CN114014670A - Preparation method of boron carbide sputtering target with characteristics of high purity and high density - Google Patents
Preparation method of boron carbide sputtering target with characteristics of high purity and high density Download PDFInfo
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- C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
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Abstract
The preparation method of the boron carbide sputtering target material with the characteristics of high purity and high density, which is provided by the invention, is applied to the high-tech fields of aerospace, national defense and military industry, nuclear energy utilization and the like. By optimizing the preparation method of the raw material powder, the particle size of the powder is reduced to the D0 value of less than or equal to 0.5 mu m on the premise of keeping high purity, so that the required sintering pressure is reduced under the condition of not adding any sintering aid, and the obtained ceramic has stable and uniform performance. The invention adopts the method of matching the graphite carbon fiber composite die and the graphite die to improve the compression strength of the die, so that the purity of the prepared single-piece boron carbide sputtering target material is more than or equal to 99.99 percent, and the density of the single-piece boron carbide sputtering target material exceeds 99.9 percent of the theoretical density. The boron carbide ceramic prepared by the method has the characteristics of low density, high hardness, high bending strength and high fracture toughness, and can be applied to the field with extremely special requirements on sputtering targets.
Description
Technical Field
The invention belongs to the technical field of ceramic sputtering targets, and particularly relates to a preparation method of a boron carbide sputtering target with the characteristics of high purity and high density.
Background
The boron carbide sputtering target is an important special ceramic sputtering target, has the characteristics of corrosion resistance, no acid-base reaction, high hardness, low density, good chemical stability and neutron absorption, and is widely applied to the high-tech fields of aerospace, national defense and military industry, nuclear energy utilization and the like. As the proportion of covalent bonds in the boron carbide sputtering target material crystal is as high as 90 percent, the grain boundary moving resistance is very high during sintering, and the sintering difficulty is very high.
The existing preparation method of the boron carbide sputtering target material generally reduces the sintering temperature and improves the bending strength and fracture toughness of the boron carbide ceramic by adding a sintering aid containing other elements such as Si, Al, Ti and the like, but the prepared boron carbide sputtering target material loses the characteristics of low density and high hardness by adding other phases; common sintering methods of the existing boron carbide sputtering target material comprise normal pressure sintering, hot pressing sintering and plasma sintering, density which can reach more than 99.9 percent of theoretical density can not be obtained by the current normal pressure sintering, and the obtained boron carbide ceramic is not ideal in performance stability and uniformity due to the limitation of sintering conditions; the ceramic with high density, uniform texture and stable performance can be obtained by hot-pressing sintering, but the hot-pressing sintering molding of the boron carbide ceramic needs very high pressure and is limited by raw material powder, a graphite mold and sintering equipment, so that the high-purity and high-density boron carbide sputtering target material cannot be prepared. A new preparation method is developed, which has very important significance for improving the performance of the ceramic materials and popularizing the application thereof.
Disclosure of Invention
The invention aims to provide a preparation method of a boron carbide sputtering target material with the characteristics of high purity and high density.
The technical scheme of the invention is as follows:
a preparation method of a boron carbide sputtering target material with the characteristics of high purity and high density comprises the following steps:
step one, mixing boric acid and carbon powder according to a mass ratio of 3.45: 1-3.6: 1, mixing, putting into an electric arc furnace using a graphite electrode for smelting, and controlling the reaction temperature to be 1900-2300 ℃ for smelting for 24 hours to obtain a boron carbide crystal block;
step two, coarse crushing the boron carbide crystal blocks by using a jaw crusher, crushing in a high-pressure roller crusher, fine crushing by using an air flow mill, and ultrafine crushing by using a sand mill in sequence to obtain a material with the particle size of less than 0.8 micron;
putting the materials into a flotation tank, adding flotation agents including kerosene and turpentine, introducing compressed air for flotation treatment to remove free carbon and surface impurities in the materials, putting the treated materials into a reaction kettle, cleaning the materials by using mixed acid of sulfuric acid and nitric acid to remove iron and metal impurities, heating the materials to 70-80 ℃ for reaction for 4 hours, dewatering the materials by using a centrifugal machine after cleaning, repeatedly washing and dewatering by using deionized water, putting the dewatered powder into a separation tank, and preferably selecting part of powder with higher quality;
drying and granulating the optimized powder by using a spray dryer, carrying out compression molding by using a hydraulic press at the pressure of 40MPa for 8 hours at the temperature of 450 ℃, matching the molded green body with a graphite mold without adding any auxiliary agent in the drying and compression molding processes, isolating the contact surface of the green body and the graphite mold by using graphite paper, sleeving a carbon-carbon fiber composite mold on the graphite mold, putting the assembled green body and mold into a hot-pressing sintering furnace, and firing to obtain the ceramic.
