Phase transformation behavior of nanocrystalline Ni-W-P alloys containing various W and P contents

In the present investigation, electroless (EL) ternary Ni-W-P coatings were prepared using hypophosphite based alkaline bath by varying sodium tungstate as tungsten source (5-80 g/L). Maximum amount of W incorporation (8.2 ± 1 wt.%) was obtained when the bath contained about 20 g/L of tungsten source. At very high concentrations of W source in the bath the deposit contained about 4 wt.% W and 2 wt.% P. All the as-deposited ternary coatings exhibited nodular surface morphology. X-ray diffractograms (XRD) obtained for as-deposited EL NiWP alloys indicated that crystallinity of the coatings increased with decrease in phosphorus content. Calculated grain size for the deposits varied from 1.2 to 12.7 nm when the tungsten source varied from 5 to 80 g/L in the bath. Higher crystallization temperatures were obtained due to W codeposition in NiP matrix. Presence of metastable phases such as Ni₅P₂ and NiP apart from stable Ni and Ni₃P was identified for the heat treated deposits (400 °C/1 h) containing lower amount of W and higher amount of P. Whereas other ternary deposits after the heat treatment predominantly revealed face centered cubic (f.c.c.) Ni (111) peak. Activation energy for the crystallization of all the alloys has been carried out by modified Kissinger method. Microhardness measurements were carried out on all the deposits isothermally heat treated at 600 °C for 1 h.     

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.     

A novel electroless plating of Ni-P-TiO2 nano-composite coatings

A new processing concept has been developed to produce nano-structured metal-matrix composite coatings. This method combines sol-gel and electroless plating techniques to prepare highly dispersive oxide nano-particle reinforced composite coatings. Transparent TiO₂ sol was added into the standard electroless plated Ni-P solution at a controlled rate to produce Ni-P-TiO₂ nano-composite coatings on Mg alloys. The coating was found to have a crystalline structure. The nano-sized TiO₂ particles (∼ 15 nm) were well dispersed into the Ni-P coating matrix during the co-deposition process. This technique can effectively avoid the agglomeration of nano-particles in the coating matrix. As a result, the microhardness of the composite coatings were significantly increased to ∼ 1025 HV₂₀₀ compared to ∼ 710 HV₂₀₀ of the conventional composite coatings produced with solid particle mixing methods. Correspondingly, the wear resistance of the new composite coatings was also greatly improved.     

Co-electrodeposition and characterization of Cu-Si3N4 composite coatings

Smooth copper coatings containing well-distributed silicon nitride particles were obtained by co-electrodeposition in acidic sulfate bath. The cathodic current density did not show significant influence on incorporated particle volume fraction, whereas the increase of particle concentration in the bath led to its decrease. The increase of stirring rate increased the amount of embedded particles. The microhardness of the composite layers was higher than that of pure copper deposits obtained under the same conditions due to dispersion-strengthening and copper matrix grain refinement and increased with the increase of incorporated particle volume fraction. The microhardness of composites also increased with the increase of current density due to copper matrix grain refining. The composite coatings presented higher strength but lower ductility than pure copper layers. Pure copper and composite coatings showed the same corrosion resistance in 0.5 wt.% H₂SO₄ solution at room temperature.     

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.     

Surface morphology and structure of Ni-P, Ni-P-ZrO2, Ni-W-P, Ni-W-P-ZrO2 coatings deposited by electroless method

Electroless binary Ni-P and ternary Ni-W-P alloy coatings and electroless composite (Ni-P-ZrO₂ and Ni-P-W-ZrO₂) nickel coatings were deposited. Baths with aminoacetic acid as the complexing agent were used. ICP measurements showed that the P content depending on the type of coating is in a range of 4.7-6.3 wt.% (at pH = 6, t = 75 °C). The tungsten content is around 1-2 wt.%. SEM examinations show that the electroless Ni-P coating has the most fine-grained structure. Grains in the form of microspheroids 20 μm in size are characteristic of the Ni-P-ZrO₂ coating. X-ray diffraction patterns show that for all the obtained coatings peak Ni(111) located around 2θ = 44° is the most intensive. After the coatings are heat treated at 400 °C for 1 h the peak becomes even sharper. The heat treatment results in a nearly double increase in crystallite size. The quaternary coatings' abrasion resistance is determined by the second-phase (ZrO₂) particles present in them.     

