锌及锌覆盖层户外大气暴露腐蚀行为的研究

户外大气暴露腐蚀造成了损失巨大,研究其腐蚀行为与规律意义重大.通过户外大气暴露腐蚀数据统计分析及腐蚀产物分析,确定了影响锌及锌覆盖层在我国典型地区大气暴露腐蚀行为的最主要的环境因子,在腐蚀动力学、腐蚀机理、腐蚀产物等方面系统研究了锌及锌覆盖层在我国典型地区的大气腐蚀规律.结果表明,相对湿度、SO2、Cl-是影响锌及锌覆盖层在北京、武汉、江津、广州典型地区大气腐蚀行为的主要环境因子.锌及锌覆盖层在上述典型地区大气腐蚀动力学以线性为特征,且腐蚀速率:江津＞广州＞武汉＞北京,与这些地区在试验时间SO2沉积率大小排列次序(江津＞广州＞武汉＞北京)相对应.锌及锌覆盖层在上述典型地区大气暴露主要腐蚀产物为:Zn4SO4(OH)6·5H2O,另含有少量Zn5Cl2(OH)8·H2O及Zn4Cl2(OH)4SO4·5H2O.     

青铜文物的光电子能谱分析

采用光电子能谱(XPS)法分析了成都金沙遗址出土铜条和方孔型器两种青铜表面锈层膜的元素及其化学状态.结果表明,两种青铜的锈层膜中都存在纯铜晶粒和PbCO3/PbO,但未发现导致"青铜病"的有害元素Cl,而在方孔型器锈层膜中发现有S2-/SO42-.铜条和方孔型器夹层锈层膜中的Sn完全以SnO2形式存在,从而使青铜合金免遭进一步腐蚀.此外,还讨论了青铜的腐蚀过程与环境的关系.     

黄铜矿细菌转化与浸出机理探讨

揭示了CuFeS2细菌氧化中的矿物转化过程,可能按如下顺序先后产生中间产物:CuFeS2→Cu9Fe9S1→6CuFeS1-x→CuS2→Cu9S5→Cu2S→CuS→Cu2O(Cu2OCl2,CuCl2,CuCl)→Cu3SO4(OH)4→CuSO4,其中Cu2O可能是黄铜矿细菌浸出过程中的关键步骤;在有或无Ag+催化的有菌和Fe(Ⅲ)的条件下,该转化过程不变;并对直接间接作用学说、Ag+催化细菌浸出机理及细菌作用模式提出了新的看法。     

冷喷涂Cu-Cu2O涂层在海水中的电化学行为

用冷喷涂技术制备Cu-Cu2O涂层,研究了其在不同海水环境下的极化行为,并建立了涂层的腐蚀过程数学模型。结果表明:在浸泡的初期Cu2O促进了涂层的局部腐蚀;随着浸泡时间的增加局部腐蚀产物进一步促进了表面氧化膜的形成;在非搅拌的静态环境下,涂层的腐蚀受CuCl2-扩散的控制;Cl-促进了涂层的腐蚀,阻碍氧化膜的形成,且Cl-对CuCl的络合是Cl-浓度的一级反应;在CuCl向Cu2O转变的过程中产生H+,使电极表面附近溶液的pH值降低,阻碍氧化膜的形成和降低耐久性,而在溶液中加入Na2B4O7-H3BO4缓冲体系,能有效地提高氧化膜的击破电位。根据本文提出的反应过程数学模型进行计算的结果,与实验结果具有很好的相符性。     

纯镁材微弧氧化膜在硫酸铜溶液中的电化学腐蚀行为

研究镁材微弧氧化膜在含Cu2+介质中的腐蚀行为对扩大其使用范围具有十分重要的意义。采用微弧氧化技术对纯镁材进行表面硅酸盐氧化处理,制备了陶瓷膜。采用扫描电镜、X射线衍射、交流阻抗谱等方法分析了微弧氧化膜在0.1 mol/L Cu SO4溶液中的腐蚀形貌、腐蚀产物组成及腐蚀行为;采用极化曲线分析了Cu2+对Cl-腐蚀的影响。结果表明:因为微弧氧化膜中的Mg O与溶液中的H+发生反应,促进了溶液中Cu2+的水解,生成更多Cu(OH)2,并吸附于膜层表面,从而阻止了腐蚀介质向膜基面的进一步扩渗,减弱了腐蚀介质对膜层的腐蚀作用;腐蚀介质Na Cl溶液中加入Cu SO4后,未加剧微弧氧化膜的破坏,反而产生了缓蚀效果。     

