CN115385695A - Flaked tungsten diboride powder containing defects as well as preparation method and application thereof - Google Patents
Flaked tungsten diboride powder containing defects as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of inorganic non-metallic hard materials, and discloses flaked tungsten diboride powder containing defects, a preparation method and application thereof. Mixing tungsten trioxide powder, boron carbide powder and carbon powder according to the molar ratio of (1) - (2.5) to (4.5-5), and then mixing the tungsten trioxide powder, the boron carbide powder and the carbon powder according to the atomic ratio W: TM =95:5 (TM = Mo or Cr), adding molybdenum trioxide powder and chromium sesquioxide powder for doping, and preparing tungsten diboride powder with different defect concentrations. The raw materials are pressed into blocks after ball milling and mixing, heated to 1300-1500 ℃ in a vacuum state and kept warm for 0.5-2 hours, and then the tungsten diboride powder with submicron level, dislocation containing, flakiness and good sintering performance is obtained after smashing, grinding and sieving, and the defect concentration can be controlled quantitatively by doping different elements. The obtained tungsten diboride powder can be applied to the fields of grinding and polishing and hydrogen catalysis, and the further obtained tungsten diboride block can be applied to the fields of corrosion-resistant materials, electrode materials and cutting tools.
Description
Technical Field
The invention belongs to the technical field of inorganic non-metallic hard materials, and particularly relates to flaked tungsten diboride powder containing defects, and a preparation method and application thereof.
Background
Tungsten diboride has been synthesized under ambient pressure for the last decades and has attracted considerable attention in various industrial applications due to its high melting point, high hardness, good chemical stability and electrical conductivity. These excellent properties make tungsten diboride a potential candidate for cutting tools, wear resistant parts, electrode materials, and the like.
In fact, similar to other transition metal borides, consolidating tungsten diboride ceramics is not an easy task due to the low self-diffusion coefficient of tungsten diboride.
The addition of the sintering additive provides a simple and effective means for enhancing the sintering reaction of the transition metal boride. The improvement of the ceramic by adding the sintering aid has limitation, and the performance of the ceramic is reduced by excessively adding the sintering aid. New processing methods must be explored to improve the sintering behavior and performance of tungsten diboride.
High quality (high purity, few impurities, fine particle size) powder and powder containing defects can both promote crystal kinetics and sintering performance of ceramics.
The high-quality tungsten diboride powder with submicron grade and high purity can be synthesized by a boron/carbon thermal reduction method.
Disclosure of Invention
In order to overcome the defects and shortcomings of difficult sintering of tungsten diboride in the prior art, the invention mainly aims to provide a preparation method of flaked tungsten diboride powder containing defects, wherein the method prepares tungsten diboride powder with different defect concentrations by doping different elements and reasonably controlling the defect concentrations; with tungsten trioxide (WO) 3 ) Powder, boron carbide (B) 4 C) The powder and carbon source powder are used as raw materials as basic formula, molybdenum trioxide (MoO) is added 3 ) Powder or chromium oxide (Cr) 2 O 3 ) The powder is doped, ball-milled and mixed, then is thermally treated in a vacuum state to obtain flaked tungsten diboride powder containing defects, and the flaked tungsten diboride powder is sintered by discharge plasma to obtain compact tungsten diboride bulk materials.
The invention also aims to provide flaked tungsten diboride powder containing defects, which is prepared by the preparation method.
The invention also aims to provide an application of the flaked tungsten diboride powder containing the defects.
The purpose of the invention is realized by the following technical scheme:
a preparation method of flaked tungsten diboride powder containing defects comprises the following operation steps:
(1) Molybdenum trioxide (MoO) 3 ) Powder and chromium oxide (Cr) 2 O 3 ) One of the powders, and tungsten trioxide (WO) 3 ) Powder, boron carbide (B) 4 C) Mixing the powder and carbon source powder together, adding a grinding ball, and carrying out ball milling under the argon protective atmosphere and at room temperature to obtain uniformly mixed powder;
(2) And compacting the uniformly mixed powder by using a dry press, preserving the heat for 0.5 to 2 hours at the temperature of 1300 to 1500 ℃ in a vacuum state, cooling and thermally treating along with a furnace, and knocking loose blocks apart to obtain flaked tungsten diboride powder containing defects.
Preferably, the tungsten trioxide in step (1) (WO) 3 ) Powder, boron carbide (B) 4 C) The mol ratio of the powder to the carbon source powder is 2 (1-2.5) to 4.5-5; mo atom and tungsten trioxide (WO) in the molybdenum trioxide powder 3 ) The molar ratio of W atoms in the powder was 5:95; cr atoms and tungsten trioxide in the chromium oxide powder (WO) 3 ) The molar ratio of W atoms in the powder was 5:95.
more preferably, the tungsten trioxide (WO) 3 ) Powder, boron carbide (B) 4 C) The mol ratio of the powder to the carbon source powder is 2 (1-1.5) to 4.7-5.
