电沉积非晶态Ni-W-B/ZrO_2复合镀层及其结构与性能

在含有二氧化锆的Ni-W-B电解液中,电沉积获得Ni-W-B/ZrO2复合镀层.用差示扫描量热分析(DSC)、X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学技术较系统地研究了Ni-W-B/ZrO2复合镀层的电沉积、热处理过程,以及镀层的结构、表面形貌、显微硬度和耐腐蚀性能.结果表明,复合镀层的质量组成为Ni47.5%、W40.9%、B0.9%和ZrO210.7%.DSC和XRD结果清楚说明,二氧化锆对基质Ni-W-B镀层的结构有明显影响,使得复合镀层的非晶态结构特征更加明显.复合镀层比Ni-W-B合金有更高的显微硬度,呈现团粒状结构,晶块之间不存在裂纹但晶界清晰可辨;二氧化锆粒子分散于Ni-W-B基质镀层中.400℃、1h热处理后,Ni-W-B基质镀层中W向镀层表面偏析,镀层呈现固溶体晶态结构特征,表面形貌特征基本不变,复合镀层的显微硬度进一步提高,抗腐蚀性能增强,但镀层表层中的二氧化锆粒子大量脱落.     

非晶态Ni-W/ZrO2复合镀层的制备、热处理及腐蚀行为

在镍钨合金电解液中, 通过搅拌使二氧化锆固体微粒悬浮, 电沉积制备Ni-W/ZrO2复合镀层. 研究结果表明, 二氧化锆粒子影响复合镀层的电沉积、表面形貌、结构、热处理过程和抗腐蚀性能; 与Ni-W合金的电沉积过程相比, 复合镀层中的W含量和电流效率均降低; 在400 ℃处理1 h后, 嵌入Ni-W本体中的ZrO2粒子脱落, W向镀层表面富集. 扫描电子显微镜(SEM)结果显示, 复合镀层呈现团粒状形态, 无裂纹. 差示扫描量热(DSC)分析结合X射线(XRD)衍射实验指出, Ni-W/ZrO2复合镀层为非晶态结构. 复合镀层的显微硬度较纳米晶Ni-W合金的高; 热处理后, 复合镀层的显微硬度和在3%氯化钠溶液中的抗腐蚀行为显著增强.     

非晶态Ni-W／ZrO2复合镀层的制备、热处理及腐蚀行为

在镍钨合金电解液中,通过搅拌使二氧化锆固体微粒悬浮,电沉积制备Ni-W/ZrO2复合镀层.研究结果表明,二氧化锆粒子影响复合镀层的电沉积、表面形貌、结构、热处理过程和抗腐蚀性能;与Ni-W合金的电沉积过程相比,复合镀层中的W含量和电流效率均降低;在400℃处理1 h后,嵌入Ni-W本体中的ZrO2粒子脱落,W向镀层表面富集.扫描电子显微镜(SEM)结果显示,复合镀层呈现团粒状形态,无裂纹.差示扫描量热(DSC)分析结合X射线(XRD)衍射实验指出,Ni-W/ZrO2复合镀层为非晶态结构.复合镀层的显微硬度较纳米晶Ni-W合金的高;热处理后,复合镀层的显微硬度和在3%氯化钠溶液中的抗腐蚀行为显著增强.     

退火前后镍钨硼合金电沉积层的结构与性能

采用电化学技术、XPS、DSC、XRD等方法研究Ni W B合金电沉积及热处理前后合金镀层的结构和显微硬度.结果表明,在Ni W B合金电沉积过程中伴随着化学沉积镍等过程以及Na2B4O7在镀层中的夹杂;Ni W和Ni W B合金电沉积层分别表现为纳米晶结构和非晶态结构;热处理过程中合金电沉积层发生晶粒粗化过程以及Ni W B合金镀层发生新相形成过程,产生Ni4W和镍硼化物如Ni2B、Ni3B等沉淀物;400 ℃热处理2 h后Ni W合金镀层有最大的显微硬度达919.8 kg•mm－2,而在500 ℃下Ni W B合金有最大的硬度达1132.2 kg•mm－2.     

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.     

镍钨磷合金电结晶机理及其镀层结构与显微硬度

应用循环伏安、恒电位阶跃和 X射线衍射（ XRD）等方法研究了 Ni-W-P合金电沉积特点和镀层结构与显微硬度 .结果表明,在以柠檬酸铵为配体的溶液中, Ni-W-P合金沉积层较 Ni-W合金有较低的电化学活性 .根据电位阶跃的 i～ t曲线分析表明,在玻碳电极上 Ni-W-P合金电结晶过程遵从扩散控制瞬时成核三维成长模式进行,随着过电位的增加,电极表面上晶核数增多 . XRD试验结果表明, Ni-W-P合金镀层呈现明显的非晶态特征 .所获得的 Ni-W-P合金电沉积层的显微硬度在 450 kg· mm－ 2左右 .     

