KR100669819B1 - Method for manufacturing ceramic powder for plasma spraying and ceramic powder using the same - Google Patents

Abstract

Disclosed is a method for preparing a thermally sprayed ceramic powder using a non-aqueous solvent and a ceramic powder prepared accordingly without adding a binder and a dispersant. In the plasma spray ceramic powder production method according to the present invention, first, a slurry containing ceramic powder and a non-aqueous solvent is prepared. Subsequently, the slurry is dried using a spray dryer to form a dry powder, and then the dry powder is prepared by heat treatment. The ceramic powder is Y ₂ O ₃ based, Al ₂ O ₃ based, TiO ₂ based, AlN based, nitride based ceramic powder, etc., and the ceramic powder is contained in 40 to 60 weight%. The non-aqueous solvent contains an ammonium salt and uses a spray dryer.

Heat treatment, non-aqueous, slurry, ceramic powder. Spray drying, ammonium salt

Description

Method for manufacturing ceramic powder for plasma spraying and ceramic powder produced accordingly {Method for manufacturing ceramic powder for plasma spraying and ceramic powder using the same}

1 is a graph showing the particle size distribution of the thermal spray Y ₂ O ₃ powder prepared according to the prior art.

2 is a graph showing the particle size distribution of the thermal sprayed Al ₂ O ₃ powder prepared according to the prior art.

3A to 3C are scanning electron microscope (SEM) images of 200 times, 2,500 times, and 20,000 times magnifications of the plasma-spray Y ₂ O ₃ powders prepared according to the prior art, respectively.

4A to 4C are scanning electron micrographs of 200 times, 2,500 times, and 20,000 times magnifications of the thermally sprayed Al ₂ O ₃ powders prepared according to the prior art, respectively.

Figure 5 is a graph showing the particle size distribution of the thermal spray Y ₂ O ₃ powder prepared in accordance with an embodiment of the present invention.

Figure 6 is a graph showing the particle size distribution of the thermal spray Al ₂ O ₃ powder prepared in accordance with an embodiment of the present invention.

7 is a graph showing the particle size distribution of the thermal sprayed AlN powder prepared according to the embodiment of the present invention.

8A and 8B are scanning electron micrographs at 200x and 2500x magnifications immediately after the spray drying step (before the heat treatment step) of the plasma sprayed Y ₂ O ₃ powder prepared according to the embodiment of the present invention.

9A and 9B are scanning electron micrographs at 200 and 2500 times magnifications immediately after the spray drying step (before the heat treatment step) of the plasma sprayed Al ₂ O ₃ powder prepared according to the embodiment of the present invention.

10a to 10c are scanning electron micrographs of 200 times, 2,500 times and 20,000 times magnification of the plasma thermal Y ₂ O ₃ powder prepared according to the embodiment of the present invention.

11a to 11c are scanning electron micrographs of 200 times, 2,500 times and 20,000 times magnification of the plasma Al ₂ O ₃ powder prepared according to an embodiment of the present invention.

12A to 12C are scanning electron micrographs at 200 times, 2,500 times, and 20,000 times magnifications of the thermal spray AlN powder prepared according to the embodiment of the present invention.

The present invention relates to a method for producing a thermally sprayed ceramic powder, and more particularly, to a plasma thermally treated yttria (Y ₂ O ₃ ) -based alumina / from a non-aqueous slurry using a spray dryer. The present invention relates to a method for producing a ceramic powder such as titanium oxide (Al ₂ O ₃ / TiO ₂ ), aluminum nitride (AlN) or nitride.

Typically, the inner material of the manufacturing equipment for manufacturing a semiconductor device or a display device is required plasma resistance and corrosion resistance. To meet these requirements, which is used to form a ceramic coating layer, such as Y ₂ O ₃ or Al ₂ O ₃ by a plasma spray method to the surface of the inner member of a semiconductor or display manufacturing equipment.

