γ Phase of WC-Co Tungsten Carbide

WC-Co tungsten carbide SEM image
WC-Co tungsten carbide is the most widely used type of tungsten carbide. In industry, it is usually alloyed by powder metallurgy sintering such as low-pressure sintering. In the liquid process of phase sintering, WC is partially dissolved in cobalt, forming a Co-W-C solid solution based on Co. The solid solution phase is γ phase. The existence of γ phase makes the grain of WC rearranged and regrown, which is beneficial to the homogenization of grain.

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Composition Change of WC-Co Tungsten Carbide

WC-Co pseudo binary phase diagram
WC-Co tungsten carbide is widely used because of its mature technology. In sintering, its components will change as the temperature changes. It is necessary to make a thorough understanding of the composition changes in the holding and cooling stage which will have a great influence on tungsten carbide. Generally, the WC-Co pseudo binary phase diagram is needed, as shown in the following figure.

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Tungsten Oxide Ceramics Varistor Performance

Tungsten oxide picture

In 1994, it was first discovered that doped tungsten oxide varistors have varistor properties. Due to the lower varistor voltage, the varistor characteristics of tungsten oxide attract attention. Later, the effects of alumina and other dopants on the pressure sensitive properties were reported. However, the varistor characteristics of tungsten oxide varistor ceramics are extremely unstable, such as poor reproducibility of electrical behavior and negative resistance behavior, and the nonlinear coefficient is much smaller than that of zinc oxide. Therefore, there are few reports on tungsten oxide varistor ceramics in foreign countries, but there are many reports on the use of tungsten oxide varistors in gas sensors.

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Tungsten Oxide Ceramic Grain Growth

Tungsten oxide picture

Because of the larger radius of oxygen atoms, poor mobility. Therefore, in the sintering process of oxide ceramics, the transmission rate of oxygen atoms determines the sintering performance of tungsten oxide ceramics.

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Tungsten Oxide Ceramic Voltammogram

Tungsten oxide picture

The graph below shows the volt-ampere characteristics of tungsten oxide ceramics sintered at different holding temperatures. The electrical non-linear behavior of varistors typically occurs at current densities in the region of 1-10 mA. From the figure we can see that at 1050 ℃ 1100 ℃ and insulation for two hours of tungsten oxide ceramics, in the current density of 1-10mA region has a non-linear volt-ampere curve. That is, the pressure sensitive characteristics are exhibited.

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Tungsten Oxide Ceramic XRD Pattern

Tungsten oxide picture

The figure is a diagram of tungsten oxide ceramics sintered at different holding temperatures. Since the crystal structure of tungsten oxide ceramics is very complicated, we narrow down the scanning angle to 20-30 ° to observe the change of the triple peak of tungsten oxide ceramics. From the figure, we can see that the crystal structure of the tungsten oxide ceramic does not change substantially when it is sintered at a temperature of 900-1000°C. However, the XRD peak of the tungsten oxide ceramic moves to a small angle when sintering at a temperature of 1050-1100°C, and the blue shift occurs.

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Holding Temperature Affects Tungsten Oxide Ceramics

Tungsten oxide picture

It can be clearly seen from the figure that as the soaking temperature increases, the grain size of the tungsten oxide ceramic increases. When the holding temperature is 900-1000°C, there are many small-sized grains in the sample. When the holding temperature is 1050-1150 ℃, the small grains in the tungsten oxide ceramics disappear, and the grains increase obviously. Also found at 1150 ℃ insulation tungsten oxide ceramics, although the larger grain size. However, its porosity is also significantly increased, the densification of tungsten oxide ceramics worsened.

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Equation of Sintering Densification

densification degree in various stages of sintering image
The sintering of tungsten carbide belongs to multicomponent liquid phase sintering. Its process can be roughly divided into 3 stages based on sintering mechanism: stage of liquid phase flow and particle rearrangement, stage of solid phase dissolution and reprecipitation and stage of solid phase sintering. Most of the densification is completed in the first two stages. Especially in the stage of particle rearrangement, the maximum amount of sintering shrinkage is completed.

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Effect of External Force on Sintering Shrinkage

effect of external force on pore contraction image
Many factors will affect the final densification effect, such as liquid solid wetting angle, liquid phase number, carbon content, heating rate and external force during sintering. For sintering of tungsten carbide, the most intense phase of the shrinkage process is the phase of liquid phase sintering. External force has a significant effect on the process of liquid-phase contraction, which is mainly reflected in the two aspects of promoting material migration and reducing porosity.

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Characteristics of Liquid Phase Sintering

WC-Co tungsten carbide image
WC-Co tungsten carbide is the most common and widely used type of tungsten carbide. The sintering of WC-Co cemented carbide is liquid phase sintering because the composition of Co and WC satisfies the conditions of liquid phase sintering. WC-Co tungsten carbide has the inherent characteristics and requirements of liquid phase sintering, such as wettability, solubility and quantity of liquid phase.

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