Phase composition, microstructure and microhardness of electroless nickel composite coating co-deposited with SiC on cast aluminium LM24 alloy substrate

Electroless Ni–P (EN) and composite Ni–P–SiC (ENC) coatings were developed on cast aluminium alloy substrate, LM24. The coating phase composition, microstructure and microhardness were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and microhardness tester, respectively, on as-plated and heat-treated specimens. The original microstructure of the Ni–P matrix is not affected by the inclusion of the hard particles SiC. No formation of Ni–Si phase was observed up to 500 °C of heat treatment. The microhardness is increased on incorporation of SiC in Ni–P matrix. The hardening mechanism is the formation of intermetallic phase Ni3P on annealing at elevated temperature.

Electroless nickel composite (Ni-P/SiC) coating - A study on interface and corrosion characteristic

Surface behaviour is of paramount importance as failure and degradation tend to initiate from the surface. Electroless composite coating (NiP/SiC) was developed using SiC as reinforcing particles. As heat treatment plays a vital role in electroless nickel coating owing to the changes in microstructure, phase structure and mechanical properties, an insight at the interface changes in chemistry and micromechanical behaviour was investigated using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) and microindentation techniques. Corrosion performance was analysed using electrochemical impedance spectroscopy (EIS). Absence of zinc and migration of copper at the interface was detected. Brittleness and microcracks was seen long the interface when indenting at load of 500 gf (Vickers). Corrosion performance is weaker than particles free coating. However, a thin blanket of NiP could enhance the resistance to corrosive medium.

Characterisation of phase composition, microstructure and microhardness of electroless nickel composite coating co-deposited with SiC on casting aluminium LM24 alloy substrate

Electroless Ni-P (EN) and composite Ni-P-SiC (ENC) coatings were developed on cast aluminium alloy, LM24. The coating phase composition, microstructure and microhardness were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and microhardness tester, respectively, on as-plated and heat-treated specimens. The original microstructure of the Ni-P matrix is not affected by the inclusion of the hard particles SiC. No formation of Ni-Si phase was observed upto 500°C of heat treatment. The microhardness is increased on incorporation of SiC in Ni-P matrix. The hardening mechanism is the formation of intermetallic phase Ni3P on annealing at elevated temperature. Overall, the composite coating (ENC) was found to be superior as compared to particles free (EN) coating in both as-deposited and heat-treated conditions.

Effect of gold on the corrosion behavior of an electroless nickel/immersion gold surface finish

The performance of surface finishes as a function of the pH of the utilized plating solution was evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests in 3.5 wt.% NaCl solution. In addition, the surface finishes were examined by x-ray diffraction (XRD), and the contact angle of the liquid/solid interface was recorded. NiP films on copper substrates with gold coatings exhibited their highest coating performance at pH 5. This was attributed to the films having the highest protective efficiency and charge transfer resistance, lowest porosity value, and highest contact angle among those examined as a result of the strongly preferred Au(111) orientation and the improved surface wettability.

Recent developments in characterising electrodeposition of anti-corrosion coatings using the wire beam electrode method

New progresses have been made during recent years in the application of the wire beam electrode (WBE, a coupled multielectrode array) for studying electroplating of metallic coatings, for monitoring the electrodeposition of polymer coatings, and for evaluating the performance of anti-corrosion coatings. The WBE allows localized electrode processes to occur over different locations of its surface under external anodic or cathodic polarization and permits monitoring of nonuniform electrodeposition processes. Several typical experiments are presented in this paper. One sample experiment is the characterization of nonuniform electroplating of nickel coating, which was achieved by mapping the distributions of currents over a WBE surface that was under cathodic polarization. Various characteristic current distribution patterns, which indicate different electrodeposition mechanisms or low covering-power, have been observed. These patterns were found to correlate with the effects of several affecting factors such as electrolyte concentration, temperature and agitation flow. Another sample experiment is the investigation of nonuniform anodic electrodeposition of polyaniline (PANI) coatings and the understanding of their anti-corrosion performance and mechanisms. Anodic polarization currents were measured from various locations over the WBE surface in order to produce anodic polarization current maps under PANI deposition.

