Al—Mn合金镀层的组成结构及其耐蚀性

研究了在低温熔盐中（低于２００℃）电沉积Ａｌ－Ｍｎ合金镀层成分的控制，镀层化学组成与结构之间的关系以脑镀层的耐蚀性能，提出影响镀层锰含量的主要因素是熔盐中锰离子的浓度，镀层含锰量在２５－４０（ｗｔ）％之间可形成非晶态结构，实验表明，Ａｌ－Ｍｎ合金镀层在０．５ｍｏｌ／ＬＨ２ＳＯ４溶液及ＮａＣｌ溶液中具有耐蚀性，非晶态结构的Ａｌ－Ｍｎ合金镀层的耐蚀性更为优异。     

电沉积Ni—Mo—P合金镀层在NaCl溶液中的腐蚀特性

用失重法，阳极率曲线，Ｘ－光电子能谱（ＸＰＳ）以及俄歇电子能谱（ＡＥＳ）研究了电沉积Ｎｉ－Ｍｏ－Ｐ合金镀层在５％ＮａＣｌ溶液中的腐蚀特性，非晶态Ｎｉ－Ｍｏ－Ｐ合金镀层比晶态Ｎｉ－Ｍｏ－Ｐ合金镀层有较低的腐蚀速度阳极极化曲线表明，Ｎｉ－Ｍｏ－Ｐ合金镀层中，镍的摩尔分数国０．７１９～０．８６８时，随镀层中磷含量的增加，腐蚀电位正移，而活化区的峰电流随镀层中钼含量的增加而增加，磷含量的活化区的峰电流以及     

机械合金化Mg/MmNi5-x(CoAlMn)x复合储氢合金的组织结构与吸氢特性

运用Ｘ射线衍射、扫描电及粒度分析等方法表征了机械合金化制备Ｍｇ／ＭｎＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ复合储氢合金的结构,通过ＰＣＴ曲线研究了基储氢性能。结果表明,在适当的球磨条件下能够获得纳米晶结构的Ｍｇ／ＭｎＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ复合储氢合金,ＭｍＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ合金相彘,复合储氢合金的活化性能及储氢量有明显提高。此外,还考察了Ｍｇ含量对复合储氢合金的组织结构及储氢性能的影响。     

Mn（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物的合成及结构

合成了４种锰（Ⅲ）－苯甲酰丙酮缩乙二胺－有机碱配合物：Ｍｎ（ｂｚａｃｅｎ）ＬＣｌＯ＿４．（Ｌ为哌嗪，吡啶，γ－甲基吡啶和乙腈），测定了配合物［Ｍｎ（ｂｚａｃｅｎ）（ＣＨ＿（３）ＣＮ）ＣｌＯ＿４］的结构．晶体属正交晶系．空间群Ｐ＿ｎｍａ．晶胞参数：ａ＝０．９０７７（１）ｎｍ，ｂ＝１．５５６３（１）ｎｍ，ｃ＝１．７２０５（２）ｎｍ，Ｖ＝２．４３０５ｎｍ￣３，Ｚ＝４，Ｄ＿ｃ＝１．４８ｇ／ｃｍ￣３，Ｄ＿ｍ＝１．４９ｇ／ｃｍ￣３．配合物呈拉长八面体结构．对配合物的电子光谱和红外光谱进行了归属．     

Nd（naph）_3－Al（i－Bu）_3催化马来酸酐和环氧丙烷交替共聚合

研究了马来酸酐和环氧丙烷的交替共聚，发现Ｎｄ（ｎａｐｈ）＿３－Ａｌ（ｉ－Ｂｕ）＿３是马来酸酐（ＭＡｎ）和环氧丙烷（ＰＯ）交替共聚的良好催化剂．用红外光谱、核磁共振研究了共聚物的结构．共聚反应动力学研究表明共聚反应与单体和催化剂浓度均呈一级关系．表观活化能为１１３ｋＪ／ｍｏｌ．     

MmNi_（3．55）Co_（0．75）Mn_（0．4）Al_（0．3）合金吸

在２２～６０℃范围内研究了贮氢合金ＭｍＮｉ＿（３．５５）Ｃｏ（０．７５）Ｍｎ＿（０．４）Ａｌ＿（０．３）（Ｍｍ为富铈混合稀土金属）在ａ和。ａ＋β相区恒温吸氢动力学过程。研究结果表明，合金在ａ相区吸氢受化学反应控速，动力学规律不受氢初压的影响。在整个ａ＋β相区吸氢过程中，受氢在合金氢化物中的扩散控速。得到相应的速率方程和表观活化能。     