Plasma spraying instantly melts the ceramic powder into a hot flame or plasma and then accelerates the molten particles at high speed to form a 0.1 to 1.0 mm thick film on the surface of the metal or ceramic substrate. Technology. This technology can improve the surface properties such as plasma resistance, corrosion resistance, abrasion resistance, oxidation resistance, insulation and heat insulation by forming a thick film layer of ceramic material having various properties on a relatively inexpensive base material. It is widely applied to the surface treatment technology of internal materials.

At present, the plasma spray ceramic powder is used to produce fine powder or raw materials by dissolving them in an arc, plasma, etc., and then pulverizing them to a size of about 20 to 100 μm, depending on the purpose.

However, the plasma-sprayed ceramic powder produced by the pulverization as described above has a polygonal shape with irregular particle shape, and thus, fluidity is easily decreased, and non-uniform injection behavior is likely to occur. When the fluidity is lowered, there is a disadvantage in that the coating layer is uneven because the ceramic powder is not sprayed in a uniform dissolved state during the spraying, and when the non-uniform spraying behavior occurs, the amount of injection per unit time is instantaneously increased. Thereby, there is a disadvantage in that large pores are locally formed in the coating layer to lower the coating layer characteristics.

In order to make up for the shortcomings of the prior art, a technique for producing ceramic powder for plasma spraying using a spray dryer has been recently developed.

Specifically, Korean Patent Registration Publication 10-0321588 discloses a slurry is prepared by a water-based method by mixing a binder and a dispersant with a predetermined amount of Cr ₂ O ₃ based or Al ₂ O ₃ / TiO ₂ based ceramic powder. It is disclosed a method of drying by pouring into a spray dryer, then drying the dried powder with a plasma flame, redissolved and dropped in water to rapidly solidify.

According to the above method, it is disclosed that an inexpensive plasma thermal spray ceramic powder can be produced by a simple process.

However, the above-described prior art still involves the following problems.

That is, the addition of a certain amount of the binder and the dispersant to the ceramic powder has a problem that can act as a contaminant during the semiconductor manufacturing process, and may cause defects in the coating layer. In addition, when the binder is added, there may be internal defects inside the fused particles in addition to the defects between the fused particles which have been pointed out as a general defect of the plasma spray coating. These particle internal defects are believed to increase due to local melting due to low heat transfer of the granulated powder during spraying and vaporization of the used binder.

In addition, the binder and the dispersant require proper control, but in the case of the binder, if a lot of stirring, a stable bubble is formed, this bubble forms pores in the granules to decrease the density, so there is an inconvenience of stirring using a low speed mixer, If the amount of added is large, there is a difficulty in the process because the incorporation of impurities or granules becomes hard in the degreasing process, and the strength of the molded product decreases when the amount of added is low.

In addition, when applied to the ceramic powder of Y ₂ O ₃ or AlN by using the above method, there is a problem that the water-based method causes a hydration phenomenon and dispersion in the water system is quite difficult. Therefore, when using the method, there is a disadvantage in that it is practically impossible to apply Y ₂ O ₃ or AlN powder, which is widely used as a coating material for semiconductor and display manufacturing equipment internal materials.

In addition, the process of spraying together with the plasma flame to re-dissolve and drop into the water to rapidly solidify has the disadvantage of increasing the cost of the powder because it requires a plasma thermal spraying apparatus.

Accordingly, it is an object of the present invention to provide a plasma spray ceramic powder production method and plasma spray ceramic powder produced according to the conventional method for overcoming the problems of the plasma spray powder produced by the conventional grinding method.

In addition, another object of the present invention is to provide a method for producing a thermal spraying ceramic powder and a ceramic powder prepared according to the present invention, which can overcome the problems of the binder and the dispersant by not adding the binder and the dispersant.

Further, another object of the present invention is to provide a plasma spray ceramic powder production method of a non-aqueous method that can also be applied to AlN system and a ceramic powder produced accordingly.

In order to achieve the object of the present invention described above, the plasma thermal spraying ceramic powder production method according to the present invention, first prepare a slurry containing the ceramic powder and the non-aqueous solvent. Subsequently, the slurry is dried using a spray dryer to form a dry powder, and then the dry powder is prepared by heat treatment.