Effect of electroless nickel interlayer on the fatigue strength of chromium electroplated AISI 4340 steel

Deposition of wear-resistant hard chromium plating leads to a decrease in the fatigue strength of the base material. Despite the effective protection against wear and corrosion, fatigue life and environmental requirements result in pressure to identify alternatives or to improve conventional chromium electroplating mechanical characteristics. An interesting, environmentally safer and cleaner alternative for the replacement of hard chronic plating is tungsten carbide thermal spray coating, applied by high velocity oxyfuel (HVOF) process.To improve the fatigue strength of aeronautical steel chromium electroplated, shot peening is a successfully used method. Multiple lacer systems of coatings are considered to have larger resistance to crack propagation in comparison with simple layer.The aim of this study was to analyze the effect of nickel underplate on the fatigue strength of hard chromium plated AISI 4340 steel in two mechanical conditions: HRc 39 and HRc 52.Rotating bending fatigue tests results indicate that the clectroless nickel plating underlayer is responsible for the increase in fatigue strength of AISI 4340 steel chromium electroplated. This behavior may be attributed to the largest toughness/ductility and compressive residual stresses which, probably, arrested or delayed the inicrocrack propagation from the hard chromium external layer. The compressive residual stress field (CRSF) induced by the electroplating process was determined by X-ray diffraction method. The evolution of fatigue strength compressive residual stress field CRSF and crack sources are discussed and analyzed by SEM. (c) 2006 Elsevier Ltd. All rights reserved.

Characterization of NiCrAlC PTA coatings

Surface tailoring with plasma transferred arc (PTA) hardfacing involves the deposition of powder mixtures to produce coatings with an almost unlimited chemical composition. PTA hardfacing is particularly important for processing low weldability alloys, such as those for high-temperature applications, of which NiCrAlC is an example. This study analyzed NiCrAlC coatings processed by PTA using a mixture of elemental powders. Deposition on AISI316L plates was carried out with currents of 100 A and 130 A to induce variations in the chemical composition of the coatings, which were also subjected to isothermal exposure at temperatures of up to 1000 ºC for up to 72 hours in an air furnace. The results show that the aluminide compounds were stable, the coatings that solidified more slowly having the highest hardness after temperature exposure and potentially being suitable for use in high-temperature abrasion environments.

Autocatalytic deposition of composite coatings

The deposition and properties of electroless nickel composite coatings containing graphite, PTFE and chromium were investigated. Solutions were developed for the codeposition of graphite and chromium with electroless nickel. Solutions for the deposition of graphite contained heavy metal ions for stability, with non-ionic and anionic surfactants to provide wetting and dispersion of the particles. Stability for the codeposition of chromium particles was achieved by oxidation of the chromium. Thin oxide layers of 200 nm thick prevented initiation of the electroless reaction onto the chromium. A mechanism for the formation of electroless composite coatings was considered based on the physical adsorption of particles and as a function of the adsorption of charged surfactants and metal cations from solution. The influence of variables such as particle concentration in solution, particle size, temperature, pH, and agitation on the volume percentage of particles codeposited was studied. The volume percentage of graphite codeposited was found to increase with concentration in solution and playing rate. An increase in particle size and agitation reduced the volume percentage codeposited. The hardness of nickel-graphite deposits was found to decrease with graphite content in the as-deposited and heat treated condition. The frictional and wear properties of electroless nickel-graphite were studied and compared to those of electroless nickel-PTFE. The self-lubricating nature of both coatings was found to be dependent on the ratio of coated area to uncoated area, the size and content of lubricating material in the deposit, and the load between contacting surfaces. The mechanism of self-lubrication was considered, concluding that graphite only produced an initial lubricating surface due to the orientation of flakes, unlike PTFE, which produced true self-lubrication throughout the coating life. Heat treatment of electroless nickel chromium deposits at 850oC for 8 and 16 hours produced nickel-iron-chromium alloy deposits with a phosphorus rich surface of high hardness. Coefficients of friction and wear rates were intially moderate for the phosphorus rich layer but increased for the nickel-iron-chromium region of the coating.

