Effects of pulse electrodeposition parameters on the properties of Ni-TiO2 nanocomposite coatings

The aim of this study is to investigate the effects of pulse electrodeposition parameters on the properties of nickel-titania composite coatings electrodeposited from a nickel Watts type bath. The effects of average current density, frequency and duty cycle on the surface morphology, crystal size, preferred orientation of the deposits and the amount of embedded nano-TiO₂ particles in the composite coatings were investigated. The results represented the optimum amount of average current density (e.g., 4 A dm⁻²) for obtaining the highest volume percentage of the incorporated titania particles and subsequently the maximum microhardness. Moreover, by increasing the frequency up to 10 Hz while reducing the duty cycle to 10% at constant peak current density, the volume percentage of particles increased to about 7% which is almost twice as much the volume percentage as deposited particles in direct current method. According to the results the composite coating exhibited obviously [1 0 0] + [2 1 1] as preferred orientation at low pulse frequency and the diffraction intensity of the [2 1 1] fiber orientation is increased, probably due to the pH increase adjacent to the electrolyte/cathode interface at higher frequencies. Also, it has been found that by reduction in the duty cycle, more titania particles were incorporated in the composite coatings and this promoted the nickel crystals growth on [1 0 0] planes and consequently the coatings preferred orientation changed from the [2 1 1] to [1 0 0] + [2 1 1] planes.     

Microstructure and surface mechanical properties of pulse electrodeposited nickel

The surface of carbon steel was modified by electrochemical deposition of Ni in a standard Watt's bath using dc and pulse plating electrodeposition. The aim was to compare the microstructure and surface mechanical properties of the deposit obtained by both techniques. Materials characterization was conducted using field emission scanning electron microscope fitted with scanning transmission electron detector, atomic force microscope and X-ray diffractometer. Nanoindentation hardness, elastic modulus, adhesion, coefficients of friction and wear rates were determined for both dc and pulse electrodeposits. Experimental results indicate that pulse electrodeposition produced finer Ni grains compared to dc plating. Size of Ni grains increased with deposition. Both dc and pulse deposition resulted in grain growth in preferred (2 0 0) orientation. However, presence of Ni (1 1 1) grains increased in deposits produced by pulse deposition. Pulse plated Ni exhibited higher hardness, creep and coefficient of friction and lower modulus of elasticity compared to dc plated Ni.     

Ni-Co-TiO2 nanocomposite coating prepared by pulse and pulse reversal methods using acetate bath

Ni-Co/nano TiO₂ (Ni-Co-TiO₂) composite coatings were prepared under pulse current and pulse reverse current methods using acetate bath. The microstructure and corrosion resistance of the coatings were characterized by means of XRD, SEM and EIS. Both the Ni-Co alloy and composite coatings exhibited single phase of Ni matrix with face centered cubic (fcc) crystal structure. The crystal orientation of the Ni-Co-TiO₂ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with Ni-Co alloy coatings. The results showed that the microstructure and performances of the coatings were greatly affected by TiO₂ content on the deposits prepared by PC and PRC methods. The microhardness and corrosion resistance were enhanced in the optimum percentage of TiO₂ composite coatings. The PRC composite coatings were exhibited from compact surface, higher microhardness and good corrosion resistance compared with that of the PC composite coating.     

Preparation and characterization of nickel nano-Al2O3 composite coatings by sediment co-deposition

Ni-Al₂O₃ composite coatings were prepared by using sediment co-deposition (SCD) technique and conventional electroplating (CEP) technique from Watt's type electrolyte without any additives. The microstructure, hardness, and wear resistance of resulting composites were investigated. The results show that the incorporation of nano-Al₂O₃ particles changes the surface morphology of nickel matrix. The preferential orientation is modified from (2 0 0) plane to (1 1 1) plane. The microhardness of Ni-Al₂O₃ composite coatings in the SCD technique are higher than that of the CEP technique and pure Ni coating and increase with the increasing of the nano-Al₂O₃ particles concentration in plating solution. The wear rate of the Ni-Al₂O₃ composite coating fabricated via SCD technique with 10 g/l nano-Al₂O₃ particles in plating bath is approximately one order of magnitude lower than that of pure Ni coating. Wear resistance for SCD obtained composite coatings is superior to that obtained by the CEP technique. The wear mechanism of pure Ni and nickel nano-Al₂O₃ composite coatings are adhesive wear and abrasive wear, respectively.     

