从三价铬镀液中电沉积可替代硬铬镀层的铬合金镀层

为了解决目前三价铬镀铬技术的一些致命缺陷，使三价铬镀铬能够最终全面取代六价铬镀铬，近几年来作者进行了大量探索性试验，逐步确定了用电镀非晶态铬合金镀层代替纯铬镀层的技术路线，并开发成功了从三价铬镀铬中电镀非晶态Ｃｒ－Ｆｅ－Ｃ合金镀层的工艺，该镀层在耐磨蚀性等主要性能上保持了传统六价铬镀层的水平，彻底消除了六价铬电镀所造成的严重环境污染问题，并在工艺性能，生产成本等方面与现有的三价铬镀铬技术相比具备一     

化学镀非晶态Ni—P层的初期沉积过程研究

化学镀非晶态Ｎｉ－Ｐ镀层初期沉积过程和沉积层状态是影响结合强度的决定性因素．对不同基体材料初期沉积的观察发现，有些非晶态镀层的初期沉积中含有微晶．微晶的产生与否与基体材料以及镀层材料晶格的错配度有关，当镀层与基体材料点阵常数相差不大，镀层的初期沉积沿基体晶格外延生长出现微晶层，反之，点阵常数相差较大时，初期沉积物中未发现微晶．     

非晶态镍磷—镍钨磷双层组合镀层的耐蚀性能研究

本文对比研究了镍磷镀层、镍钨磷镀层及非晶态镍磷和镍钨磷双层组合镀层的耐蚀性能，分别进行了各种镀层的浸渍腐蚀实验，镀层的Ｘ射线衍射图象、镀层的扫描电镜图象、以及在工厂实际的腐蚀环境里进行的腐蚀实验。实验结果表明镍磷及镍钨磷双层组合镀层的耐 性优于镍磷镀层、镍钨磷镀层的耐蚀性。     

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。     

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及镀层的耐蚀性能．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／ＬＨ＿２ＳＯ＿４熔液及ＮａＣｌ溶液中具有优良的耐蚀性,非晶态结构的Ａｌ－Ｍｎ合金镀层的耐蚀性更为优异．     

镍磷化学镀层的耐蚀性及其与磷含量的关系

用极化曲线法和交流阻抗法研究了磷含量为16.2%至23.4% (x)的不同镍磷(Ni-P)化学镀层在5%(w) NaCl溶液中的耐蚀性, 发现磷含量为21%～22% (x)时镀层的极化阻抗(Rp)出现极大值. 差示扫描量热测定也发现Ni-P合金的峰值晶化温度(Tp)在此P含量范围内存在极大值. XRD实验表明镀层呈非晶态结构. 利用描述非晶态的菱面体单元结构模型(RUSM)解释耐蚀性能和峰值晶化温度的极大值现象, 耐蚀性随P含量的变化与镀层中金属元素(Ni)和类金属元素(P)之间形成的键数有关. 通过比较镀层密度的测量值和基于RUSM的计算值, 证明了采用RUSM的合理性.     

电沉积非晶态镍磷合金的研究

本文用电化学方法, X射线衍射及电子能谱方法研究了阴极恒电位沉积非晶态镍磷合金镀层,实验结果表明,影响镍磷合金非晶结构的主要因素是镀层中的磷含量,当磷含量大于9%时,镀层具有良好的非晶结构,镀层中镍和磷主要以元素态形式存在,磷的析出具有诱导共析特点。     

代铬镀层的研究进展

六价铬会严重破坏环境并危害人类的健康,所以开发无六价铬的代铬镀层电镀工艺具有重要的现实意义。本文主要介绍了几种代铬镀层的研究进展,包括合金代装饰铬镀层、电镀及化学镀合金代硬铬镀层以及复合镀代铬镀层等,重点论述了其特点、典型电镀工艺及其应用,并结合其研究现状对代铬镀层的发展进行了展望。     

化学镀非晶态镍磷和镍钨磷双层组合镀层工艺研究

本文着重研究非晶态Ｎｉ－Ｐ和Ｎｉ－Ｗ－Ｐ双层组合镀层的化学镀工艺条件：如镀液组分及ＰＨ值等对镀层在分，镀层沉积速率的影响。实验结果表明；在苹果酸体系中化学镀镍磷镀层比较合适的艺条件为；硫酸镍０．１ｍｏｌ／Ｌ，次磷酸钠０．２５ｍｏｌ／Ｌ、苹果酸０．２０ｍｏｌ／Ｌ，琥珀酸０．１５ｍｏｌ／ｌ，ｐＨ＝４．５－５．０温度为９０℃。     

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.     

