KR102641901B1 - Carbon-silicon carbide target material and its manufacturing method and use - Google Patents

Abstract

This document provides a carbon-silicon carbide target material and its manufacturing method and uses. The manufacturing method of the carbon-silicon carbide target material includes mixing carbon powder and silicon carbide powder and then performing secondary ball milling. The carbon-silicon carbide target material is obtained by drying between ball milling, followed by molding, sintering and cooling.

Description

Carbon-silicon carbide target material and its manufacturing method and use

This application belongs to the target material technology field and relates to the carbon-silicon carbide target material technology field, for example, to the carbon-silicon carbide target material and its manufacturing method and use.

A thermal print head includes a substrate composed of an insulating material, and a substrate (substrate) on the substrate. ), a conductive electrode is formed on the base layer, a heating resistor ribbon is formed above the conductor electrode and the base layer along the main printing direction, and a protective layer is located above the conductor electrode and the heating resistor ribbon. The protective layer generally uses a method of adding a wear-resistant layer to the first insulating layer or the first insulating layer, and generally both the insulating layer and the wear-resistant layer are materials with low thermal conductivity. In the process of the heating resistor generating heat, the amount of heat generated from the heating resistor is transferred to the printing medium through the protective layer, and the printing medium changes correspondingly according to the amount of heat transferred. After the heating resistor generates heat, the amount of heat transferred to the printing medium is directly related to the thickness and thermal conductivity of the protective layer.

In the cooling process of the thermal printing head, the operating voltage stops being applied and the heating resistor stops generating heat. The ideal state is that the moment the operating voltage stops being applied, the temperature of the surface of the protective layer is lowered to the required low temperature. Since cooling in this process is implemented only through heat conduction, the protective layer must have high thermal conductivity characteristics so that the remaining heat in the protective layer is instantaneously conducted. However, in reality, the protective layer does not have high thermal conductivity, and as soon as the operating voltage is stopped, part of the large amount of heat remaining in the protective layer is conducted by the thermal printing head itself, and the other part is conducted by the printing medium. . However, the amount of heat conducted by the printing medium affects printing quality because “tailing” phenomenon easily occurs during the printing process. If the thickness of the protective layer becomes thinner, the heat transfer efficiency improves, but the wear resistance of the thermal printing head is greatly reduced, seriously affecting the performance of the thermal printing head.

Additionally, due to the material properties of the insulating layer and the wear-resistant layer itself, the wear-resistant layer and the conductive electrode do not come into direct contact, so the insulating layer must be present. However, when the insulating layer and the wear-resistant layer are in direct contact, the wear-resistant layer often falls off, so the wear resistance of the wear-resistant layer cannot be fully demonstrated, and the wear resistance of the print head is greatly reduced.

CN203651201U discloses a thermally sensitive print head that includes a substrate made of an insulating material and has a base layer installed on the substrate. In the thermally sensitive print head, a conductor electrode is formed on the base layer, and the conductor electrode has a main printing direction. Accordingly, a heating resistor ribbon is formed on the conductor electrode, and there is a protective layer on the conductor electrode and the heating resistor ribbon. The protective layer is divided into three layers, the lowest layer is an insulating layer with low abrasion resistance, and the middle layer has at least thermal conductivity. It is a high thermal conductivity layer with twice the thermal conductivity of the insulating layer, and the top layer is a wear-resistant layer. This improves the thermal response speed of the upper surface of the thermal printing head, increasing the amount of heat transferred to the upper part when the temperature rises, and the middle layer serves as a transition layer, further increasing the adhesion between the insulating layer and the wear-resistant layer, thereby increasing the wear resistance. By fully exhibiting the high hardness properties of the layer, the wear resistance of the thermal printing head can be guaranteed.

CN112010675A and CN108409330A also disclosed ceramic materials for printing that support the development of thermosensitive printing and 3D printing, respectively. However, as the thermal printing and 3D printing markets expand, the industry's demand for carbon-silicon carbide target materials that can improve printing equipment and work efficiency is increasing day by day. In addition, in order to ensure performance stability and wear resistance of the film layer during vacuum sputtering of carbon-silicon carbide target materials, target materials with relatively high density, uniform microstructure, and no pores are required.

However, due to the special performance of carbon-silicon carbide target material, the difficulty of production technology is high and subsequent processing is difficult, so it is currently difficult to produce carbon-silicon carbide target material with high density and stable performance, so it is difficult to produce in the thermal response industry. Unable to meet target quality requirements.

Therefore, it is necessary to develop a method for manufacturing a carbon-silicon carbide target material with relatively high density, uniform microstructure, and no pores.

The purpose of this application is to provide a carbon-silicon carbide target material and a manufacturing method and use thereof. The manufacturing method of the carbon-silicon carbide target material can produce a carbon-silicon carbide target material with both high density and purity; The microstructure of the obtained carbon-silicon carbide target material is uniform and has excellent target sputtering performance. When applied to the printing field, the operating efficiency and service life of printing equipment can be effectively improved, so the application prospects are broad.

In order to achieve this purpose, this application uses the following technical solutions:

First aspect: The present application provides a method for manufacturing a carbon-silicon carbide target material, which includes the following steps:

(1) mixing carbon powder and silicon carbide powder and performing first ball milling in a solvent environment to obtain a first mixed material;

(2) drying the first mixture of step (1), mixing it with a solvent and polyol, and performing a second ball milling to obtain a second mixture;

(3) The second mixture of step (2) is sequentially molded, sintered, and cooled to obtain the carbon-silicon carbide target material.

