Template-free environmentally friendly synthesis and characterization of unsupported tungsten carbide with a controllable porous framework

Tungsten carbide (WC) with controlled pore size distribution was synthesized using a novel “precursor reassembly” method. The precursor crystal was assembled by mixing ammonium metatungstate (AMT) and ammonium carbonate (AC) in distilled water, followed by hydrothermal treatment. The mesostructure, crystal phase, and amount of deposited graphitic carbon can be conveniently tuned by controlling carburizing atmosphere (CO or a CO/H2 mixture). Moreover, the influence of precursor preparation (AMT/AC mass ratio and hydrothermal temperature) on the materials was also investigated. The resultant materials with low carbon content were mesoporous WCs, which showed high specific surface areas (11.3-20.4 m2 g-1) and adjustable pore-size distributions (average pore size: 15.3-22.3 nm). A mechanism for the formation of WC with a controllable porous framework is proposed. Finally, cyclic voltammetry was used to investigate the inference of different mesoporous structure.

Synthesis of mesoporous tungsten carbide-supported platinum and its electrocatalytic activity for methanol oxidation

High activity and stability during oxidation of methanol under the relatively anode environment are two main evaluation criterias for an effective anode electrocatalyst in direct methanol fuel cell (DMFC). Mesoporous WC samples with hollow structure were prepared by gas-solid reaction at the atmosphere of CH(4)/H(2) by using airflow spray dried ammonium metatungstate (AMT). The platinum supported on this material by impregnation-vapor phase deoxidation method served as a less expensive electro anode catalyst. XRD and SEM results showed that Pt particles were well dispersed on the surface of WC. The results showed that the Pt/WC-PME exhibited an attractive catalytic activity, and methanol oxidation process in Pt/WC-PME is affected by liquid-phase mass transfer. The results also indicated that the oxidation can be improved by raising temperatures.

Low loading platinum nanoparticles on reduced graphene oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation

In this study, low loading platinum nanoparticles (Pt NPs) have been highly dispersed on reduced graphene oxide-supported WC nanocrystallites (Pt-WC/RGO) via program-controlled reduction-carburization technique and microwave-assisted method. The scanning electron microscopy and transmission electron microscopy results show that WC nanocrystallites are homogeneously decorated on RGO, and Pt NPs with a size of ca. 3 nm are dispersed on both RGO and WC. The prepared Pt-WC/RGO is used as an electrocatalyst for methanol oxidation reaction (MOR). Compared with the Pt/RGO, commercial carbon-supported Pt (Pt/C) and PtRu alloy (PtRu/C) electrocatalysts, the Pt-WC/RGO composites demonstrate higher electrochemical active surface area and excellent electrocatalytic activity toward the methanol oxidation, such as better tolerance toward CO, higher peak current density, lower onset potential and long-term stability, which could be attributed to the characterized RGO support, highly dispersed Pt NPs and WC nanocrystallites and the valid synergistic effect resulted from the increased interface between WC and Pt. The present work proves that Pt-WC/RGO composites could be a promising alternative catalyst for direct methanol fuel cells where WC plays the important role as a functional additive in preparing Pt-based catalysts because of its CO tolerance and lower price. 

Delamination and wear in drilling of carbon-fiber reinforced plastic composites using multilayer TiAlN/TiN PVD-coated tungsten carbide tools

This study aims to investigate drilling process in carbon-fiber reinforced plastic (CFRP) composites with multilayer TiAlN/TiN PVD-coated tungsten carbide drill. The effect of process parameters have been investigated in drilling of Hexcel M21-T700GC. Thrust force and torque were measured online throughout the drilling experiments. Delamination were observed using optical microscope and analyzed via a developed algorithm based on digital image processing technique. Surface roughness of each hole was measured using a surface profilometer. In addition, the progression of tool wear in various surfaces of drill was observed using tool microscope and measured using image software. Our results indicate that the thrust force and torque increased with the increasing cutting speed and feed rate. Delamination and average surface roughness that rose with the increase in feed rate, however, decreased with the increasing cutting speed. The average surface roughness tended to increase with the increase in feed rate and decrease with the increasing cutting speed in drilling of carbon-fiber reinforced plastic (CFRP). Feed rate was found as the predominant factor on the drilling outputs. Abrasive wear was observed on both flank and relief surfaces, which created edge wear on cutting edges. No sign of chipping or plastic deformation has been observed on the surfaces of drills. © 2012 The Author(s).

