激光同步辐照对电化学沉积铜组织结构及结合力的影响

目的 解决单一电化学沉积制备铜镀层沉积速度慢、沉积颗粒易团聚、晶粒生长不均匀及其与基体结合力差等问题。方法 采用沉积前激光处理、沉积过程激光同步辐照的方法,在316L不锈钢上制备铜涂层,通过光学显微镜、扫描电子显微镜、自动划痕仪分析了铜镀层表面形貌、截面厚度、涂层物相和结合力,探究了激光的增强作用和复合沉积技术下镀层的生长机制。结果 激光同步辐照促进了晶粒的高择优取向及沉积电位的正移。单一晶面的高择优取向利于提高镀层晶粒生长的均匀性,使镀层表面的凸起、孔洞明显减少,变得平整致密。同时,激光同步辐照使镀层表面粗糙度维持在一个较低的范围,使沉积质量不会随沉积时间的增加而降低,有利于电化学沉积的继续进行,实现镀层增厚。相同沉积时间(60 min)下,传统电化学沉积所得镀层的沉积厚度为62.62μm,表面粗糙度为4.741μm;而激光同步复合电化学沉积所得镀层的沉积厚度为138.39μm,表面粗糙度为0.995μm;且镀层表现出与基体更佳的结合力,与基体间的极限载荷可达98.2 N。结论 激光同步辐照提高了铜镀层的沉积效率、质量及其与基体间的结合力。     

Iridium coating prepared on rhenium substrate by electrodeposition in molten salt in the air atmosphere

Compact and smooth iridium coating was obtained on the surface of the rhenium substrate by electrodeposition from molten salts of chlorides at the temperature of 600 °C in the air. The deposition rate is about 25 μm/h at cathodic current density of 25 mA/cm². The iridium coating has a columnar structure with preferential growth orientation of <111>. The coating/substrate interface exhibits excellent adherence with no evidence of delamination, cracks, or other defects. No obvious diffusion layer is found within the as-deposited coating. The microhardness of the coating is 442 kg/mm² and the bond strength between the coating and substrate is higher than 16 MPa.     

EFFECT OF CARBON CONTENT IN SUBSTRATE ON CVD TiN COATING

Effect of carbon content of steel substrate,on the chemical vapour deposition(CVD)ofTiN has been investigated.The increment of deposition rate is linearly related to the increaseof carbon content in own substrate.The α-Fe peak,besides TiN,is revealed in X-raydiffraction pattern of TiN coating.The(220)preferred growth of TiN deposited on steelCr12MoV substrate increases with the increase of depositing temperature.Only Ti energyspectrum was found from the bright region at coating surface and the interior,while bothTi and Fe energy spectra from dark region.     

氧化铝陶瓷基板化学镀铜工艺优化

目的化学镀铜是氧化铝陶瓷基板金属化的一种重要手段,为了进一步优化氧化铝陶瓷基板化学镀铜工艺,研究了化学镀铜液配比(尤其是镀液中铜离子和甲醛含量)对氧化铝陶瓷覆铜板微结构和导电性的影响。方法在对氧化铝陶瓷基板经过前期处理后,采用化学镀铜法在基板上镀铜。采用X射线衍射仪、光学显微镜对氧化铝基板上的化学镀铜层物相和形貌进行观察。采用覆层测厚仪、四探针测试仪对化学铜镀层的膜厚和方阻进行测量。结果 XRD结果表明,不同配比镀液得到的化学镀铜层均具有较好的晶化程度,镀液中甲醛和铜含量较低的镀液可制备出晶粒更为细小的化学镀铜层。甲醛和铜离子含量均较高时,沉积速度过快,使镀铜层的均匀性和致密性不佳。但当甲醛含量较高、铜离子含量较低时,沉积速度适中,从而获得了均匀性和致密性较好的镀铜层,同时这种镀层具有良好的导电性。结论采用表面活性化学镀铜工艺,当镀液中甲醛浓度为0.25 mol/L和硫酸铜质量浓度为1.2 g/L时,无需高温热处理,即获得了均匀性和致密性俱佳的铜镀层,可满足覆铜板的使用要求。     