Hot corrosion behaviour of plasma sprayed YSZ/Al2O3 dispersed NiCrAlY coatings on Inconel-718 superalloy

Oxide dispersed NiCrAlY bond coatings have been developed for enhancing thermal life cycles of thermal barrier coatings (TBCs). However, the role of dispersed oxides on high temperature corrosion, in particular hot corrosion, has not been sufficiently studied. Therefore, the present study aims to improve the understanding of the effect of YSZ dispersion on the hot corrosion behaviour of NiCrAlY bond coat. For this, NiCrAlY, NiCrAlY + 25 wt.% YSZ, NiCrAlY + 50 wt.% YSZ and NiCrAlY + 75 wt.% YSZ were deposited onto Inconel-718 using the air plasma spraying (APS) process. Hot corrosion studies were conducted at 800 °C on these coatings after covering them with a 1:1 weight ratio of Na₂SO₄ and V₂O₅ salt film. Hot corrosion kinetics were determined by measuring the weight gain of the specimens at regular intervals for a duration of 51 h. X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy techniques were used to determine the nature of phases formed, examine the surface attack and to carry out microanalysis of the hot corroded coatings respectively. The results show that YSZ dispersion causes enhanced hot corrosion of the NiCrAlY coating. Leaching of yttria leads not only to the formation of the YVO₄ phase but also the destabilization of the YSZ by hot corrosion. For the sake of comparison, the hot corrosion behaviour of a NiCrAlY + 25 wt.% Al₂O₃ coating was also examined. The study shows that the alumina dispersed NiCrAlY bond coat offers better hot corrosion resistance than the YSZ dispersed NiCrAlY bond coat, although it is also inferior compared to the plain NiCrAlY bond coat.     

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%.     

Fabrication of A356 composite reinforced with micro and nano Al2O3 particles by a developed compocasting method and study of its properties

Aluminum/alumina composites are used in automotive and aerospace industries due to their low density and good mechanical strength. In this study, compocasting was used to fabricate aluminum-matrix composite reinforced with micro and nano-alumina particles. Different weight fractions of micro (3, 5 and 7.5 wt.%) and nano (1, 2, 3 and 4 wt.%) alumina particles were injected by argon gas into the semi-solid state A356 aluminum alloy and stirred by a mechanical stirrer with different speeds of 200, 300 and 450 rpm. The microstructure of the composite samples was investigated by Optical and Scanning Electron Microscopy. Also, density and hardness variation of micro and nano composites were measured. The microstructure study results revealed that application of compocasting process led to a transformation of a dendritic to a nondendritic structure of the matrix alloy. The SEM micrographs revealed that Al₂O₃ nano particles were surrounded by silicon eutectic and inclined to move toward inter-dendritic regions. They were dispersed uniformly in the matrix when 1, 2 and 3 wt.% nano Al₂O₃ or 3 and 5 wt.% micro Al₂O₃ was added, while, further increase in Al₂O₃ (4 wt.% nano Al₂O₃ and 7.5 wt.% micro Al₂O₃) led to agglomeration. The density measurements showed that the amount of porosity in the composites increased with increasing weight fraction and speed of stirring and decreasing particle size. The hardness results indicated that the hardness of the composites increased with decreasing size and increasing weight fraction of particles.     

Annealing temperature effect on the corrosion parameters of autocatalytically produced Ni-P and Ni-P-Al2O3 coatings in artificial seawater

Ni-P and Ni-P-Al₂O₃ amorphous alloy coatings with 9.3 and 8.3 wt.% P respectively were obtained by autocatalytic deposition at 90 °C on carbon steel substrates. The effect of annealing temperature (100, 200, 300, 400 and 500 °C) upon the corrosion parameters of the coatings in artificial seawater with pH 5.0 and 8.1 at room temperature was evaluated by potentiodynamic polarisation and electrochemical impedance spectroscopy. It was found that deposits annealed at 400 and 500 °C presented an increase of the charge transfer resistance and negligible changes on samples annealed at lower temperature. Polarisation tests showed a charge transfer controlled anodic kinetics on both Ni-P and Ni-P-Al₂O₃ deposits and diffusion controlled cathodic reaction in artificial seawater at pH 5.0 and 8.1. The coatings did not present passive behaviour in the electrolytes and impedance measurements showed a single time constant for all cases with the lowest double layer capacitance (C_dl) for samples annealed at 400 and 500 °C. The best corrosion parameters were observed on Ni-P and Ni-P-Al₂O₃ coatings annealed at temperatures higher than 400 °C, which is the temperature where crystallisation of this kind of coatings takes place.     

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.     