The ceramic powder applied to the present invention may be any one selected from the group consisting of Y ₂ O ₃ based, Al ₂ O ₃ based, TiO ₂ based, AlN based, nitride based ceramic powder, wherein the ceramic powder in the slurry is 40 To 60% by weight.

The non-aqueous solvent may include, for example, 0.1 to 3.0% by weight of an ammonium salt, and may further include alcohols such as ethanol or IPA.

Forming the dry powder, using a spray dryer, the heat treatment temperature of the heat treatment step may be carried out in the range of 1 to 10 hours in the range of 800 ℃ to 1600 ℃. On the other hand, when the ceramic powder is AlN-based or nitride-based ceramic powder, the heat treatment step is preferably carried out in a nitrogen or argon atmosphere.

Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified in many different forms, and embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art. Therefore, the scope of the present invention should not be construed as being limited to the embodiments described below. .

First, 50 wt% of Y ₂ O ₃ powder, Al ₂ O ₃ powder, or TiO ₂ powder having a particle diameter of about 0.1 to 4 μm is prepared, and then mixed with a non-aqueous solvent to prepare a slurry.

Herein, the non-aqueous solvent essentially includes an ammonium salt and further includes a solvent of alcohols, and the non-aqueous solvent is 1.5 to 1.5 by weight based on the weight of the Y ₂ O ₃ powder, Al ₂ O ₃ powder, or TiO ₂ powder. About 2.5 times, Preferably it is about 2 times. The ammonium salt is added at 0.1 to 3.0% by weight, preferably 0.5 to 1% by weight. The alcohol may include any one or both of ethanol or IPA (Isopropyl Alcohol),

At this time, when the amount of ammonium salt added is less than 0.1%, the particles cannot be uniformly dispersed in the slurry because the thickness of the ammonium salt may not be formed. If the amount of ammonium salt exceeds 3%, the zeta potential becomes zero. There is a disadvantage in that it leaves the pH range of and provides room for particles to aggregate.

Meanwhile, in the present invention, the theoretical background of adding only the non-aqueous solvent without adding the dispersant and the binder will be described. In order to uniformly disperse the slurry, there is a method of forming an electric double layer by using an electrostatic repulsive force by adjusting the pH. Another method may utilize steric repulsion with the addition of a dispersant. In the present invention, the negative effect of the dispersant and the additive is excluded by taking the method of forming the electric double layer by using the electrostatic repulsive force by the pH control. Here, the formation of the electric double layer means that when electric charges are generated on the surface of the particles, electric neutrality must be satisfied around the interface region of the particles, so that ions having opposite signs as surface charges are distributed around the particles. These ions are called counterion ions. The counterion ions are balanced against each other by the electrostatic attraction due to surface charge and the force to diffuse out of the particle surface by browniam motion. The probability of distribution decreases as it moves away from the particle surface. The interface region composed of the surface charge layer and the counterion layer is called an electric double layer. Therefore, in the present invention, by adding ammonia to form such an electric double layer it is possible to match the pH of the aqueous solution in which the zeta potential of the ceramic powder becomes zero.

In addition, since the slurry can be dispersed using only a non-aqueous solvent without adding a binder and a dispersant, it has an advantage that various problems occurring in the coating layer during mixing of impurities or coating of a thermal sprayed coating can be eliminated at an early stage. In addition, dispersion in non-aqueous solvents can be achieved by (1) adsorption of acid on the basic surface, (2) dissociation of the adsorbed acid by the movement of photons to the surface, and (3) dissociation of anions into the solution. It dissolves and the particle surface has a positive charge. However, the electrostatic repulsion in solvents is much smaller than in water, because solvents have lower ionic concentrations and dielectric constants than water. Therefore, steric stabilization is effective in dispersion in a solvent, and in the present invention, such a dispersant can be solved by using a non-aqueous solvent.

Subsequently, the process will be described. The mixed slurry is fed into a spray dryer which rotates at high speed through a tube, and is sprayed into small droplets by centrifugal force of the rotating disk to produce powder dried in the chamber.