Preparation of pulse plated GaAs films

Thin GaAs films were prepared by pulse plating from an aqueous solution containing 0.20 M GaCl₃ and 0.15 M As₂O₃ at a pH of 2 and at room temperature. The current density was kept as 50 mA cm⁻² the duty cycle was varied in the range 10-50%. The films were deposited on titanium, nickel and tin oxide coated glass substrates. Films exhibited polycrystalline nature with peaks corresponding to single phase GaAs. Optical absorption measurements indicated a direct band gap of 1.40 eV. Photoelectrochemical cells were made using the films as photoelectrodes and graphite as counter electrode in 1 M polysulphide electrolyte. At 60 mW cm⁻² illumination, an open circuit voltage of 0.5 V and a short circuit current density of 5.0 mA cm⁻² were observed for the films deposited at a duty cycle of 50%.     

Details of crystalline growth in co-deposited electroplated nickel films with hard (nano)particles

Electroplated nickel dispersion films with incorporated hard particles, primarily titanium oxide, were studied. A sufficient dispersion of nanometre-scaled particles in Watts solution was reached by application of ultrasonic energy to the galvanic bath. Crystal morphology, mean grain size and formation of textures were examined by electron backscattering diffraction (EBSD), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The typical columnar structure of pure Ni films was refined by means of ultrasound. Incorporation of micron-sized TiO₂ particles generates additional nucleation surfaces in contrast to SiC particles. Textures of the subsequent columnar nickel crystals change from 〈2 1 1〉 (silent condition) or 〈1 1 0〉 (ultrasonic condition) fibre textures in growth direction to 〈1 0 0〉 and 〈1 1 1〉 textures under the influence of nanoparticle incorporation. Moreover, nanoparticles remarkably decrease the grain size and grain aspect ratio. Their incorporation takes place inside the crystals as well as between grains.     

Study of deposition patterns of plating layers in SiC/Cu composites by electro-brush plating

SiC reinforced copper composite coatings were prepared by electro-brush plating with micron-size silicon carbide (SiC) ranging from 1 to 5 μm on pure copper sheet in this paper. The micro-structural characterizations of SiC/Cu composite coatings were performed by optical microscope and Scanning Electron Microscope (SEM) coupled with spectrometer, to study co-deposition mechanism of SiC/Cu. It was found that there were three different patterns of SiC deposition in plating layers during electro-brush plating process, i.e. the particles could deposit inside copper grains, in grain boundaries, or in holes of the surface. To investigate deposition mechanism of each pattern, size of SiC and copper grains was compared. By comparison of size of copper grains and hard particles, SiC were either wrapped in copper grains or deposited in grain boundaries. Moreover, electro-brush plating layers at different brush velocities and current densities were obtained respectively, to analyze the microstructure evolution of the composite coatings. The hardness of plating layers was measured. The results indicated at the current density of 3 A/dm², the SiC/Cu coating was compact with SiC content at a high level and the hardness reached a maximum.     

Preparation and wear resistance of pulse electrodeposited Ni-W/Al2O3 composite coatings

The aim of this work is to obtain the electroplating parameters for preparation of Ni-W/Al₂O₃ composite coating with high tungsten content, high micro-hardness and excellent wear resistance by pulse plating procedure. Our results showed that the duty cycle is a dominant parameter for the tungsten content in the coating and the tungsten content increases significantly with increasing duty cycle. The further analysis showed the great influence of tungsten content on micro-hardness of the coating. A maximum micro-hardness of about 859 Hv was obtained in pulse electrodeposited Ni-W/Al₂O₃ composite with tungsten content of 40 wt.% at a peak current density of 20 A/dm², a duty cycle of 80%, a pulse frequency of 1000 Hz and a particle loading of 10 g/L alumina in the plating bath. Although the hardness of Ni-W/Al₂O₃ composite coating was only slightly affected by the alumina content of the deposits prepared in present investigation, the alumina content effect on the tribological characteristic of Ni-W/Al₂O₃ composite coatings is significant. The friction coefficient was lowered to 0.25 and the wear loss was reduced to 1.05 mg by setting the control factors according to the values mentioned above for obtaining the coating with the highest micro-hardness.     