论企业无毒分析方法检测锡青铜化学成分

锡青铜中主要元素为Cu、Sn、Zn、Pb。2004年前，在我单位（沈阳北车西屋轨道制动机技术有限公司）化验室化学分析条件下，对锡青铜中的锡含量的测定中使用的是传统的有剧毒的分析方法。此方法是将试样用HCL—H2O2溶解。锡呈四价状态，在接触剂氯化汞存在下，隔绝空气，用次亚磷酸钠将其还原为二价，在盐酸介质中，以淀粉为指示剂，用碘酸钾标准溶液滴定。分析过程繁锁，分析时间长，在分析锡青铜时使用有毒试剂：氯化汞溶液5％，如不慎接触会对人体产生毒害。原来分别采用测试的方法，操作复杂繁琐。自2005年已采用锡青铜无剧毒分析方法，可溶样一次，联测出锡青铜中锡、锌、铅、铜的含量，还可避免毒害试剂的使用，以达到快速安全的检测手段。     

钙钛矿/钨青铜两相复合BSTN陶瓷的形成与性能研究

设计了特殊配方0.7BaO.0.3SrO·(1-y)TiO₂·yNb₂O₅, 通过过量组成控制,制备了钙钛矿相和钨青铜相共存的复相陶瓷.用XRD和阻抗仪测试了相结构及介电常数.结果表明,在形成以钙钛矿为主相的体系中,Nb₂O₅过量6mol％以上时开始形成钨青铜相;在形成以钨青铜为主相的体系中,BaO和SrO过量11mol％以上时开始形成钙钛矿相.两相含量相当的体系中,钙钛矿相几乎不固溶Nb₂O₅,而钨青铜相固溶一定量TiO₂.复相陶瓷的介电性能具有BST和SBN两相的特点.BSTN复相体系中钨青铜相的铁电/顺电转变温度随固溶TiO₂量增加而降低,随钙钛矿相增加而升高,其最低转变温度约在200℃,比纯SBN相下降90℃.     

Al2O3/CuSn6Pb6Zn3青铜复合材料的摩擦学性能研究

研究了粉末冶金法制备的Al2O3/CuSn6Pb6Zn3青铜复合材料的摩擦学性能.试验结果表明该复合材料的耐磨性较CuSn6Pb6Zn3青铜有较大的提高,并且Al2O3颗粒的粒径和体积含量均对复合材料的耐磨性有影响.     

阳极Sn含量对焦磷酸盐电镀低锡Cu-Sn合金层性能的影响

为改善焦磷酸盐电镀Cu-Sn合金层的耐蚀性能差、镀速慢、结合力差等问题,用失重试验、形貌成分分析及电化学技术等方法,研究了阳极中Sn含量对焦磷酸盐电镀Cu-Sn合金层的沉积速率、腐蚀速率、腐蚀过程和微观形貌等的影响。结果表明:当阳极中Sn含量(质量分数)为25%时,Cu-Sn合金镀层的沉积速率较大[6.32mg/(cm2·h)],镀层中Sn含量为5.80%,属于低锡青铜,镀层耐蚀性好,在5%H2SO4溶液中的失重腐蚀速率最小,为0.011 8 mg/(cm2·h),腐蚀电流密度较小(84.7μA/cm2),腐蚀电位最正(-0.405 V),腐蚀倾向最小;CuSn合金镀层的包状物颗粒大小均匀、排列紧密、无明显的表面缺陷,镀层与基体结合良好。     

