CN1274860C - Preparation method of fine-grain tungsten-copper composite material - Google Patents

Preparation method of fine-grain tungsten-copper composite material Download PDF

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CN1274860C
CN1274860C CN 03143145 CN03143145A CN1274860C CN 1274860 C CN1274860 C CN 1274860C CN 03143145 CN03143145 CN 03143145 CN 03143145 A CN03143145 A CN 03143145A CN 1274860 C CN1274860 C CN 1274860C
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powder
tungsten
carbon
ball
alloy
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CN1566387A (en
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范景莲
黄伯云
张兆森
马运柱
汪登龙
吴恩熙
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Central South University
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Central South University
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Abstract

The invention relates to the field of alloy manufacturing by using a powder metallurgy technology, which is characterized in that: pressing the powder under 200-500 MPa, placing the powder into a sintering furnace, heating to 400-700 ℃ at a temperature rising speed of 5-20 ℃ per min, preserving heat for 15-120 min, reaching the sintering temperature of 1150-1350 ℃ at a speed of 20-60 ℃ per min, and preserving heat for 30-120 min. The W-Cu alloy prepared by the invention has a fine W grain structure of 1-2 mu m, and the compactness and the mechanical property of the W-Cu alloy are superior to those of the traditional W-Cu alloy; the density is 97-99.5%, the tensile strength is 800MPa, the elongation is 3.0-5.0%, and the bending strength is 1100 MPa and 1300 MPa.