Electrochemical and microgravimetric characterization of magnetron-sputtered Fe–Cr–Ni–Ta and Fe–Cr–Ni alloy films in neutral and strongly acidic media

The Fe–Cr–Ni and Fe–Cr–Ni–Ta alloy films were deposited on quartz substrates by magnetron-sputtering using targets of AISI 316 stainless steel and in combination with pure tantalum. The conventional melting of the Fe–Cr–Ni–Ta alloy formed is virtually impossible because the melting point of tantalum is higher than the boiling points of the other components. Elemental content of the films was determined by XPS analysis. Corrosion behaviour of both alloy films was studied in 5% NaCl and 10 M HCl by electrochemical quartz crystal microgravimetry (EQCM), electrochemical impedance spectroscopy (EIS) and dc-voltammetry. The corrosion resistance of Fe–Cr–Ni–Ta appeared to be significantly higher than that of Fe–Cr–Ni in both neutral (5% NaCl) and strongly acidic (10 M HCl) media. The Fe–Cr–Ni–Ta specimen exhibited an extremely high corrosion resistance in 10 M HCl, where the corrosion rates were about one order of magnitude lower than those of Fe–Cr–Ni in neutral solution. EQCM measurements in NaCl solution indicated accumulation of corrosion products on the Fe–Cr–Ni–Ta surface, which was evident from a distinctive increase in electrode mass. By contrast, the mass of the tantalum-free alloy film decreased with a constant rate, which indicated alloy dissolution to prevail. The corrosion current calculated from the mass decrease was in good agreement with that derived from voltammetric measurements. The EQCM data showed that the corrosion resistance of the Fe–Cr–Ni–Ta alloy film in 10 M HCl was about two orders of magnitude higher than that of the Fe–Cr–Ni.     

Surface Modification by Compositionally Modulated Multilayered Zn‐Fe Alloy Coatings

Compositionally modulated multilayered alloy (CMMA) coatings of Zn-Fe were developed from acid chloride baths by single bath technique. The production and properties of CMMA Zn-Fe coatings were tailored as a function of switching cathode current densities (SCCD’s) and thickness of individual layers. Corrosion rates (CR) were measured by electrochemical methods. Corrosion resistances were found to vary with SCCD’s and the number of sub layers in the deposit. SCCD’s were optimized for production of Zn-Fe CMMA electroplates showing peak performance against corrosion. The formation of discrete Zn-Fe alloy layers having different compositions in the deposits were demonstrated by scanning electron microscopy (SEM). Improvements in the corrosion resistance of multilayered alloys are due to the inherent barrier properties of CMMA coatings as evidenced by electrochemical impedance spectroscopy (EIS). Corrosion resistance afforded by Zn-Fe CMMA coatings are explained in terms of the n-type semiconductor films at the interface, supported by Mott-Schottky’s plot. It was observed that the alloy with high w(Fe) on the top showed better corrosion resistance compared to that with the less w(Fe) on top. At optimum SCCD’s of 3.0—5.5 A•dm－2, a Zn-Fe CMMA coatings with 600 sub layers showed ca. 45 times better corrosion resistance than conventional Zn-Fe alloy of the same thickness. The deposit showed no red rust even up to 1130 h in salt spray test.     

电沉积Fe-W-ZrO2纳米复合镀层的结构与腐蚀行为

采用复合电沉积工艺制备了Fe-W-ZrO₂纳米复合镀层. 分别用扫描电子显微镜(SEM)、扫描电子显微镜附带能谱仪(EDS)、X射线衍射(XRD)、恒电位仪等技术较系统地研究了Fe-W-ZrO₂纳米复合镀层的表面形貌、成分、结构、硬度和耐蚀性. 结果表明, 复合镀层的质量组成为Fe 38.3%(w)、W52.7%(w)、ZrO₂ 9.0%(w) 时, 在ZrO₂纳米粒子的弥散强化作用下, Fe-W非晶合金镀层的裂纹状况得到明显改善, 而且复合镀层成分分布均匀, 组织致密, 结构呈现明显的非晶态特征；复合镀层比Fe-W合金有更高的显微硬度；30 ℃下, Fe-W-ZrO₂纳米复合镀层在3.5%(w)NaCl和0.5 mol·L^-1 H₂SO₄溶液中的耐蚀性较Fe-W非晶合金镀层明显提高.     