The ball milling time in the step (1) is 1-3 h; the grinding ball is made of tungsten carbide, the diameter of the grinding ball is 6.5-11 mm, and the mass ratio of the grinding ball to the grinding ball is 3-5: 1.
the pressure of the dry press briquetting in the step (2) is 3-30 MPa; the heat preservation time is 1-2 h; and grinding the loose blocks in an agate mortar after the loose blocks are knocked out, and sieving the ground loose blocks in a 200-mesh sieve to obtain flaked tungsten diboride powder with the particle size of 0.2-0.5 mu m and containing defects.
The purity of the molybdenum trioxide powder, the chromium oxide powder and the tungsten trioxide powder is more than or equal to 99 percent, and the average particle size is 0.5-2 mu m; the purity of the boron carbide powder is more than 99 percent, and the average grain diameter is 1-3 mu m; the carbon source powder is more than one of carbon black, graphite, acetylene black and phenolic resin, the purity is more than 99%, and the average grain diameter is 30 nm-1.5 mu m.
The flaked tungsten diboride powder containing the defects, which is prepared by the preparation method, is provided.
The flaked tungsten diboride powder containing the defects is applied to the fields of grinding and polishing and hydrogen catalysis.
A tungsten diboride bulk material prepared from the flaked tungsten diboride powder containing defects is prepared according to the following preparation method: putting flaked tungsten diboride powder containing defects into a graphite mould for prepressing, wherein the prepressing pressure is 3-30 MPa, and the temperature is 1500-1700 ℃ for 10min for sintering, the sintering atmosphere is argon or vacuum, and the sintering pressure is 10-30 MPa, so as to obtain the tungsten diboride bulk material.
The sintering is carried out in a spark plasma sintering furnace.
The tungsten diboride bulk material is applied to the fields of electrode materials, wear-resistant materials and cutting tools.
Compared with the prior art, the invention has the following advantages and effects:
(1) The method has high yield, the particle size of the obtained powder is submicron and the distribution range is narrow, so the method is suitable for large-scale production;
(2) The tungsten diboride powder capable of quantitatively controlling the defect concentration has good sintering performance, the density of the prepared tungsten diboride block is up to 96%, and no sintering aid is added.
(3) The tungsten diboride powder prepared by the method can be effectively used in the related industrial fields of grinding and polishing, hydrogen catalysis and the like, and the tungsten diboride block can be effectively used in the related industrial fields of electrode materials, wear-resistant materials, cutting tools and the like.
Drawings
FIG. 1 is an XRD pattern of flaked tungsten diboride powder containing defects prepared in examples 1-3.
FIG. 2 is an SEM image of the preparation of flaked tungsten diboride powder containing defects of examples 1-3.
FIG. 3 is a high resolution TEM image of flaked tungsten diboride powder containing defects prepared in examples 1-3.
Figure 4 is an XRD pattern of the tungsten diboride bulk prepared in examples 4-6.
Figure 5 is an SEM image of the tungsten diboride bulk prepared in examples 4-6.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The mixing equipment can be high-energy ball mill, vibration ball mill, planetary ball mill, field-assisted mill, plasma-assisted high-energy ball mill, etc. The sintering mode can be a hot-pressing sintering furnace, discharge plasma sintering, pressureless sintering and the like. In the following examples, a high energy ball mill (model 8000M, SPEX, USA) was used. Tungsten trioxide (WO) is used as a raw material in the following examples 3 Purity 99.9%, particle size 500 nm, shanghai lane field nanomaterial Co., ltd., china), molybdenum trioxide (MoO) 3 Purity 99.9%, particle size 1 μm, shanghai lane field nanometer materials Co., ltd., china), chromium oxide (Cr) 2 O 3 Purity 99.9%, particle size 600 nm, shanghai Naiyou nanotechnology Limited, china), boron carbide (B) 4 C, 99.9% pure, 1 micron particle size, peony river diamond boron carbide limited, china) and carbon black (99.9% pure, 30nm particle size, cabot, usa).
