CN1775425A - 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
- Publication number
- CN1775425A CN1775425A CN 200510126460 CN200510126460A CN1775425A CN 1775425 A CN1775425 A CN 1775425A CN 200510126460 CN200510126460 CN 200510126460 CN 200510126460 A CN200510126460 A CN 200510126460A CN 1775425 A CN1775425 A CN 1775425A
- Authority
- CN
- China
- Prior art keywords
- tungsten
- powder
- sintering
- composite material
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Powder Metallurgy (AREA)
Abstract
The present invention provides a superfine grain pure tungsten whose grain size can be controlled, tungsten base high specific weight alloy and tungsten-copper composite material and their preparation method. Said preparation method includes the following processes: mechanically-mixing tungsten powder and alloy elements or copper powder, die forming, forming pressure is 30-100 MPa, or cold isostatic compaction forming, forming pressure is 100-300 MPa, placing raw blank in a pyrophyllite mould, and placing said mould into a pressing machine, applying pressure with 1-10 Gpa, sintering grinding and polishing so as to obtain the invented pro duct whose relative density is 96-99%.
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 is greater than then more adopting lqiuid phase sintering method at 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 preparation method of the controlled superfine crystal particle pure tungsten material of a kind of grain size, tungsten base high-specific-gravity alloy (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
3Microhardness 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, controlled superfine crystal particle pure tungsten, tungsten base high-specific-gravity alloy and tungsten-copper composite material of a kind of crystallite dimension and preparation method thereof, 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; With tungsten powder and addition is that the alloying element of 0.1%～5% weight ratio or copper powder that addition is 10%～90% volume ratio carry out mechanical mixture; 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 six items 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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510126460XA CN100363131C (en) | 2005-12-12 | 2005-12-12 | Method for preparing grain-size-contrdlable superfine crystallite tungsten and tungsten-copper composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510126460XA CN100363131C (en) | 2005-12-12 | 2005-12-12 | Method for preparing grain-size-contrdlable superfine crystallite tungsten and tungsten-copper composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1775425A true CN1775425A (en) | 2006-05-24 |
| CN100363131C CN100363131C (en) | 2008-01-23 |
Family
ID=36765212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510126460XA Expired - Fee Related CN100363131C (en) | 2005-12-12 | 2005-12-12 | Method for preparing grain-size-contrdlable superfine crystallite tungsten and tungsten-copper composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100363131C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925727A (en) * | 2012-11-14 | 2013-02-13 | 武汉理工大学 | Preparation method for high-performance Zn@W-Cu heat composite |
| JP2016180179A (en) * | 2015-03-23 | 2016-10-13 | 三菱マテリアル株式会社 | Polycrystalline tungsten, tungsten alloy sintered compact, and method for producing 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 |
| CN112226662A (en) * | 2020-10-21 | 2021-01-15 | 广州大学 | Double-nanostructure tungsten alloy with good high-temperature stability and preparation method and application thereof |
| CN115383111A (en) * | 2022-08-26 | 2022-11-25 | 山东滨州华创金属有限公司 | Preparation process of multi-component energetic alloy material and multi-component energetic alloy material |
| CN115673327A (en) * | 2022-10-18 | 2023-02-03 | 北京工业大学 | High-strength and high-toughness tungsten alloy and preparation method thereof |
| CN115961165A (en) * | 2022-10-26 | 2023-04-14 | 西南科技大学 | Preparation method of high-dislocation-density tungsten alloy material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3226648C2 (en) * | 1982-07-16 | 1984-12-06 | Dornier System Gmbh, 7990 Friedrichshafen | Heterogeneous 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 |
-
2005
- 2005-12-12 CN CNB200510126460XA patent/CN100363131C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925727A (en) * | 2012-11-14 | 2013-02-13 | 武汉理工大学 | Preparation method for high-performance Zn@W-Cu heat composite |
| CN102925727B (en) * | 2012-11-14 | 2015-03-04 | 武汉理工大学 | Preparation method for high-performance Zn@W-Cu heat composite |
| JP2016180179A (en) * | 2015-03-23 | 2016-10-13 | 三菱マテリアル株式会社 | Polycrystalline tungsten, tungsten alloy sintered compact, and method for producing same |
