KR101190270B1 - Refining method of tantallum powder using rf plasma and tantallum powder thereof - Google Patents

Abstract

The present invention comprises a first step of increasing the brittleness of the material by embrittling hydrogen inside the tantalum material; A second step of forming a tantalum powder by pulverizing the hydrogen-tanned tantalum material; And a third step of treating the tantalum powder by an RF plasma process.
According to the present invention, the particles are spheroidized and hydrogen embrittled during the HDH process is removed to efficiently produce a high purity refined tantalum powder.

Description

REFINING METHOD OF TANTALLUM POWDER USING RF PLASMA AND TANTALLUM POWDER THEREOF}

The present invention relates to a method for refining tantalum powder using RF plasma, and more particularly, to tantalum powder prepared by HDH method and the like, and to achieve high purity refining and spheroidization using RF plasma. It relates to a refining method of and tantalum powder of high purity prepared according to the method.

Tantalum (Ta) is a metal of Group 5A with a melting point of 2996 ° C and a density of 16.6 g / cm³, and has excellent mechanical and physical characteristics such as high charge amount, low resistance temperature coefficient, ductility and corrosion resistance. It is a metal that is widely used not only in the medical industry but also in the aerospace and military industries. In particular, high density tantalum is a trend of increasing application fields mainly in the form of compound thin films such as TaC, TaN, Ta2O5, and the like, and as a target material for manufacturing thin films, the number of applications is increasing rapidly.

Meanwhile, since most of these tantalum materials depend on imports in Korea, technology that can reuse and reuse tantalum, which has already been used, is important. For example, after the waste sputtering tantalum target used in the sputtering process or the like is pulverized into a powder form, the development of a technology that can be recycled by manufacturing a high-purity tantalum target through a sintering process is required.

The manufacturing method of sputtering target can be largely divided into Ingot metallurgy method using casting melting and Powder metallurgy method using powder sintering. Particularly, powder metallurgy using powder sintering is used as a method for producing high value-added high quality sputtering target. Currently most commonly used.

The manufacturing process of the sputtering target by the powder metallurgy method is largely divided into the production of high-purity raw material powder, the production of high-density target (sintered body) after the powder production, and the machining process, the present invention relates to a high-purity powder manufacturing process .

This raw powder manufacturing process is classified as a very important core process for the production of sputtering targets, since the production of expensive, high-purity raw powders from inexpensive waste targets accounts for a high proportion of the monetization of sputtering target products. . In addition, since the characteristics of the post-process target (sintered body) are largely determined according to the characteristics of the raw material powder, the process of manufacturing the high purity powder can be said to be a very important part that determines the characteristics of the target.

Currently, raw material powder manufacturing processes in most developed countries are based on wet processes based on chemical processes. Such wet process has advantages in the manufacture of ultra fine powder, but also has a disadvantage in that it requires a long manufacturing period and requires the use of expensive and environmentally harmful chemicals.

In order to solve the problem of the wet process, the present invention manufactures a high purity powder using an inductively coupled plasma (ICP) process. The ICP process may be classified into DC plasma (Direct Current), RF plasma (Radio frequency, 0.1 to 100 MHz), and MW plasma (MicroWave, 2.45 GHz) by the frequency of the electromagnetic field.

Each of the plasmas has different characteristics because of different plasma heating mechanisms of electrons in the plasma depending on the applied electric field, and the characteristics of the plasmas are different depending on the power source and process environment. Indicates.

The present invention has been made in view of the above-described problems in the prior art, and by performing an RF plasma process on tantalum powder formed by a method of hydrogenation dehydrogenation (HDH), particles are spheroidized and emulsified during the HDH process. It is a major problem to be able to efficiently produce tantalum powder refined with high purity by removing hydrogen.

According to an aspect of the present invention, there is provided a method for refining tantalum powder using RF plasma, comprising: a first step of embrittling hydrogen inside a tantalum material to increase brittleness of the material; A second step of forming a tantalum powder by pulverizing the hydrogen-tanned tantalum material; And a third step of treating the tantalum powder by an RF plasma process.

In addition, the present invention, tantalum powder formed in the second step is preferably made in the particle size range of 100㎛ or less.

In addition, the present invention, tantalum powder formed in the second step is more preferably made in the particle size range of 25 ~ 100㎛.

In addition, in the present invention, it is preferable to remove the oxide film of the tantalum material by heat-treating the tantalum material in a hydrogen atmosphere before embrittling hydrogen inside the tantalum material in the first step.