The manufacturing method of the carbon-silicon carbide target material of the present application improves the uniformity of mixing of the carbon powder and silicon carbide powder by mixing solvent, carbon powder, and silicon carbide powder and performing ball milling. After drying, the second ball is used again. Milling is performed and polyol is added to cause an action similar to pelletizing, which improves the fluidity of the second mixture and is advantageous for firm compaction of the second mixture during the subsequent molding and sintering process, and improves the surface of the final product. By improving uniformity, surface defects are reduced and the density of the carbon-silicon carbide target material is improved.

Optionally, the particle size of the carbon powder in step (1) is less than 20 μm, for example, 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm or 20 μm, etc., but limited to the values listed above. This does not apply, and the same applies to other values not listed within the range.

Optionally, the particle size of the silicon carbide powder in step (1) is less than 10 μm, for example 5 μm, 5.6 μm, 6.2 μm, 6.7 μm, 7.3 μm, 7.8 μm, 8.4 μm, 8.9 μm, 9.5 μm or 10 μm, etc. However, it is not limited to the values listed above, and other values not listed within the range equally apply.

This application selects the particle size of the carbon powder and silicon carbide powder in the above range, which is more advantageous for uniform mixing in the first ball milling and control of the particle size of the second mixed material particles in the second ball milling, thereby making carbon-silicon carbide The density of the target material can be effectively guaranteed.

Optionally, the carbon powder in step (1) is a high purity carbon powder with a purity of ≥99.995%, and the purity may be, for example, 99.995%, 99.999%, 99.9994% or 99.9996%, but is not limited to the values listed above. The same applies to other values not listed within the range.

Optionally, the silicon carbide powder in step (1) is a high purity silicon carbide powder having a purity of ≥99.9%, for example, 99.9%, 99.92%, 99.95%, 99.96%, 99.98%, 99.99%, 99.992%. , 99.995% or 99.998%, etc., but it is not limited to the values listed above, and other values not listed within the range are equally applicable.

Optionally, the mass ratio of the carbon powder and silicon carbide powder in step (1) is 40-50:60-50, for example, 40:60, 45:60, 48:60, 50:60, 40:58, It may be 42:58, 44:59, 45:55, 48:52 or 50:50, etc., but is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the solvent in step (1) is ethanol.

Optionally, the material to ball ratio of the first ball mill in step (1) is 1 to 3:1, for example 1:1, 1.2:1, 1.5:1, 1.8:1, 2.0:1, It may be 2.2:1, 2.5:1, or 3.0:1, etc., but is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the time of the first ball milling in step (1) is ≥24h, for example, may be 24h, 25h, 26h, 28h, 30h, 32h or 35h, etc., but is not limited to the values listed above, and The same applies to other values not listed within the range.

Optionally, the ball milling medium of the first ball mill in step (1) is silicon carbide balls.

Optionally, in step (1) the first ball milling is carried out under sealed conditions.

Optionally, the drying in step (2) comprises a drying step.

Optionally, the drying temperature in step (2) is 100-140°C, for example 100°C, 105°C, 109°C, 114°C, 118°C, 123°C, 127°C, 132°C, 136°C or 140°C. etc., but it is not limited to the values listed above, and other values not listed within the range are equally applied.

Optionally, the drying time in step (2) is 8 to 16 h, for example, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h or 16 h, etc., but is not limited to the values listed above, The same applies to other values not listed within the range.

Optionally, the amount of the solvent added in step (2) is 0.1 to 1 wt% of the first mixture, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, It may be 0.7wt%, 0.8wt%, 0.9wt% or 1wt%, but it is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, in step (2) the solvent is ethanol.

Optionally, the addition amount of the polyol in step (2) is 0.1 to 5 wt%, for example 0.1 wt%, 0.5 wt%, 1.0 wt%, 1.8 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, It may be 4wt%, 4.5wt%, or 5wt%, but it is not limited to the values listed above, and other values not listed within the range equally apply.

The polyol of the present application includes glycerin or propylene glycol, and by selectively selecting glycerin, the particle size of the second mixture can be more preferably controlled.

Optionally, the material to ball ratio of the second ball mill in step (2) is 1 to 3:1, for example 1:1, 1.2:1, 1.5:1, 1.8:1, 2.0:1, It may be 2.2:1, 2.5:1, or 3.0:1, etc., but is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the time of the second ball milling in step (2) is ≥24h, for example, may be 24h, 25h, 26h, 28h, 30h, 32h or 35h, etc., but is not limited to the values listed above, and The same applies to other values not listed within the range.

Optionally, the ball milling medium of the second ball mill in step (2) is silicon carbide balls.

In the present application, silicon carbide balls can be selectively selected as the ball milling medium for the first ball milling and the second ball milling, thereby ensuring higher purity of the powder.

Optionally, in step (2) the second ball milling is carried out under sealed conditions.

In the present application, the first ball milling and the second ball milling are performed under sealed conditions, thereby preventing slurry from leaking during the powder mixing process and improving the purity of the product.

Optionally, in step (2), the material after the second ball milling is passed through a screen to obtain a second mixed material.

Optionally, the particle size range of the second mixture in step (2) is ≤200 μm, for example, 200 μm, 190 μm, 180 μm, 170 μm, 165 μm, 160 μm, 150 μm, 120 μm or 100 μm, etc., but not greater than the values listed above. It is not limited, and the same applies to other values not listed within the range.