| CN107427913A (en) * | 2015-03-23 | 2017-12-01 | 三菱综合材料株式会社 | Polycrystalline tungsten and tungsten alloy sintered body and its manufacture method |
| TWI675111B (en) * | 2015-03-23 | 2019-10-21 | 日商三菱綜合材料股份有限公司 | Poly-crystalline tungsten and poly-crystalline tungsten alloy, and method of producing same |
| CN107427913B (en) * | 2015-03-23 | 2020-02-28 | 三菱综合材料株式会社 | Polycrystalline tungsten and tungsten alloy sintered body and method for producing 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 |
| CN112226662A (en) * | 2020-10-21 | 2021-01-15 | 广州大学 | Double-nanostructure tungsten alloy with good high-temperature stability and preparation method and application thereof |
| 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 |
| CN115383111A (en) * | 2022-08-26 | 2022-11-25 | 山东滨州华创金属有限公司 | Preparation process of multi-component energetic alloy material and multi-component energetic alloy material |
| 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 |
| CN115673327A (en) * | 2022-10-18 | 2023-02-03 | 北京工业大学 | High-strength and high-toughness tungsten alloy and preparation method thereof |
| CN115673327B (en) * | 2022-10-18 | 2024-04-30 | 北京工业大学 | High-strength and high-toughness tungsten alloy and preparation method thereof |
| CN115961165A (en) * | 2022-10-26 | 2023-04-14 | 西南科技大学 | Preparation method of high-dislocation-density tungsten alloy material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100363131C (en) | 2008-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Formation of transition layer and its effect on mechanical properties of AlCoCrFeNi high-entropy alloy/Al composites | |
| Alem et al. | Microwave sintering of ceramic reinforced metal matrix composites and their properties: a review | |
| Huang et al. | Fabrication of graphite film/aluminum composites by vacuum hot pressing: process optimization and thermal conductivity | |
| CN100363131C (en) | Method for preparing grain-size-contrdlable superfine crystallite tungsten and tungsten-copper composite material | |
| Zhang et al. | Influence of Ti content on the microstructure and properties of graphite flake/Cu-Ti composites fabricated by vacuum hot pressing | |
| Li et al. | Optimized thermal properties in diamond particles reinforced copper-titanium matrix composites produced by gas pressure infiltration | |
| Kang et al. | Microstructure and thermal properties of copper–diamond composites with tungsten carbide coating on diamond particles | |
| Sharma et al. | Fundamentals of spark plasma sintering (SPS): an ideal processing technique for fabrication of metal matrix nanocomposites | |
| EP1337497B1 (en) | A heat conductive material | |
| Pillari et al. | Fabrication of W-Cu functionally graded composites using high energy ball milling and spark plasma sintering for plasma facing components | |
| CN100478467C (en) | Activated sintering preparation method of fine crystalline non-magnetic wolfram-copper alloy | |
| Bai et al. | Thermal conductivity of Cu/diamond composites prepared by a new pretreatment of diamond powder | |
| EP1114807B1 (en) | Semiconductor device or heat dissipating substrate therefor using a composite material | |
| CN109863117B (en) | Graphite/graphene composite material, heat collector, heat transfer body, heat radiator and heat radiation system | |
| Silvain et al. | Copper-carbon and aluminum-carbon composites fabricated by powder metallurgy processes | |
| CN111500892A (en) | Preparation method of large-size flaky diamond/copper composite material with ultrahigh thermal conductivity | |
| CN1957467A (en) | Heat sink made from diamond-copper composite material containing boron | |
| CN112981163B (en) | Preparation method of diamond-reinforced metal matrix composite with high surface precision and high reliability | |
| KR20120095355A (en) | Heat sink for electronic device, and process for production thereof | |
| CN1948528A (en) | Preparation method of near fully densificated high W or Mo content W-Cu or Mo-Cu composite material | |
| Chaubey et al. | Fabrication and characterization of W-Cu functionally graded material by spark plasma sintering process | |
| Wu et al. | Direct additive manufacturing of TiCp reinforced Al2O3-ZrO2 eutectic functionally graded ceramics by laser directed energy deposition | |
| CN108774699A (en) | Aluminium silicon/aluminium gold hard rock gradient composites and preparation method thereof | |
| Zhou et al. | Pressure effects on a novel W-Mo-Cu alloy by large current electric field sintering: sintering behavior, microstructure and properties | |
| Cai et al. | Microstructure and properties of Al/Sip composites for thermal management applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080123 Termination date: 20101212 |