst. Among the cathode components, an increase in proton conductive impedance in the cathode electrolyte was dominant. Furthermore, the application of ion chromatography and a newly developed proton‐induced gamma‐ray emission method to measure fluorine in the off‐gas drain revealed that decomposition of the electrolyte was dominant in the cathode catalyst layer. A decrease in fluorine in the cathode electrolyte measured by fluorine‐19 nuclear magnetic resonance confirmed this decomposition. A hypothesis is also presented concerning the cause of the performance degradation. © 2012 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.20394     

Products from Lignocellulosic Materials via Degradation Processes

Abstract

Products from lignicellulosic materials by degradation processes are reviewed based on the results of some investigations. Biomass provides a potential source of added value chemicals, such as reducing sugars, furfural, ethanol and other products by using biochemical or chemical and thermochemical. The initial degradation reactions include depolymerization, hydrolysis, oxidation, dehydration, and decarboxylation. The gas phase of pyrolitic degradation products contain mostly carbon monoxide and carbon dioxide, and minor proportions of hydrogen, methane, ethane, and propane. The liquid fraction consists mainly of water, with small proportions of acetaldehyde, propion aldehyde, butiraldehyde, acrolein, croton-aldehyde, furan, acetone, butanedione, and methanol. There are many studies on biomass conversion methods because of energy problems and environmental pollution. Ethanol is an alcohol and is fermented from sugars, starches or from lignocellulosic biomass. In order to produce bioethanol from lignocellulosic biomass, a pretreatment process is used to reduce the sample size, degrade the hemicelluloses to sugars, and open up the structure of the cellulose component. The cellulose portion is hydrolyzed by acids or enzymes into glucose sugar that is fermented to bioethanol. The sugars from the hemicelluloses are also fermented to bioethanol.     

Effect of hot drawing on properties of wet‐spun poly(L,D‐lactide) copolymer multifilament fibers

Polylactide stereocopolymer multifilament fibers were prepared by wet spinning and subsequent hot drawing. The stereocopolymers were poly‐(L,D ‐lactide) [P(L,D )LA], L/D ratio 96/4, and poly‐(L,DL ‐lactide) [P(L,DL )LA], L/DL ratio 70/30. They were dissolved in dichloromethane and coagulated in a spin bath containing ethanol. The hot‐drawing temperature was 65°C. The draw ratios (DR) were upto 4.5 to the P(L,D )LA 96/4 filaments and upto 3 to the P(L,DL )LA 70/30 filaments. Wet spinning decreased crystallinities of both copolymers. Hot drawing increased the crystallinity of the P(L,D )LA 96/4 filament but not to the level of the original copolymer, whereas the as‐spun and the hot‐drawn P(L,DL )LA 70/30 filaments were amorphous. The filament diameter, tenacity, Young's modulus, and elongation at break were dependent on the DR. The maximum tenacity (285 MPa) and Young's modulus (2.0 GPa) were achieved with the P(L,D )LA 96/4 filament at the DR of 4.5. Respectively, the maximum tenacity of the hot‐drawn P(L,DL )LA 70/30 filament was 175 MPa and Young's modulus 1.3 GPa at the DR of 3. Hot drawing slowed down in vitro degradation rate of both stereocopolymer filaments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

氟硼酸重氮盐裂解反应条件的探讨

讨论了以重氮化法合成4,4’-二氟二苯甲酮路线中的关键工艺——重氮盐裂解的各种影响因素。研究发现,通过加入Fe粉末作催化剂,将干燥的氟硼酸重氮盐分批次缓慢加入到m（重氮盐）：m（甲苯）=1：2．6的甲苯溶剂中裂解,反应可以十分平稳、温和地进行,并且其收率可以稳定在85％左右,含量达94％以上（气相色谱）。     

Kinetic study on the first stage during thermal degradation of polystyrene

The kinetic parameters of the first stage of polystyrene degradation have been investigated to elucidate the reaction mechanisms using the flow reactor system. The decrease in molecular weight of polystyrene was recorded at minute intervals over the temperature range 310°–390°C. Generally, the first and second stages were observed by thermogravimetric analysis (t.g.a.), however in the early stage of the degradation volatile yields of at least 5% occurred. Therefore, using t.g.a. analysis it is difficult to detect this earlier stage. It became evident that the first stage in the earlier part of the reaction could be detected by g.p.c. analysis. We have observed the hidden kinetic parameters of the nature of the first stage of the polystyrene degradation. The results indicate that the main chains were degraded randomly with the small quantitative volatile groups in the first stage and the rates of decrease in molecular weight in the first stage against reaction temperatures were evaluated as log k_s = 12.0 ? 41300/RT.     

浅谈交联电缆的接地故障

重点介绍了交联电缆绝缘击穿接地的主要原因——水树枝劣化机理，阐述了降低水树枝劣化速率的主要对策及寻找交联电缆接地故障点的方法。     

Muscle tissue structural changes and texture development in sea bream, Sparus aurata L., during post-mortem storage

Sea bream, Sparus aurata L., specimens were studied in pre-rigor (3 h) and during the following post-mortem days: 1, 5, 10, 15 and 22. Muscle and textural parameters were evaluated on 6 specimens/stage. Structural results showed scarce fibre-to-fibre detachment on pre-rigor, which increased during the post-mortem degradation. Ultrastructural changes revealed rapid muscle degradation. In pre-rigor myofibrils were detached to both sarcolemma and endomysium. Intermyofibrillar spaces increased and some mitochondriae and sarcoplasmic reticulum were swollen. After 1 day, the sarcolemma appeared occasionally disrupted and the interfibrillar spaces increased. From 5 to 10 days, the I-band and Z line presented some alterations, although these were more severe at 15-22 days. Thus, in these two last stages, loss of I-band, Z line and actin filaments was observed, that coincides with the alteration of the hexagonal arrangement in these advanced stages. Also, the fragmentation of myofibrils increased from 5 to 10 days on. Sarcolemma and endomysium were gradually disrupted throughout the post-mortem stages with total loss at 22 days. Consequently, the interfibrillar spaces increased at last stages. Autophagic mechanisms increased from 5 days on, with an intense destruction of all the intracytoplasmic organelles. Textural parameters decreased from pre-rigor until 5-10 days, mainly associated to detachment of myofibers to sarcolemma-endomysium.     

高温PEMFC的性能衰减研究与一维数值模拟

以PBI/H3PO4体系高温质子交换膜燃料电池为研究对象,进行了500h恒负载条件下的连续寿命实验,运用电化学电位扫描技术和交流阻抗技术测试了电池在连续运行过程中的电化学活性面积(AEC)和电池内阻的变化,实验结果表明在500h的连续寿命实验中,电池性能衰减的主要原因是高温操作条件下由于催化剂的烧结造成的电化学活性面积的损失。同时,建立了基于高温体系的一维数学模型,利用电化学方法测试得到的两个重要参数——体交换电流密度和电池内阻作为模型输入参数,计算了电极扩散层的反应气体浓度分布,运用模型模拟了电池在连续寿命实验中不同时间的稳态极化曲线,模拟结果和实验结果基本一致。     

110kV变压器绝缘电阻降低的试验分析及处理

维护变压器绝缘电阻在正常值范围运行至关重要。对110 kV变压器绝缘降低现象进行分析,认为是变压器在安装过程中遭遇下雨进水受潮所致。经对变压器干燥处理后绝缘电阻合格。指出绝缘电阻测量和数据分析中存在的问题。