Optionally, the flatness of the surface of the second mixture after molding in step (3) is ≤0.5mm, for example 0.1mm, 0.15mm, 0.19mm, 0.20mm, 0.28mm, 0.30mm, 0.37mm, 0.40mm, It may be 0.46mm or 0.5mm, but it is not limited to the values listed above, and other values not listed within the range equally apply.

The present application can improve the performance of the carbon-silicon carbide target material after sintering by ensuring that the flatness after molding is ≤0.5mm.

Optionally, the molding in step (3) includes charging the second mixture into a mold, tightly packaging it using packaging material, and then compacting it.

Since carbon-silicon carbide powder is light and smooth, selecting and using a packaging material can effectively prevent the powder from being pulled out of the mold during the sintering process, improving sintering performance and product yield.

Optionally, in step (3) the packaging material is carbon fiber fabric.

Optionally, step (3) further includes cold pressing between the molding and sintering.

Optionally, the cold pressing in step (3) includes artificially applying pressure to the mold so that it is compressed and cannot move further.

Optionally, step (3) includes vacuum pumping and shielding gas filling between the molding and sintering.

Optionally, the vacuum pumping in step (3) is to vacuum pump until the absolute vacuum degree is ≤100Pa, for example, the absolute vacuum degree is 50Pa, 56Pa, 62Pa, 67Pa, 73Pa, 78Pa, 84Pa, 89Pa, 95Pa, or It may be 100Pa, etc., but it is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the time of vacuum pumping in step (3) is ≥40min, for example 40min, 42min, 43min, 45min, 48min, 50min, 52min, 55min, 60min, 65min or 70min, etc., but the value listed above. It is not limited to , and other values not listed within the range are equally applied.

In this application, the speed of vacuum pumping is controlled by controlling the total vacuum pumping time, and the powder is prevented from being pulled out during the vacuum pumping process, thereby significantly improving the density of the final carbon-silicon carbide target material and preventing cracks in the target material ( Reduces the risk of crack occurrence.

Optionally, in step (3), the protective gas is filled until the gauge pressure is -0.08 to -0.1 MPa, for example, the gauge pressure is -0.08 MPa, -0.082 MPa, -0.085 MPa, -0.09 MPa, It may be -0.095 MPa or -0.1 MPa, etc., but it is not limited to the values listed above, and other values not listed within the range also apply equally.

Optionally, the shielding gas in step (3) includes argon gas.

Optionally, the sintering in step (3) includes: raising the temperature to a first temperature through a first temperature increase under the condition filled with a protective gas; Again, the temperature is raised to the second temperature through the second temperature increase and the second warming is performed; While performing the second warming, the pressure is increased to the second pressure through a second pressure increase, and the pressure is maintained until the second warming is completed; Continuing to increase the temperature to the third temperature through a third temperature increase, and performing vacuum pumping until the third temperature increase is completed in the third temperature increase process; The third temperature is maintained, the pressure is increased to the third pressure through the third pressure increase, and then the third thermal insulation is performed.

Optionally, the present application uses a combination of a three-stage temperature increase and a two-stage pressure increase step, which is more advantageous in improving the sintering effect and ultimately improves the density of the carbon-silicon carbide target material.

Optionally, in step (3), the rate of the third temperature increase is slower than the rate of the second temperature increase and the rate of the second temperature increase is slower than the rate of the first temperature increase.

Optionally, the rate of the first temperature increase in step (3) is 8-12°C/min, for example 8°C/min, 8.5°C/min, 8.9°C/min, 9.4°C/min, 9.8°C/min. , 10.3℃/min, 10.7℃/min, 11.2℃/min, 11.6℃/min or 12℃/min, etc., but it is not limited to the values listed above, and other values not listed within the range are equally applicable. do.

Optionally, the first temperature in step (3) is 1400-1500°C, for example 1400°C, 1412°C, 1423°C, 1434°C, 1445°C, 1456°C, 1467°C, 1478°C, 1489°C or 1500°C. It may be ℃, etc., but it is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the second temperature increase rate in step (3) is 4-6°C/min, for example 4°C/min, 4.3°C/min, 4.5°C/min, 4.7°C/min, 4.9°C/min, It may be 5.2℃/min, 5.4℃/min, 5.6℃/min, 5.8℃/min or 6℃/min, but it is not limited to the values listed above, and other values not listed within the range also apply equally. .

Optionally, the time length of the second warming in step (3) is 40-100min, for example, may be 40min, 47min, 54min, 60min, 67min, 74min, 80min, 87min, 94min or 100min, etc., but It is not limited to the value, and the same applies to other values not listed within the range.

Optionally, the second temperature in step (3) is between 1750°C and 1850°C, for example 1750°C, 1762°C, 1773°C, 1784°C, 1795°C, 1806°C, 1817°C, 1828°C, 1839°C or 1850°C. It may be ℃, etc., but it is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the time length of the second boosting in step (3) is 12-25min, for example, 12min, 14min, 15min, 17min, 18min, 20min, 21min, 23min, 24min or 25min, etc., but It is not limited to the value, and the same applies to other values not listed within the range.

Optionally, the second pressure in step (3) is between 7 and 9 MPa, for example 7 MPa, 7.3 MPa, 7.5 MPa, 7.7 MPa, 7.9 MPa, 8.2 MPa, 8.4 MPa, 8.6 MPa, 8.8 MPa or 9 MPa, etc. However, it is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the rate of the third temperature increase in step (3) is 1-3.5°C/min, for example 1°C/min, 1.3°C/min, 1.6°C/min, 1.9°C/min, 2.2°C/min. , 2.5℃/min, 2.7℃/min, 3℃/min, 3.3℃/min or 3.5℃/min, etc., but it is not limited to the values listed above, and other values not listed within the range are equally applicable. do.