硫酸盐体系三价铬沉积机理及镀层表征

在新研发的硫酸盐三价铬镀厚铬的镀液体系中, 运用线性扫描伏安法(LSV)和循环伏安法(CV)对三价铬在铜电极表面的电沉积过程进行研究, 并运用X射线荧光测厚仪、扫描电子显微镜(SEM)、X射线能量色散谱(EDS)、X射线衍射仪(XRD)、显微硬度计和Tafel曲线表征铬镀层厚度、形貌、组成、结构、显微硬度及在3.5wt% NaCl溶液中的耐蚀性. 结果表明, 在该体系中三价铬的沉积过程分两步进行(Cr³⁺ + e →Cr²⁺ , Cr²⁺ + 2e → Cr), 第一步得到1个电子, 受电化学过程和扩散过程共同控制, 第二步得到2个电子, 为扩散控制下的不可逆过程; 该镀层为瘤状纳米晶结构, 镀层中含有少量的铁元素(1.10 wt%), 显微硬度达到789.2 Hv, 镀层在3.5wt% NaCl溶液中的腐蚀电位(E_corr)为-0.29 V, 腐蚀电流密度(j_corr)为9.26×10^-5 A·dm^-2.     

复合电沉积的最新研究动态

综述近年来国内外复合电沉积技术最新研究动态.重点探讨纳米复合镀层,电催化复合镀层以及光活性复合镀层等方面的研究现状和发展趋势.纳米复合镀层比一般的复合镀层具有更高的硬度,更好的耐磨性和耐蚀性;电催化复合镀层则可在纯金属电极,合金电极的基础上进一步降低电极反应的过电位.以金属氧化物,导电聚合物作为基质材料的电催化复合镀层已为现代复合电沉积技术开辟了一个新领域.     

制备方法对负载型纳米ZrO2/Al2O3复合载体性能的影响

采用浸渍-沉淀法制备了负载型纳米ZrO2/Al2O3复合载体.采用X射线衍射、N2物理吸附、差示扫描量热(DSC)和程序升温脱附等技术考察了浸渍方式和干燥方法对复合载体的表面性能、热稳定性和晶相结构的影响.结果表明,ZrO2/Al2O3复合载体中没有生成ZrO2-Al2O3复合氧化物或固溶体,纳米ZrO2仅负载在Al2O3的表面.微波干燥法制备的ZrO2/Al2O3复合载体的比表面积(158.7 m2/g)较大,最可几孔径为19.4 nm,ZrO2的粒度为4.2 nm,晶相结构为四方相ZrO2.微波诱导作用使ZrO2/Al2O3复合载体表面产生了新的酸碱中心,微波干燥法制备的ZrO2/Al2O3复合载体具有较强的热稳定性,在873~1 073 K范围内DSC曲线没有出现吸热峰,而其它干燥方法制备的复合载体在903~1 023 K范围内出现了较明显的吸热峰,表明复合载体表面的部分四方相ZrO2转变为单斜相ZrO2(m-ZrO2).对超声波处理过的复合载体进行微波干燥能进一步提高纳米ZrO2与Al2O3之间的相互作用,纳米粒子的粒度(3.4 nm)更小,分布更均匀,但没有改变ZrO2的晶相结构.     

氟硼酸镀液二氧化铅电沉积

研究了在氟硼酸或其掺杂镀液中于Pt基底电沉积PbO2镀层的电化学和结构性质.循环伏安测试、XRD分析和SEM形貌观察表明,BF4-可提高二氧化铅电沉积速率;电沉积的PbO2晶型为β-PbO2;F-、Fe3+共掺杂影响晶体生长的择优取向及镀层形貌,电沉积的FB/F-Fe-PbO2镀层整齐致密;电沉积过程增大电流密度可改变生长晶面取向.     

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.     

Electrodeposition, Structure and Corrosion Resistance of Nanocrystalline Ni-W Alloy

Ni—W alloy was electrodeposited from the electrolyte solution containing sodium tungstate, nickel sulfate and ammonium citrate. The electrodeposition, heat treatment, structure, surface morphology and corrosion resistance in w=0.03 NaCl solution, of Ni-W alloys were studied by means of DSC, XRD, SEM and electrochemical techniques. The results showed that the obtained Ni-W alloy electrodeposit with W weight content (Ww=0.471) was presented in more typical nanocrystaUine, After heat treatment at 400 ℃ for 1 h, the phase structure of the deposits was not obviously changed whereas the agglomerate for the reunion of tiny grains on deposit surface caused the granule in a more smooth morphology, the microhardness was slightly increased and the corrosion resistance was enhanced.     

Mesoporous carbon/zirconia composites: a potential route to chemically functionalized electrically-conductive mesoporous materials

Mesoporous nanocomposite materials in which nanoscale zirconia (ZrO(2)) particles are embedded in the carbon skeleton of a templated mesoporous carbon matrix were prepared, and the embedded zirconia sites were used to accomplish chemical functionalization of the interior surfaces of mesopores. These nanocomposite materials offer a unique combination of high porosity (e.g., ～84% void space), electrical conductivity, and surface tailorability. The ZrO(2)/carbon nanocomposites were characterized by thermogravimetric analysis, nitrogen-adsorption porosimetry, helium pychnometry, powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Comparison was made with templated mesoporous carbon samples prepared without addition of ZrO(2). Treatment of the nanocomposites with phenylphosphonic acid was undertaken and shown to result in robust binding of the phosphonic acid to the surface of ZrO(2) particles. Incorporation of nanoscale ZrO(2) surfaces in the mesoporous composite skeleton offers unique promise as a means for anchoring organophosphonates inside of pores through formation of robust covalent Zr-O-P bonds.     