Here, the spray dryer used a centrifugal spray dryer, the working conditions of the centrifugal spray dryer, the input hot air temperature is 80 ℃, the output hot air temperature is 60 ℃, the slurry temperature is 25 ℃, slurry feed rate is 40 to 100 g / mim, and a disk rotational speed of 7060 rpm was used. However, it should be noted that the above-described spray dryer may be used in a variety of spray dryers, such as rotary or nozzle type, and the spray drying operating conditions may be applied to those skilled in the art. For example, the disc rotation speed is applicable even at 6000 to 11000 rpm.

According to the above-mentioned spray drying method, it can be seen that the average size of the spray-dried particles is suitable for use as plasma thermal ceramic powder when the particle size of the powder is only about 10 to 100 μm.

Then, the dried ceramic powder is heat-treated to remove impurities and metal contaminants. The heat treatment is performed for about 1 to 10 hours in the range of 800 to 1600 ° C. However, preferably, it is made in about 3 to 5 hours in the range of 1400-1500 degreeC.

In this case, when the heat treatment temperature is performed at 800 ° C. or lower, sufficient strength is not formed in the powder itself. When the heat treatment temperature is higher than 1600 ° C., the size of the powder itself is increased, and the powders themselves are sintered or neck-bonded. In addition, a process of dry crushing of the powder has to be added, and as the heat treatment temperature is increased, additional cost problems are caused by the temperature rise. Therefore, the heat treatment temperature is preferably made within the range of 800 to 1600 ℃. In this example, 1500 ° C was maintained.

On the other hand, in the heat treatment holding time, when less than 1 hour can not give sufficient strength to the powder, when it exceeds 10 hours, the powder itself may cause sintering or neck bonding and the heat treatment cost may increase. Therefore, the heat treatment holding time should be 1 to 10 hours, preferably 3 to 5 hours. In this example, 3 hours was maintained.

On the other hand, when using AlN powders other than Y ₂ O ₃ , Al ₂ O _3, or TiO ₂ based powders, the above-described conditions are used as they are, except that the atmosphere is maintained in nitrogen or argon atmosphere during the heat treatment.

Hereinafter, with reference to the drawings will be described a comparative example according to the present invention and the prior art.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the particle size distribution of the thermal spray Y ₂ O ₃ powder manufactured by the prior art grinding | pulverization. As can be seen from this figure, since the particle size distribution is distributed sporadically in the range of 1.0 µm to 100 µm, the particle size appears in various ways. Therefore, a large amount of fine powder during plasma coating may cause a lot of powder loss, and the coating layer may not be uniform, thereby reducing the quality of the coating. In addition, it can be seen that clogging may occur during transport to the plasma gun.

In contrast, referring to FIG. 5, the particle size distribution of the thermal spray Y ₂ O ₃ powder prepared according to the present invention does not cause the above-described problems of the prior art because of its large slope. 1, 2, 5, and 6, the horizontal axis represents the particle diameter and the vertical axis represents the volume%, respectively, to indicate the particle size distribution of the powder.

FIG. 2 is a view showing a particle size distribution of plasma sprayed Al ₂ O ₃ powder prepared by the prior art grinding, and FIG. 6 is a view showing a particle size distribution of plasma sprayed Al ₂ O ₃ powder prepared according to the present invention. to be. As can be seen from the figure, it can be seen that the particle size distribution of the present invention has a larger slope than the particle size distribution of the prior art. In other words, it can be seen that even inexpensive and simple processes of the present invention can obtain more effects that can be obtained in the prior art.

Microstructure photographs of plasma thermal Y ₂ O ₃ powder and Al ₂ O ₃ powder prepared by the pulverization of the prior art, shown in FIGS. 3A to 3C and 4A to 4B, and FIGS. 8A and 8B and FIG. Plasma sprayed Y ₂ O ₃ powder and Al ₂ O ₃ powder before the heat treatment step prepared according to the invention, shown in FIGS. 9a and 9b, and after the heat treatments shown in FIGS. 10a to 10c and 11a to 11c. Comparing the plasma sprayed Y ₂ O ₃ powder and Al ₂ O ₃ powder of the prior art powder, the shape and size of the particles of the powder is very unevenly formed and the internal structure of the particles (Fig. 3c, 4c) It can be seen that particles having a particle size of 3 μm and a few nm are largely entangled with each other and the surface of the particles themselves is not smooth and the fluidity may be deteriorated. In contrast, the plasma spray powder according to the present invention has a uniform shape of the particles before the heat treatment, and in the case of the powder after the heat treatment, since the internal structure is very dense and completely melted, the apparent density and fluidity It can be seen that it is increased to improve the properties of the coating layer.