载铂铝交联蒙脱土的烷烃芳构化特性──Ⅰ．载铂铝交联蒙脱土对烷烃的择形芳构化作用

对比考察了Ｐｔ／ＫＬ沸石，Ｐｔ／Ａｌ２Ｏ３和载铂铝交联蒙脱土（Ｐｔ／Ａｌ－ＣＬＭ）催化剂对不同碳原子数烷烃的芳构化特性．脉冲微反的评价结果表明：Ｐｔ／Ａｌ－ＣＬＭ比Ｐｔ／Ａｌ２Ｏ３和Ｐｔ／ＫＬ具有较高的转化ｎ－Ｃ８，ｎ－Ｃ９为其对应芳烃的选择性，在转化ｎ－Ｃ８时，产物中的间、对位二甲苯收率很高，而转化ｎ－Ｃ９时有高的正丙苯收率．采用１２９Ｘｅ－ＮＭＲ、ＸＲＤ和孔分布测定考察了Ｐｔ／Ａｌ－ＣＬＭ和Ｐｔ／ＫＬ、Ｐｔ／Ａｌ２Ｏ３之间孔结构的差异．结果表明：由于ｎ－Ｃ８，ｎ－Ｃ９在反应过程中其过渡态的极限尺寸与Ｐｔ／Ａｌ－ＣＬＭ０．９ｎｍ左右的层间域相匹配，因而它对ｎ－Ｃ８，ｎ－Ｃ９具有择形芳构化作用．     

细胞色素P-450模拟酶的快速混合停流时间分辨吸收谱研究 Ⅱ.Mn~Ⅲ(Por.)Cl-PhIO体系

采用快速混合停流技术,考察了在实际反应条件下,不同锰卟啉配合物ＭｎⅢ（Ｐｏｒ．）Ｃｌ（Ｐｏｒ．＝ＴＰＰ、ＴＭＯＰＰ和ＴＦＰＰ）与单氧给体ＰｈＩＯ构建的细胞色素Ｐ－４５０模拟酶体系催化活性物种的生成及催化烯烃环氧化过程．在氧给体ＰｈＩＯ作用下,ＭｎⅢ（Ｐｏｒ．）Ｃｌ均生成了高价锰氧卟啉配合物和双核μ－氧锰卟啉配合物;但ＭｎⅢ（ＴＰＰ）Ｃｌ和ＭｎⅢ（ＴＭＯＰＰ）Ｃｌ存在严重的氧化分解,而ＭｎⅢ（ＴＦＰＰ）Ｃｌ不易氧化分解,且它的催化环氧化活性最高．     

二氯二苯基锡与单核苷酸配位作用的研究

研究了二氯二苯基锡（Ｐｈ＿２ＳｎＣｌ＿２）与核酸的基本组成单元──单核苷酸在水相中的配位作用，并用热分析、傅利叶变换红外光谱和￣１Ｈ、￣（３１）Ｐ超导核磁共振谱对新配合物Ｐｈ＿２Ｓｎ（５＇－ＡＭＰ）·Ｈ＿２Ｏ、Ｐｈ＿２Ｓｎ（５＇－ＣＭＰ）·Ｈ＿２Ｏ和Ｐｈ＿２Ｓｎ（５＇－ＧＭＰ）进行了详细的表征。结果表明，在配合物中锡仅与单核苷酸的磷酸根结合，给出了配合物的可能结构。     

Mn－Ag／γ－Al_2O_3催化剂中氧的性能

本文运用ＴＰＲ、ＴＰＤ－ＭＳ、ＸＲＤ等技术研究了Ｍｎ－Ａｇ／γ－Ａｌ_２Ｏ_３催化剂的还原性能和再氧化能力．结果表明，Ｍｎ－Ａｇ／γ－Ａｌ_２Ｏ_３中银物相由Ａｇ￣０和Ａｇ_２Ｏ组成，锰物相由β－ＭｎＯ_２和Ｍｎ２Ｏ_３组成．Ｍｎ／γ－Ａｌ_２Ｏ_３催化剂的ＴＰＲ有二个还原峰，分别是ＭｎＯ_２和Ｍｎ_２Ｏ_３的还原．Ａｇ促使ＭｎＯ_２和Ｍｎ_２Ｏ_３的还原明显向低温方向移动，而且ＭｎＯ_２和Ｍｎ_２Ｏ_３的还原峰融合成一个还原峰．Ｍｎ－Ａｇ／γ－Ａｌ_２Ｏ_３的ＴＰＤ有三个脱氧峰，随着Ａｇ含量增加，峰Ⅰ向高温方向移动，Ｍｎ￣（４＋）２ｐ３／２的电子结合能增加，并且催化剂的再氧化能力增强．催化剂ＣＯ的氧化活性与催化剂的再氧化能力有很好的对应关系．     

