Electrodeposition of sol-enhanced nanostructured Ni-TiO2 composite coatings

A novel electroplating method has been developed to produce nanocrystalline metal-matrix nano-structured composite coatings. A small amount of transparent TiO₂ sol was added into the traditional electroplating Ni solution, leading to the formation of nanocrystalline Ni-TiO₂ composite coatings. These coatings have a smooth surface. The Ni nodules changed from traditional pyramid-like shape to spherical shape. The grain size of Ni was also significantly reduced to the level of 50 nm. It was found that the amorphous anatase TiO₂ nano-particles (∼ 10 nm) were highly dispersed in the coating matrix. The microhardness was significantly increased from 320 HV₁₀₀ of the traditional Ni coating to 430 HV₁₀₀ of the novel composite coating with 3.26 wt.% TiO₂. Correspondingly, the wear resistance of the composite coating was improved by ∼ 50%.     

Investigation on the corrosion and oxidation resistance of Ni-Al2O3 nano-composite coatings prepared by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique from a Watt's type electrolyte containing nano-Al₂O₃ particles. The corrosion resistance and high temperature oxidation resistance of resulting composite coatings were investigated. It was found that the incorporation of nano-Al₂O₃ particles in Ni matrix refined the Ni crystal and changed the preferential orientation of composite coatings. Meanwhile, the corrosion and oxidation resistance were improved after the incorporation of nano-Al₂O₃ particles into Ni matrix. The nano-Al₂O₃ content in deposits plays an important role for improving the corrosion and oxidation protection. The corrosion and oxidation resistance of Ni-Al₂O₃ nano-composite coatings produced via SCD technique are superior to that of CEP technique. Compared to pure Ni and Ni-Al₂O₃ composite coatings fabricated using CEP technique, the Ni-7.58 wt.% Al₂O₃ composite coating obtained by SCD technique exhibits better corrosion resistance and enhanced high temperature oxidation resistance. Moreover, the mechanism of corrosion and high temperature oxidation resistance of Ni-Al₂O₃ nano-composite coatings are discussed.     

纳米氧化铝粒子对化学镀镍-磷合金晶化行为的影响

通过化学复合镀制备纳米氧化铝粒子增强镍-磷合金复合镀层,并对所得表面纳米复合材料进行透射电镜显微分析(TEM)、扫描电镜显微分析(SEM)、X射线衍射分析(XRD)、能谱成分分析(EADX)和示差扫描量热分析(DSC).结果表明:纳米粒子在复合镀层中含量较高且分布均匀;所得镀层是中磷非晶态.纳米粒子使得复合镀层晶化温度降低,显微硬度值比镍-磷合金镀层明显提高.在一定条件下热处理,复合镀层晶化,硬度值大幅提高.     

Improved microhardness and wear resistance of the as-deposited electroless Ni-P coating

The coatings with different phosphorus contents were obtained by varying the ratio of lactic acid to acetic acid in the electroless plating bath. With the increase of phosphorus content, the structure of the electroless Ni-P coating transformed from nanocrystalline to a mixture of nanocrystalline and amorphous phases, then to amorphous phase. A record high hardness value of 910 HV_0.1 of as-deposited Ni-P coating was obtained at 7.97 at.% phosphorus content, and high wear resistance was accordingly achieved. The refined nanocrystalline grains with an average size of ~ 4 nm were found to be responsible for the record high hardness and improved wear resistance of the as-deposited Ni-P coating.     

Mechanical and tribological performance of Al2O3-TiO2 coatings elaborated by flame and plasma spraying

Mechanical properties and wear rates of Al₂O₃-13 wt.% TiO₂ (AT-13) and Al₂O₃-43 wt.% TiO₂ (AT-43) coatings obtained by flame and atmospheric plasma spraying were studied. The feed stock was either ceramic cords or powders. Results show that the wear resistance of AT-13 coatings is higher than that of AT-43 and it seems that the effect of hardness on wear resistance is more important than that of toughness. Additionally, it was established that, according to conditions used to elaborate coatings and the sliding tribological test chosen, spray processes do not seem to have an important effect on the wear resistance of these coatings.     