Description

The preparation method of thin brilliant tungsten-carbon/carbon-copper composite material
Technical field
The present invention relates to nano material technology and powder metallurgy technology alloying field, particularly prepare the complete fine and close thin brilliant tungsten-carbon/carbon-copper composite material of high strength, it be with element powders after mixing, again under liquid medium, add tensio-active agent,, then adopt sintering to be prepared from through high-energy ball milling.
Background technology
The W-Cu matrix material has the advantage of W and Cu, its density height, thermal expansivity are low, the property led is good, thermal conductivity is good, is widely used as in contact material, electrode materials and the modern microelectronics information industry and is used as electronic package material and heat sink materials such as microwave power device substrate, web member, radiating subassembly.Traditional preparation process W-Cu composite process is generally high-temperature liquid-phase around connection and infiltration method.Adopt the density of the prepared alloy material of high-temperature liquid-phase sintering to have only about 94-95%, add activators such as Ni, Co and adopt the activation solution phase sintering, can make density reach 98-99%, but the electroconductibility and the heat conductivility of alloy had adverse influence.Adopt the infiltration of copper method can make alloy reach 99% density, but the infiltration of copper method has limited the composition of alloy, the gained microstructure is thick simultaneously, and the mechanical property of alloy is extremely low.
The existing abroad report of the preparation method of relevant W-Cu composite powder.United States Patent (USP) United States Patent 5,956,560 discloses a kind of method that adopts chemical coating method with W powder coated with uniform one deck Cu powder, is mingled with but this method is easy to introducing, and can not produces the powder that reaches nanoscale.The patent No. is United States Patent 5,352,269 disclose a kind of method that adopts the spraying thermal conversion to prepare the nanophase composite powder, this patent adopts spraying drying and fluidized bed to prepare the following nanophase WC-Co composite powder of 100nm, but report does not prepare nanophase W-Cu composite powder.
Domesticly do not see relevant ultra-fine, nanometer W-Cu composite powder patent report and high-strength thin-crystal tungsten-carbon/carbon-copper composite material preparation technology report.But the existing abroad research of preparation method to preparation nanometer W-Cu composite powder.People such as U.S. Jim-Chun Kim are at The Inter-national Journal of Powder Metallurgy (1999, No.4,47-55) adopt mechanical alloying to obtain the nanocrystalline W-30Cu composite powder that grain fineness number is 20nm to the W-30Cu mixed powder in " MetalInjection Molding of Nano-structured W-Cu Composite Powder ", it is that 1 μ m, density are 97% alloy material that this powder obtains crystal grain at 1200 ℃ of sintering.People such as Jim-Chun Kim adopts mechanical alloying can not prepare the nearly complete fine and close and good W-Cu matrix material of mechanical property obviously.People such as G.G.Lee are at Powder Metallurgy (2000, No.1,79-82) " Synthesis of highdensity ultrafine W/Cu Composite alloy by Mechano-thermo ChemicalProcess " adopts machinery-thermochemistry synthesis technique nanometer W-Cu composite powder, this method is a raw material with ammonium metawolframate and cupric nitrate, be mixed with solution, adopt spraying drying to obtain nanometer W-Cu composite powder then, it is thin brilliant W-Cu alloy about 1 μ m that this powder obtains microstructure at 1050 ℃ of-1200 ℃ of sintering, but does not appear in the newspapers about the density and the mechanical property of alloy.People such as Srikanth Raghunathan are at P/M Science ﹠amp; Technol-ogy (1999, No.1,9-14) " Synthesis and Evaluation of advanced nano-crystalline tungsten based materials ".This article has reported that employing sodium wolframate crystal and neutralized verdigris crystal are raw material, and it is mixed with mixing solutions, obtains W-Cu sosoloid colloid, and the gauge that the W particle surface is coated with Cu is 25-75nm.But coat-thickness differs, and adopts this method technological process too complicated, is unsuitable for batch preparations nanometer W-Cu composite powder, and in this article not the sintering character to powder report.
Summary of the invention
The objective of the invention is to fully utilize the strong point of prior art, overcome the weak point of prior art, thereby preparation has the high fine and close thin brilliant W-Cu matrix material of high tensile property.With the W-Cu alloy material of this method preparation, grain structure is 1-2 μ m; The tensile break strength height reaches 700-800MPa, and unit elongation is 3.5-5.0%; Density is more than 99%, overcomes the shortcoming of mechanical properties such as traditional W-Cu composite density is low, no tensile strength.
The present invention is for achieving the above object, and the scheme of employing is:
1. the moiety of alloy is: (1-x) W-x Cu, x are 5%-50wt%;
2. W and two kinds of powder of Cu were mixed in proportion 12 hours, obtain the W-Cu mixed powder;
3. mixed powder is put into the ball grinding cylinder of high energy ball mill, add tungsten ball or sintered carbide ball, ratio of grinding media to material is 5: 1~20: 1, adds medium than the liquid ball-milling medium that is 0.8~2.0, the tensio-active agent that adds 1-5wt% carries out high-energy ball milling, vacuumizes to reach 1 * 10 -2Pa feeds protective atmosphere (N2, Ar etc.), and the ball milling time is 5-60 hour, obtains powder liquid;
4. powder liquid is carried out drying, making grain-size is 20-50nm, and granularity is the nanocrystalline W-Cu composite powder of 0.2 μ m-0.5 μ m;
