一种二氯四氨合钯(Ⅱ)镀钯试剂的生产工艺及应用

钯镀层具有优良的耐腐蚀性、耐磨性、耐光性和电器性能。广泛应用于电器连接点、连接器IC引导线架和印制板(PCB)等电子电器零件中和装饰品工业。同时钯镀层比金镀层廉价,使用过程中不涉及氰化物等剧毒化学品,生产过程安全便捷,因而可用钯镀层替代传统使用的金镀层。本文研制了一种制备高纯二氯四氨合钯[Pd(NH_3)_4cl_2]的生产工艺,该生产工艺简单稳定安全,生产设备条件要求低,通过加入脱水剂能大大提高产品产量,经电镀实验验证得到的钯镀层各项性能指标优良,媲美硬金镀层。     

9Cr18不锈钢表面不同耐磨镀层的微观结构及耐磨性

针对9Cr18不锈钢的耐磨需求，选用硬铬镀层、Ni-P化学镀层、Ni-c BN/h BN复合镀层等3种镀层，通过扫描电镜、划痕法、球盘磨损试验等研究了其在微观结构、结合力、常温及高温耐磨性等方面的差异。结果表明，3种镀层的硬度均可达800 HV以上，但Ni-c BN/h BN复合镀层的硬度略高；经过预镀镍处理后Ni-c BN/h BN复合镀层与基体之间的结合强度高达68 MPa，但硬铬镀层与基体的结合力较差；Ni-P化学镀层和Ni-c BN/h BN复合镀层在常温下的耐磨性相当，但Ni-c BN/h BN复合镀层在200℃下的耐磨性略优；硬铬镀层在摩擦应力作用下涂层出现明显剥落、黏着磨损严重，耐磨性较差。Ni-c BN/h BN复合镀层更宜选作9Cr18不锈钢表面的耐磨镀层。     

Pd—Co合金电镀

1　前言在电子工业的接触器触点材料和装饰品等用途中,为了提高产品外观、耐蚀性、耐磨性、耐扩散性和可焊性,往往在产品表面施镀贵金属镀层,使其在严酷恶劣的环境下,仍可维持外观品质,长期高可靠接触性,确保低阻抗、无噪声的接点。然而存在的问题有:(1)金之类的贵金属价格高,制造成本高;(2)往往要镀镍打底,品质管理困难,在装饰品用途中,镍镀层会对人体皮肤引起过敏。于是人们试图以钯镀层代替金镀层,但纯钯镀层质地较软,难以满足使用要求。人们以钯镀层为契机,致力于除镍之外的钯合金镀层的研究,例如ＰｄＡｇ、ＰｄＣｏ、ＰｄＦｅ、ＰｄＲ…     

机械泵旋片基材表面化学镀Ni-P/PTFE复合镀层

在机械泵旋片用45Mn钢板表面制备了化学镀Ni-P/PTFE复合镀层,并研究了PTFE的质量浓度对化学镀Ni-P/PTFE复合镀层的沉积速率、耐磨性、耐蚀性及表面形貌的影响。结果表明:适当增加PTFE的质量浓度,有利于加快沉积速率,提高化学镀Ni-P/PTFE复合镀层的耐磨性和耐蚀性。化学镀Ni-P/PTFE复合镀层表面呈胞状形貌,PTFE均匀分布在表面。当PTFE的质量浓度为8 g/L时,化学镀Ni-P/PTFE复合镀层具有最佳的耐磨性和耐蚀性。     

SiC_p/Al复合材料化学镀镍-磷的工艺研究

采用钯盐对SiCp/Al复合材料表面进行活化,化学镀后在复合材料表面获得Ni-P镀层。利用扫描电镜(SEM)、能谱成分分析仪(EDS)、极化曲线、X射线衍射仪(XRD)以及热震测试等手段对镀层的性能进行了研究,并观察了镀覆过程中镀层表面形貌的变化。结果表明:钯盐的活化作用较好,钯原子优先在复合材料的基体晶界、SiCp/Al界面及SiCp表面粗糙处形成催化活化中心;铝合金基体与SiCp增强相表面均被镀覆,且镀层光亮、致密、连续,耐蚀性好,结合力高,属于中磷镀层。     