Further, the high purity boric acid in step one requires: the purity is more than or equal to 99.99 percent, the sulfate is less than or equal to 0.015 percent, Fe, Cl and other impurities are less than or equal to 0.001 percent, and the ash content of the high-purity graphite is less than or equal to 10 ppm.
Further, in the second step, the boron carbide crystal blocks are coarsely crushed by a jaw crusher, crushed in a high-pressure roller crusher and finely crushed by an air flow mill in sequence until the D50 is 50 μm.
Further, the inner cavity of the grinding body of the sand mill used in the step two and the part of the stirring paddle in contact with the powder are coated with boron carbide ceramic plates, and the grinding medium used in the sand mill is boron carbide ceramic balls; the temperature of the slurry is kept not to exceed 45 ℃ in the whole grinding process by a circulating water cooling mode.
Further, dewatering for 3-5 times in the third step until the conductivity of the cleaning and dewatering is less than or equal to 30 mu S/cm.
Further, in the fourth step, the assembled green body and the mold are placed into a hot-pressing sintering furnace, the furnace is vacuumized until the vacuum degree is less than or equal to 0.05pa, the temperature is gradually increased to 1950-.
Furthermore, the carbon-carbon fiber composite material mold used in the fourth step requires that the tensile strength is more than or equal to 3000MPa, and the tensile elastic modulus is more than or equal to 40000 MPa.
The invention has the beneficial effects that: by optimizing the preparation method of the raw material powder, the particle size of the powder is reduced to the D0 value (the maximum particle) of less than or equal to 0.5 mu m on the premise of keeping high purity, so that the required sintering pressure is reduced under the condition of not adding any sintering aid, and the obtained ceramic has stable and uniform performance. The invention adopts the method of matching the graphite carbon fiber composite die and the graphite die to improve the compression strength of the die, so that the purity of the prepared single-piece boron carbide sputtering target material is more than or equal to 99.99 percent, and the density of the single-piece boron carbide sputtering target material exceeds 99.9 percent of the theoretical density. The invention has the advantages that firstly, the purity of boron carbide is controlled; secondly, the granularity of the powder used for sintering is finer on the basis of maintaining the purity, so as to reduce the pressure required by sintering and stabilize the performance of the ceramic; thirdly, the mould prepared by the carbon-carbon fiber composite material increases the pressure which can be applied by sintering, and improves the compactness of the ceramic. The boron carbide ceramic prepared by the method keeps the characteristics of low density and high hardness, and meanwhile, the bending strength and the fracture toughness are obviously improved compared with the prior hot-pressed sintered boron carbide, so that the special requirements of the sputtering target material on the ceramic performance can be met.
Drawings
FIG. 1 is an X-ray diffraction pattern of the boron carbide ceramic prepared in example 1;
FIG. 2 is a schematic scanning electron microscope of the boron carbide ceramic prepared in example 2;
FIG. 3 is a schematic scanning electron microscope of the boron carbide ceramic prepared in example 2;
FIG. 4 is the flexural strength of the boron carbide ceramic prepared in example 2;
FIG. 5 is the hardness of the boron carbide ceramic prepared in example 2;
FIG. 6 is the fracture toughness of the boron carbide ceramic prepared in example 2.
Detailed Description
A specific embodiment of the present invention is described in detail below, but it should be understood that the scope of the present invention is not limited by the specific embodiment.