Optionally, the third temperature in step (3) is 1950-2050°C, for example 1950°C, 1962°C, 1973°C, 1984°C, 1995°C, 2006°C, 2017°C, 2028°C, 2039°C or 2050°C. It may be ℃, etc., but it is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, in step (3), vacuum pumping is carried out in the third temperature raising process until the absolute vacuum becomes ≤100Pa, for example, the absolute vacuum may be 100Pa, 95Pa, 90Pa, 85Pa, 80Pa, 75Pa or 70Pa. However, it is not limited to the values listed above, and other values not listed within the range equally apply.

Optionally, the time length of the third step-up in step (3) is 40-80min, for example, may be 40min, 45min, 50min, 54min, 58min, 60min, 67min, 70min, 76min or 80min, etc., but It is not limited to the value, and the same applies to other values not listed within the range.

Optionally, the third pressure in step (3) is 30-40 MPa, for example, 30 MPa, 32 MPa, 33 MPa, 34 MPa, 35 MPa, 36 MPa, 37 MPa, 38 MPa, 39 MPa or 40 MPa, etc., but limited to the values listed above. This does not apply, and the same applies to other values not listed within the range.

Optionally, the time length of the third warming in step (3) is 150-220min, for example, may be 150min, 160min, 166min, 170min, 180min, 189min, 197min, 205min, 213min or 220min, etc., but It is not limited to the value, and the same applies to other values not listed within the range.

Optionally, the cooling in step (3) is carried out by stopping the heating, reducing the temperature to the second temperature, releasing the pressure, introducing a shielding gas and cooling with the furnace to the fourth temperature after the sintering is completed. This includes completing cooling.

Optionally, the temperature reduction in step (3) is by natural cooling with the furnace.

Optionally, the shielding gas in step (3) includes argon gas.

Optionally, the fourth temperature in step (3) is ≦200°C, for example 20°C, 40°C, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C or 200°C. etc., but it is not limited to the values listed above, and other values not listed within the range are equally applied.

Optionally, after said cooling in step (3), the method further includes mechanically processing said carbon-silicon carbide target material.

As an optional technical solution of the present application, the manufacturing method includes the following steps:

(1) Carbon powder with a particle size of less than 20 μm and silicon carbide powder with a particle size of less than 10 μm are mixed according to a mass ratio of 40 to 50:60 to 50, and first ball milling is performed with silicon carbide balls in an ethanol environment under sealed conditions to obtain a first ball mill. Obtaining a mixed material, the time of first ball milling is ≥24h, and the ratio of material to ball is 1~3:1.

(2) After the first mixture in step (1) is dried, it is mixed with ethanol in an amount of 0.1 to 1 wt% of the first mixture and polyol in an amount of 0.1 to 5 wt% of the first mixture, and sealed under sealed conditions. The second ball milling is performed with silicon carbide balls, the time of the second ball milling is ≥24h, and the material after ball milling is passed through a screen to obtain a second mixed material.

(3) After the second mixture in step (2) is molded, the flatness of the surface of the second mixture is ≤0.5mm, and after cold pressing again, it is vacuum pumped so that the absolute vacuum degree is ≤100Pa, and the gauge pressure is Fill the protective gas until -0.08~-0.1MPa, and proceed with the first temperature increase to 1400~1500℃ at a rate of 8~12℃/min under the condition of filling the protective gas.

A second temperature increase is performed to 1750-1850°C at a rate of 4-6°C/min, and a second warming is performed for 40-100 minutes. At the same time as the second warming, the second pressure is increased until it reaches 7 to 9 MPa within 12 to 25 minutes, and the pressure is maintained until the second warming is completed.

The third temperature increase continues to 1950 to 2050°C at a rate of 1 to 3.5°C/min, and vacuum pumping is performed until the third temperature increase is completed in the third temperature increase process, but the absolute vacuum degree is ≤100Pa. Vacuum pump until. Maintain the temperature at 1950~2050℃, increase the pressure to 30~40MPa within 40~80min, and then proceed with the third warming for 150~220min. After the third warming is completed, the heating is stopped, the temperature is reduced to 1750-1850°C, the pressure is released, and protective gas is introduced to cool the furnace to ≤200°C to obtain the carbon-silicon carbide target material.

The manufacturing method provided in this application improves the mixing method of carbon powder and silicon carbide powder, improves the uniformity of the product surface microstructure, reduces surface defects, and achieves a specified three-step temperature increase and three-step pressure increase during sintering. By combining the processes, the density of the product was significantly improved.

Second aspect: The present application provides a carbon-silicon carbide target material, which is obtained by manufacturing the carbon-silicon carbide target material according to the method for producing a carbon-silicon carbide target material according to the first aspect.

The target material obtained by manufacturing in the first aspect of the present application has relatively high density and purity, excellent performance, and good application prospects.

Third aspect: The present application provides the use of the carbon-silicon carbide target material according to the second aspect in thermal printing or 3D printing.

The density of the carbon-silicon carbide target material obtained by manufacturing in this application is ≥95.9%, and the density is ≥99% and purity is ≥99.7% under relatively excellent conditions, and magnetron sputtering (Magnetron) for the purity and density of the target material is used. sputtering), and by being used in the wear-resistant layer of the thermal printing head, it can improve the work efficiency and service life of thermal printing equipment.