Hard coatings on elastomers for reduced permeability and increased wear resistance

In this study, three different elastomers, namely hydrogenated nitrile butadiene rubber, fluoroelastomer and silicone, have been subjected to two different hard metallised coatings by ion implantation process. The three different elastomers are commonly used in various seal applications, where reduced wear and gas permeability are essential in maintaining seal performance and functionality. Samples of these rubbers have been coated with chromium coating in one set of tests. In the second set of tests, samples of elastomers have been coated with tungsten carbide coating being deposited on all the three different elastomers. Wear, gas permeability and mechanical behaviour of the coated samples were compared with each other and with the control uncoated elastomers. All the coated samples showed good reduction in gas permeability. With the use of metallised coatings, there has been improved resistance to wear in all the coated samples. Adhesion strength and effect of coating on the elastomer have been investigated by mechanical testing. Mechanical tests revealed good adhesion of metal coatings on all the rubber samples, and there was no detrimental effect on the mechanical properties after coating. © 2012 Institute of Materials, Minerals and Mining.

Comparative study of tool life and hole quality in drilling of CFRP/titanium stack using coated carbide drill

The use of hybrid materials including carbon fiber reinforced plastics (CFRPs) and lightweight metals such as titanium are increasing particularly in aerospace applications. Multi-material stacks require a number of holes for the assembly purposes. In this research, drilling trials have been carried out in CFRP, Ti-6Al-4V and CFRP/Ti-6Al-4V stack workpieces using AlTiN coated tungsten carbide drill bit. The effects of process parameters have been investigated. The thrust force, torque, burr formation, delamination, surface roughness and tool wear have been analyzed at various processing condition. The experimental results have shown that the thrust force, torque, burr formation and the average surface roughness increase with the increased feed rate and decrease with the increased cutting speed in drilling of Ti-6Al-4V. In drilling CFRP, delamination and the average surface roughness has similar tendency with the cutting parameters however thrust force and torque rises with the increased cutting speed. The results showed that after making 15 holes in CFRP/Ti-6Al-4V stack, measured thrust forces were increased by 20% in CFRP and by 45% in Ti-6Al-4V. Delamination was found to be much smaller in drilling of CFRP in stack from compared to drilling single CFRP. Tool life was significantly shortened in drilling of stack due to the combination of the wear mechanisms.

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

Interpretation of electrochemical measurements made during micro-scale abrasion-corrosion

This paper brings together and analyzes recent work based on the interpretation of the electrochemical measurements made on a modified micro-abrasion-corrosion tester used in several research programmes. These programmes investigated the role of abradant size, test solution pH in abrasion-corrosion of biomaterials, the abrasion-corrosion performance of sintered and thermally sprayed tungsten carbide surfaces under downhole drilling environments and the abrasion-corrosion of UNS S32205 duplex stainless steel. Various abrasion tests were conducted under two-body grooving, three-body rolling and mixed grooving-rolling abrasion conditions, with and without abrasives, on cast F75 cobalt-chromium-molybdenum (CoCrMo) alloy in simulated body fluids, 2205 in chloride containing solutions as well as sprayed and sintered tungsten carbide surfaces in simulated downhole fluids. Pre- and post-test inspections based on optical and scanning electron microscopy analysis are used to help interpret the electrochemical response and current noise measurements made in situ during micro-abrasion-corrosion tests. The complex wear and corrosion mechanisms and their dependence on the microstructure and surface composition as a function of the pH, abrasive concentration, size and type are detailed and linked to the electrochemical signals. The electrochemical versus mechanical processes are plotted for different test parameters and this new approach is used to interpret tribo-corrosion test data to give greater insights into different tribo-corrosion systems. Thus new approaches to interpreting in-situ electrochemical responses to surfaces under different abrasive wear rates, different abrasives and liquid environments (pH and NaCl levels) are made. This representation is directly related to the mechano-electrochemical processes on the surface and avoids quantification of numerous synergistic, antagonistic and additive terms associated with repeat experiments. (C) 2010 Elsevier Ltd. All rights reserved.

WC/CNT, WC/CNT/Pt Composite Material and Preparation Process Therefor and Use Thereof. (International Patent)

(EN)Disclosed are a WC/CNT， WC/CNT/Pt composite material and a preparation process therefor and use thereof. The WC/CNT/Pt composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, carbon nanotubes and platinum nano particles, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward, and the platinum nano particles growing on the surfaces of the mesoporous spherical tungsten carbide and carbon nanotubes. The WC/CNT composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, and carbon nanotubes, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward. The WC/CNT/Pt composite material of the present invention can be used as an electro-catalyst in a methanol flue battery, significantly improving the catalytic conversion rate and the service life of the catalyst. The WC/CNT composite material can be used as an electro-catalyst in the electro-reduction of a nitro aromatic compound, significantly improving the efficiency of organic electro-synthesis.

