CN100363131C - Method for preparing grain-size-contrdlable superfine crystallite tungsten and tungsten-copper composite material - Google Patents
Method for preparing grain-size-contrdlable superfine crystallite tungsten and tungsten-copper composite material Download PDFInfo
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- CN100363131C CN100363131C CNB200510126460XA CN200510126460A CN100363131C CN 100363131 C CN100363131 C CN 100363131C CN B200510126460X A CNB200510126460X A CN B200510126460XA CN 200510126460 A CN200510126460 A CN 200510126460A CN 100363131 C CN100363131 C CN 100363131C
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Abstract
The present invention provides a composite material of grain size controllable superfine grain pure tungsten, tungsten base high density alloy and tungsten copper and a preparing method thereof, which belongs to the technical field of a high melting metal and a metal base heat sink material. The present invention has the specific technology that tungsten powder and alloy elements or copper powder are mechanically mixed, and the processed tungsten powder or mixed powder is in compression moulding forming, with forming pressure of 30 to 100MPa, or the processed tungsten powder or mixed powder is in cold isostatic forming, with forming pressure of 100 to 300MPa. A formed raw blank is arranged in a pyrophyllite mould, and is put into a press machine with six surface tops or two surface tops. Firstly, a pressure of 1 to 10GPa is applied to a sample, and both ends of the sample are sintered by applying alternating current of 10 to 25kW. A sintered body is polished by grinding, and relative density of the sintered body is 96 to 99%. The present invention has the advantages that superfine grain tungsten base block materials with grain sizes which are equivalent to the grain sizes of initial tungsten powder are obtained. The initial component content can be kept. The superfine grain tungsten base block materials which are obtained by preparation has good mechanical properties and good heat shock resistance.
Description
Technical field
The invention belongs to refractory metal and Metal Substrate heat sink material technical field, particularly provide a kind of crystallite dimension controlled superfine crystal particle pure tungsten, tungsten-copper composite material that tungsten base high-specific-gravity alloy and copper content can be adjusted from 10%～90% (being volume ratio) and preparation method thereof.
Background technology
The infusibility tungsten sill that the present invention relates to comprises pure tungsten material, tungsten base high-specific-gravity alloy (as W-Ni-Cu, W-Ti, W-Zr etc.) and tungsten-copper composite material.Pure tungsten and tungsten base high-specific-gravity alloy material have the advantage of high-melting-point, high density, high strength, high rigidity and high-wearing feature, in addition, its thermal coefficient of expansion is little, corrosion stability and antioxygenic property is good and electrical and thermal conductivity performance is good, has therefore all obtained using very widely in stratosphere, national defense industry and civilian industry.As counterweight and vibration-absorptive material on gyrorotor and the aircraft, in military project, be used as armor-piercing bullet and shrapnel etc., in medical industry, be used as the X-ray-preventing shielding material, in civilian industry, be used as high-density alloy oscillator electrode material on the mobile phone etc.
Tungsten-copper composite material is the main two phase structure pseudo-alloy of forming by W, Cu, have the good thermal conductivity and the programmable coefficient of expansion, heat sink substrate as microelectronics Packaging such as CPU, IC, solid state microwave pipes, can realization and the matched well sealing-in of semiconductor silicon, GaAs, aluminium oxide and beryllium oxide, play the effect of supporting and heat radiation.Tungsten-copper composite material has good anti-arc erosion, resistance fusion welding and characteristics such as high strength, high rigidity in addition, is widely used as electrical contact material, electric resistance welding, spark machined and plasma electrode material.Tungsten-copper composite material militarily has been used as the military project transpiration material, and some other new purposes is also just in research and development, and as the guide material of magnetic artillery, it uses hear resistance, high conductivity and the performances such as arc resistant, friction resistant of Tungsten-copper Composites.
According to every characteristic of tungsten sill, various new may application also in research and development constantly, as in nuclear fusion experimental device as towards plasma material; As the reinforcement of heavy load sliding friction axle sleeve, as the sealed solid spare that rotates and move at a high speed; Require no magnetic, low bulk, high elastic modulus, the parts of specific (special) requirements such as radiation-resistant glass in the various instrument and meters; In integrated circuit of new generation, because wiring is more and more thinner, the needs of heat radiation and heatproof all will enlarge the demand of tungsten substrate material, and Metal Packaging also will develop to refractory material in addition.