镁合金表面Ni-P/Ni镀层的制备与性能研究

在镁合金表面先化学镀Ni-P层,再电镀Ni,获得高耐蚀性Ni-P/Ni镀层,并用静态腐蚀浸泡法研究了化学镀时间和电镀时间对所得镀层在5%NaCl溶液中的耐蚀性能的影响。结果表明,先化学镀40 min,再电镀15 min所得的Ni-P/Ni镀层具备高耐蚀性能,电化学测试结果表明,此种镀层在酸性和碱性溶液中都具有较好的耐蚀性能。在200℃热处理24 h后,Ni-P/Ni镀层的耐蚀性提高,同时外层Ni层的显微硬度从HV460增大到HV550。镀层侧面的SEM照片显示,镀层均匀致密,与基体结合良好,化学镀层与电镀层之间没有明显的界限。     

Zinc modified polypyrrole coating on mild steel

Polypyrrole (PPy) films (∼ 1.7 μm thick) have been electrodeposited on mild steel (MS) substrates from 0.1 M pyrrole containing aqueous oxalic acid solution, by using cyclic voltammetry technique. Then, the polymer coatings were modified with deposition of zinc particles (∼ 1 mg/cm²), at a constant potential value of − 1.20 V in 0.2 M ZnSO₄ solution. The corrosion performance of zinc modified PPy coating has been investigated in 3.5% NaCl solution, by using electrochemical impedance spectroscopy and anodic polarisation curves. Also, the corrosion behaviours of zinc modified PPy coated platinum and single PPy coated MS samples have been investigated, for comparison. It was shown that zinc modified coating exhibited very low permeability and provided important cathodic protection to MS for considerably long immersion period. The voluminous zinc corrosion products are formed during exposure time in aggressive solution, giving rise to a blocking effect on the porous structure and led to effective barrier behaviour of zinc modified PPy coating, even after 96 h of exposure time to corrosive solution.     

A method for polyaniline coatings on solid polystyrene surfaces and electroless copper deposition

A new efficient method is presented for electroless copper deposition on solid polystyrene surfaces via polyaniline (PANI) coatings. It was demonstrated that, partial polymerization of aniline by catalytic air oxidation in the presence of dissolved polystyrene (PS) (M_n: 87.000 K) gives viscous solution of PANI-PS mixture in aniline. Direct application of the polymerization mixture with copper catalyst onto polystyrene sheets (5 × 15 cm) resulted in extension of the polymerization by air oxygen to give a smooth PANI-PS composite layer on the host surface. Treatment of the surface with a similar PANI solution without PS gave Emeraldine base film with homogenously dispersed copper. Reduction of the surface copper by diluted hydrazine (5%) yielded zero-valent copper serving as seed points for accumulation of more copper from an electroless plating solution in the following process. Experiments showed that, the method presented offers a simple pathway to produce excellent copper deposits on PS substrate. This method is superior to traditional electroless plating process, since tedious surface etching and expensive palladium activation steps are being avoided. The surface characteristics were examined by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), adhesion tests and contact angle measurements. The results showed that, the electroless plating process gives a homogeneous and highly robust copper layer with 34.2 μm of thickness within 48 h. Adhesion of the copper layer to the underlining surface was satisfactory as inferred from pull-off measurements (1.6 N/mm²).     

The production of a multi-walled carbon nanotube/hexamethylene diisocyanate nanocomposite coating on copper by electrophoretic deposition

A multi-walled carbon nanotube (MWCNT)/hexamethylene diisocyanate (HDI) composite coating with excellent microstructural homogeneity was produced on copper substrate from aqueous suspensions using electrophoretic deposition (EPD). The concentrations of different additives were optimized to obtain stable suspensions of MWCNT. At the optimum EPD condition, a coating of thickness 170 μm was obtained at voltage of 30 V and deposition time of 3 min with well dispersed MWCNT in the polymer matrix. The deposit yield increased linearly with deposition time. The adhesive strength of the MWCNT/HDI composite coating was assessed qualitatively by peel test. The composite coated specimen showed greater resistance to corrosion in the chloride containing environment with inhibiting efficiency 96.65%. The mechanism for adhered coating is due to better wetting of HDI on copper substrate followed by acid-base reaction between metal hydroxide and polymeric resin. The potential application of the nanocomposite coatings could be protecting copper based metallic structure in marine environment.     