The embodiment of the invention provides a preparation method of a boron carbide sputtering target material with the characteristics of high purity and high density;
example 1
500kg of high-purity boric acid and 145kg of high-purity graphite powder are mixed according to the weight ratio of 3.45: 1, mixing 12 parts, smelting in an electric arc furnace using a high-purity graphite electrode for 24 hours, controlling the temperature at 1900 ℃ to obtain boron carbide crystal blocks, crushing the boron carbide crystal blocks to pieces smaller than 5cm by using a jaw crusher, crushing the boron carbide crystal blocks to a particle size smaller than 0.6mm by using a high-pressure double-roll crusher, crushing the boron carbide crystal blocks to D50 of about 50 microns by using an air flow mill, putting the optimized powder into a sand mill, adding deionized water, grinding to D100 smaller than or equal to 0.8 microns, putting the powder into a flotation tank, adding kerosene and turpentine, and introducing compressed air for flotation treatment. Adding 10% nitric acid and sulfuric acid mixed acid into the floated material, heating to 80 ℃, and stirring while heating until the material reacts for 4 hours. Dewatering the washed material in a centrifuge using electrical conductivity
Washing with deionized water of less than or equal to 30 mu S/cm for 40 minutes. And (4) placing the materials after the dehydration washing into a separation tank for separation, and placing the carefully selected materials into a spray dryer for granulation. And matching the molded green body with a graphite mold, placing the green body and the mold, which are assembled by isolating the contact surface of the green body and the graphite mold with graphite paper, into a hot-pressing sintering furnace, vacuumizing until the vacuum degree is less than or equal to 0.05pa, gradually heating to 1950 ℃, heating at a speed of less than or equal to 20 ℃/min, and pressurizing the ceramic heating element when the temperature is reached. The specific X-ray diffraction results of the boron carbide ceramics prepared under the conditions are shown in a scanning electron microscope of figure 1, figure 2 and figure 3.
Example 2
By using the same raw materials as in example 1, 500kg of high-purity boric acid and 138kg of high-purity graphite powder were mixed in a ratio of 3.6: 1, adding the mixture into an electric arc furnace using a high-purity graphite electrode for smelting for 24 hours, controlling the temperature to be 2050 ℃ to obtain a boron carbide crystal block, crushing the boron carbide crystal block to a block of less than 5cm by using a jaw crusher, crushing the boron carbide crystal block to a particle size of less than 0.6mm by using a high-pressure double-roll crusher, crushing the boron carbide crystal block by using an air flow mill until the D50 is about 50 mu m, adding the optimized powder into a sand mill, adding deionized water, and grinding the powder until the D100 is less than or equal to 0.8 mu m, adopting the same steps as the example 1, matching the molded green body with a graphite mold, placing the green body and the mold, which are separated and assembled by using graphite paper on the contact surface of the green body and the graphite mold into a hot-pressing sintering furnace, vacuumizing until the vacuum degree is less than or equal to 0.05pa, gradually heating to 2050 ℃, and heating speed is less than or equal to 20 ℃/min. The specific sample bending strength versus temperature is shown in FIG. 4, the hardness versus temperature is shown in FIG. 5, and the fracture toughness versus temperature is shown in FIG. 6.
The experiment of the invention is completed on a vacuum hot-pressing sintering furnace imported from the United states, and the experimental result shows that the proportion of the high-purity boric acid and the high-purity graphite powder is 3.45: 1-3.6: 1, and smelting in an electric arc furnace using a high-purity graphite electrode to obtain a boron carbide crystal block, wherein the purity of the boron carbide crystal block is high; the ground powder is dried and granulated by a spray dryer and is molded by a hydraulic press, and no auxiliary agent is added in the drying and molding processes, so that the purity of boron carbide is improved; placing the assembled green body and the mold into a hot-pressing sintering furnace, vacuumizing until the vacuum degree is less than or equal to 0.05pa, gradually heating to 1950-2050 ℃, heating at the speed of less than or equal to 20 ℃/min, and pressurizing a ceramic heating element when the temperature is reached, wherein the average bending strength of the boron carbide ceramic prepared by the method is 383MPa, the average hardness is 3051HVI, and the average fracture toughness is 4.35KIC。
The above disclosure is only for the specific embodiment of the present invention, but the embodiment of the present invention is not limited thereto, and any variations that can be made by those skilled in the art should fall within the scope of the present invention.
