Kinetics of Solid-State Reactions in Heterogeneous Catalysis from Time-Resolved X-Ray Absorption Spectroscopy

The potentials of X-ray absorption spectroscopy (XAS) (quantitative phase composition and average valence together with a short-range order structure analysis) combined with a time-resolution in the second range make time-resolved (TR-) XAS a powerful tool for investigating the reactivity of solids in catalysis and solid-state chemistry. General aspects of TR-XAS investigations are discussed (i.e., instrumentation, data analysis). In addition, some experiments illustrate how the kinetics of solid-state reactions in heterogeneous catalysis can be elucidated from TR-XAS studies.     

局部表面改性紫铜方柱阵列池沸腾传热特性和机理

以局部表面改性的紫铜直方柱和梯度方柱阵列为研究对象，实验研究了表面润湿性、表面形貌和表面活性剂对池沸腾换热性能和气泡生长特性的影响。实验工质为去离子水，浓度分别为100、200、400、800 mg·L^-1的异丙醇溶液和正庚醇溶液。实验结果表明：方柱阵列表面镀银之后润湿性变差，表面产生的气泡数量减少。向去离子水中添加异丙醇或正庚醇后，在热通量为66.1～202 kW·m^-2时，气泡脱离直径变小、数目减少，而当热通量增至413 kW·m^-2时，活性剂能够有效阻碍气泡合并，故池沸腾传热系数随着浓度增加先减小后增大。上下层宽分别0.5 mm和1 mm、间距为2 mm的梯度方柱阵列结构有助于气泡的合并，但由于促进了固体表面气膜的形成，从而降低了沸腾换热性能。     

Changes in the Peeled Surfaces of Copper Thin Films Deposited on Polyimide Substrates After Heat Treatment

Peel strength between a copper (Cu) thin film and a polyimide (pyromellitic dianhydride-oxydianiline, or PMDA-ODA) substrate is reduced by heat treatment at 150°C in air. In this work, we investigated the peel strength, the morphology of the interface between Cu films and polyimide substrates using optical microscopy and electron microscopy, and chemical change of the interface using Auger electron spectroscopy (AES) and micro X-ray photoelectron spectroscopy (XPS). The analysis showed that CuO “lumps” were present on the peeled surface of PMDA-ODA after heat treatment at 150°C in air. The peeled surfaces of other polyimide substrates were also analyzed: biphenyl dianhydride-para phenylene diamine (BPDA-PDA) and biphenyl dianhydride-oxydianiline (BPDA-ODA). CuO lumps were present on the peeled surface of BPDA-ODA after the heat treatment, but not that of BPDA-PDA. Compared with the adhesion strength for the Cu thin film, the adhesion strength was high for the Cu/PMDA-ODA and Cu/BPDA-ODA laminates, but the adhesion strength was very low for the Cu/BPDA-PDA laminate. This low strength is the reason that CuO lumps were not detected on the peeled surface of the BPDA-PDA substrate. These CuO lumps were related to the adhesion degradation of the Cu/polyimide laminates after the heat treatment.     

个旧有色冶化公司一期低浓度铜烟气制酸工程简介

介绍90 kt/a铜冶炼烟气制酸装置的设计和运行情况。采用三段式净化工艺与污水处理系统相结合, 有效地解决了用高砷、氟铜精砂生产硫酸的问题。采用多孔板支撑缩放管气体换热器与高蓄热能力的转化器相结合,在转化器进口平均φ(SO2)约4％,而生产负荷仅为设计能力(270t/d)的74％的条件下,转化系统仍能维持自热平衡。     

2-氯-5-三氯甲基吡啶电化学脱氯合成2-氯-5-氯甲基吡啶

对2-氯-5-三氯甲基吡啶(TCMP)采用电化学脱氯合成2-氯-5-氯甲基吡啶(CCMP),考察了支持电解质、阴极材料及目数、反应温度和电流密度等工艺条件对上述反应的影响和TCMP及其脱氯中间产物的脱氯电位。结果表明:在乙酸锂、氯化锂、高氯酸锂、氯化铵、四丁基高氯酸铵中,乙酸锂为最佳支持电解质。各阴极材料上CCMP收率从高到低次序为:铜>铅>石墨>银>锌>镍。在优化条件下〔阴极液:含10%(体积分数)乙酸+5%(体积分数)水+0.2 mol/L乙酸锂+0.1 mol/L TCMP的甲醇溶液;阴极:80目铜网;反应温度:30℃;电流密度:前期电流密度为333 A/m~2,后期为166 A/m~2〕,0.1 mol/L TCMP能较高效地转化为CCMP,其收率可达56.9%。TCMP脱氯成2-氯-5-二氯甲基吡啶(DCMP)的电位明显正于DCMP脱氯成CCMP的脱氯电位,后者与CCMP进一步脱氯的电位则非常接近。     