The % purity and composition content mentioned in this application each refer to the mass content.

Compared with the prior art, the present application has at least the following beneficial effects:

(1) The method for manufacturing the carbon-silicon carbide target material provided in this application controls the particle size of the second mixture through a secondary ball milling step, ultimately improving the uniformity of the surface of the carbon-silicon carbide target material, Reduced surface defects.

(2) The manufacturing method of the carbon-silicon carbide target material provided in this application ensures the density of the product and has excellent performance by performing sintering using a three-stage temperature increase and a two-stage pressure increase operation.

(3) The density of the carbon-silicon carbide target material provided in this application is ≥95.9%, and under relatively good conditions, the density is ≥99% and the purity is ≥99.7%, meeting the thermal response industry's requirements for target materials. satisfies.

1 is a surface texture diagram of a carbon-silicon carbide target material provided in Example 1 of the present application;
Figure 2 is a surface texture diagram of the carbon-silicon carbide target material provided in Comparative Example 3 of the present application.

Below, the technical idea of this application is further explained by combining the attached drawings and specific implementation methods.

Below, the present application is further described in detail. However, the following examples are only simple examples of the present application and are not intended to represent or limit the scope of the claims of the present application, and the claims of the present application are based on the claims.

1. Example

Example 1

This embodiment provides a method for manufacturing a carbon-silicon carbide target material, which includes the following steps:

(1) Carbon powder with a particle size of less than 20 μm and silicon carbide powder with a particle size of less than 10 μm are mixed according to a mass ratio of 45:55, and first ball milling is performed with silicon carbide balls in an ethanol environment under sealed conditions to obtain a first mixed material. , the time of the first ball milling is 48h, and the ratio of material to balls is 2:1.

(2) The first mixture in step (1) is dried at 120°C for 12 h, then mixed with ethanol in an amount of 0.5 wt% of the first mixture and glycerin in an amount of 1 wt% of the first mixture, and sealed. Under the following conditions, the second ball milling is performed with silicon carbide balls, the time of the second ball milling is 48 hours, the material after ball milling is passed through a screen to obtain a second mixture, and the particle size of the second mixture is 120 to 160 μm. am.

(3) The second mixture obtained in step (2) is charged into a graphite mold, and the outside of the second mixture is wrapped with high-density carbon fiber cloth and compressed to ensure that the surface flatness of the second mixture is 0.35 mm or less after molding. do. The mold is placed in a vacuum sintering furnace, the mold is kept horizontal after placement, and artificial pressure is applied to the mold, and cold pressing is performed until it is compressed and cannot move. After cold pressing, vacuum pump for 60 minutes until the absolute vacuum is below 90Pa. Vacuum pumping is terminated, argon gas is filled into the vacuum sintering furnace until the gauge pressure is -0.09 MPa, and argon gas filling is stopped. While filling the argon gas, the first temperature increase is carried out to 1450°C at a rate of 10°C/min.

A second temperature increase is performed to 1800°C at a rate of 5°C/min, and a second warming is performed for 60 minutes. After raising the temperature to 1800°C, the second pressure is immediately increased to 8 MPa within 20 minutes at the same time as the second insulation, and the pressure is maintained until the second insulation is completed.

The third temperature increase continues to 2000°C at a rate of 3°C/min, and vacuum pumping is performed until the third temperature increase is completed in the third temperature increase process, and vacuum pumping is performed until the absolute vacuum degree becomes 100 Pa or less. do. The temperature is maintained at 2000°C and the third pressure increase is performed within 60 min until it reaches 35 MPa, and then the third warming is performed for 180 min. After the third warming is completed, the heating is stopped, the temperature is reduced to 1850℃, the pressure is released, the protective gas is introduced, the furnace is cooled to 100℃, and the product is taken out and reduced to the required size by ball milling, wire cutting, etc. Processing is performed to obtain the carbon-silicon carbide target material.

Example 2

This embodiment provides a method for manufacturing a carbon-silicon carbide target material, which includes the following steps:

(1) Carbon powder with a particle size of less than 20 μm and silicon carbide powder with a particle size of less than 10 μm are mixed according to a mass ratio of 40:60, and first ball milling is performed with silicon carbide balls in an ethanol environment under sealed conditions to obtain a first mixed material. , the time of the first ball milling is 24h, and the ratio of material to ball is 1:1.

(2) The first mixture in step (1) is dried at 100°C for 16 h, then mixed with ethanol in an amount of 0.1 wt% of the first mixture and glycerin in an amount of 5 wt% of the first mixture, and sealed. Under the following conditions, the second ball milling is performed with silicon carbide balls, the time of the second ball milling is 28 hours, the material after ball milling is passed through a screen to obtain a second mixture, and the particle size of the second mixture is 130 to 180 μm. am.

(3) The second mixture from step (2) is charged into a graphite mold, and the outside of the second mixture is wrapped with high-density carbon fiber cloth and compressed to ensure that the flatness of the surface of the second mixture after molding is 0.5 mm or less. do. The mold is placed in a vacuum sintering furnace, the mold is kept horizontal after placement, and artificial pressure is applied to the mold, and cold pressure is applied until it is compressed and cannot move. After cold pressing, vacuum pump for 50 minutes until the absolute vacuum is below 100Pa. Vacuum pumping is terminated, argon gas is filled into the vacuum sintering furnace until the gauge pressure is -0.08 MPa, and argon gas filling is stopped. While filling the argon gas, the first temperature increase is carried out to 1400°C at a rate of 8°C/min.

