CN1288968A - Preparation of zirconium carbide particle-reinforced composite tungsten material - Google Patents
Preparation of zirconium carbide particle-reinforced composite tungsten material Download PDFInfo
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- CN1288968A CN1288968A CN 99120173 CN99120173A CN1288968A CN 1288968 A CN1288968 A CN 1288968A CN 99120173 CN99120173 CN 99120173 CN 99120173 A CN99120173 A CN 99120173A CN 1288968 A CN1288968 A CN 1288968A
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Abstract
The preparation method of tungsten based composite material using zirconium carbide particles as reinforcing particles is characterized by that in said tungsten based composite material the volume content of the carbide particles is 10%-50%, and its preparation method is one of compressorless sintering, hot-pressure sintering or thermal isostalic pressure sintering, sintering temp. is 1900 deg.C-2300 deg.C and its sintering atmosphere can be hydrogen gas, argon gas, nitrogen gas or vacuum. Said invention is aimed at raising room-temp. and high-temp. mechanical property of tungsten, and improving oxidation resistance and corrosion resistance of tungsten.
Description
The present invention proposes a kind of preparation method of zirconium carbide particle-reinforced composite tungsten material.
Metal-base composites more and more is subjected to people's extensive attention, and it strengthens body and is generally particle, whisker (or staple fibre) and fiber.Metal-base composites has high specific tenacity, specific rigidity, higher high temperature strength than its matrix alloy.Its preparation method mainly contains powder metallurgy sintered method (comprising pressureless sintering, hot pressed sintering and HIP sintering), casting (comprising stirring casting, extrusion casting and spray up n. etc.).Metal-base composites is the nearly two domestic and international focus materials of research during the last ten years, and mechanical property that it is excellent and heat physical properties preferably impel people constantly to develop novel material.For tungsten, because its high fusing point (being about 3410 ℃) and high mechanical behavior under high temperature and under hot environment, be used widely.But the intensity of tungsten can improve and significantly decline with temperature, and in some special hot environments, requires material that good ablation resistance, antioxidant property and low thermal conductivity are arranged, thereby single tungsten member is difficult to be applied under these environment.
The present invention seeks to propose to prepare the processing method of zirconium carbide particle-reinforced composite tungsten material.
Main points of the present invention are with the enhancing body of zirconium carbide particle as tungsten, join in the tungsten basal body, form carbide particle and strengthen composite tungsten material, and wherein tungsten is matrix.In matrix material, the volume fraction of carbide is 10%-50%, and optimum value is 15%-35%.As matrix tungsten, can adopt the pure tungsten powder, purity is preferably in more than 99%, and its particle diameter is about 2 μ m-10 μ m, is preferably 3 μ m-8 μ m; Also can be with doped tungsten powder as tungsten basal body, hotchpotch can be elements such as Na, K; Can in tungsten, add a spot of ThO in addition
2, HfC, Y
2O
3Deng diffusing particle, tungsten is formed dispersion-strengthened, the weight percent of these diffusing particles is about 0.2-2%.Add a small amount of alloying element Re or Mo in tungsten, form alloying strengthening, be used to improve the hot strength of tungsten, the add-on of these alloying elements is about 0.5%-5% (weight percent).The purity of enhanced granule zirconium carbide is being best more than 98% generally, and grain diameter is μ m-10 μ m O.1, is preferably 0.1 μ m-5 μ m.Zirconium carbide is non-stoichiometric compound, and its chemical formula is ZrC
x, wherein the x value is 0.6-1.The present invention also can join the enhancing body of titanium carbide granule as tungsten in the tungsten basal body, forms carbide particle and strengthens composite tungsten material.The purity of enhanced granule titanium carbide is being best more than 98% generally, and grain diameter is 0.1 μ m-10 μ m, is preferably 0.1 μ m-5 μ m.Titanium carbide is non-stoichiometric compound, and its chemical formula is TiC
x, wherein the x value is 0.6-1.Single employing titanium carbide or zirconium carbide particle are used to strengthen tungsten basal body as strengthening body, also can be used to strengthen tungsten basal body to titanium carbide and the two mixing of zirconium carbide jointly.In the time of necessary, also can replace fully or partly replace titanium carbide or zirconium carbide, form the advanced composite material of one or both even three kinds of compound enhancing tungsten basal bodies of carbide particle with hafnium carbide, tantalum carbide or niobium carbide etc.
