Tungsten Oxide in Polymer Electrolyte Fuel Cell Electrode

Development of new alternative electrode materials is essential in order for the polymer electrolyte fuel cell (PEFC) to be able to reach a broad market. Today, high platinum loadings are required, especially on the cathode, to obtain sufficient activity for oxygen reduction. In addition, electrode degradation causes loss of catalyst surface area and requires high initial loadings to maintain the cell performance over time. There are problems related to Pt also on the anode side where poisoning of the catalyst, by e.g. CO, reduces the activity.

Approaches to improve the electrodes and reduce their costs are continuously evaluated and include alternative catalysts or supports as well as new structures and morphologies of the catalyst layer. Alternative catalysts, based on non-precious metals, Pt alloys/mixtures, and/or novel supports should preferably reduce the total amount of Pt, increase the activity, and be stable in the fuel cell environment. The support material can influence the activity by spill-over effects as well as changing the electronic structure of the catalyst. New support materials can improve the activity, utilization, and stability of the catalyst or of the support itself.

Tungsten oxide is a material which has been extensively investigated for a wide range of applications, mainly, due to its unique electrochromic properties but also for its electrocatalytic activities. The electrochromism allows tungsten oxide to intercalate/deintercalate ions (of e.g. H, Li, Na, K, Pb, Cd) into its structure in the formation of tungsten bronzes. The most widely studied form is the hydrogen tungsten bronze where protons are inserted in the oxide structure as HxWO3 and 0 < x < 1. The bronze formation mechanism has been the subject for numerous studies and it is suggested that the hydrogen atoms form hydroxyl bonds in the tungsten oxide.

WO3 Electrode SEM

The bronze formation is greatly affected by the water content, porosity, and also crystallinity, which in turn affect the catalytic properties of tungsten oxide. At the same time as protons can be incorporated in the WOx structure, they also have a significant mobility which means that WOx functions as a proton conductor under these conditions. Since the hydrogen tungsten bronze formation is dependent on the water content, large variation in conductivity has been reported when varying the relative humidity. Moreover, Pt supported on tungsten oxide has been shown to affect the bronze formation and both an increased intensity of the hydrogen intercalation/deintercalation peaks as well as a shift of the peak potential to higher potentials has been reported.

Tungsten oxide has been evaluated both as support and active catalyst in fuel cell anode as well as cathode electrodes. Sole tungsten oxide has displayed activity for hydrogen oxidation, which was attributed to high porosity and high surface area. Combined Pt and tungsten oxide based catalysts have been investigated for methanol/ethanol oxidation, CO oxidation, hydrogen oxidation as well as oxygen reduction. For methanol oxidation, the Pt on WOx system has shown improved efficiency over Pt catalyst due to both the spill-over of hydrogen from Pt to WOx but also the ability of WOx to provide oxygen atoms at low potentials and thereby avoiding CO-poisoning. Others have attributed the improved performance to an increased electrochemical active surface area (ECSA) of Pt on WOx.

Tungsten oxide is also relatively stable in acidic environment, which is a prerequisite for use in polymer electrolyte fuel cell applications. However, some dissolution of tungsten oxides has been reported. In a previous study, we examined the impact of different metal oxides on the stability and activity of platinum in thin model cathodes in a PEFC. Pt on WOx did exhibit an improved activity for oxygen reduction and possibly also an improved stability compared to Pt alone. Interesting features such as reduced platinum oxide formation and platinum catalyzed hydrogen tungsten bronze formation were also seen when Pt was deposited on WOx.

 

Hollow Ball Tungsten Trioxide Photocatalyst

tungsten trioxideTungsten trioxide has been researched a lot, because of its unique physical and chemical properties, such as electrochromic, gas properties, photoluminescence. In addition, the tungsten oxide has non-toxic, and narrow band gap (2.4eV ~ 2.8eV), as a semiconductor material used in the visible light photocatalyst catalytic reactions of organic matter in sewage catalytic degradation. Hollow structural material has both inner and outer surfaces, and can take advantage of multiple reflections of light into the interior, which has a unique application.
 