Effect of applied current on the electrodeposited Ni-Al2O3 composite coatings

Nano-sized Al₂O₃ ceramic particles (50 nm) were co-deposited with nickel using electrodeposition technique to develop composite coatings. The coatings were produced in an aqueous nickel bath at different current densities and the research investigated the effect of applied current on microstructure and thickness of the coatings. The variation in some mechanical properties such as hardness, wear resistance, and the adhesive strength of the composite coatings is influenced by the applied current and this was also studied. The morphology of the coatings was characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. The hardness, wear resistance, and bond strength of the coatings were evaluated by Vickers micro-hardness test, pin-on-disc test, and tensile test, respectively. Results showed that the Al₂O₃ particles were uniformly distributed in the coatings, and the coatings deposited at a current density of 0.01 A/cm² was most favorable in achieving a maximum current efficiency which causes the co-deposition of a maximum amount of Al₂O₃ particles (4.3 wt.%) in the coatings. The increase in Al₂O₃ particles in the coatings increased the mechanical properties of the Ni-Al₂O₃ composite coatings by grain refining and dispersion strengthening mechanisms.     

The effect of SiC particles added in electroless Ni-P plating solution on the properties of composite coatings

To verify the relationship between the properties of composite coatings prepared on Q235 steel and the SiC content of electroless Ni-P-SiC composite coatings, systematic experiments with varied SiC contents and surfactants have been conducted. The experimental results indicated the approximate linear relation between the SiC content and the hardness of composite coatings. With the increasing of SiC content, wear resistance increases correspondingly. In particular, the effect of SiC content on the corrosion resistance of Ni-P-SiC composite coatings immersed in different corrosive solutions (i.e. 5% H₂SO₄, 20% NaOH and 3.5% NaCl) is explored, followed by a comparative analysis of the corrosion resistance between Ni-P and Ni-P-SiC coatings. Corrosion test indicates that NaOH solution makes no differences in the corrosion resistance between Ni-P coatings and electroless Ni-P-SiC composite coatings, both being uncorroded. Exposed to NaCl solution, the corrosion resistance of electroless Ni-P-SiC composite coatings decreases gradually with the increasing of SiC content in coatings. In H₂SO₄ solution, the corrosion resistance of coatings increases initially and decreases afterwards with the sustained increasing of SiC content in coatings, and the optimized corrosion resistance is obtained at a SiC content of 9.41 wt.%. Finally, a competent electroless Ni-P-SiC composite plating process producing a high wear resistance and sound corrosion resistance of the coatings is obtained.     

A study of electroless copper-phosphorus coatings with the addition of silicon carbide (SiC) and graphite (Cg) particles

Copper composite coating with graphite (C_g) and/or silicon carbide (SiC) particles were deposited by electroless plating. The surface morphology of the coatings that were analysed using scanning electron microscopy (SEM) showed that Cu particles were uniformly distributed. The obtained coating thickness was approximately ± 5 μm. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques were used to characterise the structure and to study the phase transition of the coatings, respectively. Phases such as Cu, Cu₂O, Cu₃P, Cu₃Si, SiC and C_g were observed from X-ray diffraction patterns and the presence of Cu₂O, Cu₃P and Cu₃Si was confirmed by differential scanning calorimetry (DSC) studies. The results demonstrated that SiC and C_g particles have little influence on the phase transition of the coating. The hardness and wear resistance of Cu-P composite coatings were improved with the incorporation of SiC particles. The friction coefficient of Cu-P composite coatings decreased with the incorporation of C_g particles. Atomic force microscopy (AFM) results of coatings showed that the roughness of the coatings increased with the incorporation of SiC to the Cu-P coatings and decreased with the incorporation of C_g. Cu-P-C_g-SiC composite coatings showed a moderate roughness, hardness between Cu-P-SiC and Cu-P-C_g coatings, had low friction and good anti-wear properties. The anti corrosion resistance of the electroless Cu-P composite coatings on carbon steel were studied in 3.5% NaCl and 1 M HCl solutions by the potentiodynamic polarisation technique. The study revealed that the corrosion resistance increased with the incorporation of SiC particles in the Cu-P and Cu-P-C_g matrix but reduced with the incorporation of graphite.     