Electrochemical behaviour of high phosphorus electroless Ni–P–Si3N4 composite coatings

Abstract

A high phosphorus electroless nickel bath was used to prepare plain Ni–P and composite coatings containing submicrometre size silicon nitride particles. Deposits were characterised for their composition, morphology and electrochemical behaviour. Codeposition of particles in a Ni–P matrix has not influenced the phosphorus content (10 wt-%). Surface morphology of plain Ni–P deposits was smooth; the composite deposits became slightly rough with small nodules due to particle incorporation. Cross-sectional examination of composite coating revealed that the particles were uniformly distributed throughout the thickness of the coating. Potentiodynamic polarisation and electrochemical impedance studies were carried out in 3·5 wt-% sodium chloride solution in non-deaerated condition. Potentiodynamic polarisation studies showed that the corrosion current density value obtained for composite coatings is lower than that for plain Ni–P coatings. Electrochemical impedance spectroscopy studies showed that the coating resistance of the composite coating is higher than that of plain Ni–P coating. This was further confirmed by SEM analysis of corroded samples.     

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.     

The study of NiAl-TiB2 coatings prepared by electro-thermal explosion ultrahigh speed spraying technology

NiAl-TiB₂ composite coatings with 0, 10 and 20 wt.% TiB₂ were synthesized on the Ni-based superalloy substrate using electro-thermal explosion ultrahigh speed spraying technology. The microstructure analysis shows that the coatings consist of submicron grains. The bond between coatings and substrate is metallic cohesion. TiB₂ as a powerful reinforcement is doped in NiAl for increasing its hardness. The isothermal oxidation test is carried out for the composite coatings at 1100 °C in air. The result shows that the oxidation resistance of NiAl coating is higher than that of NiAl-10TiB₂ and NiAl-20TiB₂ coatings. The phases of oxides on the coatings during the process at high temperature have been analyzed by X-ray diffraction. The results show that Al₂O₃ and Cr₂O₃ coexistence on surface of NiAl coating, while Al₂O₃, Cr₂O₃, TiO₂ and a small amount of NiO form on surface of NiAl-10TiB₂ and NiAl-20TiB₂ coatings after oxidation for 4 h.     

Improvement in the properties of nickel by nano-Cr2O3 incorporation

Nano-ceramic composite coatings were prepared by the electrodeposition method using sulphamate electrolyte. Nickel was chosen as the metal matrix and nano-Cr₂O₃ particles were chosen as the reinforcement. The surface morphology and the particle distribution in the coating were analysed using field emission scanning electron microscope (FESEM). The particle content was obtained using energy dispersive X-ray analysis (EDAX). A change in the surface morphology of Ni was seen on the incorporation of Cr₂O₃ particles. The coatings were characterized for their structure and no change in the diffraction pattern was seen between plain Ni and Ni-Cr₂O₃ composite. The mechanical property like microhardness and tribological behaviour of the nano-composite coatings was studied and it was observed that the incorporation of Cr₂O₃ particles enhanced the mechanical properties of Ni matrix. The nano-composites were analysed for their thermal stability and corrosion resistance. An improvement in thermal stability was observed but no change in the corrosion behaviour of Ni was seen on the incorporation of nano chromium oxide particles.     

The effects of nano-SiO2 additive on the zinc phosphating of carbon steel

In this paper, nano-SiO₂ was used as an accelerator for improving the microstructure and the corrosion resistance of phosphate coating on carbon steel. The chemical composition and microstructure of the coatings were analyzed by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM). The effects of nano-SiO₂ on weight, roughness and corrosion resistance of the phosphate coatings were also investigated. Results show that the compositions of phosphate coating were Zn₃(PO₄)₂·4H₂O (hopeite), and Zn₂Fe(PO₄)₂·4H₂O (phosphophylite). The phosphate coatings became denser due to the addition of nano-SiO₂ which reduced the size of the crystal clusters. The average weight of phosphate coatings approximately linearly increased with the nano-SiO₂ content in the bath from 0 to 4 g/L, and the phosphate coatings formed in bath containing 2 g/L nano-SiO₂ showed the highest corrosion resistance in 5 wt.% sodium chloride solution at ambient temperature. Nano-SiO₂ would be widely utilized as a phosphating additive to replace the traditional nitrite, due to its less pollutant and its better quality of the coating.     

Investigations on synthesis of HfB2 and development of a new composite with TiSi2

This paper presents the results of investigation carried out on synthesis and densification of monolithic HfB₂ and the effect of TiSi₂ as sinter additive. Pure phase HfB₂ was prepared by boron carbide reduction of HfO₂ and hot pressed to full density with the addition of TiSi₂. Isothermal oxidation study of this composite was carried out at 850 °C up to 64 h. Formation of HfB₂ was seen at 1200 °C but pure HfB₂ was formed at a much higher temperature of 1875 °C in vacuum. Hot pressing of HfB₂ at 1850 °C and 35 MPa pressure gave a compact of 80% TD. Addition of TiSi₂ helped in achieving a much higher density at a lower temperature of 1600 °C and a pressure of 20 MPa. A fully dense composite of HfB₂ and TiSi₂ was obtained with 15% TiSi₂. Hardness and fracture toughness of this composite were 27.4 ± 1.9 GPa and 6.6 ± 0.2 MPa m^1/2, respectively. Considerable deflection was observed in the crack propagation in composites. Oxidation studies indicated the formation of HfO₂, SiO₂, TiO₂ and HfSiO₄ with some glassy phase and the composite with 15% TiSi₂ was seen to be completely covered with a protective glassy layer.     