TC4合金表面Cu/micro-WC复合镀层和Cu/nano-WC复合镀层的性能

在TC4合金表面分别制备了Cu/micro-WC复合镀层和Cu/nano-WC复合镀层。比较了两种复合镀层的表面形貌、化学成分和显微硬度,同时分析了两种复合镀层的摩擦特性。结果表明:两种复合镀层都由Cu、W、C元素组成,显微硬度都明显低于TC4合金的显微硬度;摩擦试验前后,两种复合镀层表面轮廓曲线的形态都存在明显的不同;与Cu/micro-WC复合镀层相比,Cu/nano-WC复合镀层的表面形貌较好,W元素的质量分数较高,耐磨性较强。     

专利实例

钯—镍合金镀层人们正在注意使用钯—镍合金镀层代替金。经常有一些新的电解液被批准为专利。日本的一个专利使用一种芳香硫酰胺、萘磺酸和一种无机盐作络合剂。推荐使用如下的溶液配方: 钯(以四—氨基—氯化亚钯加入) 10克/升镍(以硫酸镍铵加入)10克/升硫酸铵 50克/升溶液的温度为30℃,pH7.2(用KOH调),电流密度为11安/分米~2,使用黄铜作阳极,可获得厚度达10微米的镀层。镀层     

化学镀镍–磷合金层表面化学镀金工艺及其性能

采用化学镀镍–磷/化学镀钯/置换镀金(ENEPIG)工艺获得镍/钯/金组合镀层,对比分析了它与化学镀镍/置换镀金(ENIG)、化学镀镍/化学镀金(ENEG)工艺的相关沉积特征及镀层耐蚀性能。镀金过程中开路电位和沉积速率均发生明显的变化,反映了基体电极表面状态的变化。ENEG工艺的化学镀金过程中的平台电位最正,沉积速率最快。与ENIG工艺的置换镀金相比,ENEPIG工艺中置换镀金的平台电位更正,对基体的腐蚀也更慢,所得置换镀金层更致密,具有良好的耐腐蚀性能。综合对比ENIG、ENEG、ENEPIG工艺所得3种镀层,ENEPIG工艺的镀层性能最优。     

新型无氨无氯钯镍合金高速电镀液

介绍了Palluna(R)ACF-100钯镍合金电镀工艺,其流程主要包括:碱性除油或电解除油,酸洗,光亮或半光亮镀镍,镍活化,镀钯镍合金,镀硬金或金钴合金.镀钯镍合金的最佳工艺条件为:Pd 15 g/L,Ni 16g/L,温度60℃,pH 5.5,阴极电流密度60 A/dm2.所得合金含钯80%(质量分数),镀速可达14μm/min.镀层结合力好、延展性高,耐磨、焊接性能优良,混合流动气体腐蚀测试结果令人满意.该工艺无氨无氯,操作容易,镀液使用寿命长.     

高镍Pd-Ni合金组成与性能研究

研究了在以Ｐｄ（ＮＨ３）Ｃｌ２、ＮｉＳＯ４·６Ｈ２Ｏ和ＮＨ４Ｃｌ为基本组成的镀液中,Ｎｉ２＋浓度对高镍的钯镍合金（Ｎｉ含量＞１０ｗｔ％）镀层组成、硬度、孔隙率、耐蚀性、接触电阻和可焊性等的影响。结果表明,在一定的工艺条件下,可以根据需要控制镀液中Ｎｉ／Ｐｄ来获得不同含镍量的钯镍合金镀层,其含镍量４０％左右的钯镍合金镀层具有较高的硬度、较少的孔隙、较好的耐蚀性及较低的接触电阻、合格的可焊性,因此在电子工业中可以代替硬金镀层。     

镍基纳米SiC-Al2O3复合电刷镀层的组织及性能

在45#钢基体上制备了n-Al2O3/Ni和n-SiC–Al2O3/Ni复合刷镀层,采用能谱仪(EDS)、X射线衍射仪(XRD)、扫描电镜(SEM)和T-11球盘式磨损试验机等设备对比研究了2种复合刷镀层的组织及性能。EDS分析结果表明,n–Al2O3/Ni复合刷镀层中纳米颗粒特征元素Al的质量分数为5.65%,n-SiC–Al2O3/Ni复合刷镀层中纳米颗粒特征元素Al的质量分数为5.63%,Si元素的质量分数为4.86%。SEM分析结果表明,与n-Al2O3/Ni复合刷镀层相比,n-SiC–Al2O3/Ni复合刷镀层的表面更加平整,组织更加细化。n-SiC–Al2O3/Ni和n-Al2O3/Ni复合刷镀层的显微硬度分别为587HV和555HV,n-SiC–Al2O3/Ni复合刷镀层的耐磨性是n-Al2O3/Ni复合刷镀层的1.7倍。     