In addition, in the present invention, the process of embrittling hydrogen in the tantalum material in the first step, step 1-1 to maintain the tantalum material in a hydrogen atmosphere and 600 ~ 800 ℃ temperature for a predetermined time; It characterized in that it comprises a; 1-2 step to lower the temperature of the tantalum material to 500 ~ 600 ℃ or less.

The high purity tantalum powder according to the present invention is produced by the above-described refining method of the tantalum powder using the RF plasma, characterized in that the particles are spheroidized and the embrittled hydrogen is removed.

According to the present invention, a tantalum powder having a particle size in the range of 25 to 100 µm is formed by a HDH (Hydrogenation DeHydrogenation) method, and by performing an RF plasma process on the tantalum powder, the particles are spheroidized and hydrogen emulsified during the HDH process. Is removed to efficiently prepare the tantalum powder refined to high purity.

In addition, according to the present invention, since hydrogen contained in the RF plasma process is removed, there is no need to undergo a separate dehydrogenation process in the HDH process.

In addition, according to the present invention, it is possible to manufacture and recycle high-purity tantalum powder through the HDH process and the RF plasma process for the waste tantalum material that has already been used in the process such as sputtering, and to the expensive tantalum material The replacement effect is expected.

Figure 1a and 1b is a photograph showing the powder microstructure before the RF plasma process in Experimental Example 1 of the present invention.
Figure 2 is a graph showing the particle size before the RF plasma process in Experimental Example 1 of the present invention.
Figure 3a and 3b is a photograph showing the powder microstructure after the RF plasma process in Experimental Example 1 of the present invention.
Figure 4 is a graph showing the particle size of the powder after the RF plasma process in Experimental Example 1 of the present invention.
Figure 5a and 5b is a photograph showing the powder microstructure before the RF plasma process in Experimental Example 2 of the present invention.
Figure 6 is a graph showing the particle size before the RF plasma process in Experimental Example 2 of the present invention.
Figure 7a and 7b is a photograph showing the powder microstructure after the RF plasma process in Experimental Example 2 of the present invention.
Figure 8 is a graph showing the particle size of the powder after the RF plasma process in Experimental Example 2 of the present invention.
Figure 9 is a graph showing the XRD analysis before and after the RF plasma process in Experimental Examples 1 and 2 of the present invention.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the method for refining the tantalum powder using the RF plasma and the high purity tantalum powder prepared according to the method.

1a and 1b, Figure 2 shows the powder microstructure and the particle size before the RF plasma process in Experimental Example 1 of the present invention, Figures 3a and 3b, Figure 4 powder after the RF plasma process in Experimental Example 1 of the present invention Microstructure and powder particle size are shown. And 5a and 5b, Figure 6 shows the powder microstructure and particle size before the RF plasma process in Experimental Example 2 of the present invention, Figures 7a and 7b, Figure 8 after the RF plasma process in Experimental Example 2 of the present invention Powder microstructure and powder particle size are shown. 9 shows XRD analysis before and after the RF plasma process in Experimental Examples 1 and 2 of the present invention.

The present invention is characterized by pulverizing a tantalum material to form a powder by using a HDH (Hydrogenation DeHydrogenation) process, and then treating the tantalum powder by an RF plasma process.

Therefore, first of all, the process of pulverizing the tantalum material by using the HDH process to form a powder briefly.

The HDH process for forming the tantalum powder includes a hydrogen embrittlement process that largely reduces hydrogen inside the tantalum material, and a process of pulverizing the hydrogen embrittled tantalum material.

The hydrogen embrittlement process of reducing hydrogen in the tantalum material is performed by heat treating the tantalum material in a hydrogen atmosphere for a predetermined time. For example, the tantalum material is heated to a temperature of 600 to 800 ° C. in a hydrogen atmosphere. After that, the temperature is maintained for 1 to 3 hours, and the temperature of the tantalum material is lowered to 500 to 600 ° C. or less.

As such, when the tantalum material is maintained at a temperature of 600 to 800 ° C. for a predetermined time during hydrogen embrittlement, an oxide film inside the tantalum material is removed to create an atmosphere in which hydrogen can be reduced. At temperatures below 600 ° C., the oxide film inside the tantalum material is not removed and hydrogen embrittlement is difficult. On the other hand, since hydrogen embrittlement is performed at a relatively low temperature, the hydrogen embrittlement is difficult due to excessive high temperature even at a temperature exceeding 800 ° C, and also increases the manufacturing cost due to unnecessary energy consumption.