Cum-Fen/Ti1-xSnxO2复合催化剂的脱硝性能及抗硫活性

采用共沉淀法制备Ti1-x Snx O2复合氧化物,浸渍负载质量分数10％的CuOx和FeOy活性组分,制备一系列Cum-Fen/Ti1-x Snx O2催化剂.探究不同Ti/Sn和Cu/Fe(物质的量比)对Cum-Fen/Ti1-x Snx O2催化剂的NH3-SCR反应活性的影响.研究结果表明,Ti0.67 Sn0.33 O2载体可促进活性组分CuOx和FeOy的相互作用.当Cu/Fe为3:1时,在300℃ 下NOx的转化率达到91.3％;向反应体系通入286 mg/m3 SO2反应3 h后,NOx的转化率仅下降2.6％.X射线光电子能谱(XPS)、程序升温还原(H2-TPR)、程序升温脱附(NH3-TPD和NOx-TPD)的表征表明,CuOx和FeOy之间存在相互作用,与单一的Cu/Ti0.67 Sn0.33 O2和Fe/Ti0.67 Sn0.33 O2对比,复合催化剂表面吸附氧浓度相对增加15％ ～33％,总酸量增大56％,从而提高了催化剂脱硝活性.     

Exponential fitting using integral equations

The fitting of a function y =\documentclass{article}\pagestyle{empty}\begin{document}$ \sum\nolimits_{i = 1}^n {A_i {\rm{e}}^{\lambda ix}} $\end{document} to experimental data is considered. Integral equations are developed which have the functions \documentclass{article}\pagestyle{empty}\begin{document}$ \sum\nolimits_{i = 1}^n {A_i {\rm{e}}^{\lambda ix}} $\end{document} as their solutions for n = 1, 2, 3, These integral equations are used to find the frequencies λ_i. Examples are worked out to illustrate the method. The method is shown to be capable of extension to other functions.     

Thermal Decomposition of Molecular Materials {\{{\rm N}(n{-}{\rm C}_{4}{\rm H}_{9})_{4}[{\rm M}^{\rm II} {\rm Fe}^{\rm III}({\rm C}_{2} {\rm O}_{4})_{3}]\}_{\infty},\,{\rm M}^{\rm II} = {\rm Zn},\, {\rm Co},\, {\rm Fe}}

Thermal decomposition of oxalate-based molecular precursors, namely ${\{{\rm N}(n{-} {\rm C}_{4} {\rm H}_{9})_{4}[{\rm Zn}^{\rm II}{\rm Fe}^{\rm III}({\rm C}_{2} {\rm O}_{4})_{3}]\}_{\infty}, \{{\rm N}(n{-}{\rm C}_{4}{\rm H}_{9})_{4}[{\rm Co}^{\rm II}{\rm Fe}^{\rm III}({\rm C}_{2}{\rm O}_{4})_{3}]\}_{\infty}}$ , and ${\{{\rm N}(n{-}{\rm C}_{4} {\rm H}_{9})_{4}[{\rm Fe}^{\rm II}{\rm Fe}^{\rm III}({\rm C}_{2}{\rm O}_{4})_{3}]\}_{\infty}}$ , abbreviated as BuZnFe, BuCoFe, and BuFeFe, respectively, are studied using thermogravimetry (TG) in the temperature range from ~300?K to ~675?K at multiple heating rates. This study also deals with how the thermal decomposition of the complexes proceed stepwise through a series of intermediate reactions. The effect of the divalent metal M^II on the nature of thermal decomposition of the complexes, reflected in their TG profiles in terms of number of steps involved, is reported in this study. The temperature range of thermal decomposition steps for BuZnFe, BuCoFe, and BuFeFe with the same heating rates are studied systematically. Two different isoconversional methods, namely an improved iterative method and a model-free method are employed to calculate the kinetic parameters, and thus the most probable reaction mechanism of thermal decomposition is determined. Based on kinetic parameters, the important thermodynamic parameters such as the changes of entropy, enthalpy, and Gibbs free energy are estimated for the activated complex formation from the precursors. Considering the mass loss during the different thermal decomposition steps of BuZnFe, BuCoFe, and BuFeFe, observed in the thermogravimetry profiles, the overall reactions of the thermal decompositions are demonstrated.     