Mechanical and corrosion behavior of amorphous and crystalline electroless Ni–W–P coatings

Two types of electroless Ni–W–P coatings: nanocrystalline with low P and amorphous with higher P content are investigated. Scanning probe microscopy is applied to study their morphology. Textured nanocrystalline coatings consist of coarse pyramids built of nanometer thick lamellas. The surface morphology of amorphous coatings is much finer and uniform. Nanohardness of all coatings depends on W content. Microhardness is increasing during the heat treatment up to 350 °C due to nickel phosphide precipitation affected by tungsten also. The wear resistance of nanocrystalline Ni–W–P coatings is much higher than that of amorphous in spite of the similar tungsten content in both. Lower corrosion resistance of amorphous Ni–W–P coatings is found by weight loss method during long-term immersion in 5 % NaCl. Electrochemical tests by potentiodynamic polarization curves in two model corrosion media—solutions of 0.5 M H₂SO₄ and 5 % NaCl—are performed. The corrosion of bi-layered Ni–W–P/Ni–P and Ni–W–P/Ni–Cu–P deposits on mild steel is also investigated. The results prove that an electroless Ni–W–P coating on mild steel extremely improves its mechanical and corrosion behavior. It is demonstrated that in addition to deposit’s structure and composition, the distribution and chemical state of alloy ingredients are also responsible for its properties.     

Electrolessly Plated Ni-Zn（Fe）-P Alloy and Its Corrosion Resistance Properties

The autocatalytic deposition of Ni-Zn(Fe)-P alloys has been carried out on substrate of carbon steel from a bath containing nickel sulfate, zinc sulfate, sodium hypophosphite, sodium citrate and boric acid. The effects of pH and the molar ratio of NiSO4/ZnSO4 on the deposition rate and the composition of deposits have been studied. It was found that the presence of zinc sulfate in the bath has an inhibitory effect on the alloy deposition. The structure and the surface morphology of Ni-Zn(Fe)-P coatings were characterized with XRD and SEM, respectively. The alloys plated under the experimental conditions consisted of an amorphous phase coexisting with a crystalline cubic Ni phase (poly-crystalline). The surface morphology of the coating is dependent on the deposition parameters. The corrosion resistance of the Ni-Zn(Fe)-P deposits was examined via mass loss tests and anodic polarization measurements, respectively. The results show that the surface morphologies of the deposits and the corrosion resistance of the deposits have been improved. The results of mass loss tests almost accord with those of anodic polarization measurements. The corrosion mechanisms of Ni-Zn(Fe)-P alloys in NaCl and NaOH solutions were investigated by means of EDX. The deposit immersed in an NaCI or an NaOH solution contains more content of oxygen and less contents of the metals(except Fe) than that placed in air, which shows that the NaCl or NaOH solution can accelerate the oxidation of the deposit.     

Electrochemical Behavior of Dental Ni‐Cr Wirolloy Coated with Eco‐friendly Films in Artificial Saliva

The electrochemical corrosion behavior of the non‐precious Ni‐Cr Wirolloy, being used in dentistry, was investigated before and after applying of two types of eco‐friendly coatings, polyvinyl silsesquioxane (PVS) and nano‐hydroxyapatite (nHAP) separately in artificial saliva solution at 37 °C for 14 d of immersion. The study aimed to investigate the effectiveness of the introduced coating films in enhancing the corrosion resistance of the alloy, and in decreasing the leaching of the toxic Ni ions from the alloy into the environment. The electrochemical corrosion investigation methods used are; open circuit potential (OCP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques. The evaluated results revealed that the electrochemically coated alloy with PVS. prepared at cathodic potential showed higher corrosion resistance and more stable film compared to that prepared by conventional dip‐coating method. At the same time, the nHAP electrochemically coated film provided the best anti‐corrosion properties over all examined time intervals. The obtained results were confirmed via surface analysis, which assured the formation of the prepared coatings on the alloy surface. Chemical analysis of the corrosion product/solutions showed that the effect of electrochemically deposited nHAP and PVS. polymer films in suppression of Ni ions leaching is similar and slightly higher than that of the chemically coated PVS. one; however, all of them are efficient in decreasing the leaching of the risky Ni ions into the solution.     