Copper coated nickel foam as current collector for H2S-containing syngas solid oxide fuel cells

Copper coated nickel foam with Cu/Ni ratio of 2.5 was fabricated using electrochemical plating and characterized using XRD, SEM, EDS and Van der Pauw four point conductivity measurements. Copper coated nickel foam exhibited good stability of electronic conductivity and mechanical strength during more than 150 h exposure to 500 ppm H₂S-containing syngas at 750 °C. In contrast, uncoated nickel foam readily underwent severe carbon deposition and brittle fracture resulting in dramatic increase of electronic resistance under the same testing conditions. Copper coated nickel foam is a promising current collector for H₂S-containing syngas solid oxide fuel cells (SOFCs).     

Electrochemical deposition and tribological behaviour of Ni and Ni-Co metal matrix composites with SiC nano-particles

Metal matrix composites reinforced with nano-sized particles have attracted scientific and technological interest due to the enhanced properties exhibited by these coatings. Ni-SiC composites have gained widespread application for the protection of friction parts in the automobile industry. The influence of variables like SiC content, current density and stirring speed on microhardness of nano-composite coatings has been studied. The improved microhardness was associated with the reduction in crystallite size determined by X-ray diffraction studies. The influence of incorporation of nano-SiC in hardened Ni-Co alloy matrix was also studied. It was observed that for 28 wt.% Co content in the matrix the microhardness was higher compared to 70 wt.% for a given nano-SiC content. This was associated to the crystal phase of Ni-28Co-SiC being fcc compared to hcp phase exhibited by Ni-70Co-SiC. The wear resistance of pure Ni, Co and nano-composite coatings was studied using pin-on-disc wear tester under dry sliding condition. The volumetric wear loss indicated that, the wear resistance of Ni-SiC nano-composite is better than that of pure nickel deposit. The wear resistance of Ni-Co composites was observed to be superior to Ni composite. The wear behaviour of Ni and Ni-28Co composite was in accordance with the Archard's law. However, the superior wear characteristic exhibited by Ni-70Co-SiC composite followed the reverse Archard's behaviour.     

A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment

A novel Ni based coating - plasma electrolytic oxidation (PEO) pre-treatment followed by electroless nickel (EN) plating - has been developed to produce pore free Ni coatings on AZ91 magnesium alloy. The application of the PEO film between the nickel coating and the substrate acts as an effective barrier and catalytic layer for the subsequent nickel plating. The potentiodynamic tests indicated that the corrosion current density of the PEO + EN plating on AZ91 decreased by almost two orders of magnitudes compared to the traditional EN coating. Salt fog spray testing further proved this improvement. More importantly, the new technique does not use Cr⁺⁶ and HF in its pretreatment, therefore is a much environmentally friendlier process.     

Nanostructured core-shell Ni deposition on SiC particles by alkaline electroless coating

In this study, core-shell nanostructured nickel formation on silicon carbide (SiC) ceramic powders was achieved through the electroless deposition method using alkaline solutions. To produce a nano core-shell Ni deposition on the SiC surfaces, process parameters such as pH values, the type of reducer material, deposition temperature, stirring rate and activation procedure among others were determined. Full coverage of core-shell nickel structures on SiC surfaces was achieved with a grain size of between 100 and 300 nm, which was approximately the same deposition thickness on the SiC surfaces. The surface morphology of the coated SiC particles showed a homogenous distribution of nanostructured nickel grains characterized by scanning electron microscopy and X-ray diffraction techniques. The nanostructures of the crystalline Ni coatings were observed to be attractive for achieving both good bonding and dense structure. The thin core shell-structure of Ni on the SiC surfaces was assessed as a beneficial reinforcement for possible metal matrix composite manufacturing.     