Claims (8)
1. A preparation method of a boron carbide sputtering target material with the characteristics of high purity and high density is characterized by comprising the following steps:
step one, mixing boric acid and carbon powder according to a mass ratio of 3.45: 1-3.6: 1, mixing, putting into an electric arc furnace using a graphite electrode for smelting, and controlling the reaction temperature to be 1900-2300 ℃ for smelting for 24 hours to obtain a boron carbide crystal block;
step two, coarse crushing the boron carbide crystal blocks by using a jaw crusher, crushing in a high-pressure roller crusher, fine crushing by using an air flow mill, and ultrafine crushing by using a sand mill in sequence to obtain a material with the particle size of less than 0.8 micron;
putting the materials into a flotation tank, adding flotation agents including kerosene and turpentine, introducing compressed air for flotation treatment to remove free carbon and surface impurities in the materials, putting the treated materials into a reaction kettle, cleaning the materials by using mixed acid of sulfuric acid and nitric acid to remove iron and metal impurities, heating the materials to 70-80 ℃ for reaction for 4 hours, dewatering the materials by using a centrifugal machine after cleaning, repeatedly washing and dewatering by using deionized water, putting the dewatered powder into a separation tank, and preferably selecting part of powder with higher quality;
drying and granulating the optimized powder by using a spray dryer, carrying out compression molding by using a hydraulic press at the pressure of 40MPa for 8 hours at the temperature of 450 ℃, matching the molded green body with a graphite mold without adding any auxiliary agent in the drying and compression molding processes, isolating the contact surface of the green body and the graphite mold by using graphite paper, sleeving a carbon-carbon fiber composite mold on the graphite mold, putting the assembled green body and mold into a hot-pressing sintering furnace, and firing to obtain the ceramic.
2. The production method according to claim 1, wherein in the second step, the boron carbide crystal mass is coarsely crushed by a jaw crusher, finely crushed by a high-pressure pair roller crusher and finely crushed by an air jet mill in this order to D50 of 50 μm.
3. The preparation method according to claim 1 or 2, characterized in that the inner cavity of the grinding body of the sand mill and the part of the stirring paddle in contact with the powder used in the step two are coated with boron carbide ceramic plates, and the grinding medium used in the sand mill is boron carbide ceramic balls; the temperature of the slurry is kept not to exceed 45 ℃ in the whole grinding process by a circulating water cooling mode.
4. The preparation method according to claim 1 or 2, characterized in that the assembled green body and the mold are placed into a hot-pressing sintering furnace in the fourth step, the furnace is vacuumized until the vacuum degree is less than or equal to 0.05pa, the temperature is gradually raised to 1950-.
5. The preparation method according to claim 3, wherein the assembled green body and the mold are placed into a hot-pressing sintering furnace in the fourth step, the furnace is vacuumized until the vacuum degree is less than or equal to 0.05pa, the temperature is gradually raised to 1950 and 2050 ℃, the temperature raising speed is less than or equal to 20 ℃/min, and when the temperature is reached, the ceramic heating element is pressurized.
6. The preparation method according to claim 1, 2 or 5, wherein the carbon-carbon fiber composite mold used in the fourth step requires a tensile strength of not less than 3000MPa and a tensile elastic modulus of not less than 40000 MPa.
7. The preparation method according to claim 3, wherein the carbon-carbon fiber composite material mold used in the fourth step requires tensile strength of not less than 3000MPa and tensile elastic modulus of not less than 40000 MPa.
8. The preparation method according to claim 4, wherein the carbon-carbon fiber composite material mold used in the fourth step requires tensile strength of not less than 3000MPa and tensile elastic modulus of not less than 40000 MPa.
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| US20200172441A1 (en) * | 2018-11-29 | 2020-06-04 | Purdue Research Foundation | Novel boron carbide composite |
| CN111233479A (en) * | 2020-01-25 | 2020-06-05 | 大连正兴磨料有限公司 | Preparation method of high-purity, high-density and large-size boron carbide ceramic |
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| GB1380125A (en) * | 1971-04-14 | 1975-01-08 | Commw Scient Ind Res Org | Abrasion resistant compositions |
| US7635458B1 (en) * | 2006-08-30 | 2009-12-22 | Ppg Industries Ohio, Inc. | Production of ultrafine boron carbide particles utilizing liquid feed materials |
| US20090082191A1 (en) * | 2007-09-14 | 2009-03-26 | Ken Hirota | Boron carbide ceramic and manufacturing method thereof |
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| CN105439163A (en) * | 2015-12-03 | 2016-03-30 | 沈阳化工大学 | Method for preparing high-purity boric acid for boron carbide |
| US20200172441A1 (en) * | 2018-11-29 | 2020-06-04 | Purdue Research Foundation | Novel boron carbide composite |
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