5. base substrate is shaped nanocrystalline W-Cu composite powder under the pressure of 200-500MPa;
6. pressed compact is put into sintering oven and carry out sintering, feed protective atmosphere H 2Or cracked ammonium or vacuum; Heat-up rate with 5 ℃/min-20 ℃/min is raised to 400 ℃-700 ℃, behind the insulation 5min-120min again the speed with 20 ℃/min-60 ℃/min be raised to 1150 ℃-1350 ℃ of sintering temperatures, insulation 30min-120min obtains the fine and close W-Cu alloy that W crystal grain and the mutually equally distributed no copper that bonds ooze out.Its density reaches 98%-99.5%, and W crystal grain is 1-2 μ m, and the tensile strength of alloy is 700-900MPa, and unit elongation is 3.0-5.0%, and bending strength is 1000-1100MPa.
Liquid medium is methyl alcohol, ethanol, acetone, gasoline or CCl 4
Tensio-active agent is polyoxyethylene glycol (PEG), tween 20, stearic acid (SA), paraffin (PW), OP emulsifying agent, sodium laurylsulfonate, N, the N dimethyl formamide.
The tensio-active agent that adds be a kind of, two or three.
Advantage of the present invention and positively effect are embodied in:
1. compare with Cu infiltration method with conventional high-temperature liquid-phase sintering, the density height of the W-Cu matrix material that this invention technology is prepared, the W-Cu alloy density for preparing than ordinary method exceeds about 6%.
2. compare with ordinary method, adopt the prepared W-Cu matrix material grain structure of this invention technology tiny, have only 1.0 μ m-2.0 μ m, Cu more is evenly distributed in the phase interface of W phase mutually, and no Cu oozes out mutually.
3. compare with ordinary method, adopt the mechanical property of W-Cu matrix material of this invention technology preparation good, its tensile strength can reach 700-900MPa, and unit elongation can reach 3.0-5.0%, and bending strength can reach 1100-1300MPa.
4. compare with conventional infiltrating method, adopt this invention technology that the composition of alloy is had no special requirements, composition can be adjusted in a big way, preparation technology's program simplification.
5. in high-energy ball milling, add liquid medium and tensio-active agent, reached effective refinement tungsten particle, the shortcoming of having avoided the powder agglomeration caking and having glued wall, simultaneously again when high-energy ball milling liquid medium can make all even purpose that reaches even refinement of powder thorough mixing as fluid, reduced the wearing and tearing that direct impact caused between ball and the ball.And tensio-active agent evenly is coated on the very thin protective membrane of powder surface formation one deck; prevent that powder surface from directly causing the phenomenon of body of powder oxidation with extraneous the contact; overcome nanometer powder and stored difficult problem, reduced powder and be mingled with, improved the powder process rate.
6. this thin brilliant W-Cu alloy material can be used as electronic package material better because the density height has overcome traditional W-Cu material and caused the high shortcoming of leak rate owing to density is low as packaged material.
7. this thin brilliant W-Cu matrix material has good tensile mechanical properties, bring possibility to carrying out deformation processing to a certain extent, thereby further improve the mechanical property of this alloy material, be suitable for the high military project material of processability, may in particular for providing as broken first property of medicine cover.
Embodiment
Be described further below in conjunction with example.
Embodiment 1:
1. take by weighing 400g tungsten powder and 100g copper powder, powder was mixed 12 hours in the general milling machine, obtain the original mixed powder;
2. the original mixed powder is put into the ball grinding cylinder of high energy ball mill, added 2500g tungsten ball, add 400ml liquid medium and 5g polyoxyethylene glycol (PEG),, vacuumize, reach 1 * 10 with the lid sealing -2Pa feeds high-purity N again 2Atmosphere protection, ball milling 20 hours obtains powder liquid;
3. liquid body of powder is carried out drying, obtain having the ultra-fine W-Cu composite powder of nanocrystalline structure; Powder is packed in the bag, and seal;
4. with the composite powder press forming, compacting pressure is 300MPa, obtains pressed compact;
5. pressed compact is put into the sintering oven sintering, risen to 600 ℃ with the heat-up rate of 10 ℃/min, insulation 30min, the heat-up rate with 50 ℃/min rises to 1200 ℃ then, insulation 120min; Adopt H 2As protective atmosphere, furnace cooling, obtaining the tungsten grain degree is 1 μ m, and drawing and stretching breaking tenacity is 700-800MPa, and unit elongation is the alloy material of 3.5%-5.0%.
Embodiment 2:
1. at first take by weighing 350g tungsten powder and 150g copper powder, powder was mixed 10 hours in the general milling machine, obtain the original mixed powder;
2. the original mixed powder is put into the ball grinding cylinder of high energy ball mill, added the 2500g Stainless Steel Ball, add 500ml liquid medium and 10g polyoxyethylene glycol (PEG),, vacuumize, reach 1 * 10 with the lid sealing -2Pa feeds the high-purity Ar atmosphere protection again, and the ball milling time is 40 hours, obtains powder liquid;
3. liquid body of powder is carried out drying, obtain having the ultra-fine W-Cu composite powder of nanocrystalline structure; Powder is packed in the bag, and sealing;
4. with powder pressing, compacting pressure is 500MPa, obtains pressed compact;
5. pressed compact is put into sintering oven, raise 600 ℃ with the heat-up rate of 8 ℃/min, insulation 30min, the heat-up rate with 30 ℃/min is raised to 1200 ℃ then, insulation 120min; Adopt cracked ammonium as protective atmosphere, furnace cooling then, obtaining the tungsten grain degree is 1 μ m, and drawing and stretching breaking tenacity is 700-800MPa, and unit elongation is the alloy material of 3.5%-5.0%.