Codeposition of SiC particles with electrolytic cobalt in the presence of Cs ions

Electrodeposition of SiC particles with cobalt matrix in the presence of cesium ions was studied. The influence of Cs⁺ concentration (0-37.6 mM) on the cathodic polarization curves was determined in galvanostatic and potentiodynamic measurements. It was found that the presence of Cs⁺ in the solution enhanced adsorption of Co²⁺ ions on SiC, but preferential cesium adsorption occurred simultaneously. The last phenomena resulted in cesium incorporation in the composite coating. Surface charge of SiC powder and amounts of functional groups on SiC surface were determined. The particles incorporation into deposits was only little dependent on cesium concentration in the bath. Structure of the composite coatings was studied by microscopic observations. Microhardness of the deposits was also determined.     

Electrodeposition and characterization of Ni-Y2O3 composite

Nano-sized Y₂O₃ particles were codeposited with nickel by electrolytic plating from a nickel sulfate bath. The effects of the incorporated Y₂O₃ on the structure, morphology and mechanical properties (including microhardness, friction coefficient and wear resistant) of Ni-Y₂O₃ composite coatings were studied. It is observed that the addition of nano-sized Y₂O₃ particles shows apparent influence on the reduction potential and pH of the electrolyte. The incorporated Y₂O₃ increases from 1.56 wt.% to 4.4 wt.% by increasing the Y₂O₃ concentration in the plating bath from 20 to 80 g/l. XRD results reveal that the incorporated Y₂O₃ particles favour the crystal faces (2 0 0) and (2 2 0). SEM and AFM images demonstrate that the addition of Y₂O₃ particles causes a smooth and compact surface. The present study also shows that the codeposited Y₂O₃ particles in deposits decrease the friction coefficient and simultaneously reduce the wear weight loss. Ni-Y₂O₃ composite coatings reach their best microhardness and tribological properties at Y₂O₃ content 4.4 wt.% under the experiment conditions.     

Preparation, characterization and microwave absorption properties of electroless Ni-Co-P-coated SiC powder

Silicon carbide particles reinforced nickel-cobalt-phosphorus matrix composite coatings were prepared by two-step electroless plating process (pre-treatment of sensitizing and subsequent plating) for the application to lightweight microwave absorbers, which were characterized by scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), vibrating sample magnetometer (VSM) and vector network analyzer, respectively. The results show that Ni-Co-P deposits are uniform and mixture crystalline of α-Co and Ni₃P and exhibit low-specific saturation magnetization and low coercivity. Due to the conductive and ferromagnetic behavior of the Ni-Co thin films, high dielectric constant and magnetic loss can be obtained in the microwave frequencies. The maximum microwave loss of the composite powder less than −32 dB was found at the frequency of 6.30 GHz with a thickness of 2.5 mm when the initial atomic ratio of Ni-Co in the plating bath is 1.5.     

Friction and wear properties of the co-deposited Ni-SiC nanocomposite coating

Ni-SiC nanocomposite coatings were produced by electrodeposition from a nickel sulfate bath containing SiC nanoparticles with an average particle size of 30 nm. The characteristics of the coatings were assessed by scanning electron microscopy and microhardness test. The friction and wear performance of Ni-SiC nanocomposite coatings and Ni film were comparatively investigated sliding against Si₃N₄ ceramic balls under non-lubricated conditions. The results indicated that compared to Ni film, Ni-SiC nanocomposite coating exhibited enhanced microhardness and wear resistance. The effect of SiC nanoparticles on the friction and wear resistance is discussed in detail.     