Step of the present invention is: 1. zirconium carbide particle and tungsten powder are mixed, hybrid mode is wet mixing, blending agent can be ethanol, acetone etc., can add steel ball or Ceramic Balls (alumina balls or zirconia ball etc.) to improve mixing efficiency, mixed powder and blending agent be put in the plastic tank or in the steel drum mix, mixing time is 8-36 hour; 2. in drying baker, dry again after mixing, evaporate the blending agent of ethanol or acetone simultaneously, and remove steel ball or Ceramic Balls etc.; 3. with the powder that mixes, coldmoulding at room temperature, then hot pressed sintering earlier, also can be without the direct hot pressed sintering of coldmoulding, sintering temperature is 1900 ℃-2300 ℃, pressuring method is unidirectional or two-way pressurization, exert pressure and be that 15-45MPa, sintered heat insulating time are 0.5-5 hour.Sintering atmosphere is hydrogen, argon gas, nitrogen or vacuum.In above step, also zirconium carbide particle and tungsten powder can be mixed, hybrid mode is mixed for doing, and mixing time is 8-36 hour.Can add steel ball or Ceramic Balls to improve batch mixing efficient.Sintering process also can adopt the powder cold-press moulding that will mix, pressureless sintering in addition.Sintering temperature is 1900 ℃-2300 ℃, and the sintered heat insulating time is 1-10 hour.Sintering atmosphere is hydrogen, argon gas, nitrogen or vacuum.With the powder isostatic cool pressing that mixes, again through HIP sintering.Sintering temperature is 1900 ℃-2300 ℃, and the sintered heat insulating time is 0.5-5 hour, and sintering pressure is 20-200MPa.Sintering atmosphere is hydrogen, argon gas, nitrogen or vacuum.The present invention can operate titanium carbide granule and tungsten powder by above-mentioned steps.
Can be used to make some component under the hyperthermal environments of weak oxide following short period of time of atmosphere work with the material of the present invention preparation.
Embodiment 1:
Median size is about 2.5 μ m, purity titanium carbide powder and the median size more than 99% is about 3.5 μ m, the tungsten powder of purity more than 99% per-cent: TiC: W=30 by volume: 70 do and mix, and add steel ball and make ball-milling medium.Mix and take out compound after 36 hours, put into graphite jig, in vacuum oven, directly carry out hot pressed sintering, make the titanium carbide granule volume fraction and be 30% tungsten-based composite material.Sintering process is: insulation is 1 hour in the time of 2000 ℃, and unidirectional moulding pressure is 20MPa, and vacuum tightness is 1.3 * 10
-2Pa.The density of matrix material is 96%-98%.The bending strength of the three-point bending method test under the room temperature is about 770MPa, and the fracture toughness property of testing with the single notched beam method is 8MPam
1/2, the three-point bending bending strength of matrix material in the time of 1000 ℃ is about 1000MPa.
Embodiment 2:
Median size is about 2.5 μ m, purity zirconium carbide powder and the median size more than 99% is about 3.5 μ m, the tungsten powder of purity more than 99% per-cent: ZrC: W=30 by volume: 70 do and mix, and add steel ball and make ball-milling medium.Mix and take out compound after 24 hours, put into graphite jig, in vacuum oven, directly carry out hot pressed sintering, make the zirconium carbide particle volume fraction and be 30% tungsten-based composite material.Sintering process is: insulation is 1 hour in the time of 2100 ℃, and unidirectional moulding pressure is 20MPa, and vacuum tightness is 1.3 * 10
-2Pa.The density of matrix material is 90%-92%.The bending strength of the three-point bending method test under the room temperature is about 700MPa, and the fracture toughness property of testing with the single notched beam method is 9MPam
1/2, the three-point bending bending strength of matrix material in the time of 1000 ℃ is about 800MPa.
Embodiment 3:
Median size is about 2.5 μ m, purity zirconium carbide powder and the median size more than 99% is about 3.5 μ m, the tungsten powder of purity more than 99% per-cent: ZrC: W=30 by volume: 70 carry out wet mixing, and the adding zirconia ball is made ball-milling medium, ethanol is made dispersion agent.Mix and take out compound after 10 hours, put into graphite jig after the oven dry, in vacuum oven, directly carry out hot pressed sintering, make the zirconium carbide particle volume fraction and be 30% tungsten-based composite material.Sintering process is: insulation is 1.5 hours in the time of 2000 ℃, and unidirectional moulding pressure is 25MPa, and vacuum tightness is 1.3 * 10
-2Pa.The density of matrix material is 90%-92%.The bending strength of the three-point bending method test under the room temperature is about 710MPa, and the fracture toughness property of testing with the single notched beam method is 8.5MPam
1/2, the three-point bending bending strength of matrix material in the time of 1000 ℃ is about 800MPa.