Along with the expansion of application,, comprise high density, high structural homogeneity and high heat, electrical property etc. to the quality and the demands for higher performance of tungsten sill.In order to reach high mechanical property, adopt ultra-fine and crystallite infusibility tungsten alloy material more and more to become the development trend of infusibility tungsten-bast alloy and composite thereof.Ultra-fine and crystallite infusibility tungsten alloy material can improve the mechanical property of material significantly.But because ultra-fine grain (particularly nanometer-size die) is active big, in sintering, grow up rapidly,, be difficult to obtain the material of ultra-fine crystalline substance if do not controlled.For example according to reports, the powder sintered 5min of nanometer W-Cu can be densified, but grain growth is very rapid in sintering, is not easy to control.Mainly be to adopt to add grain growth inhibitor such as VC, TaC, TiC, ZrC, La at present
2O
3, ThO
2Deng method control growing up of crystal grain.In addition, new nano material sintering technology has begun to use, comprises plasma activated sintering and Rapid Thermal isostatic pressing method.
For tungsten-copper composite material, along with the variation of copper content, usually need to adopt different preparation methods, 50% when following, often adopt infiltration method to prepare as copper content, copper content then more adopted lqiuid phase sintering method at big sub 50% o'clock.Also there is not at present a kind of simple and effective method can prepare copper content adjustable tungsten-copper composite material arbitrarily simultaneously.
Summary of the invention
The object of the present invention is to provide the controlled superfine crystal particle pure tungsten material of a kind of grain size, tungsten base from preparation method than heavy metal (as W-Ni-Cu, W-Ti-Cu etc.) and tungsten-copper composite material.Strengthen the sintering of tungsten sill and the sintering time of shortening tungsten sill, avoid contingent grain growth phenomenon in sintering process.
The present invention can prepare the controlled superfine crystal particle pure tungsten material of crystallite dimension, tungsten base high-specific-gravity alloy (as W-Ni-Cu, W-Ti-Cu etc.) and tungsten-copper composite material by selecting varigrained tungsten powder.Concrete technology is:
The preparation of a, raw material: select the tungsten powder of granularity＜10 μ m,, need carry out granulation in advance to it, to improve its processability when tungsten powder particle-size during less than 1 μ m; Tungsten powder and alloying element (addition 0.1%～5% is weight ratio) need be carried out mechanical mixture for tungsten base high-specific-gravity alloy; Described alloying element is Cu, Ni, Zr, one or both among the Ti; Tungsten powder and copper powder (addition 10%～90% is volume ratio) need be carried out mechanical mixture for tungsten-copper composite material;
The moulding of b, green compact: the tungsten powder or the mixed powder of above-mentioned processing are carried out compression molding, and briquetting pressure is 30--100MPa; Or cold isostatic compaction, briquetting pressure is 100-300MPa;
The sintering of c, green compact: the green compact of forming are placed a pyrophillite mould, put into press; At first sample is applied the pressure of 1-10GPa, pressure is two-way pressurization or six pressurizations; The alternating current that the sample two ends are applied 10-25kW carries out sintering then, and be 30 seconds-3 minutes conduction time, behind the energising sintering, continues pressurize 0.5-3 minute; Sintered body is through grinding and polishing, and relative density is 96-99%.
The invention has the advantages that: adopt the method for energising sintering under the hyperpressure to prepare grain size controlled tungsten matrix body material and tungsten-copper composite material, apply hyperpressure with the sintering of strengthening the tungsten sill and the sintering time that shortens the tungsten sill, avoid contingent grain growth phenomenon in sintering process.Applying high alternating current makes the tungsten base substrate obtain the sintering temperature that needs by the self-resistance heating.Tungsten-copper composite material is in sintering process, and copper tangible fusion can not take place runs off, and can keep initial component content.The ultra-fine grain tungsten matrix body material and the tungsten-copper composite material that prepare have mechanical property and thermal-shock resistance preferably, be suitable for electronic package material, the heat deposition material, electrical contact material and high temperature resistant plasma wash away parts, as divertor material in the nuclear fusion device etc.