A second temperature increase is performed to 1750°C at a rate of 4°C/min, and a second warming is performed for 40 minutes. After raising the temperature to 1750°C, a second pressure increase is carried out immediately at the same time as the second warming until it reaches 7 MPa within 12 minutes, and the pressure is maintained until the second warming is completed.

The third temperature increase continues to 2000°C at a rate of 1°C/min, and vacuum pumping is performed until the third temperature increase is completed in the third temperature increase process, and vacuum pumping is performed until the absolute vacuum degree becomes 90 Pa or less. do. After maintaining the temperature at 2000°C and proceeding with the third pressure increase until it reaches 30 MPa within 80 min, the third warming is performed for 280 min. After the third warming is completed, the heating is stopped, the temperature is reduced to 1750℃, the pressure is released, argon gas is introduced, the furnace is cooled to 200℃, and the product is taken out and reduced to the required size by ball milling, wire cutting, etc. processing to obtain the carbon-silicon carbide target material.

Example 3

This embodiment provides a method for manufacturing a carbon-silicon carbide target material, which includes the following steps:

(1) Carbon powder with a particle size of less than 18 μm and silicon carbide powder with a particle size of less than 9 μm are mixed according to a mass ratio of 50:50, and first ball milling is performed with silicon carbide balls in an ethanol environment under sealed conditions to obtain a first mixed material. , the time of the first ball milling is 36h, and the ratio of material to balls is 3:1.

(2) The first mixture in step (1) was dried at 140°C for 8 h, and then mixed with ethanol in an amount of 1 wt% of the first mixture and glycerin in an amount of 0.1 wt% of the first mixture, The second ball milling is performed with silicon carbide balls under sealed conditions. The time of the second ball milling is 36 hours. The material after ball milling is passed through a screen to obtain a second mixture, and the particle size range of the second mixture is 140 ~ It is 200μm.

(3) The second mixture obtained in step (2) is charged into a graphite mold, and the outside of the second mixture is wrapped with high-density carbon fiber cloth and then pressed, so that the flatness of the surface of the second mixture after molding is 0.4 mm or less. guaranteed. The mold is placed in the vacuum sintering furnace again, the mold is kept horizontal after placement, and artificial pressure is applied to the mold, and cold pressure is applied until it is compressed and cannot move. After cold pressing, vacuum pump for 55 minutes until the absolute vacuum is below 90Pa. Vacuum pumping is terminated, argon gas is filled into the vacuum sintering furnace until the gauge pressure is -0.1 MPa, and argon gas filling is stopped. While filling the argon gas, the first temperature increase is carried out to 1500°C at a rate of 12°C/min.

A second temperature increase is performed to 1850°C at a rate of 6°C/min, and a second warming is performed for 100 minutes. After raising the temperature to 1850°C, the second pressure is immediately increased to 9 MPa within 25 minutes at the same time as the second insulation, and the pressure is maintained until the second insulation is completed.

The third temperature increase continues to 2050°C at a rate of 3.5°C/min, and vacuum pumping is performed until the third temperature increase is completed in the third temperature increase process, and vacuum pumping is performed until the absolute vacuum degree becomes 90 Pa or less. do. After maintaining the temperature at 2050°C and proceeding with the third pressure increase until it reaches 40 MPa within 40 min, the third warming is performed for 150 min. After the third thermal insulation is completed, the heating is stopped, the temperature is reduced to 2050℃, the pressure is released, argon gas is introduced, the furnace is cooled to 200℃, and the product is taken out and reduced to the required size by ball milling, wire cutting, etc. processing to obtain the carbon-silicon carbide target material.

Example 4

This example provides a method for manufacturing a carbon-silicon carbide target material, and everything else is the same as Example 1 except that the particle size range of the carbon powder in step (1) is 5 to 30 μm.

Example 5

This example provides a method for manufacturing a carbon-silicon carbide target material, and everything else is the same as Example 1 except that the particle size of the silicon carbide powder in step (1) is 5 to 20 μm.

Example 6

This example provides a method for manufacturing a carbon-silicon carbide target material, and everything else is the same as Example 1 except for replacing glycerin with propylene glycol in step (2).

Example 7

This embodiment provides a method for manufacturing a carbon-silicon carbide target material, and in the manufacturing method, in step (3), the second insulation and the second pressure increase to 35 MPa at the same time and the third pressure increase are all other than Example 1. Same as

Example 8

This embodiment provides a method for manufacturing a carbon-silicon carbide target material, in which the second temperature is directly raised to 2050°C without proceeding with the third temperature increase in step (3), and the second warming is performed for 250 minutes. 2 Everything else is the same as Example 1 except that the second and third pressure boosts are sequentially performed in the warming process.

Example 9

This example provides a method for manufacturing a carbon-silicon carbide target material, and in the manufacturing method, everything else is the same as Example 1 except that the vacuum pumping time after cold pressing is 34 minutes.

Comparing Example 1 and Example 9, the vacuum pumping time of Example 1 is relatively long, the powder is not easily extracted, and the density of the final product is clearly higher than that of the carbon-silicon carbide target material of Example 9. .

2. Comparative example

Comparative Example 1

This comparative example provides a method for manufacturing a carbon-silicon carbide target material, and all procedures except for performing ball milling directly in the first ball mill for 96 h without proceeding with step (2) in the manufacturing method are the same as in Example 1. same.