Microstructure and electromagnetic properties of Al18B4O33w/Co composite particles prepared by electroless plating method

Al₁₈B₄O₃₃w/Co composite particles were prepared successfully through electroless plating Co on Al₁₈B₄O₃₃ whiskers. The growth behavior of the coatings, the effect of the process parameters and the electromagnetic properties of the prepared Al₁₈B₄O₃₃w/Co composite particles were investigated. The reduced Co nucleated first on the pre-activated surface of the whiskers to form insular particles which then grew larger gradually and eventually merged together to form continuous coatings. The reaction rate increased but the mass gain decreased with the increase of the bath pH and the bath temperature. The crystallinity of the deposited Co decreased with the increase of phosphorous content as well as the bath temperature. The effect of loading is much weaker compare to that of bath pH and bath temperature. The permittivity and the permeability of the prepared Al₁₈B₄O₃₃w/Co composite particles are markedly higher than those of the raw Al₁₈B₄O₃₃ whiskers in microwave band. Relaxation resonance is found in the samples with thick Co coatings due to the presence of eddy current, which deteriorates the permeability of the Al₁₈B₄O₃₃w/Co composite particles.     

ZrO2 加入量对Zr-8Al合金化学复合镀性能的影响

对Zr-8Al合金进行了化学复合镀Ni-P-ZrO_2处理,并研究了不同ZrO_2粒子加入量制备的复合镀层的显微结构、显微硬度、耐磨性和抗蚀性。结果表明,与单纯化学镀Ni-P镀层相比,Ni-P-ZrO_2复合镀层的显微硬度值显著提高,ZrO_2的添加量为4 g/L获得复合镀层显微硬度最高,耐磨性好;在3.5%(质量分数)NaCl溶液中耐蚀性虽有所下降,但腐蚀后镀层完整,仍具有较好的抗蚀性。Zr-8Al合金表面采用4 g/L ZrO_2粒子制备的Ni-P-ZrO_2复合镀层兼具很好的耐磨性和较好的耐蚀性,适用于既要耐磨又要抗蚀的空间活动构件。     

Characterization of electrodeposited Ni-TiO2 nanocomposite coatings

Nanocomposites containing titania nanoparticles in a nickel matrix have been prepared by means of electrocodeposition from two different types of nickel plating baths, viz. an acidic sulfamate and an alkaline pyrophosphate bath. The surface charge and sedimentation behavior of the titania particles in these electrolytes were characterized by zeta potential and stability measurements. A maximum particle incorporation of 4.3 wt.% titania was found for the alkaline pyrophosphate bath. The structure and mechanical properties of the coatings have been investigated as a function of the particle content. The surface morphology and microstructure of the nickel matrix was significantly altered due to the presence of titania nanoparticles. In the case of both nickel baths, the Vickers microhardness showed a tendency to increase with the amount of particle incorporation. The wear resistance increased with decreasing current density and due to the particle incorporation.     