The specific embodiment
Embodiment 1: the grain size of tungsten is the preparation of the pure tungsten block materials of 0.2 μ m.
With granularity is that the tungsten powder of 0.2 μ m at first carries out granulation, in cold isostatic press, carry out moulding, briquetting pressure is 200MPa, the base substrate of forming is put into the pyrophillite mould after being machined to certain size, at 8GPa, input power is to carry out sintering under the effect of 23kW alternating current, and sintering time is 2 minutes.The gained sample is behind grinding and polishing, and recording density is 18.53g/cm
3, microhardness is 1169.80MPa, and bending strength is 596.29MPa, and the room temperature thermal conductivity is 105.1W/mk.
Embodiment 2: the grain size of tungsten is the preparation of the pure tungsten block materials of 1 μ m.
With granularity is that the tungsten powder of 1 μ m carries out moulding in cold isostatic press, briquetting pressure is 200MPa, and the base substrate of forming is put into the pyrophillite mould after being machined to certain size, at 6GPa, input power is to carry out sintering under the effect of 23kW alternating current, and sintering time is 2 minutes.The gained sample is behind grinding and polishing, and recording density is 18.63g/cm
3, microhardness is 772.30MPa, and bending strength is 561.12MPa, and the room temperature thermal conductivity is 128.5W/mk.
Embodiment 3: the grain size of tungsten is the preparation of the pure tungsten block materials of 7 μ m.
With granularity is that the tungsten powder of 1 μ m carries out moulding in cold isostatic press, briquetting pressure is 200MPa, and the base substrate of forming is put into the pyrophillite mould after being machined to certain size, at 6GPa, input power is to carry out sintering under the effect of 23kW alternating current, and sintering time is 1 minute.The gained sample is behind grinding and polishing, and recording density is 18.89g/cm
3, microhardness is 592.20MPa, and bending strength is 461.21MPa, and the room temperature thermal conductivity is 97.77W/mk.
Embodiment 4: the grain size of tungsten is the preparation of the W-Ni-Cu high-density alloy of 1 μ m.
With granularity is that the tungsten powder of 1 μ m and granularity are carried out mechanical mixture for Ni powder and Cu powder about-300 orders, and the addition of Ni powder and Cu powder is 2.5vol%.Mixed stamping of powder moulding, briquetting pressure are 50MPa, and the base substrate of forming is put into the pyrophillite mould, and at 8GPa, input power is to carry out sintering under the effect of 23kW alternating current, and sintering time is 1 minute.The gained sample is behind grinding and polishing, and recording density is 18.59g/cm
3, microhardness is 792.20MPa, bending strength is 576.58MPa.
Embodiment 5: the grain size of tungsten is the preparation of the W-Cu alloy of 0.5 μ m.
With granularity is that tungsten powder and the granularity of 0.5 μ m carried out mechanical mixture for-200 purpose Cu powder, and the addition of Cu is 5vol%.Mixed stamping of powder moulding, briquetting pressure are 50MPa, and the base substrate of forming is put into the pyrophillite mould, and at 8GPa, input power is to carry out sintering under the effect of 20kW alternating current, and sintering time is 1 minute.The gained sample is behind grinding and polishing, and recording density is 18.19g/cm
3, microhardness is 989.50MPa, bending strength is 591.58MPa.
Embodiment 6: the grain size of tungsten is the preparation of the tungsten-copper composite material (copper content is 50vol%) of 1 μ m.
With granularity is that tungsten powder and the granularity of 1 μ m carried out mechanical mixture for-300 purpose Cu powder, and the addition of Cu is 50vol%.Mixed stamping of powder moulding, briquetting pressure are 50MPa, and the base substrate of forming is put into the pyrophillite mould, and at 8GPa, input power is to carry out sintering under the effect of 13kW alternating current, and sintering time is 1 minute.The gained sample is behind grinding and polishing, and recording density is 13.67g/cm
3, the room temperature thermal conductivity is 194.77W/mk.
Embodiment 7: the grain size of tungsten is the preparation of the tungsten-copper composite material (copper content is 25vol%) of 1 μ m.