Example 1
1. Mixing tungsten trioxide powder, boron carbide powder and carbon black according to a molar ratio of 2:1.075:4.9, weighing, placing in a ball milling tank, adding six tungsten carbide grinding balls with the size of 11mm, wherein the mass ratio of the balls to the mixed powder is 4:1, ball-milling for 1 hour in an argon environment to obtain uniformly mixed powder;
2. and prepressing and molding the mixed powder by using a dry press, carrying out vacuum heat preservation for 1 hour at the temperature of 1400 ℃, cooling, then knocking loose blocks, grinding and sieving in an agate mortar to obtain flaked tungsten diboride powder containing defects.
Example 2
1. Tungsten trioxide powder, molybdenum trioxide, boron carbide powder and carbon black are mixed according to a molar ratio of 1.9:0.1:1.075:4.9, weighing, placing in a ball milling tank, adding six tungsten carbide grinding balls with the size of 11mm, wherein the mass ratio of the balls to the mixed powder is 4:1, ball-milling for 1 hour in an argon environment to obtain uniformly mixed powder;
2. and prepressing and molding the mixed powder by using a dry press, carrying out vacuum heat preservation for 1 hour at the temperature of 1400 ℃, cooling, then knocking loose blocks, grinding and sieving in an agate mortar to obtain flaked tungsten diboride powder containing defects.
Example 3
1. Mixing tungsten trioxide powder, chromium oxide, boron carbide powder and carbon black according to a molar ratio of 1.9:0.05:1.075:4.9, weighing, placing in a ball milling tank, adding six tungsten carbide grinding balls with the size of 11mm, wherein the mass ratio of the balls to the mixed powder is 4:1, ball-milling for 1 hour in an argon environment to obtain uniformly mixed powder;
2. and prepressing and molding the mixed powder by using a dry press, carrying out vacuum heat preservation for 1 hour at the temperature of 1400 ℃, cooling, then knocking loose blocks, grinding and sieving in an agate mortar to obtain flaked tungsten diboride powder containing defects.
Figure 1 is an XRD pattern of flaked tungsten diboride powder containing defects prepared in examples 1-3. The phase composition of the composite powder can be seen in fig. 1. The dominant phase of all samples can be determined as WB 2 Type WB 2 (P63/mmc, ICCD PDF # 43-1386). At W 0.95 Mo 0.05 B 2 And W 0.95 Cr 0.05 B 2 No Mo or Cr containing phase could be detected in the powder sample of (a). Except for WB 2 Type WB 2 Also, moB can be detected 2 Type WB 2 (R-3m, ICCD PDF # 31-1407).
Figure 2 is an SEM image of the flaked tungsten diboride powder containing defects prepared in examples 1-3. From FIG. 2, it can be seen that WB was doped 2 The appearance is gradually changed into obvious sheet shape, and the size grain diameter is also increased from 300nm to about 400 nm.
FIG. 3 is a high resolution TEM image of flaked tungsten diboride powder containing defects prepared in examples 1-3. As can be seen from the figure, W is a group element
Mo
And Cr
The degree of lattice distortion caused by doping is different when the atomic radius is different, wherein W 0.95 Cr 0.05 B 2 Is the largest as a result of the large atomic radius difference.
Example 4
Taking the tungsten diboride powder obtained in the example 1, putting the tungsten diboride powder into a graphite die for prepressing, and sintering by using a discharge plasma sintering furnace at 1600 ℃ for 10 minutes under the protection atmosphere of argon and the sintering pressure of 30MPa to obtain tungsten diboride (WB) 2 ) And (3) blocking.
Example 5
Taking the tungsten diboride powder obtained in the embodiment 2, putting the tungsten diboride powder into a graphite mould for prepressing, and sintering the tungsten diboride powder by using a discharge plasma sintering furnace at 1600 ℃ for 10 minutes under the protection atmosphere of argon and the sintering pressure of 30MPa to obtain tungsten diboride (W) 0.95 Mo 0.05 B 2 ) And (3) a block body.
Example 6
Taking the tungsten diboride powder obtained in the example 3, putting the tungsten diboride powder into a graphite mold for prepressing, and sintering by using a discharge plasma sintering furnace at 1600 ℃ for 10 minutes under the protection atmosphere of argon and the sintering pressure of 30MPa to obtain tungsten diboride (W) 0.95 Cr 0.05 B 2 ) And (3) a block body.