Nanostructured Metal Oxide Coatings for Electrochemical Energy Conversion and Storage Electrodes

The realization of an energy future based on safe, clean, sustainable, and economically viable technologies is one of the grand challenges facing modern society. Electrochemical energy technologies underpin the potential success of this effort to divert energy sources away from fossil fuels, whether one considers alternative energy conversion strategies through photoelectrochemical (PEC) production of chemical fuels or fuel cells run with sustainable hydrogen, or energy storage strategies, such as in batteries and supercapacitors. This dissertation builds on recent advances in nanomaterials design, synthesis, and characterization to develop novel electrodes that can electrochemically convert and store energy.

Chapter 2 of this dissertation focuses on refining the properties of TiO2-based PEC water-splitting photoanodes used for the direct electrochemical conversion of solar energy into hydrogen fuel. The approach utilized atomic layer deposition (ALD); a growth process uniquely suited for the conformal and uniform deposition of thin films with angstrom-level thickness precision. ALD’s thickness control enabled a better understanding of how the effects of nitrogen doping via NH3 annealing treatments, used to reduce TiO2’s bandgap, can have a strong dependence on TiO2’s thickness and crystalline quality. In addition, it was found that some of the negative effects on the PEC performance typically associated with N-doped TiO2 could be mitigated if the NH3-annealing was directly preceded by an air-annealing step, especially for ultrathin (i.e., < 10 nm) TiO2 films. ALD was also used to conformally coat an ultraporous conductive fluorine-doped tin oxide nanoparticle (nanoFTO) scaffold with an ultrathin layer of TiO2. The integration of these ultrathin films and the oxide nanoparticles resulted in a heteronanostructure design with excellent PEC water oxidation photocurrents (0.7 mA/cm2 at 0 V vs. Ag/AgCl) and charge transfer efficiency.

In Chapter 3, two innovative nanoarchitectures were engineered in order to enhance the pseudocapacitive energy storage of next generation supercapacitor electrodes. The morphology and quantity of MnO2 electrodeposits was controlled by adjusting the density of graphene foliates on a novel graphenated carbon nanotube (g-CNT) scaffold. This control enabled the nanocomposite supercapacitor electrode to reach a capacitance of 640 F/g, under MnO2 specific mass loading conditions (2.3 mg/cm2) that are higher than previously reported. In the second engineered nanoarchitecture, the electrochemical energy storage properties of a transparent electrode based on a network of solution-processed Cu/Ni cores/shell nanowires (NWs) were activated by electrochemically converting the Ni metal shell into Ni(OH)2. Furthermore, an adjustment of the molar percentage of Ni plated onto the Cu NWs was found to result in a tradeoff between capacitance, transmittance, and stability of the resulting nickel hydroxide-based electrode. The nominal area capacitance and power performance results obtained for this Cu/Ni(OH)2 transparent electrode demonstrates that it has significant potential as a hybrid supercapacitor electrode for integration into cutting edge flexible and transparent electronic devices.

Porous polyurethane coatings bonded onto surface-modified titanium substrates for the growth of an endothelial cell layer