Physical and electrochemical characterizations of Ni-SiO2 nanocomposite coatings

Advances in materials performance often require the development of composite system. In the present investigation, SiO₂-reinforced nickel composite coatings were deposited on a mild steel substrate using direct current electrodeposition process employing a nickel acetate bath. Surface morphology, composition, microstructure and crystal orientation of the Ni and Ni-SiO₂ nanocomposite coatings were investigated by scanning electron microscope, energy dispersive X-ray spectroscopy and X-ray diffraction analysis, respectively. The effect of incorporation of SiO₂ particles in the Ni nanocomposite coating on the microhardness and corrosion behaviour has been evaluated. Smooth composite deposits containing well-distributed silicon oxide particles were obtained. The preferred growth process of the nickel matrix in crystallographic directions <111>, <200> and <220> is strongly influenced by SiO₂ nanoparticles. The average crystallite size was calculated by using X-ray diffraction analysis and it was ~23 nm for electrodeposited nickel and ~21 nm for Ni-SiO₂ nanocomposite coatings. The crystallite structure was fcc for electrodeposited nickel and Ni-SiO₂ nanocomposite coatings. The incorporation of SiO₂ particles into the Ni matrices was found to improve corrosion resistance of pure Ni coatings. The corrosion potential (E _corr) in the case of Ni-SiO₂ nanocomposite coatings had shown a negative shift, confirming the cathodic protective nature of the coating. The Ni-SiO₂ composite coatings have exhibited significantly improved microhardness (615 HV) compared to pure nickel coatings (265 HV)     

Carbon nanotube field emission cathodes fabricated with chemical displacement plating

A new approach for making field emission cathodes consisting of carbon nanotubes (CNTs) is discussed. The authors used a chemical displacement technique to fabricate field emission cathodes by co-depositing CNTs/nickel composite onto the surface of a zinc-coated soda-lime glass. There are several advantages of this displacement method for preparing field emission cathodes such as the uniform distribution of CNTs in the composite cathodes, low cost of consumed CNTs, low cost of instrument and equipment, feasibility of large-area mass production, and stability of plating solution, which can be used for many times and still remain useful after a long-time storage. The results show that, after the CNT purification and dispersion processes, a CNT content of 1.0 g/L, a pH value of 7.0, and a temperature of 50 ± 3 °C are the optimal process conditions which give better CNT distribution in the CNTs/Ni composite emitter and better field emission performance. The CNTs/Ni composite deposited with a plating solution which has been used for tens of times has an emission effect similar to those deposited with a new solution.     

Microstructure and properties of Ni-Co/nano-Al2O3 composite coatings by pulse reversal current electrodeposition

Ni-Co/nano-Al₂O₃ (Ni-Co/Al₂O₃) composite coatings were prepared under pulse reversal current (PRC) and direct current (dc) methods respectively. The microstructure of coatings was characterized by means of XRD, SEM and TEM. Both the Ni-Co alloy and composite coatings exhibit single phase of Ni matrix with face-centered cubic (fcc) crystal structure, and the crystal orientation of the Ni-Co/Al₂O₃ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with alloy coatings. The hardness, anti-wear property and macro-residual stress were also investigated. The results showed that the microstructure and performance of the coatings were greatly affected by Al₂O₃ content and the electrodeposition methods. With the increasing of Al₂O₃ content, the hardness and wear resistance of the composite coatings enhanced. The PRC composite coatings exhibited compact surface, high hardness, better wear resistance and lower macro-residual stress compared with that of the dc composite coatings.     

Effect of the dispersibility of ZrO2 nanoparticles in Ni-ZrO2 electroplated nanocomposite coatings on the mechanical properties of nanocomposite coatings

ZrO₂ nanoparticles was uniformly co-deposited into a nickel matrix by electroplating of nickel from a Watts bath containing particles in suspension which were monodispersed with dispersant under DC electrodeposition condition. It was found that morphology, orientation and hardness of the nanocomposite coatings with monodispersed ZrO₂ nanoparticles had lots of difference from the nanocomposite coatings with agglomerated ZrO₂ nanoparticles and pure nickel coatings. Especially, the result of hardness showed that only a very low volume percent (less than 1 wt.%) of monodispered ZrO₂ nanoparticles in Ni-ZrO₂ nanocomposite coatings would result in higher hardness of the coatings. The hardness of Ni-ZrO₂ nanocomposite coatings with monodispersed and agglomerated ZrO₂ nanoparticles were 529 and 393 HV, respectively. The hardness value of the former composite coatings was over 1.3 times higher than that of the later. All these composite coatings were two-three times higher than that of pure nickel plating (207 HV) prepared under the same condition. The strengthening mechanisms of the Ni-ZrO₂ nanocomposite coatings based on a combination of grain refinement strengthening from nickel matrix grain refining and dispersion strengthening from dispersion state of ZrO₂ nanoparticles in the coatings.