WC/CNT, WC/CNT/Pt Composite Material and Preparation Process Therefor and Use Thereof. (US patent)

Disclosed are a WC/CNT， WC/CNT/Pt composite material and a preparation process therefor and use thereof. The WC/CNT/Pt composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, carbon nanotubes and platinum nano particles, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward, and the platinum nano particles growing on the surfaces of the mesoporous spherical tungsten carbide and carbon nanotubes. The WC/CNT composite material comprises mesoporous spherical tungsten carbide with a diameter of 1-5 microns, and carbon nanotubes, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward. The WC/CNT/Pt composite material of the present invention can be used as an electro-catalyst in a methanol flue battery, significantly improving the catalytic conversion rate and the service life of the catalyst. The WC/CNT composite material can be used as an electro-catalyst in the electro-reduction of a nitro aromatic compound, significantly improving the efficiency of organic electro-synthesis.

SEM-EDX of morphology of electroless nickel coatings with tin and tungsten

Electroless plating of binary Ni-P, ternary Ni-Sn-P and Ni-W-P, and quaternary Ni-W-Sn-P alloy coatings was carried out in alkalicitrate baths. After the plating, several kinds of test were carried out to determine the improvement in the characteristics and properties due to the additional elements as well as to study the change in behaviour when heat treatment was applied to these coatings. The coatings were subjected to X-ray diffraction analysis where it was found that all the coatings were amorphous. Interesting surface morphology features were examined using scanning electron microscopy. Addition of a third element improved the hardness.

Titania and tungsten doped titania thin films on glass; active photocatalysts

Acidification of an isopropanol solution containing mixtures of [Ti(OPri)(4)] and [W(OEt)(5)] produced solutions from which various TiO2, WO3 and TiO2/WO3 thin films could be obtained by dip coating and annealing. The films were analysed by X-ray diffraction, SEM/EDAX, Raman, electronic spectra, contact angle and photoactivity with respect to destruction of an over layer of stearic acid. The TiO2/WO3 films were shown to be mixtures of two phases TiO2 and WO3 rather than a solid solution TixWyO2. The 2% tungsten oxide doped titania films were shown to be the most effective photocatalysts. All of the TiO2 and TiO2/WO3 films showed light induced superhydrophillicity. (C) 2002 Elsevier Science Ltd. All rights reserved.

Micro-scale wear characteristics of electroless Ni-P/SiC composite coating under two different sliding conditions

The electroless nickel composite (ENC) with various silicon carbide contents was deposited onto aluminium alloy (LM24) substrate. The wear behaviour and the microhardness of the composite coating samples were investigated and compared with particles free and aluminium substrate samples using micro-scale abrasion tester and microhardness tester respectively. The wear scar marks and wear volume were analysed by optical microscope. The wear tracks were further studied using scanning electron microscopy (SEM). The embedded particles were found to get pressed into the matrix which helps resisting further wearing process for composite samples. However, random orientation of microcuts and microfallow were seen for ENC sample but more uniform wearing was observed for EN sample. The composite coating with low content of SiC was worn minimum. Early penetration into the substrate was seen for samples with higher SiC content. Microhardness was improved after heat treatment for all the samples containing various SiC content. Under dry sliding condition, inclusion of particles in the matrix did not improve the wearing resistance performance in as-deposited state. The wearing worsened as the content of the particles increased generally. However, on heat treatment, the composite coatings exhibited improved wear resistance and the best result was obtained from the one with low particle contents.

Insight of the interface of electroless Ni-P/SiC composite coating on aluminium alloy, LM24

Electroless nickel composite coatings with silicon carbide, SiC, as reinforcing particles deposited with Ni–P onto aluminium alloy, LM24, having zincating as under layer were subjected to heat treatment using air furnace. The changes at the interface were investigated using scanning electron microscope (SEM) and energy dispersive X-ray (EDX) to probe the chemistry changes upon heat treatment. Microhardness tester with various loads using both Knoop and Vickers indenters was used to study the load effect clubbed with the influence of second phase particles on the coating at the vicinity of the interface. It was observed that zinc was absent at the interface after elevated temperature heat treatment at 400–500 °C. Precipitation of copper and nickel with a distinct demarcation (copper rich belt) along the coating interface was seen with irregular thickness of the order of 1 μm. Migration of copper from the bulk aluminium alloy could have been the factor. Brittleness of the coating was confirmed on heat treatment when indented with Vickers. However, in composite coating the propagation of the microcrack was stopped by the embedded particles but the microcracks continue in the matrix when not interrupted by second phase particles (SiC).