Studies have shown that tungsten trioxide hollow ball prepared at lower temperature has the advantages not only improve utilization of light sources of catalyst, but also reduced the cost of catalyst. The method for preparing tungsten oxide hollow balls is as follows:
1. Weigh the appropriate amount of curing polystyrene microspheres, and then ultrasonic disperse it in anhydrous ethanol to form a colloidal solution;
2. Weigh the appropriate amount of tungsten hexachloride (WCl6), then add into the colloidal solution obtained in Step 1, then the turns from white to yellow;
3. After the WCl6 completely dissolved, slowly add the appropriate amount of deionized water, then the solution turns dark blue;
4. Place the system in a water bath at 70 ° C for stirring mechanically for 24 hours, cool down to the room temperature;
5. Centrifuged and washed several times with deionized water, then dried in 60°C, then placed in a muffle furnace for a heat treatment, wherein the heat treatment process: first calcined at 200 ° C for one hour, so that to completely decompose the sulfur polystyrene microspheres, and then calcined at 300°C for 3 hours, and finally we get hollow ball tungsten trioxide photocatalyst (Microscopic observation that the surface is roughness, an has portion of tungsten oxide hydrate).
Noted: the mass ratio of vulcanization polystyrene microspheres and WCl6is 1: 2; and the volume ratio of anhydrous ethanol which is added and deionized water is 4: 1; and mass of WCl6(g) and ratio of anhydrous ethanol (mL) is 1: 100.
 
Testing showed that the prepared hollow balls tungsten trioxide as photocatalyst, the photocatalytic degradation rate of Rhodamine B (RhB) can reach 86.61% (after 60 minutes of illumination).

 

Spherical Tungsten Powder Application in Cathode Substrate

Cathode as the electron emission source of vacuum device, its research direction and development have the large influence on the development level of vacuum devices even weapons systems.
 
Modern dispenser cathode nowadays is one of the key researches of cathode. The common structures are usually composed of three parts: the porous tungsten matrix, emitting material and heater assembly. Of which the porous tungsten matrix is the framework and launch materials’ support of the entire cathode. As can be seen from the hot cathode development course, the porous tungsten matrix is the results of hot cathode constant pursuit of high emission current density and high reliability. Properties of the porous tungsten matrix, especially the pore structure and the pore distribution will directly affect the emission size, low evaporation rate, emission uniformity and lifetime of the cathode. In the actual production, it requires that the cathode matrix have a uniform distribution of pores of 24-26%. The porous tungsten matrix processes include compression molding process and the sintering process, the development of process is dependent on the progress in powder metallurgy process level, as well as affected by the matrix powder properties. If the matrix porosity and pore distribution can be reasonable controlled by process control, there will be a positive role in the cathode research.
 
Spherical tungsten powder has the advantages of regular shape, good uniformity and adequate liquidity. These advantages are especially suitable for the automatic press with the automatic filling, and the porous tungsten matrix can be obtained with the suitable size of pore and uniform distribution, compared to conventional tungsten powder, it has quite a lot of advantages. During the process of spherical tungsten powder producing the cathode, relationship between the initial porosity and compaction pressure is in line with Heckel's Law. Cathode pulse emission test results show that in 1050 ℃, cathode substrate prepared by spherical tungsten powder can obtain inflection current density of 20.46A / cm2, which can fully meet the current needs of engineering applications.
 
Tungsten Powder

Tungsten Powder Classification Application in Coarse Tungsten Carbide Powder Production

Coarse grain WC-Co alloys with high hardness and high toughness, is widely used in mining drilling tools, oil drilling tools, stamping dies, wear resistant parts, high temperature and high pressure resistance, metal pressure processing tools, steel rolling roll ring, hard surface materials and so on. With the rapid development of Chinese economy, the application of tungsten carbide wear-resistant material is widely growing.
 