Claims (6)

1. the preparation method of thin brilliant tungsten-carbon/carbon-copper composite material, it is by after the W-Cu powder mixes, again through high-energy ball milling, and interpolation liquid medium and tensio-active agent, drying obtains nanometer W-Cu composite powder then, then adopts solid state sintering to be prepared into the high-compactness alloy, it is characterized in that:
1. the moiety of alloy is: (1-x) W-xCu, x are 5-50wt%, and main component is W;
2. W and two kinds of powder of Cu were mixed in proportion 12 hours, obtain the W-Cu mixed powder;
3. mixed powder is put into the ball grinding cylinder of high energy ball mill, add tungsten ball or sintered carbide ball, ratio of grinding media to material is 5: 1~20: 1, adds medium than the liquid ball-milling medium that is 0.8~2.0, the tensio-active agent that adds 1-5wt% carries out high-energy ball milling, vacuumizes to reach 1 * 10 -2Pa feeds protective atmosphere, and the ball milling time is 5-60 hour, obtains powder liquid;
4. powder liquid is carried out drying, making grain fineness number is 20-50nm, and granularity is the W-Cu super fine composite powder of the nanocrystalline structure of 0.2-0.5 μ m;
5. base substrate is shaped nanocrystalline W-Cu composite powder under the pressure of 200~500MPa;
6. pressed compact is put into sintering oven and carry out sintering, feed protective atmosphere H 2Or cracked ammonium or vacuum; Heat-up rate with 5 ℃/min-20 ℃/min is raised to 400 ℃-700 ℃, behind the insulation 5min-120min again the speed with 20 ℃/min-60 ℃/min be raised to 1150 ℃-1350 ℃ of sintering temperatures, insulation 30min-120min, obtaining density is that 98-99.5%, W crystal grain are that 1-2 μ m, tensile strength are the W-Cu alloy of 700-800MPa;
2. according to the preparation method of claim 1 crystallization tungsten-carbon/carbon-copper composite material, it is characterized in that: described liquid medium is methyl alcohol, ethanol, acetone, gasoline or CCl 4
3. according to the preparation method of claim 1 crystallization tungsten-carbon/carbon-copper composite material, it is characterized in that: described tensio-active agent is a polyoxyethylene glycol, tween 20, stearic acid, paraffin, OP emulsifying agent, sodium laurylsulfonate, N, one or both in the dinethylformamide.
4. according to the preparation method of claim 1 crystallization tungsten-carbon/carbon-copper composite material, it is characterized in that: the tensio-active agent of adding be a kind of, two or three.
5. according to the preparation method of claim 1 crystallization tungsten-carbon/carbon-copper composite material, it is characterized in that: prepare thin brilliant W-Cu alloy material with powder metallurgy technology, it is characterized in that:
1. take by weighing 400g tungsten powder and 100g copper powder, powder was mixed 12 hours in the general milling machine, obtain the original mixed powder;
2. the original mixed powder is put into the ball grinding cylinder of high energy ball mill, added 2500g tungsten ball, add 400ml liquid medium and 5g polyoxyethylene glycol,, vacuumize, reach 1 * 10 with the lid sealing -2Pa feeds high-purity N again 2Atmosphere protection, ball milling 20 hours obtains powder liquid;
3. liquid body of powder is carried out drying, obtain having the ultra-fine W-Cu composite powder of nanocrystalline structure;
4. with the composite powder press forming, compacting pressure is 300MPa, obtains pressed compact;
5. pressed compact is put into the sintering oven sintering, risen to 600 ℃ with the heat-up rate of 10 ℃/min, insulation 30min, the heat-up rate with 50 ℃/min rises to 1200 ℃ then, insulation 120min; Adopt H 2As protective atmosphere, furnace cooling, obtaining the tungsten grain degree is 1 μ m, and drawing and stretching breaking tenacity is 700-800MPa, and unit elongation is the alloy of 3.5%-5.0%.
6. according to the preparation method of claim 1 crystallization tungsten-carbon/carbon-copper composite material, it is characterized in that:
1. at first take by weighing 350g tungsten powder and 150g copper powder, powder was mixed 10 hours in the general milling machine, obtain the original mixed powder;
2. the original mixed powder is put into the ball grinding cylinder of high energy ball mill, added the 2500g Stainless Steel Ball, add 500ml liquid medium and 10g polyoxyethylene glycol,, vacuumize, reach 1 * 10 with the lid sealing -2Pa feeds the high-purity Ar atmosphere protection again, and the ball milling time is 40 hours, obtains powder liquid;
3. liquid body of powder is carried out drying, obtain having the ultra-fine W-Cu composite powder of nanocrystalline structure;
4. with powder pressing, compacting pressure is 500MPa, obtains pressed compact;
5. pressed compact is put into sintering oven, raise 600 ℃ with the heat-up rate of 8 ℃/min, insulation 30min, the heat-up rate with 30 ℃/min is raised to 1200 ℃ then, insulation 120min; Adopt cracked ammonium as protective atmosphere, furnace cooling then, obtaining the tungsten grain degree is 1 μ m, and drawing and stretching breaking tenacity is 700-800MPa, and unit elongation is the alloy of 3.5%-5.0%.
CN 03143145 2003-06-13 2003-06-13 Preparation method of fine-grain tungsten-copper composite material Expired - Fee Related CN1274860C (en)