Comparative Example 2

This comparative example provides a method for manufacturing a carbon-silicon carbide target material, and everything else is the same as Example 1 except that glycerin is not added in step (2).

Comparative Example 3

This comparative example provides a method for manufacturing a carbon-silicon carbide target material, except that step (1) is not performed in the above manufacturing method and step (2) is performed directly using the two types of powder as the first mixture. All are the same as Example 1.

3. Tests and results

The shape of the surface of the carbon-silicon carbide target material after molding was observed. Here, the surface of the carbon-silicon carbide target material obtained by manufacturing in Example 1 and Comparative Example 3 is as shown in Figures 1 and 2, respectively. As can be seen, in Example 1, a secondary ball milling mixed method was used, the surface was smooth, the microstructure was uniform, and there were significantly fewer defects than Comparative Example 3, and the density in Comparative Example 3 was Although only 98.0%, the density in Example 1 is higher and sputtering performance is excellent.

In Comparative Example 1 and Comparative Example 2, the texture uniformity of the surface of the carbon-silicon carbide target material after molding was worse than Example 1, and the density in Comparative Example 1 and Comparative Example 2 was only 98.4% and 97.9%, respectively, and the surface defects is clearly higher than that of Example 1, and the performance of the target material is relatively poor.

In Examples 2 to 9, the texture uniformity of the surface of the carbon-silicon carbide target material was better than that of Comparative Examples 1 to 2, and there were fewer defects in the surface microstructure.

Comparing Example 1 and Examples 4 to 5, in Example 1, carbon powder and silicon carbide powder with smaller particle sizes were used, and the uniformity of the surface texture was higher than that of Examples 4 to 5, and defects were reduced. This is even less. As a result, a carbon-silicon carbide target material with fewer surface defects can be obtained by additionally controlling the particle size range of the carbon powder and silicon carbide powder raw materials.

The density of the carbon-silicon carbide target material prepared in the above examples and comparative examples was measured using the drainage method and glow discharge mass spectrometry, and the measurement results are shown in Table 1.

Density (%) Whether cracks occur or not Example 1 99.8 no Example 2 99.3 no Example 3 99.1 no Example 4 99.0 no Example 5 99.1 no Example 6 99.6 no Example 7 97.3 crack occurs Example 8 95.9 no

From Table 1, we can confirm several things:

(1) As can be seen by summarizing Examples 1 to 6, cracks do not occur and the density is ≥99.0% by the additional comprehensive process conditions and secondary ball milling method of the carbon-silicon carbide target material provided in this application. A phosphorus carbon-silicon carbide target material can be obtained, and its surface microstructure is uniform, has few defects, and has excellent sputtering performance.

(2) As can be seen by combining Example 1 and Example 7, Example 1 used a three-step pressure boosting method, and when compared with the two-step pressure boosting of Example 7, the density of the target material of Example 1 is higher. The degree reaches 99.8% and no cracks occur. However, the density of Example 7 is only 97.3%, and there is a risk of cracking. Accordingly, the present application additionally shows that density is significantly improved and crack occurrence problems are reduced through a method of optimizing the pressure increase during sintering.

(3) As can be seen by combining Example 1 and Example 8, Example 1 used a three-step temperature increase method, and when compared with the two-step pressure increase of Example 8, the density of the target material of Example 1 is higher. The density reaches 99.8% and no cracks occur, but the density of Example 8 is only 95.9%. Accordingly, the present application additionally shows that density is significantly improved through a method of optimizing the temperature increase during sintering.

In summary, the carbon-silicon carbide target material provided in this application can significantly reduce surface defects and improve microstructure uniformity through the secondary ball milling method, resulting in a density of 95.9. %, and under relatively favorable conditions, the density can reach 99.0% or more, the sputtering performance is excellent, and the application prospects are broad.

The applicant states that although the detailed process equipment and process sequence of the present application have been described through the above examples, the present application is not limited to the detailed equipment and process sequence. That is, this does not necessarily mean that the present application can be implemented only by relying on the detailed process equipment and process sequence.

Claims (13)