Influence of deposition technique on the protective properties of epoxy films

The electrochemical impedance spectra, the anodic polarization curves and the time dependence of paint capacitance and paint resistance have been used in this paper to evaluate the protective properties of epoxy films on carbon steel substrate. The coatings were formed using four deposition techniques (brushing, immersion, cathodic and anodic electrodeposition) with the aim to determine the effect of deposition type on the anticorrosive performances of epoxy paint. Interpretation of Nyquist and Bode impedance spectra with the immitance analysis Equivcrt. programme has established an electrical equivalent circuit with two time constants fitted to describe the electrodeposited epoxy/carbon steel system in the 3 % sodium chloride solution and an electrical equivalent circuit with four time constants fitted in case of epoxy films applied by brush or immersion. The anodic polarisation measurements show nobler corrosion potentials and smaller dissolution current densities for the carbon steel in the presence of the electrodeposited films in comparison with epoxy coatings applied by brush or with the immersion technique. The values of the porosity, water uptake, and ionic transport through the film emphasize the higher performances of the electrodeposited films, characterized by uniformity, porosity absence, low water permeability and few conductive pathways.     

Growth of bismuth telluride thin film on Pt by electrochemical atomic layer epitaxy

An automated thin-layer flow cell electrodeposition system was developed for growing Bi2Te3 thin film by ECALE. The dependence of the Bi and Te deposition potentials on Pt electrode was studied. In the first attempt,this reductive Te underpotential deposition (UPD)/reductive Bi UPD cycle was performed to 100 layers. A better linearity of the stripping charge with the number of cycles has been shown and confirmed a layer-by-layer growth mode, which is consistent with an epitaxial growth. The 4 : 3 stoichiometric ratio of Bi to Te suggests that the incomplete charge transfer in HTeO reduction excludes the possibility of Bi2Te3 formation. X-ray photoelectron spectroscopy (XPS) analysis also reveals that the incomplete charge transfer in HTeO2^ occurs in Te direct deposition. The effective way of depositing Bi2Te3 on Pt consists in oxidative Te UPD and reductive Bi UPD. The thin film deposited by this procedure was characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS). A polycrystalline characteristic was confirmed by XRD. The 2 : 3 stoichiometric ratio was confirmed by XPS. The SEM image indicates that the deposit looks like a series of buttons about 0.3 - 0.4/~m in diameter, which is corresponding with calculated thickness of the epitaxial film. This suggests that the particle growth appears to be linear with the number of cycles, as it is consistent with a layer by layer growth mode.     

Cathodic reduction of the duplex oxide films formed on copper in air with high relative humidity at 60 °C

The cathodic reduction of duplex air-formed oxide film on copper was performed at a constant current density of i_c = −50 μA cm⁻² in deaerated 0.1 M KCl solution to investigate the sequence of cathodic reduction of each oxide layer and its mechanism. The single-phase thick CuO film on copper was also cathodically reduced at i_c = −50 μA cm⁻² or −2.5 mA cm⁻². The surface characterizations of the air-formed oxide film and single-phase CuO film before cathodic reduction and after partial or complete cathodic reduction were performed by XPS and X-ray diffraction, respectively.The two plateau regions appeared in the potential vs. time curve during cathodic reduction of the duplex air-formed oxide film on copper, while one plateau region was observed in the potential-time curve during cathodic reduction of the single-phase CuO film on copper. The potential in the first plateau region for the air-formed film coincided with that in the plateau region for the CuO film. The results of XPS and X-ray diffraction suggested that in the first plateau region, the outer CuO layer is directly reduced to metallic Cu, while in the second plateau region, the inner Cu₂O layer is reduced to metallic Cu.     