With granularity is that tungsten powder and the granularity of 1 μ m carried out mechanical mixture for-300 purpose Cu powder, and the addition of Cu is 25vol%.Mixed stamping of powder moulding, briquetting pressure are 50MPa, and the base substrate of forming is put into the pyrophillite mould, and at 8GPa, input power is to carry out sintering under the effect of 13kW alternating current, and sintering time is 50 seconds.The gained sample is behind grinding and polishing, and recording density is 11.167g/cm
3, the room temperature thermal conductivity is 247.77W/mk.
Claims (1)
1. the preparation method of controlled superfine crystal particle pure tungsten, tungsten base high-specific-gravity alloy and the tungsten-copper composite material of a crystallite dimension, it is characterized in that: technology is:
The preparation of a, raw material: select the tungsten powder of granularity＜10 μ m,, need carry out granulation in advance to it, to improve its processability when tungsten powder particle-size during less than 1 μ m; When preparation tungsten base high-specific-gravity alloy and tungsten-copper composite material, need be that the alloying element of 0.1%～5% weight ratio or copper powder that addition is 10%～90% volume ratio carry out mechanical mixture with tungsten powder and addition; Described alloying element is Cu, Ni, Zr, among the Ti 1～2 kind;
The moulding of b, green compact: the tungsten powder or the mixed powder of above-mentioned processing are carried out compression molding, and briquetting pressure is 30-100MPa; Or cold isostatic compaction, briquetting pressure is 100-300MPa;
C, biscuit sintering: the green compact of forming are placed the pyrophillite mould, put into cubic apparatus or belt type press; At first sample is applied the pressure of 1-10GPa, pressure is two-way pressurization or six pressurizations; The alternating current that the sample two ends are applied 10-25kW carries out sintering then, and be 30 seconds～3 minutes conduction time, behind the energising sintering, continues pressurize 0.5～3 minute; Sintered body is through grinding and polishing, and relative density is 96-99%.
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| CN102925727B (en) * | 2012-11-14 | 2015-03-04 | 武汉理工大学 | Preparation method for high-performance Zn@W-Cu heat composite |
| JP6677875B2 (en) * | 2015-03-23 | 2020-04-08 | 三菱マテリアル株式会社 | Polycrystalline tungsten and tungsten alloy sintered body and method for producing the same |
| CN110938760A (en) * | 2019-12-28 | 2020-03-31 | 泰州市华诚钨钼制品有限公司 | Preparation method of molybdenum-copper composite material by adopting nano yttrium powder dispersion strengthening |
| CN112226662B (en) * | 2020-10-21 | 2021-11-02 | 广州大学 | Double-nanostructure tungsten alloy with good high-temperature stability and preparation method and application thereof |
| CN115383111B (en) * | 2022-08-26 | 2023-12-19 | 山东滨州华创金属有限公司 | Preparation process of multi-component energy-containing alloy material and multi-component energy-containing alloy material |
| CN115961165A (en) * | 2022-10-26 | 2023-04-14 | 西南科技大学 | Preparation method of high-dislocation-density tungsten alloy material |
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| EP0098944A2 (en) * | 1982-07-16 | 1984-01-25 | DORNIER SYSTEM GmbH | Tungsten alloy powder |
| CN1164451A (en) * | 1997-05-23 | 1997-11-12 | 冶金工业部钢铁研究总院 | Method for making hard alloy roll for rolling cold-rolled twisted steel |
| US6187087B1 (en) * | 1998-12-31 | 2001-02-13 | Materials Modification, Inc. | Method of bonding a particle material to near theoretical density |
| CN1590572A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Sintering technology of nano-grade tungsten cobalt mixed powder |
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| EP0098944A2 (en) * | 1982-07-16 | 1984-01-25 | DORNIER SYSTEM GmbH | Tungsten alloy powder |
| CN1164451A (en) * | 1997-05-23 | 1997-11-12 | 冶金工业部钢铁研究总院 | Method for making hard alloy roll for rolling cold-rolled twisted steel |
| US6187087B1 (en) * | 1998-12-31 | 2001-02-13 | Materials Modification, Inc. | Method of bonding a particle material to near theoretical density |
| CN1590572A (en) * | 2003-08-25 | 2005-03-09 | 金益民 | Sintering technology of nano-grade tungsten cobalt mixed powder |
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