Temperature dependences of density and ultrasound velocity of the eutectic Bi-44.6 wt.% Pb melt

Measurements of temperature dependences of density d and ultrasound velocity V _s of the eutectic Bi-44.6 wt.% Pb alloy were performed from eutectic temperature up to 550–900^°C. Density was studied using gamma absorption method. Ultrasound velocity was determined by pulse phase method. The dependences V _s(T) and d(T) are linear in temperature interval of measurements and can be approximated by the equations: $$\displaylines{ V_{\rm s} (T) = 1788 - 0.269\;(T - 398)\ {\rm m} \cdot {\rm s}^{ - 1}.\cr d(T) = 10271 - 1.29\;(T - 398)\ {\rm kg} \cdot {\rm m}^{- 3} .\cr} $$ These results are found to be in good agreement with data of other works.     

Lebensdauer- und Dauerfestigkeitsabschätzung von zugdruckwechsel- und zugschwellbeanspruchtem Stahl mittels Temperaturmessung

Estimation of the Endurance and the Fatigue Limit of Steel by Measuring Specimens′ Temperatures. Microplastic deformation processes are pre-requisites for fatigue crack formation within metallic materials. If the testing frequency of a specimen, cyclically stressed by a progressively-increasing load test, is not too low it is no great metrological problem to ascertain that special stress amplitude, σ_f,th (f ? fatigue limit, th ? thermometrical), at which specimen's temperature begins to rise due to the start of ‘remarkable’ microplastic deformations. Investigations of this kind, recently carried out by rotating bending showed a very good correspondence between σ_f,th and a statistically ascertained estimate of the fatigue limit, \documentclass{article}\pagestyle{empty}\begin{document}$ \hat \sigma _{({\rm P} \simeq {\rm 0}\%{\rm)}} $\end{document} (P ? Probability of fracture), derived from comparatively performed Wöhler-tests. The purpose of this paper is to investigate the relationship between σ_f,th and \documentclass{article}\pagestyle{empty}\begin{document}$ \hat \sigma _{({\rm P} \simeq {\rm 0}\%{\rm)}} $\end{document} for some carbon steels when cyclically stressed by push-pull and pulsating tensile loading, respectively. Both, unnotched and notched specimes were tested. Moreover, thermometrically monitored Wöhler-tests revealed that temperature measurements can provide a short-cut prediction of specimens′ lives. Above all it has to be mentioned that a reliable clue is gettable at a very early experimental stadium whether the cyclic stressed specimen will later become a ‘break’ or – normally much later – a ‘run-out’.     

Numerical integration of structural dynamics equations including natural damping and periodic forcing terms

This paper shows that it is comparatively simple to analyse algorithms for the numerical integration of the Space discretized equations from structural dynamics when applied to \documentclass{article}\pagestyle{empty}\begin{document}$\ddot x + \mu \dot x\omega ^2 x = p{\rm e}^{ist} $\end{document}, instead of the usual \documentclass{article}\pagestyle{empty}\begin{document}$ \ddot x + \omega ^2 x = 0 $\end{document}, and suggests that this should be done in order to gain some insight into the effect with natural damping and/or a periodic forcing term. The method is illustrated on some three- and four-time-level schemes.     

Interface structure and strain development during compression tests of Al2O3/Nb/Al2O3 sandwiches

The interface structure of an Al₂O₃/Nb/Al₂O₃ sandwich produced by solid-state diffusion bonding was investigated in detail by various transmission electron microscopy (TEM) methods. The joint possessed at one interface a , , and on the other interface a and orientation relationship. At both interfaces, misfit dislocations formed to compensate the lattice mismatch as found by high-resolution transmission electron microscopy (HRTEM). Electron energy-loss near edge structure (ELNES) studies revealed that the interface is terminating with an Al layer resulting in Al–Nb bonds. Identical sandwiches were investigated on the meso- and macroscopic scale by performing compression tests and simultaneously monitoring the strain development at (001)_Nb and crystal faces. The full-field optical strain measurements (FFOM) revealed that the strain is localized at the interfaces when observed at the (001)_Nb face while it is along the maximum shear directions of 36–54° inclined to the interface when observed at the face. The strain localization along a specific maximum shear direction results in the cleavage of Al₂O₃, always initiating from the interface possessing the and orientation relationship.     