高黏附性超疏水表面的制备及耐腐蚀性

利用电化学沉积技术在碳钢基底上制备了Co-Ni过渡层,再通过双辉等离子表面合金化技术(DGPSA)在过渡层上沉积了Cr涂层,经全氟辛基三氯硅烷(PFTEOS)溶液修饰后,制备出了具有高黏附性的超疏水表面。利用扫描电镜(SEM)、EDS、X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、接触角测量仪、电化学测试等方法表征了涂层的形貌、物相组成、润湿性能、粘附性以及耐腐蚀性能,探究了DGPSA技术不同沉积时间对Cr涂层表面形貌和润湿性能的影响。结果表明,在沉积温度为750 ℃,沉积时间30 min 时,制备出了具有微纳米乳突状结构的高黏附性超疏水表面,水滴接触角达到159°,水滴在样品倾斜180°也不发生滚落。电化学测试结果证明制备的超疏水表面具有出色的耐腐蚀性能,对碳钢基底起到了良好的腐蚀防护作用。     

乙二胺对铜基材浸镀银的影响

为了克服铜基材在简单银盐溶液中浸镀银时易产生浮银层的问题,利用容量滴定法、电化学方法和扫描电子显微分析等手段,研究了添加络合剂乙二胺对铜基材浸镀银沉积速度、沉积过程以及镀层形貌的影响.结果表明:添加络合剂乙二胺后,不仅使银在铜基材表面的沉积速度减小,还使吸附的银原子沿铜基材表面生长,从而获得均匀致密的银镀层.     

Electrochemical studies on the electrodeposited Zn-Ni-Co ternary alloy in different media

The electroplating of ternary Zn-Ni-Co alloy, surface morphology and corrosion resistance were investigated and contrasted with the characteristics of Zn-Ni electrodeposits. The investigation of electrodeposition was carried out using cyclic voltammetry and galvanostatic techniques, while potentiodynamic polarization resistance and anodic linear sweeping voltammetry techniques were used for corrosion study. Under the examined conditions, the electrodeposition of the alloy was of anomalous type. It was found that the obtained Zn-Ni-Co alloy exhibited more preferred surface appearance and better corrosion resistance compared to Zn-Ni alloy that electrodeposited at similar conditions. During the cathodic scan of cyclic voltammetry, a cathodic peak at − 574 mV is appeared and correlated with the deposition of sulfur liberated from the reduction of sulphate group in the presence of H⁺. Up to four anodic peaks were obtained by cyclic voltammetry technique, two correlated with zinc oxidation from pure deposited Zn and γ-Ni₅Zn₂₁ phases and two correlated with oxidation of cobalt and nickel, were observed. The phase structure, surface morphology and chemical composition of the deposits were characterized by means of X-ray diffraction analysis, scanning electron microscopy and atomic absorption spectroscopy, respectively.     

Si含量对多元等离子体浸没离子注入与沉积技术制备TiAlSiN涂层微结构和机械性能的影响(英文)

采用多元等离子体浸没离子注入与沉积制备TiAlSiN纳米复合涂层,利用EDX,XRD,SEM,XPS,纳米探针和划痕试验对涂层成分组成、微结构和机械性能进行测试分析。XRD测试表明,TiAlSiN涂层具有较强的TiN(200)择优取向。XPS测试表明,TiAlSiN涂层中也含有AlN、Si3N4、Al2O3和Ti2O3。与制备的TiN涂层相比,当涂层中的Si含量为0.9%时,TiAlSiN涂层表现出较高的硬度,达32GPa,但涂层的断裂韧性和结合强度较低;当涂层中的Si含量增加至6.0%时,TiAlSiN涂层具有超高的硬度57GPa,并表现出较好的断裂韧性和结合强度。     

Ti-Al-N 涂层的组织结构与摩擦学性能

目的采用多元等离子体注入与沉积(MPIIID)技术制备Ti-Al-N涂层,系统研究涂层的微观组织结构、力学性能与摩擦学特性。方法借助XRD,XPS,SEM和TEM等,观察分析Ti-Al-N涂层的微观组织结构与物相组成,采用纳米压入试验仪、布氏硬度试验仪、摩擦磨损试验仪和激光共聚焦显微镜等测试分析Ti-Al-N涂层的力学性能、膜基结合力和摩擦磨损性能。结果 Ti-Al-N涂层表现出较高的膜-基结合强度。Al元素掺杂诱发Ti-Al-N涂层发生严重晶格畸变。当Al原子数分数为6.18%时,Ti-Al-N涂层以c-TiAlN相结构为主,表现出超高硬度(达到39.83 GPa);随着Al元素含量增加,涂层中的软质h-TiAlN相结构增多,硬度随之下降。摩擦试验结果表明,低Al含量Ti-Al-N涂层的抗磨损能力良好,其主要磨损机制为磨粒磨损;高Al含量Ti-Al-N涂层的抗磨损能力较差,其主要磨损机制倾向粘着磨损。结论 MPIIID技术成功实现了Ti-Al-N涂层的低温制备与成分调控,低Al含量的Ti-Al-N涂层具有优良的力学性能和优异的抗磨损能力。     