Metallization on polymer by catalyzation in supercritical CO2 and electroless plating in dense CO2 emulsion

In this study we propose a novel technique for electroless plating on polymer substrates using a dense CO₂ beyond the critical point. Ni–P thin films were fabricated by a novel, hybrid technique consisting of two processes: catalyzation in supercritical CO₂ with Pd bis-acetylacetonate and electroless plating in emulsion with dense carbon dioxide. These catalyzation processes were discussed by atomic force microscopic images and the roughness of the surface. Catalyzation in supercritical CO₂ enabled the nucleation of a large number of Pd nuclei on a polyimide substrate without chemical pretreatment, and the deposition of a uniform Ni–P metal film. Conventional catalyzation without chemical pretreatment led to the deposition of only a few nuclei in sparse, island-like formations. The deposition behavior of Pd nuclei in supercritical CO₂ was different from that in conventional catalyzation. When a polyimide was catalyzed in supercritical CO₂ and plated by conventional electroless plating in electrolyte solution, the plated film was pocked with small, peeled sections formed via the hydrogen bubbles of the sub-reaction and nodules formed via crystal growth of Ni–P. In contrast, the electroless plating in emulsion with dense CO₂ produced a uniformly plated film without peeling or nodules. The improved uniformity was attained by the solubility and diffusivity of the dense CO₂ beyond the critical point in the emulsion.     

A new method for electroless Ni-P plating on AZ31 magnesium alloy

Coating Ni-P films on AZ31 magnesium alloys via electroless plating and organic coatings (organsilicon heat-resisting varnish), was studied. An organic coating was proposed as the interlayer between Ni-P coating and AZ31magnesium alloy substrate, to replace the traditional chromium oxide plus HF pretreatment. The Ni-P deposited on the interlayer was also characterized by its structure, morphology and corrosion-resistance. The interlayer on the substrate not only reduces the corrosion of magnesium during Ni-P plating process, but also reduces the potential difference between the matrix and the second phase. The result of the cross-cut test indicates the adhesion between the substrate and the interlayer is good enough. A Ni-P film with fine and dense structure was obtained on the AZ31 magnesium alloy. The electrochemical measurements show that the sample with Ni-P film exhibits lower corrosion current density and more positive corrosion potential than the substrate. Furthermore, the Ni-P coating on the AZ31 magnesium alloy exhibits high corrosion resistance in the rapid corrosion test illustrated in this paper. The method proposed in this work is environmentally friendly: no fluoride or hexacalent chromium compounds are used. In addition, it provides a new concept for plating the metals, which are considered difficult to plate due to high reactivity.     

Preparation of nanostructured Ni/Al2O3 composite coatings in high magnetic field

Ni/Al₂O₃ composite coatings were prepared by a novel method from a modified Watt's type electrolyte containing nano-Al₂O₃ particles, where a high magnetic field was imposed in the direction parallel to an electrolytic current instead of mechanical agitation. Effects of magnetic field on the content of particles, surface morphology, microhardness and wear resistance of plating layer were investigated. It was found that the high magnetic field played an important role in the formation of composite coatings. The amounts of nano-Al₂O₃ particles in the composite coating increased with increasing of magnetic flux density and reached a maximum value at 8 T, then reduced slightly. The microhardness and wear resistance of the nanocomposite coatings also enhanced with increasing of magnetic flux density as compared to that of pure Ni coating fabricated in the absence of magnetic field. That was because the co-deposited nano-Al₂O₃ particles were uniformly distributed in the Ni matrix and contributed to greatly increase the microhardness and wear resistance of the composite coatings. Moreover, the mechanism of action of high magnetic field was discussed preliminarily.     

Thermal conductive properties of Ni-P electroless plated SiCp/Al composite electronic packaging material

Electroless plated SiC_p/Al composites with a high thermal conductivity are required for electronic packaging application. In this paper, in-plane thermal conductive properties of SiC_p/Al composites with and without electroless plated Ni-P coatings are compared, and influence of various characteristics of Ni-P coatings are investigated. It is found that in addition to thickness of the coatings, phosphorus concentration and microstructure of the plated layers also influence the thermal conductive properties of plated composites. Based on the results, it is suggested that a low phosphorus concentration and a properly tailored crystalline microstructure of the Ni-P coatings, together with a reasonable choice of coating thickness, may contribute to optimization of thermal conductive properties of the composite material.     