V2.1TiNi0.4Zr0.06Cu0.03M0.10 (M=Cr,Co, Fe,Nb, Ta)储氢合金的微结构及电化学性能

采用磁悬浮感应熔炼方法制备了V2.1TiNi0.4Zr0.06Cu0.03M0.10(M=Cr, Co, Fe, Nb, Ta)储氢电极合金, 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、电子衍射能谱(EDS)分析和电化学测试等手段系统研究了添加元素M对合金微结构与电化学性能的影响. 结果表明, 所有合金均由BCC结构的V基固溶体主相和C14型Laves第二相组成, 且第二相沿主相晶界形成三维网状分布; Cr、Nb 和Ta元素主要分布在合金主相中, 而Co和Fe元素主要分布在第二相中. 电化学性能测试表明, 在V2.1TiNi0.4Zr0.06Cu0.03合金中掺加Cr、Co、Fe、Nb或Ta元素后, 虽然会降低最大放电容量, 但能有效抑制合金中V和Ti的腐蚀溶出, 提高电极充放电循环稳定性; 同时还能明显改善合金的高倍率放电性能. 相比之下, V2.1TiNi0.4Zr0.06Cu0.03Cr0.10合金具有最佳的综合电化学性能.     

非晶态Ni-W-B合金的电沉积及其热处理前后的性能

To strengthen the properties of Ni-W alloy, dimethylamine borane （DMAB） was added to an alloy Ni-W electrolyte solution and a ternary Ni-W-B alloy was electrodeposited. The electrodeposition, crystallographic structure, surface morphology, heat treatment and corrosion resistance, of the alloy were studied by DSC, XRD, SEM and electrochemical techniques. The results showed that the structure of the alloy was greatly affected by the cooperation of boron compound. DSC experiment combined with X-ray diffractometry indicated that the obtained Ni-W-B alloy was still in amorphous structure although W content in the alloy was decreased by the addition of DMAB. After heat treatment at 400 ℃ for 1 h, the microhardness was increased from 612 to 947 kg.mm^-2 that was com- parative to Cr coating. The appearance of the as-plated coating was in f＇me and slice grains and kept almost no change after heat treatment. In w=0.03 NaC1 solution the as-plated coating presented very good corrosion resistance. After the coating was heat-treated its corrosion resistance was enhanced.     

Study on corrosion resistance of electroplating zinc–nickel alloy coatings

Electrodeposited zinc–nickel alloy coatings have been widely adopted for surface treatment of automobile body steel sheet for high corrosion resistance. The corrosion behavior of the coatings has been related with the components of nickel, and the zinc–nickel alloy passive coatings have much higher corrosion resistance than that of zinc–nickel alloy coatings. In the present paper, the corrosion resistance behavior of the zinc–nickel alloy coatings obtained by new process and formulation has been studied by means of the electrochemistry test and neutral salt spray test. And it is discovered that the properties of corrosion resistance of zinc–nickel alloy passive coatings were better than that of zinc passive coatings, Cadmium passive coatings and alloys of electrodeposited cadmium–titanium. The components of corrosion productions, in terms of X‐ray diffraction (XRD), are mainly ZnO, ZnCl₂ · 4Zn(OH)₂ and small quantity of 2ZnCO₃· 3Zn(OH)₂. The component of zinc–nickel alloy coatings has been investigated with Glow Discharge Optical Emission Spectrometry (GDA‐750). And it is found that as the thickness of zinc–nickel alloy coatings increases, the component of zinc increases from beginning to end, but the peak value of nickel appears and an enrichment of nickel in the coatings comes into being. Because the electrodeposited zinc–nickel alloy coatings exhibit different alloy phases as a function of their alloy composition, in this paper, the crystal structure changing with the different component of nickel has been studied in terms of XRD. The result shows that electrodeposited zinc–nickel alloy has different phases: α‐phase, a solid solution of zinc in nickel with an equilibrium solubility of about more than 79% nickel; γ‐phase, an intermediate phase with a composition Ni₅Zn₂₁; η‐phase, a solid solution of nickel in zinc with less than 5% nickel; and δ‐phase (Ni₃Zn₂₂) appeared from η‐phase to α‐phase with increasing content of nickel. Copyright © 2009 John Wiley & Sons, Ltd.     

Properties of Ni-W alloy coatings on steel substrate

Ni-W alloy coatings were prepared on the steel substrate at the temperature of 60°C. The content of tungsten in coatings was increased with the growing cathodic current density. The increase of the corrosion resistance of Ni-W alloy coatings with the rising content of tungsten was confirmed by the measurement of anodic polarization curves. Annealed coatings showed better antioorrosion properties than the non-annealed ones. The properties of annealed coatings including their corrosion resistance depend on the tungsten content, too.