Microstructure and corrosion behavior of electroless deposited Ni-P/CeO2 coating

Electroless Ni-P/nano-CeO2 composite coating was prepared in acidic condition, and its microstructure and corrosive property were compared with its CeO2-free counterpart. Scanning electronic microscopy （SEM） and X-ray diffraction （XRD） spectrometer were used to examine surface morphology and structure of the as-plated coating. Differential scanning calorimeter （DSC） and transmission electronic microscopy （TEM） were used to study the coating＇s phase change at high temperature. The coating＇s corrosive behavior in 3%NaCl ＋ 5%H2SO4 solution was also investigated. The results showed that Ni-P coating had partial amorphous structure mixed with nano-crystals, while the Ni-P/CeO2 coating had perfect amorphous structure. In high-temperature condition, Ni3P precipitation and Ni crystallization took place in both coatings but at different temperatures, while the Ni-P/CeO2 coating had sintered phase of NiCe2O4 spinels. The anti-corrosion property was better in the CeO2-containing coating, and this was due to its less liability to undergo local-cell corrosion than its CeO2-free counterpart. Ni-P/CeO2 coating＇s pure amorphous structure was the result of Ni＇s hindered crystal-typed deposition and P＇s promoted deposition.     

Effect of TiO2–Ti and TiO2–TiN composite coatings on corrosion behavior of NiTi alloy

Two kinds of biocompatible coatings were produced in order to improve the corrosion resistance of nickel titanium (NiTi) alloy. A titanium oxide–titanium (TiO₂–Ti) composite was coated on NiTi alloy using electrophoretic method. After the coating process, the samples were heat‐treated at 1000 °C in two tube furnaces, the first one in argon atmosphere and the second one in nitrogen atmosphere at 1000 °C. The morphology and phase analysis of coatings were investigated using scanning electron microscopy and X‐ray diffraction analysis, respectively. The electrochemical behavior of the NiTi and coated samples was examined using polarization and electrochemical impedance spectroscopy tests. Electrochemical tests in simulated body fluid demonstrated a considerable increase in corrosion resistance of composite‐coated NiTi specimens compared to the non‐coated one. The heat‐treated composite coating sample in nitrogen atmosphere had a higher level of corrosion resistance compared to the heat‐treated sample in argon atmosphere, which is mainly due to having nitride phases. Copyright © 2014 John Wiley & Sons, Ltd.     

Surface Properties of Graphene Functionalized TiO2/nHA Hybrid Coatings Made on Ti6Al7Nb Alloys via Plasma Electrolytic Oxidation (PEO)

Nano-hydroxyapatite (nHA)-matrix coatings containing graphene nanosheets (GNS)-nHA were coated on Ti6Al7Nb alloys by plasma electrolytic oxidation (PEO) treatment for the improvement of their surface properties. Crystallographic properties, functional groups, and elemental analysis of coatings were characterized by XRD, ATR–FTIR, and EDS analysis. Surface morphological changes of the coated surfaces were investigated by AFM and SEM. The electrochemical corrosion behavior of the coatings was examined by using the potentiodynamic scanning (PDS) tests under in-vitro conditions in simulated body fluid (SBF). The results showed that the GNS was successfully deposited in ceramic matrix coatings on Ti6Al7Nb alloys. Also, the microstructural observations revealed that the coatings have a porous and rough structure. The XRD and ATR–FTIR quantitative analysis have proved the appearance of HA and GNS in the coating layers. An increase in the coating thickness, surface hardness, and anatase/rutile transformation rate was determined, while the GNS ratio in the coating layers was increased. The microhardness of the nHA coating reinforced with 1.5 wt% GNS was measured at 862 HV, which was significantly higher than that of GNS-free (only nHA) coating (584 HV). The best in-vitro resistance to corrosion in SBF was observed in the nHA/1.5GNS wt% coating.     

Polysulfone-ZrO(2) surface interactions. The influence on formation, morphology and properties of zirfon-membranes

The interaction between polysulfone and ZrO(2) particles is studied as a function of the particle sintering temperature in order to understand the role of ZrO(2) on the formation, morphology, and properties of organo-mineral composite membranes. The adsorption between the sintered ZrO(2) and the constituents of polysulfone, 2,2-diphenylpropane and diphenyl sulfone, is investigated using high-pressure liquid chromatography. The influence of the polymer-ZrO(2) interaction on the flow behavior of the casting suspension is registered via viscoelastic measurements. The organo-mineral composite membranes are formed by immersion precipitation in water, and the resulting membrane morphology is analyzed using high-resolution SEM. The zirconia concentration in the top-layer of the composite structure is determined by XPS. Finally, the link between the polymer-filler interactions, the membrane formation process, and the resulting membrane structure and properties is established.