Improving the surface hardness and wear resistance of Ti3SiC2 by boronizing treatment

In order to modify surface properties of Ti₃SiC₂, boronizing was carried out through powder pack cementation in the 1100-1400 °C temperature range. After boronizing treatment, one mixture layer, composed of TiB₂ and β-SiC, forms on the surface of Ti₃SiC₂. The growth of the coating is processed by inward diffusion of boron and obeys a linear rule. The boronizing increases the hardness of Ti₃SiC₂ from 3.7 GPa to a maximal 9.3 GPa and also significantly improves its wear resistance.     

Thermal conductivity and thermal cycle life of La2O3 and HfO2 doped ZrO2-Y2O3 coatings produced by EB-PVD

The effects of La₂O₃ and HfO₂ addition on thermal conductivity and thermal cycle life of EB-PVD YSZ coatings were investigated. La₂O₃ and HfO₂ were selected as additives, because they significantly suppress the sintering of YSZ. The developed coating showed low thermal conductivity as well as high resistance to sintering. Burner rig tests confirmed that the developed coating have a superior thermal insulating effect and have a longer life than that of a coating with conventional composition.     

Wear and corrosion resistance behaviours of autocatalytic electroless plating

Nickel–boron coatings were deposited on steel and aluminium substrates. Their morphology, roughness, hardness, wear resistance and electrochemical properties were investigated. A comparison between the coated systems was carried out. The plated aluminium was found to present better roughness and corrosion resistance behaviours than coated steel. The wear resistance of both coated systems is very similar. The aluminium-based system presents a more noble electrochemical behaviour than the coated steel.     

Microstructure and mechanical properties of Al2O3-Cr2O3 composite coatings produced by atmospheric plasma spraying

Al₂O₃, Al₂O₃-Cr₂O₃ and Cr₂O₃ coatings were deposited by atmospheric plasma spraying. Phase composition of powders and as-sprayed coatings was determined by X-ray diffraction. Electron probe microanalyzer was employed to investigate the polished and fractured surface morphologies of the coatings. Mechanical properties including microhardness, fracture toughness and bending strength were evaluated. The results indicate that the addition of Cr₂O₃ is conducive to the stabilization of α-Al₂O₃. Compared with the pure Al₂O₃ and Cr₂O₃ coatings, Al₂O₃-Cr₂O₃ composite coatings show lower porosities and denser structures. Heterogeneous nucleation of α-Al₂O₃ occurs over the isostructural Cr₂O₃ lamellae and partial solid solution of Al₂O₃ and Cr₂O₃ might be occurring as well. Furthermore, grain refining and solid solution strengthening facilitate the mechanical property enhancement of Al₂O₃-Cr₂O₃ composite coatings.     

Degradation behaviour of ZrO2-Ni/Al gradient coatings in molten Zn

In order to improve the corrosion resistance of metallic materials in molten zinc, ZrO₂-Ni/Al gradient coatings were sprayed on the surface of the Fe-0.35-0.44 wt.% C steel. The corrosion behaviour and corrosion mechanism of the ZrO₂-Ni/Al gradient coatings in molten zinc were studied. The ZrO₂-Ni/Al gradient coatings on the surface of steels prolonged the lifetime of samples and changed the corrosion behaviour of the samples in molten zinc. The lifetime of the ZrO₂-Ni/Al gradient coatings immersed in molten zinc at 620 °C is 28 days, which is 4 times as long as that of the general ZrO₂ coatings. The ZrO₂-Ni/Al gradient coatings were corroded in molten zinc at 620 °C, which was caused by zinc atom diffusing along the crystal boundary and pores of the ZrO₂-Ni/Al gradient coatings, and reacting with Ni/Al particle in the ZrO₂-Ni/Al gradient coatings. The corrosion mechanism of the coatings in molten zinc at 620 °C was crystal boundary corrosion, pitting corrosion and reaction corrosion.