Cardiovascular diseases refer to the class of diseases that involve the heart or blood vessels (arteries and veins). Examples of medical devices for treating the cardiovascular diseases include ventricular assist devices (VADs), artificial heart valves and stents. Metallic biomaterials such as titanium and its alloy are commonly used for ventricular assist devices. However, titanium and its alloy show unacceptable thrombosis, which represents a major obstacle to be overcome. Polyurethane (PU) polymer has better blood compatibility and has been used widely in cardiovascular devices. Thus one aim of the project was to coat a PU polymer onto a titanium substrate by increasing the surface roughness, and surface functionality. Since the endothelium of a blood vessel has the most ideal non-thrombogenic properties, it was the target of this research project to grow an endothelial cell layer as a biological coating based on the tissue engineering strategy. However, seeding endothelial cells on the smooth PU coating surfaces is problematic due to the quick loss of seeded cells which do not adhere to the PU surface. Thus it was another aim of the project to create a porous PU top layer on the dense PU pre-layer-coated titanium substrate. The method of preparing the porous PU layer was based on the solvent casting/particulate leaching (SCPL) modified with centrifugation. Without the step of centrifugation, the distribution of the salt particles was not uniform within the polymer solution, and the degree of interconnection between the salt particles was not well controlled. Using the centrifugal treatment, the pore distribution became uniform and the pore interconnectivity was improved even at a high polymer solution concentration (20%) as the maximal salt weight was added in the polymer solution. The titanium surfaces were modified by alkli and heat treatment, followed by functionlisation using hydrogen peroxide. A silane coupling agent was coated before the application of the dense PU pre-layer and the porous PU top layer. The ability of the porous top layer to grow and retain the endothelial cells was also assessed through cell culture techniques. The bonding strengths of the PU coatings to the modified titanium substrates were measured and related to the surface morphologies. The outcome of the project is that it has laid a foundation to achieve the strategy of endothelialisation for the blood compatibility of medical devices. This thesis is divided into seven chapters. Chapter 2 describes the current state of the art in the field of surface modification in cardiovascular devices such as ventricular assist devices (VADs). It also analyses the pros and cons of the existing coatings, particularly in the context of this research. The surface coatings for VADs have evolved from early organic/ inorganic (passive) coatings, to bioactive coatings (e.g. biomolecules), and to cell-based coatings. Based on the commercial applications and the potential of the coatings, the relevant review is focused on the following six types of coatings: (1) titanium nitride (TiN) coatings, (2) diamond-like carbon (DLC) coatings, (3) 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer coatings, (4) heparin coatings, (5) textured surfaces, and (6) endothelial cell lining. Chapter 3 reviews the polymer scaffolds and one relevant fabrication method. In tissue engineering, the function of a polymeric material is to provide a 3-dimensional architecture (scaffold) which is typically used to accommodate transplanted cells and to guide their growth and the regeneration of tissue. The success of these systems is dependent on the design of the tissue engineering scaffolds. Chapter 4 describes chemical surface treatments for titanium and titanium alloys to increase the bond strength to polymer by altering the substrate surface, for example, by increasing surface roughness or changing surface chemistry. The nature of the surface treatment prior to bonding is found to be a major factor controlling the bonding strength. By increasing surface roughness, an increase in surface area occurs, which allows the adhesive to flow in and around the irregularities on the surface to form a mechanical bond. Changing surface chemistry also results in the formation of a chemical bond. Chapter 5 shows that bond strengths between titanium and polyurethane could be significantly improved by surface treating the titanium prior to bonding. Alkaline heat treatment and H2O2 treatment were applied to change the surface roughness and the surface chemistry of titanium. Surface treatment increases the bond strength by altering the substrate surface in a number of ways, including increasing the surface roughness and changing the surface chemistry. Chapter 6 deals with the characterization of the polyurethane scaffolds, which were fabricated using an enhanced solvent casting/particulate (salt) leaching (SCPL) method developed for preparing three-dimensional porous scaffolds for cardiac tissue engineering. The enhanced method involves the combination of a conventional SCPL method and a step of centrifugation, with the centrifugation being employed to improve the pore uniformity and interconnectivity of the scaffolds. It is shown that the enhanced SCPL method and a collagen coating resulted in a spatially uniform distribution of cells throughout the collagen-coated PU scaffolds.In Chapter 7, the enhanced SCPL method is used to form porous features on the polyurethane-coated titanium substrate. The cavities anchored the endothelial cells to remain on the blood contacting surfaces. It is shown that the surface porosities created by the enhanced SCPL may be useful in forming a stable endothelial layer upon the blood contacting surface. Chapter 8 finally summarises the entire work performed on the fabrication and analysis of the polymer-Ti bonding, the enhanced SCPL method and the PU microporous surface on the metallic substrate. It then outlines the possibilities for future work and research in this area.