Embodiment 4:
Median size is about 2.5 μ m, purity titanium carbide powder and the median size more than 99% is about 3.5 μ m, the tungsten powder of purity more than 99% per-cent: TiC: W=20 by volume: 80 carry out wet mixing, and the adding steel ball is made ball-milling medium, ethanol is made dispersion agent.Mix and take out compound after 15 hours, put into graphite jig after the oven dry, in vacuum oven, directly carry out hot pressed sintering, make the titanium carbide granule volume fraction and be 20% tungsten-based composite material.Sintering process is: insulation is 3 hours in the time of 1900 ℃, and unidirectional moulding pressure is 35MPa, and vacuum tightness is 1.3 * 10
-2Pa.The density of matrix material is 92%-94%.The bending strength of the three-point bending method test under the room temperature is about 850MPa, and the fracture toughness property of testing with the single notched beam method is about 9MPam
1/2The three-point bending bending strength of matrix material in the time of 1000 ℃ is about 900MPa.
Embodiment 5:
Median size is about 2.5 μ m, purity zirconium carbide powder and the median size more than 99% is about 3.5 μ m, the tungsten powder of purity more than 99% per-cent: ZrC: W=20 by volume: 80 carry out wet mixing, and the adding steel ball is made ball-milling medium, ethanol is made dispersion agent.Mix and take out compound after 10 hours, put into punching block after the oven dry, 200MPa colded pressing 15 minutes, blank is taken out put into graphite jig then, directly carried out hot pressed sintering in vacuum oven, made the zirconium carbide particle volume fraction and be 20% tungsten-based composite material.Sintering process is: insulation is 0.5 hour in the time of 2200 ℃, and unidirectional moulding pressure is 15MPa, and vacuum tightness is 1.3 * 10
-2Pa.The density of matrix material is 91%-94%.The bending strength of the three-point bending method test under the room temperature is about 700MPa, and the fracture toughness property of testing with the single notched beam method is about 8.3MPam
1/2The three-point bending bending strength of matrix material in the time of 1000 ℃ is about 950MPa.
Embodiment 6:
Median size is about 2.5 μ m, purity zirconium carbide powder and the median size more than 99% is about 3.5 μ m, the tungsten powder of purity more than 99% per-cent: ZrC: W=25 by volume: 75 carry out wet mixing, and the adding zirconia ball is made ball-milling medium, ethanol is made dispersion agent.Mix and take out compound after 20 hours, encapsulate after the oven dry, put into the hot isostatic pressing stove, sintering is 45 minutes under 2100 ℃, 150MPa pressure, makes the zirconium carbide particle volume fraction and be 25% tungsten-based composite material.The density of matrix material is 94%-98%.The bending strength of the three-point bending method test under the room temperature is about 850MPa, and the fracture toughness property of testing with the single notched beam method is about 10MPam
1/2, the three-point bending bending strength of matrix material in the time of 1000 ℃ is about 900MPa.
Claims (5)
1. the preparation method of a zirconium carbide particle-reinforced composite tungsten material is characterized in that:
Operation according to the following steps:
(1) zirconium carbide particle and tungsten powder are mixed, hybrid mode is wet mixing, and blending agent can be ethanol, acetone, can add steel ball or Ceramic Balls, mixed powder and blending agent is put in the steel drum mixes, and mixing time is 8-36 hour;
(2) in drying baker, dry again after the mixing, evaporate the blending agent of ethanol or acetone simultaneously, and remove steel ball or Ceramic Balls;
(3) with the powder that mixes, coldmoulding at room temperature earlier, hot pressed sintering then, also can be without the direct hot pressed sintering of coldmoulding, sintering temperature is 1900 ℃-2300 ℃, and pressuring method is unidirectional or two-way pressurization, and exerting pressure is 15-45MPa, the sintered heat insulating time is 0.5-5 hour, and sintering atmosphere is hydrogen, argon gas, nitrogen or vacuum.
2. preparation method according to claim 1 is characterized in that: zirconium carbide particle and tungsten powder are mixed, and hybrid mode is mixed for doing, and mixing time is 8-36 hour, can add steel ball or Ceramic Balls.
3. preparation method according to claim 1 is characterized in that: with the powder cold-press moulding that mixes, and pressureless sintering, sintering temperature is 1900 ℃-2300 ℃, and the sintered heat insulating time is 1-10 hour, and sintering atmosphere is hydrogen, argon gas, nitrogen or vacuum.
4. preparation method according to claim 1, it is characterized in that: with the powder isostatic cool pressing that mixes, again through HIP sintering, sintering temperature is 1900 ℃-2300 ℃, the sintered heat insulating time is 0.5-5 hour, sintering pressure is 20-200MPa, and sintering atmosphere is hydrogen, argon gas, nitrogen or vacuum.
5. preparation method according to claim 1 is characterized in that: zirconium carbide particle can be a titanium carbide granule.