Figure 4 is an XRD pattern of the tungsten diboride bulk prepared in examples 4-6. The phase composition of the synthetic tungsten diboride mass can be seen in figure 4. The major phase of all samples can be determined as WB 2 Type WB 2 (P63/mmc, ICCD PDF # 43-1386). MoB present in tungsten diboride powders 2 Type WB 2 Also converted into WB 2 Type WB 2 。
Figure 5 is an SEM image of the tungsten diboride bulk prepared in examples 4-6. It can be seen from FIG. 5 that in the synthesis of tungsten diboride bulk, WB 2 Because of more pores, the density is only 93%, W 0.95 Mo 0.05 B 2 And W 0.95 Cr 0.05 B 2 The mesopores are obviously reduced, and the compactness is respectively 95 percent and 96 percent. The sintering activity of each powder is different depending on the defect concentration, and W having the highest defect concentration 0.95 Cr 0.05 B 2 The sintering properties are also best.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of flaked tungsten diboride powder containing defects is characterized by comprising the following operation steps:
(1) Mixing one of molybdenum trioxide powder and chromium oxide powder with tungsten trioxide powder, boron carbide powder and carbon source powder, adding a grinding ball, and performing ball milling under the condition of argon protective atmosphere and room temperature to obtain uniformly mixed powder;
(2) And compacting the uniformly mixed powder by using a dry press, preserving the heat for 0.5 to 2 hours at the temperature of 1300 to 1500 ℃ in a vacuum state, cooling and thermally treating along with a furnace, and knocking loose blocks apart to obtain flaked tungsten diboride powder containing defects.
2. The method for preparing flaked tungsten diboride powder containing defects according to claim 1, wherein the method comprises the following steps: the molar ratio of the tungsten trioxide powder, the boron carbide powder and the carbon source powder in the step (1) is 2 (1-2.5) to 4.5-5; the molar ratio of Mo atoms in the molybdenum trioxide powder to W atoms in the tungsten trioxide powder is 5:95; the molar ratio of Cr atoms in the chromium sesquioxide powder to W atoms in the tungsten trioxide powder is 5:95.
3. the method for preparing flaked tungsten diboride powder with defects according to claim 2, wherein the flaked tungsten diboride powder with defects is prepared by the following steps: the molar ratio of the tungsten trioxide powder to the boron carbide powder to the carbon source powder is 2 (1-1.5) to 4.7-5.
4. The method for preparing flaked tungsten diboride powder containing defects according to claim 1, wherein the method comprises the following steps: the ball milling time in the step (1) is 1-3 h; the grinding ball is made of tungsten carbide, the diameter of the grinding ball is 6.5-11 mm, and the mass ratio of the grinding ball to the grinding ball is 3-5: 1.
5. the method for preparing flaked tungsten diboride powder with defects according to claim 1, wherein the method comprises the following steps: the pressure of the dry press briquetting in the step (2) is 3-30 MPa; the heat preservation time is 1-2 h; and grinding the loose blocks in an agate mortar after the loose blocks are knocked out, and sieving the ground loose blocks in a 200-mesh sieve to obtain flaked tungsten diboride powder with the particle size of 0.2-0.5 mu m and containing defects.
6. The method for preparing flaked tungsten diboride powder containing defects according to claim 1, wherein the method comprises the following steps: the purity of the molybdenum trioxide powder, the chromium oxide powder and the tungsten trioxide powder is more than or equal to 99 percent, and the average particle size is 0.5-2 mu m; the purity of the boron carbide powder is more than 99 percent, and the average grain diameter is 1-3 mu m; the carbon source powder is more than one of carbon black, graphite, acetylene black and phenolic resin, the purity is more than 99%, and the average grain diameter is 30 nm-1.5 mu m.
7. Flaked tungsten diboride powder containing defects, which is prepared by the preparation method of any one of claims 1 to 6.
8. The application of the flaked tungsten diboride powder containing defects according to claim 7 in the fields of grinding and polishing and hydrogen catalysis.
9. A tungsten diboride bulk material made from the flaked tungsten diboride powder containing defects of claim 7, characterized in that: the tungsten diboride bulk material is prepared according to the following preparation method: putting flaked tungsten diboride powder containing defects into a graphite mould for prepressing, wherein the prepressing pressure is 3-30 MPa, and the temperature is 1500-1700 ℃ for 10min for sintering, the sintering atmosphere is argon or vacuum, and the sintering pressure is 10-30 MPa, so as to obtain the tungsten diboride bulk material.
10. The use of a tungsten diboride bulk material according to claim 9 in the field of electrode materials, wear resistant materials and cutting tools.