The tantalum material is maintained at 600 to 800 ° C. for 1 to 3 hours. If the time is too short, the oxide film may be partially removed. If the time is too long, unnecessary energy consumption may occur and the formation of the oxide film may be affected. Or adversely affect impurities.

In addition, the reason for maintaining the temperature for a certain time after the temperature rise is to reliably and completely remove the oxide film in the tantalum material, and also to minimize the reaction between the thermometer in the equipment where the hydrogen embrittlement process occurs and the actual internal temperature difference. For sake.

When the oxide film of tantalum material is removed by heating the tantalum material to a temperature of 600 to 800 ° C. in a hydrogen atmosphere for 1 to 3 hours, the tantalum material is lowered to a temperature of 500 to 600 ° C. or lower. Hydrogen is reduced to the inside of the material.

Subsequently, the bulk hydrogenated tantalum material is pulverized. At this time, the tantalum material itself is a high-strength and high ductility material, but inherently brittle, but through the hydrogen embrittlement process hydrogen is injected into the tantalum material to become brittle, very easily hydrogen embrittlement tantalum bulk material It can be crushed.

Tantalum powder formed through the HDH process, the particles are not spheroidized, but formed in a square shape, and embrittled hydrogen remains to form TaH. Therefore, there is a need for a process of subsequently treating the tantalum powder by an RF plasma process to spheroidize the tantalum powder particles and simultaneously remove the embrittled hydrogen to increase the purity.

On the other hand, a general thermal plasma process is a process of removing impurities and inducing sphericalization by surface tension by vaporizing or melting a target material using a plasma heat source of 5000 ° C. or higher. The two main types of thermal plasma processes include DC plasma, which has been developed based on thermal spraying or welding, and RF plasma, which has been developed with a focus on powder high purity. In the case of DC plasma, there are great advantages in terms of productivity and equipment cost, so that some mass production is applied to low melting point materials. However, the contamination yield of electrode (W) and crucible (Crucible) and the collection yield when using expensive rare metals There is a disadvantage in terms of improvement.

Therefore, in the present invention, tantalum powder is refined using an RF plasma process which is free of contamination from electrodes and crucibles and has an advantage in terms of high purity and collection yield.

On the other hand, after the embrittlement of hydrogen in the tantalum material through the HDH process to increase the brittleness of the material, the hydrogen is embrittled tantalum material to form a tantalum powder, wherein the tantalum powder formed according to the particle size In the subsequent RF plasma process, the spheroidization and refining efficiency will be different.

That is, if the particle size of the powder formed through the HDH process is too large, it becomes difficult to receive energy enough to cause particle size spheroidization of the tantalum powder due to the characteristics of the RF plasma. Conversely, if the particle size of the powder formed through the HDH process is too small, the phenomenon that the powder particles evaporate during the RF plasma process may occur.

Therefore, in the present invention, it is preferable that the particle size of the powder formed through the HDH process is limited to the range of 25 to 100 μm so that the tantalum powder particles can receive energy enough to cause particle size spheroidization during the RF plasma process and not evaporate at the same time. Do.

Hereinafter, an experimental example of a method for refining tantalum powder using the RF plasma according to the present invention will be described.

[Experimental Example 1]

In Experimental Example 1, an RF plasma process was performed on a tantalum powder having a particle size range of 0.1 to 100 μm and an average particle size of 41 μm through an HDH process.

As shown in Figures 1a and 1b and 2, the powder particles do not have a spherical shape, but have a rectangular structure, and the particle size range is relatively wide.

In order to refine the tantalum powder, an RF plasma process was performed according to the conditions of Table 1 below.

Torch power Plasma gas Feed rate Oxygen Content / Phase Reactor Pressure 60 kW Sheath Gas Ar-> 85 lpm
Central Gas He-> 17 lpm 46 g / min 1270ppm / Ta ₂ H 101 kPa

As a result of performing the refining process for the tantalum powder according to the RF plasma process conditions according to Table 1, the fine powder having a crushed angular shape as shown in Figs. 3a, 3b and 4 did not occur spheroidization, Partially spherical powder particle size can be obtained only for powders of a certain size or more. And the average particle size of tantalum powder was increased from 41㎛ before the process to 50㎛ after the RF plasma process. The reason for the increase in the size of the particle size is that the particle size decreases because the square powder is carved out as it is spheroidized, and the overall average particle size increases because the extremely fine powders evaporate and disappear.