Oxidation Behavior of C/SiC Composite with CVD SiC-B4C Coating in a Wet Oxygen Environment

A two-layered self healing coating with a B₄C internal layer and a SiC external layer is prepared on C/SiC composite by chemical vapor deposition (CVD). Microstructure and component of the coating was analyzed by SEM, EDS, and XRD. Oxidation behavior of SiC-B₄C coated C/SiC composite was compared with SiC-SiC coated C/SiC in an environment of at 700°C, 1,000°C and 1,200°C for 100 h, respectively. It is demonstrated that the SiC-B₄C coating is more efficient to protect the composite from oxidation than SiC-SiC coating below 1,000°C due to the self healing behavior. After oxidized at 700°C for 100 h, the residual flexural strength of SiC-B₄C coated C/SiC is about 86%, and that of SiC-SiC coated is about 64%. While after oxidized at 1,200°C, the former is about 86% and the later is about 89%. This is due to the enhanced evaporation of B₂O₃ at higher temperature.     

Manufacturing of cellular β-SiAlON/β-SiC composite ceramics from cardboard

Light-weight, cellular β-SiAlON/SiC ceramics were produced via dip-coating of an Al/Si-powder containing preceramic polymer slurry into corrugated cardboard. The coated cardboard preforms were pyrolyzed in Ar-atmosphere at 1200°C, where the cellulose fibres decomposed into carbon. Simultaneously the Al/Si melt infiltrated into the porous carbon and formed β-SiC. Subsequent nitridation at temperatures between 1200–1530°C resulted in the formation of a β-SiC-containing composite. Different pre-oxidation treatment resulted in a variation of the oxygen content in the solid solution phase (z = 0.6–1.2).     

The thermal behaviour of copper diphosphates made by wet process

Copper diphosphates (Cu₂P₂O₇ · 5H₂O, Cu_1.6K_0.8P₂O₇ · 1.7H₂O, and Cu_1.5K_1.0P₂O₇ · 2.8H₂O) were made by mixing aqueous solutions of tetrapotassium diphosphate and copper dichloride. When the diphosphates were heated, the decomposition of the diphosphates to orthophosphate was observed at a temperature lower than 150° C. The orthophosphate was polymerized by condensation to polyphosphates in the temperature range of about 150 to 450° C. The polyphosphates reorganized to diphosphate at 450 to 550° C according to the following reaction:

The Influence of Oxygen/Argon Ratio on the Structure and Surface Morphology of GaBa2Cu3O7?δ Films Deposited by RF Magnetic Sputtering

$\mathrm{GaBa}_{2}\mathrm{Cu}_{3}\mathrm{O}_{7\mbox{-}\delta}$ thin films have been grown on CeO₂ cap layer by RF magnetic sputtering with different oxygen/argon partial pressure ratio from 2:1 to 1:5. The CeO₂ cap layers were fabricated by pulse laser deposition (PLD) on YSZ/CeO₂/Ni-5%W alloy substrate and had good properties in structure and surface morphology. We study the relationship between oxygen/argon ratio and the performance of the $\mathrm{GaBa}_{2}\mathrm{Cu}_{3}\mathrm{O}_{7\mbox{-}\delta}$ film in order to find out the optimized deposition condition. The structure and surface morphology of the $\mathrm{GaBa}_{2}\mathrm{Cu}_{3}\mathrm{O}_{7\mbox{-}\delta}$ thin films were measured by X-ray diffraction (XRD), Field emission scanning electron microscope (FE-SEM), Atomic force microscopy (AFM). It was found that the texture and surface performance of $\mathrm{GaBa}_{2}\mathrm{Cu}_{3}\mathrm{O}_{7\mbox{-}\delta}$ film, such as growth orientation, grain roughness, grain size and surface morphology, are deeply affected by the oxygen/argon ratio. And the film??s performance was the best when the oxygen/argon partial pressure ratio is 1:1.