Cr–C/h-BN 自润滑复合镀层的制备与摩擦学性能

在三价铬Cr–C镀液中添加1~5 g/L的h-BN自润滑微粒,运用直流电沉积技术在Q235碳素结构钢基体上制备了Cr–C/h-BN复合镀层。利用扫描电镜(SEM)、X射线衍射仪(XRD)、显微硬度计、摩擦磨损试验机等设备分析了h-BN微粒添加量、电流密度等工艺参数对镀层组织和性能的影响。结果表明:在电流密度20 A/dm2,h-BN添加量3 g/L的条件下,可获得h-BN微粒体积分数为6.15%的复合镀层。h-BN微粒的添加改善了Cr–C合金镀层的耐磨性,Cr–C/h-BN复合镀层在室温干摩擦条件下的磨损率减少了22%,平均摩擦因数由原先的0.49降低至0.31。     

电流密度对5,5-二甲基乙内酰脲体系电镀银的影响

采用5,5-二甲基乙内酰脲体系在黄铜及不锈钢基体上沉积厚度为6μm左右的银镀层,镀液组成和工艺条件为:硝酸银25 g/L,5,5-二甲基乙内酰脲80 g/L,烟酰胺60 g/L,碳酸钾40 g/L,复合光亮剂(包含2-巯基苯骈噻唑、1,4-丁炔二醇和十二烷基硫酸钠)2 mL/L,pH 10.5,温度60°C,电流密度0...     

Sol-enhanced electroplating of nanostructured Ni-TiO2 composite coatings—The effects of sol concentration on the mechanical and corrosion properties

Novel sol-enhanced Ni-TiO₂ nano-composite coatings were electroplated by adding a transparent TiO₂ sol into the traditional electroplating Ni solution. It was found that the structure, mechanical properties and corrosion resistance of the nano-composite coatings were largely determined by the sol concentration. The higher sol concentration in the plating electrolyte led to a higher content of TiO₂ nano-particles in the coating matrix. The coating prepared at the sol concentration of 12.5 mL/L had the best microhardness, wear resistance and corrosion resistance. Adding excessive sol to the electrolyte changed the surface microstructure, caused cracking on the coating surface and deteriorated the properties. It was demonstrated that the corrosion resistance of the composite coatings is determined by two factors: surface microstructure and incorporation of TiO₂ nano-particles.     

超音速火焰喷涂碳化钨-钴铬涂层替代电镀硬铬的研究

采用超音速火焰喷涂(HVOF)工艺在300M钢基体上制备了WC-CoCr涂层,研究了其显微结构、显微硬度、相组成、耐磨性和耐蚀性,并与300M钢电镀硬铬试样进行了性能对比。研究结果表明,HVOF工艺制备的WC-CoCr涂层性能优良,耐磨性和耐蚀性优于电镀硬铬镀层,可以替代电镀硬铬作为耐磨涂层使用。     

Tribological and electrochemical behavior of thick Cr-C alloy coatings electrodeposited in trivalent chromium bath as an alternative to conventional Cr coatings

Alternative process to hexavalent chromium plating, substitute materials and new designs are urgently needed owing to the requirement of “clean” manufacture. This comparative study was conducted to systematically investigate the tribological and electrochemical behavior of the Cr-C alloy coatings electrodeposited from a trivalent chromium bath and the hard Cr coatings electrodeposited from conventional hexavalent chromium bath, using reciprocating ball-on-disc tribometer and electrochemical analyzer. The electroplated Cr-C alloy coatings with thickness of 50 μm and acceptable quality that can be used for wear resistance as well as corrosion resistance purposes were produced successfully. The results show that the as-deposited Cr-C alloy coatings exhibited crack-free surface and amorphous/microcrystalline structure. The following heat treatment resulted in the cracked surface and the increase in hardness for the electroplated Cr-C alloy coatings. In contrast, the conventional Cr coatings exhibited cracked surface and their hardness decreased with the increase in annealing temperature. The electroplated Cr-C alloy coatings after heat treatment at 200 °C for 1 h exhibited better wear resistance than the conventional Cr coatings. In regard to the electrochemical behavior, the as-deposited Cr-C alloy coatings exhibited better corrosion resistance than the conventional Cr coatings. Therefore, the electroplated Cr-C alloy coatings are environmentally acceptable candidates to replace the conventional Cr coatings.     