Traditional manufacturing processes of coarse tungsten carbide powder are molybdenum wire furnace high temperature reduction and carbon tube furnace high temperature carbonization; in the 90s, mainly the reduction in the middle temperature and the carbonization in high temperature of tungsten oxide doped, this process can produce coarse tungsten carbide powder of about 301xm ~ 401xm; high temperature carbonization adding cobalt and nickel, to get extremely coarse carbide powder; Kennametallne in US developed the aluminum heat production of tungsten carbide and the Russian Research Institute of chemical technology has developed the tungsten concentrate "furnace" thermite reduction method, tungsten carbide can be produced directly from tungsten concentrate, X-ray diffraction analysis of the metal phase containing tungsten carbide obtained by this method shows that the product contains only a tungsten carbide phase, and the grains are coarse; H.C. Stark Co., Ltd. has developed  a process that reduction and carbonization treatment to the tungsten oxide powder by the presence of the alkali metal compounds, producing ultra-coarse single crystal tungsten carbide and thus prepare hard metal . Some coarse tungsten carbide powder produced by the processes above has uneven widespread size, incomplete crystallization, and with much fine particles and abroad particle size distribution; some methods have high requirements of equipment or great impact on environment. A lot of information discusses the micro structure of tungsten carbide powder with the presence of native inheritance among tungsten powder,  the form and structure of tungsten powder directly affect the properties of tungsten carbide. By studying the carbonization process of tungsten powder re-grading, there is an effective solution to the powder clipping coarse or fine powder, manufacturing coarse grain tungsten carbide powder.
 
Powder properties can be measured not only by the particle size of the powder, but also the powder size, the structure and composition, particle morphology, surface characteristics of the particles and the like must be considered. After classification treatment, A1 powder grain has better morphology consistency. According to the proportion, the particles, the size and shape suffered different gravity and different resistance of medium in the air, being graded with different sedimentation rates, can effectively change the physical properties of the powder. At the same time, despite the use of airflow and iron container as the carrier grades, there is little effect on the oxygen and the iron powder and other trace elements. Within the range of performance indicators, it will not have a negative impact on the process behind the process.
 
Tungsten Powder

Tungsten Carbide Circular Saw Blade Used for Woods Processing

Tungsten carbide materials have high hardness, high strength and excellent wear and corrosion resistance, which have been widely used in cutting tools. Especially the conventional steel circular saw blade used in woods processing has been gradually replaced by tungsten carbide circular saw blade, which has higher cutting accuracy and longer service life. Currently, tungsten carbide circular saw blade has been developing towards ultra-thin, and the swage set generally can reach 1.0mm – 2.0mm, and outer diameter typically in the range 125mm - 305mm. In addition, in the home building process as well as a variety of decorative materials processing also used by tungsten carbide circular saw blade, which can effectively improve utilization of wood, products quality, reduce energy consumption, so it has a broad application prospect.

Tungsten carbide ultra-thin circular saw blade manufacturing process includes the manufacture and heat treatment of saw plate and edges, blade geometry design, leveling blade saws, the saw blade mechanical machining, serrated welding, serrated saws and coating surface treatment technology. It has advantages as follow:
1. Small sawing width, lower cutting wastage, higher lumber recovery. Compared with conventional saw blade, it narrows 18% - 30%, the smallest ultra-thin blade edge reaches 1.0mm, which can meet the special needs of the products, such as piano keyboard, audio and so on. By reducing the cutting losses, can significantly improve the processing of sheet metal and precious materials processing timber utilization, conserve resources, improve processing efficiency;
2. Less wood crumbs by cutting, it will not cause pollution and has lower power consumption.

Currently, the main use of carbide circular saw blades in the field of wood processing in the following areas:
1. Multilayered wood flooring table board split: Use of carbide circular saw blade sawing table board will not damage the wood fibers, makes the wood natural texture, surface cracks will not appear after painting.
2. Pencil board: Early in the 1970s, American enterprises have adopted the kerf width of 1.3mm ultra-thin circular saw blades cutting board 5mm thick pencil, and introduced computers into thin blade maintenance;
3. In addition, tungsten carbide circular saw blade has been widely used in wooden shutters, piano keys, skis, audio, ping-pong racket and some other precious wood furniture manufacturing.

tungsten carbide circular saw blade

 

 

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