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|---|---|---|---|---|
| CN116495739A (en) * | 2023-05-08 | 2023-07-28 | 广东工业大学 | Tungsten diboride-silicon carbide composite powder with uniform size, and composite ceramic, preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1115630A (en) * | 1954-11-18 | 1956-04-26 | Cie Des Meules Norton | Borides production process |
| US4929417A (en) * | 1989-04-21 | 1990-05-29 | Agency Of Industrial Science And Technology | Method of manufacture metal diboride ceramics |
| JPH02190440A (en) * | 1989-01-18 | 1990-07-26 | Nippon Steel Corp | Guide roll for hot rolling |
| SE9203288D0 (en) * | 1991-11-08 | 1992-11-04 | Max Planck Gesellschaft | PLATFORM TILES OF COMPOUNDS OF A1B2-AND W2B5-TYPES UNDER THE REPAIR |
| JP2011136876A (en) * | 2009-12-28 | 2011-07-14 | Sumitomo Osaka Cement Co Ltd | Method for manufacturing metal boride sintered compact, lanthanum boride sintered compact, and target using the lanthanum boride sintered compact |
| CN107285329A (en) * | 2017-05-27 | 2017-10-24 | 广东工业大学 | A kind of wolfram diboride hard material and its preparation method and application |
| CN108557834A (en) * | 2018-05-15 | 2018-09-21 | 广东工业大学 | A kind of preparation method of four tungsten boride superhard materials of chromium doping |
| US20190135646A1 (en) * | 2017-11-08 | 2019-05-09 | The Regents Of The University Of California | Metal borides and uses thereof |
| AT16480U1 (en) * | 2018-04-20 | 2019-10-15 | Plansee Composite Mat Gmbh | Target and method of making a target |
| CN113233470A (en) * | 2021-05-21 | 2021-08-10 | 中国科学院宁波材料技术与工程研究所 | Two-dimensional transition metal boride material, and preparation method and application thereof |
-
2022
- 2022-07-28 CN CN202210899419.XA patent/CN115385695B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1115630A (en) * | 1954-11-18 | 1956-04-26 | Cie Des Meules Norton | Borides production process |
| JPH02190440A (en) * | 1989-01-18 | 1990-07-26 | Nippon Steel Corp | Guide roll for hot rolling |
| US4929417A (en) * | 1989-04-21 | 1990-05-29 | Agency Of Industrial Science And Technology | Method of manufacture metal diboride ceramics |
| SE9203288D0 (en) * | 1991-11-08 | 1992-11-04 | Max Planck Gesellschaft | PLATFORM TILES OF COMPOUNDS OF A1B2-AND W2B5-TYPES UNDER THE REPAIR |
| JP2011136876A (en) * | 2009-12-28 | 2011-07-14 | Sumitomo Osaka Cement Co Ltd | Method for manufacturing metal boride sintered compact, lanthanum boride sintered compact, and target using the lanthanum boride sintered compact |
| CN107285329A (en) * | 2017-05-27 | 2017-10-24 | 广东工业大学 | A kind of wolfram diboride hard material and its preparation method and application |
| US20190135646A1 (en) * | 2017-11-08 | 2019-05-09 | The Regents Of The University Of California | Metal borides and uses thereof |
| CN111770893A (en) * | 2017-11-08 | 2020-10-13 | 加利福尼亚大学董事会 | Metal borides and their use |
| AT16480U1 (en) * | 2018-04-20 | 2019-10-15 | Plansee Composite Mat Gmbh | Target and method of making a target |
| CN108557834A (en) * | 2018-05-15 | 2018-09-21 | 广东工业大学 | A kind of preparation method of four tungsten boride superhard materials of chromium doping |
| CN113233470A (en) * | 2021-05-21 | 2021-08-10 | 中国科学院宁波材料技术与工程研究所 | Two-dimensional transition metal boride material, and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| EZGI HATIPOGLU ET AL.: "Design of metal-substituted tungsten diboride as an efficient bifunctional electrocatalyst for hydrogen and oxygen evolution", vol. 46, pages 17540 * |
| OMASZ MO´SCICKI ET AL.: "Properties of Spark Plasma Sintered Compacts and Magnetron Sputtered Coatings Made from Cr, Mo, Re and Zr Alloyed Tungsten Diboride", vol. 11, pages 1378 * |
| 邹灿辉;龙莹;郑鑫;张锦阳;林华泰;: "三元过渡金属硼化物Os_(1-x)Ru_xB_2的制备及其结构和性能研究", 无机材料学报, no. 07 * |
| 郭伟明;谭大旺;吴利翔;林华泰;伍尚华;: "B_4C/TiB_2复相陶瓷硬度压痕的尺寸效应", 材料研究学报, no. 12 * |
| 韩D君;董鹏;喇培清;魏玉鹏;郭鑫;盛捷;兰伟;: "NaCl含量对盐助燃烧合成超细硼化钨粉体相组成和粒度的影响及其作用机制", 稀有金属材料与工程, no. 01 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116495739A (en) * | 2023-05-08 | 2023-07-28 | 广东工业大学 | Tungsten diboride-silicon carbide composite powder with uniform size, and composite ceramic, preparation method and application thereof |
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