穆斯堡尔谱研究电镀镍铁合金层

用穆斯堡尔谱研究了电镀镍铁合金层的形成过程,镀液中Al~(3 ),Mn~(2 ),Cr~(3 ),Zn~(2 )及Cu~(2 )等离子的存在对镀层组成、织构等的影响以及不同铬处理后镍铁镀层的织构和耐蚀性;分析了铬、锰等元素在其中所起的作用;并初步探讨了形成层状结构的原因.     

稀土对电沉积Ni-P合金镀层耐蚀性的影响

研究了稀土对电沉积Ｎｉ－Ｐ合金度层耐蚀性及组织的影响,通过浸泡实验和极化曲线的测定。得出在镀液中添加一定量的稀土元素能显著改善镀层的耐蚀性能。ＸＲＤ,ＴＥＭ,ＥＤＳ结果表明,稀土元素具有促进Ｎｉ－Ｐ合金形成非晶组织的作用,由于稀土的加入,在远低于８％的Ｐ含量下,获得了以非晶态为主的组织。     

The conditions of formation and stability of quasi-crystalline phases in aluminum-manganese alloys

The conditions of formation, stability, and thermodynamic properties of the icosahedral and decagonal quasi-crystalline phases in the Al-Mn system were studied experimentally. The thermodynamic properties of equilibrium crystalline Al-Mn compositions over the composition and temperature ranges 0–26 at % Mn and 628–1193 K, respectively, and of melts over wide temperature and composition ranges (1043–1670 K and 0–50.1 at % Mn) were determined. Measurements were made by the integral variant of the effusion method under the conditions of an ultrahigh oilless vacuum and Knudsen mass spectrometry. An original technique based on the initiation and study of equilibria in reactions of the alloys with special admixtures of sodium or magnesium fluorides with the formation of volatile products was used to extend the interval of measurements to low temperatures. Complete, reliable, and consistent data on the thermodynamic properties of icosahedral and decagonal quasi-crystalline and crystalline phases based on aluminum and Al-Mn melts were obtained for the first time. Al-Mn melts were shown to contain associates of three types, AlMn, Al₂Mn, and Al₅Mn. The contributions of covalent interactions to the Gibbs energy and enthalpy of mixing was found to be by far predominant. The thermodynamic properties of alloys of the same chemical composition in the quasi-crystalline and equilibrium crystalline states were compared. The decagonal phase was found to be more stable than icosahedral quasi-crystals. The difference of the Gibbs energies of quasi-crystals of the two types and crystalline compositions increased as the temperature lowered. Arguments in favor of the entropy nature of the stabilization of quasi-crystals were obtained. These phases, like metallic glasses, are only an intermediate state between liquids and crystals and cannot be ground stable alloy states. The conditions of obtaining quasi-crystalline phases from melts were found to be controlled by the appearance of a substantial fraction of icosahedral short-range order in liquids in the region of compositions where associates of a certain kind (Al₅Mn) were formed in substantial amounts, x(Al₅Mn) ≥ 0.11.     

Pulse plating effect on microstructure and corrosion properties of Zn–Ni alloy coatings

The influence of pulse plating parameters on the surface morphology, grain size, lattice imperfection and corrosion properties of Zn–Ni alloy has been studied. The coatings were electrodeposited in an alkaline cyanide-free solution. AFM was applied for surface morphology examination, XRD measurements were carried out for phase composition and texture analysis, electron probe microanalysis was used for alloy chemical composition studies, while electrochemical techniques were applied for corrosion performance evaluation. The pulse plated Zn–Ni coatings appeared to consist of the γ-Zn₂₁Ni₅ phase and the composition of the alloy depended on the plating parameters. The grain size, lattice imperfection and homogeneity of grain distribution were established to be the main factors determining corrosion behaviour of the coating. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005     

化学镀镍磷镀层及其耐蚀性研究

针对工业实际对提高防护层防腐、耐磨性能的要求,对化学镀镍磷镀层的方法,镀敷液配方等进行了分析,对其腐蚀率进行了测定,并对镀层性能进行了表征;讨论了影响腐蚀率的若干重要因素;对有关工艺进行了优化,从而在多种基质上获得了抗腐蚀性较好的镍磷镀层,初步研究证明,其性能优于电镀方法所获得的镀层.     