Sintering technology for micro heat pipe with sintered wick

In order to study reasonable sintering technological parameters and appropriate copper powder size range of micro heat pipe (MHP) with the sintered wick, the forming principle of copper powders in wicks and MHP’s heat transfer capabilities were first analyzed, then copper powders with different cell sizes and dispersions were sintered in RXL-12-11 resistance furnace under the protection of the hydrogen at different sintering temperatures for different durations of sintering time, and finally the sintered wicks’ scanning electron microscope (SEM) images and their heat transfer capabilities were analyzed. The results indicate that the wick sintered with copper powders of larger cell size or smaller size range has better sintering properties and larger heat transfer capabilities; and that the increase of either sintering temperatures or sintering time also helps to improve the wick’s sintering properties and heat transfer capabilities, and the former affects more obviously than the latter. Considering both its manufacturing cost and performance requirements, it is recommended that copper powders with the size range of 140–170 μm are sintered at 900–950°C for 30–60 min in practical manufacturing. In addition, two approaches to improve wick’s porosity are also proposed through theoretical analysis, which suggests that the larger the wick’s porosity, the better the heat transfer capabilities of the MHP.     

基于CAFE法的单晶铜杆热型连铸过程晶体生长模拟

基于元胞自动机(CA)和有限元(FE)耦合法对单晶铜杆热型连铸过程中晶粒生长及演化过程进行了模拟,获得了稳定状态下铸棒内温度分布及液固相界面的位置和形态,模拟了连铸初期沿热流方向细小等轴晶快速合并形成柱状晶的过程,采用截面形态和极图法分析了定向凝固条件下各个生长时刻的晶粒形貌和晶粒生长取向以及晶粒竞争生长过程中的快速淘汰和慢速淘汰阶段,为热型连铸工艺优化提供了依据。     

粉煤灰制备沸石负载氧化铜处理酸性大红GR废水

以粉煤灰为原料,用碱熔-水热合成法制备沸石并负载氧化铜处理酸性大红GR废水。采用正交试验法考察了m（灰）/m（碱）比、m（灰）/m（水）比、煅烧温度和晶化时间对出水中色度和COD指标的影响,并确定了沸石制备的最佳工艺条件为m（灰）/m（碱）比1.2：1、m（灰）/m（水）比1：9,焙烧温度500℃和晶化时间10 h。将最佳条件下制备的沸石负载氧化铜并与过氧化氢联合催化氧化处理酸性大红GR废水,获得了满意的结果：出水中色度和COD指标达到25（稀释倍数）和105 mg.L-1,分别低于纺织染整工业污染排放标准GB 4287—92规定的一级和二级排放标准。制备的沸石经XRD表征,确定为NaA型沸石相。     

石油烃、Cu2+单一与复合污染对沙蚕的毒性效应

在实验室模拟条件下研究了石油烃、Cu2+单一与复合污染对沙蚕的毒性效应.试验的结果表明,沙蚕的死亡率与石油烃、Cu2+的浓度呈显著相关关系.其半数致死浓度LC50分别为:30.2～116.26μg/L(石油烃);449.52～1130.34μg/L(Cu2+).沙蚕体内Cu2+的积累量随着暴露溶液中Cu2+浓度的上升而增加,当Cu2+的浓度>500μg/L时,这一变化十分显著;而沙蚕体内石油烃的含量随着暴露溶液中石油烃浓度的升高无显著变化.而Cu2+和石油烃复合污染对沙蚕的毒性作用较为复杂,在不同的处理中,表现出了协同和拮抗两种作用方式.同时,在Cu2+与石油烃复合污染条件下,沙蚕体内Cu2+的积累量也有显著变化.在复合处理组中,当Cu2+的浓度达到500μg/L时,Cu2+在沙蚕体内的积累量与Cu2+单一污染相比,Cu2+在沙蚕体内积累量相比显著降低.     

Antibacterial and corrosive properties of copper implanted austenitic stainless steel

Copper ions were implanted into austenitic stainless steel (SS) by metal vapor vacuum arc with a energy of 100 keV and an ions dose range of (0.5-8.0)×1017 cm-2. The Cu-implanted SS was annealed in an Ar atmosphere furnace. Glancing X-ray diffrac-tion (GXRD), transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) were used to reveal the phase compositions, microstructures, and concentration profiles of copper ions in the implanted layer. The results show that the antibacterial property...