In-situ EQCM evaluation of the formation of UPD and OPD during electrodeposition of Pb on gold

Underpotential (UPD) and overpotential (OPD) deposition of Pb from a perchlorate solution on gold substrate was studied using in-situ electrochemical quartz crystal microbalance (EQCM) method. Cyclic voltammograms and current-transients recorded during potentiostatic electrochemical deposition were measured simultaneously with EQCM data including frequency and resistance. Results show that underpotential deposition (UPD) of Pb occurs before overpotential deposition (OPD) of Pb starts to grow, based on both massogram and cyclic voltammogram. The OPD of Pb grows at higher overpotentials which significantly influence the mechanism of nucleation and growth. EQCM reveals that the mass to charge ratio of OPD is different at different overpotentials, owing to the mechanism of nucleation and growth and possible roughening of grown Pb or hydrogen evolution. A comparison between our experimental data with the Scharifker-Hills theory based on non-dimensional plots shows an instantaneous mechanism. Scanning electron microscope taken from the electrodeposited lead on gold confirms the behaviour exhibiting almost same size of nuclei.     

Characterization of nanocrystalline Co–W coatings on Cu substrate,electrodeposited from a citrate-ammonia bath

Cobalt–tungsten nanocrystalline coatings were electrodeposited on copper substrate using different current densities. The deposited coatings were single phase solid solution with an average grain size of about 18 nm, showing a nodular type of surface morphology. By increasing the deposition current density, the density of nodules was increased, with no obvious variation in grain size. Electrochemical impedance spectroscopy (EIS) confirmed the codeposition of tungsten through reduction of tungsten oxide film formed during the electrodeposition process. However, the role of ternary complexes in the bath cannot be ruled out, especially at lower cathodic potentials. The Co–W coating deposited at lower current densities showed higher tungsten content, microhardness, wear resistance and friction coefficient. However, this coating showed an inferior corrosion resistance. By increasing the deposition current density, a low tungsten coating with high corrosion resistant was obtained. This is attributed to the lower value of exchange current density of water reduction in the present of oxygen (i₀^H2O) achieved on the coating with lower tungsten content.     

铜合金表面超音速微粒沉积镍基涂层的耐蚀性能研究

目的研究铜合金表面镍基合金涂层的耐腐蚀性能,解决铜合金表面腐蚀损伤问题。方法采用超音速微粒沉积技术在黄铜表面制备镍基合金涂层,通过电化学方法和中性盐雾实验对黄铜基体及镍基合金涂层的耐腐蚀性能进行测试。结果涂层的腐蚀电流密度较基体降低了34倍。涂层表面生成的连续且致密的氧化膜阻止了腐蚀的进一步发生,在盐雾腐蚀时间进行到500 h时,腐蚀速度接近于零,涂层腐蚀缓慢。结论超音速微粒沉积技术可以制备耐腐蚀性能优异的镍基合金涂层,并且可以显著提高黄铜的基体耐蚀性。     

Octanethiol coating of nano-sized copper powders using the vapor self-assembled monolayer method

Recent research has focused on preventing copper oxidation for direct wiring applications. In this study, a novel coating method was developed for nano-sized copper powders using vapor self-assembled monolayer (VSAM). The surfaces of oxidized and non-oxidized copper powders were studied to determine whether they can be coated with a vapor form of octanethiol. It was found that non-oxidized copper powders were successfully coated with the vapor form of octanethiol according to X-ray photoelectron spectroscopy (XPS) analysis. However, due to the partial coating of self-assembled monolayer (SAM) on a copper surface, a very small amount of copper oxide was detected when the coating mechanism was verified using Atomic Force Microscopy (AFM). Overall, the vapor form of octanethiol successfully adhered to the surface of nanosized copper powders, constituting the novel method of preventing oxidation. A complete coating method for the nano-sized copper powders must be developed in future research.