On the other hand, it can be seen that the AlN powders shown in FIGS. 7 and 12A to 12C also have good particle characteristics similar to those of the Y ₂ O ₃ and Al ₂ O ₃ powders described above.

In addition, the apparent density of the conventionally used Y ₂ O ₃ powder is 1.286 g / cm ³ whereas the apparent density of the final Y ₂ O ₃ powder heat-treated according to the present invention is 1.287 g / cm ³ inexpensive and simple process It can be seen that also shows a similar effect to the prior art.

In addition, although the flow rate of the powder of Y ₂ O ₃ used in the prior art was not good enough to measure the flow rate, the flow rate of the final Y ₂ O ₃ powder heat-treated according to the present invention is 0.19 g / sec, In comparison, the fluidity was good.

In the case of Al ₂ O ₃ , the apparent density of Al ₂ O ₃ powder used in the past was 0.749 g / cm 3 and the flowability was unmeasurable, whereas the apparent density of the final Y ₂ O ₃ powder heat-treated according to the present invention. And the fluidity is 1.063 g / cm ³ and 0.63 g / sec, respectively.

In addition, AlN is not conventionally used as a plasma spray powder, but the final powder heat treated according to the present invention has an apparent density and a flow rate of 0.868 gcm ³ and 0.21 g / sec, respectively. It can be seen that enough.

Therefore, according to the above-described configuration of the present invention, it is possible to overcome the problem of the thermal spraying powder produced by conventional grinding in a simple process.

In addition, it is possible to overcome the problems of the binder and the dispersant by adding a binder and a dispersant in preparing the plasma spray powder.

In addition, according to the production method of the present invention, it is possible to provide a plasma spray ceramic powder production method of the non-aqueous method that can be applied to Y ₂ O ₃ and AlN system.

Claims (11)

Preparing a slurry by mixing ceramic powder with a non-aqueous solvent, wherein the non-aqueous solvent is a solvent capable of forming an electric double layer on the surface of the ceramic powder particles; Drying the slurry using a spray dryer to form a dry powder; Plasma thermal spraying ceramic powder manufacturing method comprising the heat treatment of the dry powder. The method of claim 1, The ceramic powder is a plasma spray ceramic powder manufacturing method, characterized in that selected from the group consisting of Y ₂ O ₃ based, Al ₂ O ₃ based, TiO ₂ based, AlN-based, nitride-based ceramic powder. The method of claim 2, The ceramic powder in the slurry is a plasma thermal ceramic powder manufacturing method characterized in that it comprises 40 to 60% by weight. The method of claim 1, The non-aqueous solvent is a plasma thermal ceramic powder manufacturing method comprising an ammonium salt. The method of claim 4, wherein The ammonium salt is a plasma thermal ceramic powder manufacturing method characterized in that it comprises 0.1 to 3.0% by weight. The method of claim 4, wherein The non-aqueous solvent is a plasma thermal ceramic powder manufacturing method characterized in that it further comprises alcohol. The method of claim 6, The alcohol is a plasma thermal ceramic powder manufacturing method characterized in that it comprises any one or both of ethanol or IPA. The method of claim 1, The heat treatment temperature of the heat treatment step is a plasma spray ceramic powder manufacturing method, characterized in that performed in the range of 1 to 10 hours in the range of 800 ℃ to 1600 ℃. The method of claim 1, When the ceramic powder is an AlN-based or nitride-based ceramic powder, the heat treatment is a plasma spray ceramic powder manufacturing method, characterized in that performed in a nitrogen or argon atmosphere. Plasma thermal spraying ceramic powder prepared by the method of claim 1. delete

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