Electrodeposition of Zinc–Nickel Alloys from Ammonium Oxalate Electrolytes

The electrodeposition of zinc–nickel alloys (5–16 at % Ni) from the ammonium oxalate electrolytes is studied. It is shown that the ratio between the alloy components has an effect on the corrosion resistance of the coatings, their structure, chemical and phase composition, and microhardness.     

稀土盐对铝合金阳极化过程的影响

在阳极化溶液中添加稀土盐得到的铝合金氧化膜在腐蚀试验中表现出优良的耐蚀性能,现场椭圆法对阳极氧化过程的研究结果表明,稀土盐的加入,对椭圆编振参数的振荡方式没有显著影响,但却使振荡的周期和振幅发生了一些变化,由此可以推知,稀土盐的加入并未改变氧化膜的组成,但却在一定程度上影响了成膜过程,使膜的结构发生了变化。对椭圆数据进行定量分析的结果进一步表明：加入稀土盐后,氧化膜多孔层生长速率加快,阻挡层厚度增加,多孔部分变得更加致密,这种结构上的变化是阳极化膜耐蚀性能得以提高的主要原因,EDAX和TEM分析结果也证实了椭圆法研究的结果。     

Electrochemical deposition and corrosion stability of Zn–Co alloys

Electrochemically deposited Zn–Co alloys under various deposition conditions were investigated using anodic linear sweep voltammetry for phase structure determination, scanning electron microscopy for surface morphology analysis, atomic absorption spectroscopy for determination of chemical composition, and polarization measurements and open circuit potential measurements for determination of corrosion properties. The influence of deposition current density, temperature, and composition of deposition solution on the phase structure and corrosion properties of Zn–Co alloys was studied. It was shown that the ratio of cobalt to zinc ions in the plating bath strongly affects the chemical content and phase structure, as well as corrosion stability, of Zn–Co alloys. Zn–Co alloys deposited from plating baths with the lowest and the highest ratios of cobalt and zinc ions exhibited the lowest corrosion rate.     

化学沉积Ni-Mo-P合金及其性能

以柠檬酸钠为络合剂、硼酸为缓冲剂在碱性介质中化学沉积Ni-Mo-P合金,用浸泡实验和阳极极化实验系统研究了不同工艺条件下所得镀层在3.5%(bymass)NaCl介质的耐腐蚀性能.考察工艺参数(pH和多钼酸根离子浓度)对沉积速率、镀层组成、结构和显微硬度的影响.实验发现,沉积工艺对镀层硬度有影响,但对镀层结构几乎无影响.镀层中钼含量越高,其硬度也越大.但多钼酸根离子在沉积过程中起阻碍作用,致使镀层中钼含量不高(不超过20%,byatom).Ni-Mo-P合金镀层具有较好的耐腐蚀性;由不同工艺条件所得的镀层其耐腐蚀能力不同,但各镀层在NaCl溶液中的阳极极化行为相似.浸泡实验与阳极极化实验结果基本吻合.     

Process aspects of electroless deposition for nickel–zinc–phosphorous alloys

Electroless deposition of Ni–Zn–P thin film was considered as a barrier film on a galvanic Zn or Ni–Zn sacrificial layer in a multicomponent corrosion protective coating on steel. The incorporation of zinc on the chemical composition of electroless Ni–Zn–P coating was studied. The effect of operating conditions such as temperature, pH value and concentration of zinc sulphate was investigated. Some physical characteristics such as morphology, structure, corrosion properties of Ni–Zn–P coatings were assessed in parallel with those of Ni–P. Inclusion of Zn to Ni–P is accompanied by the transformation of the coating structure from amorphous to crystalline. The effect of adding nonionic surfactant to the plating solution on the composition and surface morphologies was also investigated. The results indicate that nonionic surfactant has no effect on the Zn % in the deposit layer, but it affects the surface morphology and improves the corrosion resistance of Ni–Zn–P layers. Copyright © 2005 John Wiley & Sons, Ltd.