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CN102161097A (en) * 2011-01-29 2011-08-24 中南大学 Preparation method of novel fine grained tungsten copper electrode material
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CN103045885B (en) * 2012-12-27 2014-08-20 中南大学 Preparation method for high-density fine grain tungsten copper alloy
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CN104164579B (en) * 2014-07-28 2016-05-18 四川大学 Multicomponent alloy based on tungsten-potassium-sodium alloy and preparation method thereof
CN104593626B (en) * 2015-01-07 2016-08-24 陕西理工学院 Ni-Fe base high temperature coheres the preparation method of phase cemented carbide
CN104588655A (en) * 2015-01-13 2015-05-06 马鞍山市兴隆铸造有限公司 Preparation technology for high-strength high-conductivity copper alloy guide lines
CN105057680B (en) * 2015-07-29 2018-03-27 昆山德泰新材料科技有限公司 A kind of preparation method of mechanical alloying copper-tungsten powder
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CN105734318A (en) * 2016-04-21 2016-07-06 长沙微纳坤宸新材料有限公司 Method for preparing nano-gradient composite W-Cu material
CN106282714A (en) * 2016-09-23 2017-01-04 西安理工大学 A kind of preparation method of self-lubricating copper tungsten material
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CN109852861B (en) * 2019-02-28 2020-07-03 北京工业大学 Low-temperature rapid preparation method of high-density nanocrystalline tungsten-copper-based bulk composite material
CN112391565A (en) * 2020-11-30 2021-02-23 湖南航天磁电有限责任公司 Preparation method of ZrC dispersion strengthened tungsten-copper composite material
CN113151723A (en) * 2021-04-10 2021-07-23 广州市华司特合金制品有限公司 Tungsten-copper alloy material applied to products in 5G field and preparation method thereof
CN112975307B (en) * 2021-05-11 2021-07-30 陕西斯瑞新材料股份有限公司 Method for improving brazing strength of tungsten-copper part
CN116275017A (en) * 2023-02-25 2023-06-23 湖南顶立科技股份有限公司 Tungsten copper powder for additive manufacturing, preparation method and tungsten copper component

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