In addition, as shown in FIG. 9, as a result of XRD analysis for Experimental Example 1, tantalum (Ta) and hydrogen hydrate Ta ₂ H before hydrogen embrittlement were analyzed together. This result is due to the hydrogen reduction of fine powders that are not spheroidized and refined by RF plasma. Therefore, it is confirmed that the particle size control of the initial powder has a great effect on the refining effect by the spheroidization and hydrogen reduction reaction in the RF plasma process. Can be. Since the evaporation occurs in the case of the ultra fine powder, it can be seen that the fine powder having a predetermined size or less does not occur in spheroidization.

As can be seen through Experimental Example 1, when the initial tantalum powder has a particle size of 100 μm or less, spheroidization and high-purity refining effects occur through an RF plasma process, but in the case of powder particles that are too small, an RF plasma process Evaporation will reduce the spheroidizing and refining effects.

[Experimental Example 2]

In Experimental Example 2, an RF plasma process was performed on the tantalum powder having a particle size range of 25 to 100 μm and an average particle size of 63 μm through the HDH process.

As shown in Figures 5a and 5b and 6, the powder particles do not form a spherical shape, but have a rectangular structure, and the particle size range is relatively wide.

In order to refine the tantalum powder, an RF plasma process was performed according to the conditions of Table 2 below.

Torch power Plasma gas Feed rate Oxygen Content / Phase Reactor Pressure 60 kW Sheath Gas Ar-> 85 lpm
Central Gas He-> 17 lpm 46 g / min 942ppm / Ta ₂ H 101 kPa

As a result of refining the tantalum powder according to the RF plasma process conditions according to Table 2, as shown in FIGS. 7A, 7B and 8, 90% or more of TaH powder particles were reduced and spheroidized into pure Ta particles. . Through Experimental Example 2, it can be seen that spheroidization easily occurs when the powder particle size becomes 25 µm or more. In addition, the spheroidization efficiency can be increased due to the narrowing of the size range.

In addition, as shown in Figure 9, XRD analysis of the Experimental Example 2 as a result of the hydrate Ta ₂ H does not appear, the hydrogen reduction reaction appeared in the front surface only the tantalum particles as a raw material.

As can be seen through Experimental Example 2, when the particle size of the initial tantalum powder is limited to the range of 25 ~ 100㎛, the refining effect of spheroidization and high purity through the RF plasma process is most efficiently generated.

And the results of oxygen analysis for each RF plasma process of Experimental Examples 1 and 2 described above are described in Table 3 below.

powder Oxygen content Before RF Plasma Process After RF Plasma Process Experimental Example 1 1270 ppm 755 ppm Experimental Example 2 942 ppm 448 ppm

Referring to Table 3, the oxygen content before the RF plasma process of Experimental Examples 1 and 2 was found to be 1270ppm and 942ppm, respectively. Therefore, it can be seen that the oxygen powder has a relatively high oxygen content due to the low RF plasma efficiency. In addition, the oxygen content after the RF plasma process of Experimental Example 2 was reduced to 448ppm, the final purity of the tantalum powder showed a value of 99.9% or more (raw sample 2N-> 3N or more). As a result, the spheroidization efficiency was shown to affect the efficiency of the oxygen content.

While the invention has been shown and described with respect to the specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. Anyone with it will know easily.

Claims (6)

A first step of embrittling hydrogen in the tantalum material to increase brittleness of the material;
A second step of forming a tantalum powder by pulverizing the hydrogen-tanned tantalum material;
A third step of treating the tantalum powder by an RF plasma process;
Including,
Tantalum powder formed in the second step is made of a particle size range of 25 ~ 100㎛,
Before the embrittlement of hydrogen in the tantalum material in the first step, the tantalum material is heat-treated in a hydrogen atmosphere to remove the oxide film of the tantalum material,
The process of embrittling hydrogen in the tantalum material in the first step,
Step 1-1 to maintain the tantalum material in a hydrogen atmosphere and 600 ~ 800 ℃ temperature for a predetermined time;
Step 1-2 to lower the temperature of the tantalum material to 500 ~ 600 ℃ or less;
Refining method of tantalum powder using an RF plasma comprising a. delete delete delete delete A high purity tantalum powder produced by the refining method according to claim 1, wherein particles are spheroidized and embrittled hydrogen is removed.

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