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| CN99120173A CN1083492C (en) | 1999-09-17 | 1999-09-17 | Preparation of zirconium carbide particle-reinforced composite tungsten material |
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| CN99120173A CN1083492C (en) | 1999-09-17 | 1999-09-17 | Preparation of zirconium carbide particle-reinforced composite tungsten material |
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| CN1083492C CN1083492C (en) | 2002-04-24 |
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| US8790724B2 (en) | 2003-04-04 | 2014-07-29 | Unigen, Inc. | Formulation of dual cycloxygenase (COX) and lipoxygenase (LOX) inhibitors for mammal skin care |
| CN103975414A (en) * | 2012-07-03 | 2014-08-06 | 株式会社东芝 | Tungsten alloy part, and discharge lamp, transmitting tube and magnetron using same |
| CN103998634A (en) * | 2012-05-29 | 2014-08-20 | 株式会社东芝 | Tungsten alloy part, and discharge lamp, transmitting tube, and magnetron using same |
| CN104878266A (en) * | 2015-06-04 | 2015-09-02 | 中国科学院合肥物质科学研究院 | Tungsten-zirconium carbide-rhenium alloy with high-temperature stability and preparation method thereof |
| CN109161771A (en) * | 2018-11-22 | 2019-01-08 | 江苏经纬阀业有限公司 | Novel tungsten alloy and preparation method thereof |
| CN113430439A (en) * | 2021-06-28 | 2021-09-24 | 北京理工大学 | Phase distribution uniformity control method of high-toughness active tungsten alloy |
| CN114934207A (en) * | 2022-05-20 | 2022-08-23 | 北京科技大学 | Method for preparing high-strength high-plasticity dispersion-strengthened tungsten alloy |
| CN114959338A (en) * | 2022-05-16 | 2022-08-30 | 北京科技大学 | Method for preparing high-strength high-plasticity tungsten alloy through mechanical alloying |
| CN114959341A (en) * | 2022-05-20 | 2022-08-30 | 北京科技大学 | Method for preparing high-strength high-plasticity refractory alloy |
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- 1999-09-17 CN CN99120173A patent/CN1083492C/en not_active Expired - Fee Related
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| US8790724B2 (en) | 2003-04-04 | 2014-07-29 | Unigen, Inc. | Formulation of dual cycloxygenase (COX) and lipoxygenase (LOX) inhibitors for mammal skin care |
| CN106783459B (en) * | 2012-05-29 | 2019-02-26 | 株式会社东芝 | Tungsten alloy component and discharge lamp, transmitting tube and the magnetron for using the tungsten alloy component |
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| EP3778939A1 (en) * | 2012-05-29 | 2021-02-17 | Kabushiki Kaisha Toshiba | Method for producing a tungsten alloy part |
| EP2857534A4 (en) * | 2012-05-29 | 2016-02-10 | Toshiba Kk | Tungsten alloy part, and discharge lamp, transmitting tube, and magnetron using same |
| US10395879B2 (en) | 2012-05-29 | 2019-08-27 | Kabushiki Kaisha Toshiba | Tungsten alloy part, and discharge lamp, transmitting tube, and magnetron using the same |
| CN106783459A (en) * | 2012-05-29 | 2017-05-31 | 株式会社东芝 | Tungsten alloy part and the discharge lamp using the tungsten alloy part, transmitting tube and magnetron |
| CN103998634A (en) * | 2012-05-29 | 2014-08-20 | 株式会社东芝 | Tungsten alloy part, and discharge lamp, transmitting tube, and magnetron using same |
| CN103975414B (en) * | 2012-07-03 | 2017-03-08 | 株式会社东芝 | Tungsten alloy part and the discharge lamp using this tungsten alloy part, transmitting tube and magnetron |
| CN103975414A (en) * | 2012-07-03 | 2014-08-06 | 株式会社东芝 | Tungsten alloy part, and discharge lamp, transmitting tube and magnetron using same |
| CN104878266A (en) * | 2015-06-04 | 2015-09-02 | 中国科学院合肥物质科学研究院 | Tungsten-zirconium carbide-rhenium alloy with high-temperature stability and preparation method thereof |
| CN109161771A (en) * | 2018-11-22 | 2019-01-08 | 江苏经纬阀业有限公司 | Novel tungsten alloy and preparation method thereof |
| CN113430439A (en) * | 2021-06-28 | 2021-09-24 | 北京理工大学 | Phase distribution uniformity control method of high-toughness active tungsten alloy |
| CN114959338A (en) * | 2022-05-16 | 2022-08-30 | 北京科技大学 | Method for preparing high-strength high-plasticity tungsten alloy through mechanical alloying |
| CN114934207A (en) * | 2022-05-20 | 2022-08-23 | 北京科技大学 | Method for preparing high-strength high-plasticity dispersion-strengthened tungsten alloy |
| CN114959341A (en) * | 2022-05-20 | 2022-08-30 | 北京科技大学 | Method for preparing high-strength high-plasticity refractory alloy |
| CN114959341B (en) * | 2022-05-20 | 2024-06-04 | 北京科技大学 | Method for preparing high-strength high-plasticity refractory alloy |
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| CN1083492C (en) | 2002-04-24 |
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