In the method of manufacturing a carbon-silicon carbide target material,
(1) mixing carbon powder and silicon carbide powder and obtaining a first mixed material through first ball milling in a solvent environment;
(2) drying the first mixture of step (1), mixing it with a solvent and polyol, and performing a second ball milling to obtain a second mixture;
(3) sequentially molding, sintering, and cooling the second mixture of step (2) to obtain the carbon-silicon carbide target material; Method for producing a carbon-silicon carbide target material comprising. According to claim 1,
A method for producing a carbon-silicon carbide target material in which the particle size of the carbon powder in step (1) is less than 20 μm. According to claim 1,
A method for producing a carbon-silicon carbide target material in step (1) wherein the particle size of the silicon carbide powder is less than 10 μm. The method according to any one of claims 1 to 3,
In step (1), the mass ratio of the carbon powder and silicon carbide powder is 40 to 50:60 to 50;
In step (1) the solvent is ethanol;
In step (1), the ratio of materials to balls in the first ball milling is 1 to 3:1;
The time of the first ball milling in step (1) is ≥24h;
In step (1), the ball milling medium of the first ball milling is silicon carbide balls;
In step (1), the first ball milling is performed under sealed conditions. The method according to any one of claims 1 to 3,
The amount of the solvent added in step (2) is 0.1 to 1 wt% of the first mixture;
In step (2) the solvent is ethanol;
In step (2), the amount of polyol added is 0.1 to 5 wt% of the first mixture. The method according to any one of claims 1 to 3,
In step (2), the material to ball ratio of the second ball milling is 1 to 3:1;
The time of the second ball milling in step (2) is ≥24h;
The ball milling medium of the second ball milling in step (2) is silicon carbide balls;
In step (2), the second ball milling is performed under sealed conditions;
In step (2), the material after the second ball milling is passed through a screen to obtain a second mixed material;
In step (2), the particle size range of the second mixture is ≤200μm. The method according to any one of claims 1 to 3,
In step (3), the flatness of the surface of the second mixture after molding is ≤0.5mm. The method according to any one of claims 1 to 3,
A method of producing a carbon-silicon carbide target material further comprising cold pressing between the molding and sintering in step (3). The method according to any one of claims 1 to 3,
Step (3) includes vacuum pumping and protective gas filling between the molding and sintering;
In step (3), the vacuum pumping is performed until the absolute vacuum becomes ≤100Pa;
The vacuum pumping time in step (3) is ≥40min;
In step (3), the protective gas is filled until the gauge pressure is -0.08~-0.1Mpa;
In step (3), the protective gas is a method of producing a carbon-silicon carbide target material including argon gas. The method according to any one of claims 1 to 3,
In step (3), the sintering includes raising the temperature to a first temperature through a first temperature increase under the condition that a protective gas is filled;
A second temperature is raised to the second temperature, and a second warming process is performed; At the same time as the second insulation, the pressure is secondly increased to the second pressure, and the pressure is maintained until the second insulation is terminated;
Continuing to raise the temperature a third time to a third temperature, vacuum pumping is performed until the third temperature increase is completed in the third temperature raising process; After maintaining the third temperature and increasing the pressure to the third pressure, the third warming is performed;
In step (3), the rate of the third temperature increase is slower than the rate of the second temperature increase and the rate of the second temperature increase is slower than the rate of the first temperature increase;
In step (3), the first temperature increase rate is 8 to 12°C/min;
In step (3), the first temperature is 1400-1500°C;
In step (3), the rate of the second temperature increase is 4 to 6°C/min;
In step (3), the time length of the second warming is 40 to 100 min;
In step (3), the second temperature is 1750-1850°C;
The time length of the second boosting in step (3) is 12 to 25 min;
In step (3), the second pressure is 7 to 9 MPa;
In step (3), the third temperature increase rate is 1 to 3.5°C/min;
In step (3), the third temperature is 1950-2050°C;
In step (3), vacuum pumping is performed until the absolute vacuum degree becomes ≤100Pa in the third temperature raising process;
The time length of the second boosting in step (3) is 40 to 80 min;
In step (3), the third pressure is 30-40 MPa;
In step (3), the third thermal insulation time length is 150 to 220 min. The method according to any one of claims 1 to 3,
In step (3), the cooling is completed by stopping the heating after the sintering is completed, reducing the temperature to the second temperature, releasing the pressure, introducing a protective gas, and cooling to the fourth temperature with the furnace. Contains;
In step (3), the temperature reduction is natural cooling with the furnace;
In step (3), the protective gas includes argon gas;
In step (3), the fourth temperature is ≤200°C. The method according to any one of claims 1 to 3,
(1) Carbon powder with a particle size of less than 20 μm and silicon carbide powder with a particle size of less than 10 μm are mixed according to a mass ratio of 40 to 50:60 to 50, and first ball milling is performed with silicon carbide balls in an ethanol environment under sealed conditions to obtain a first ball mill. Obtaining a mixed material, the time of first ball milling is ≥24h, and the ratio of material to ball is 1~3:1;
(2) After the first mixture in step (1) is dried, it is mixed with ethanol in an amount of 0.1 to 1 wt% of the first mixture and polyol in an amount of 0.1 to 5 wt% of the first mixture, and sealed under sealed conditions. Performing second ball milling with silicon carbide balls, the time of the second ball milling being ≥24h, passing the material after ball milling through a screen to obtain a second mixed material;
(3) After the second mixture in step (2) is molded, the flatness of the surface of the second mixture is ≤0.5mm, and after cold pressing again, vacuum pumping is performed until the absolute vacuum degree is ≤100Pa, and the gauge Filling the shielding gas until the pressure is -0.08~-0.1MPa, and first raising the temperature to 1400~1500℃ at a rate of 8~12℃/min under the conditions of filling the shielding gas; Includes;
A second temperature increase is performed to 1750-1850°C at a rate of 4-6°C/min, and a second warming is performed for 40-100 minutes; At the same time as the second warming, the second pressure is increased until it reaches 7 to 9 MPa within 12 to 25 minutes, and the pressure is maintained until the second warming is completed;
The third temperature increase continues to 1950 to 2050°C at a rate of 1 to 3.5°C/min, and vacuum pumping is performed until the third temperature increase is completed in the third temperature increase process, but the absolute vacuum degree is ≤100Pa. The temperature is maintained at 1950-2050°C, the pressure is increased to 30-40 MPa within 40-80 min, and then the temperature is maintained for 150-220 min. After the third warming is completed, the heating is stopped, the temperature is reduced to 1750 ~ 1850 ℃, the pressure is released, the protective gas is introduced, and the carbon-silicon carbide target material is obtained by cooling to ≤200 ℃ with the furnace. Method for manufacturing silicon carbide target material. A carbon-silicon carbide target material obtained by manufacturing using the method for producing a carbon-silicon carbide target material according to any one of claims 1 to 3.