A new TiB2 + CrSi2 composite – Densification,characterization and oxidation studies

A new composite of TiB₂ with CrSi₂ has been prepared with excellent oxidation resistance. Dense composite pellets were fabricated by hot pressing of powder mixtures. Microstructural characterization was carried out by XRD and SEM with EDAX. Mechanical and physical properties were evaluated. Extensive oxidation studies were also carried out. A near theoretical density (99.9% TD) was obtained with a small addition of 2.5 wt.% CrSi₂ by hot pressing at 1700 °C under a pressure of 28 MPa for 1 h. The microstructure of the composite revealed three distinct phases, (a) dark grey matrix of TiB₂, (b) black phase – rich in Si and (c) white phase – Cr laden TiB₂. Hardness and fracture toughness were measured as 29 ± 2 GPa and 5.97 ± 0.61 MPa m^1/2, respectively. Crack branching, deflection and bridging mechanisms were responsible for the higher fracture toughness. With increase in CrSi₂ content, density, hardness and fracture toughness values of the composite decreased. Thermo gravimetric studies revealed the start of oxidation of the composite at 600 °C in O₂ atmosphere. Isothermal oxidation of these composites showed better oxidation resistance by formation of a protective oxide layer. TiO₂, Cr₂O₃ and SiO₂ phases were identified on the oxidized surface. Effects of CrSi₂ content, temperature and duration of oxidation on the oxide layer formation are reported. Activation energy of the composite was calculated as ∼110 kJ/mol using Arrhenius equation. Diffusion controlled mechanism of oxidation was observed in all the composites.     

Deposition and corrosion resistance of electroless Ni-PCTFE-P nanocomposite coatings

The present work deals with the process of electroless deposition and electrochemical corrosion behavior of nickel-polychlorotrifluoroethylene-phosphorous (Ni-PCTFE-P) nanocomposite coatings. The process of autocatalytic-catalytic reduction of Ni in nickel sulfate and sodium hypophosphate solution with PCTFE suspended particles has been employed for the formation of the electroless Ni-PCTFE-P composite coatings. Surface morphology and composition of the composite coatings are characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) measurements and X-ray diffraction (XRD) analysis. Corrosion behavior of coatings is evaluated using open-circuit potential (E_OCP) measurements, electrochemical impedance spectroscopy (EIS) and polarization techniques in 3.5 wt.% NaCl solution. The study reveals significant shift in corrosion potential towards the noble direction, decrease in corrosion current density, increase in charge transfer resistance and decrease in double‐layer capacitance values with the incorporation of PCTFE particles in the Ni-P matrix. The significant improvement in corrosion resistance observed for Ni-PCTFE-P nanocomposite coatings (25.3 kΩ cm²) compared to Ni-P (16 kΩ cm²) could have resulted from the microstructural differences of pure Ni-P with Ni-PCTFE-P nanocomposite coatings.     

Characterisation of HVOF sprayed Cr3C2-50(Ni20Cr) coating and the influence of binder properties on solid particle erosion behaviour

The coating Cr₃C₂ with 50 wt.% Ni20Cr deposited by high velocity oxy-fuel (HVOF) spray process was characterized in detail to investigate the effect of annealing on the solid particle erosion behaviour and understand the influence of the binder properties. Systematic characterization of the coating was carried out using electron microscopy (scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron probe microanalysis (EPMA)), X-ray diffraction (XRD), microindentation and nanoindentation techniques. The solid particle erosion tests were done on the as-sprayed coating and coatings annealed at 400 °C, 600 °C and 800 °C using silica erodent particles. The coefficient of restitution of the coated samples was also measured by WC ball impact tests to simulate dynamic impacts. The as-sprayed coating consisted of primary carbides and binder that was a mixture of amorphous and nanocrystalline phases. Annealing leads to recrystallisation of binder phase and precipitation of secondary carbides. The coating hardness and binder ductility change with annealing temperature. The erosion resistance improves with annealing up to 600 °C. In the as-sprayed coating, the amorphous phase, inter-splat boundaries and the elastic rebound characteristics affect the erosion response. While in the case of the coating annealed at 600 °C, the presence of ductile crystalline binder, fine carbide precipitates and embedment of erodent particles together improve solid particle erosion resistance.