Modification of Cr/CrN composite structure by Fe addition and its effect on decorative performance and corrosion resistance

A CrN ceramic coating is a promising substitution for electroplated Cr (Ⅵ) hard coatings; however, it has not yet replaced a decorative Cr (Ⅵ) layer owing to its low reflectivity of visible light and relatively poor corrosion resistance. A Cr/CrN composite structure can address these shortcomings. Our recent work demonstrated that an addition of Fe can facilitate the densification of hot-pressed Cr sputtering targets and enhance the mechanical properties of Cr/CrN composite coatings. In this work, we focus on reporting optical properties and corrosion resistance of the Fe-modified Cr/CrN layers for decorative applications, and clarifying the effect of Fe on these performances. The results show that Fe can increase the amount of metallic phase in the Cr/CrN composite structure and helps enhance its reflectance in the visible region. The composite coating deposited by Cr₉₀Fe₁₀ (at.%) target/alloy exhibits a greater reflectivity of visible light and a better corrosion resistance than those of a single-phase CrN coating. This is attributed to its fine microstructure, which is beneficial for a dense and smooth surface. The color of the coating can be controlled by both the partial pressure ratio of N₂ during deposition and the Fe content in the Cr-Fe sputtering target. The present results show that the addition of Fe can lead to the reduction in the processing cost of Cr targets, enhance the mechanical properties of the composite coatings, and broaden the deposition window. Such cost-effective Fe-modified Cr/CrN composite coatings are expected to be used in various decorative applications.     

Effect of bath ionic strength on adhesion and tribological properties of pure nickel and Ni-based nanocomposite coatings

The effect of electrolytic chemical concentration on wear-resistance, corrosion-resistance, adhesion and wettability properties of pure nickel and nickel–alumina composite coatings has been investigated in this paper. Coatings were electroplated over steel substrates under constant pulse conditions using pulse electrodeposition technique. Corrosion-resistance results show that the anti-corrosion properties are increasing with medium concentration (MC) both for pure nickel and nickel–alumina composite coating. For anti-wear properties, the MC showed increasing trend in case of pure nickel coatings but decreased in nickel–alumina composite coatings. In composite coating, the higher and low concentrations of electrolyte showed the higher wear resistance properties. Furthermore, the influence of electrolyte concentration on changing surface morphologies, mechanical, wettability and adhesion properties have been investigated and reported here. Surface morphologies of the synthesized coatings were studied with scanning electron microscopy (SEM) and energy-dispersive spectroscopy. Coatings surface mapping and wear analyses were examined by using 3D white light interferometry.     

Effect of BEO in the electrodeposition process of Ni/diamond composite coatings for preparation of ultra-thin dicing blades: Experiments and theoretical calculations

Ni/diamond dicing blades is the main tool for scribe of silicon wafer at present. In order to decrease the width of dicing slot on the wafer, it is necessary to reduce the thickness of blades, and to increase the hardness, toughness and wear resistance of the Ni/diamond composite coatings in the process of electrodeposition. In this paper, 1,4-bis(2-hydroxyethoxy)-2-butyne (BEO) was used as an organic additive in the composite baths containing nickel amino-sulfonate, nickel chloride, boric acid, sodium dodecyl sulfate (SDS) and diamond particles in sizes of 3–5?µm, in order to improve the properties of Ni/diamond coatings and produce ultra-thin Ni/diamond dicing blades. The textures of Ni/diamond composite coatings were mainly Ni (200) and Diamond (111) since the addition of BEO in the baths inhibited the growth of Ni (111) and Ni (220). Quantum chemical calculations and molecular dynamics (MD) simulations showed that BEO could adsorb at the nickel surface strongly and inhibit the electrodeposition of nickel atoms. With the increase in concentration of BEO in the baths, the cathodic polarization potentials shifted to more negative direction and the thicknesses of the coatings decreased. Adding the appropriate amount of BEO (0.1–0.2?g/L) in the baths, the roughness of the coating decreased the number of individual diamond particles in the coating increased, and the hardness and the wear resistance of the coating was improved. When the thickness of Ni/diamond composite coating on aluminum alloy wheeled substrate was 15?µm, the width of its dicing slot was 22?µm. However, the addition of BEO in the bath cannot change the adhesive wear mechanism of the coating.