CN1539579A - Method for preparing high diffusive composite powder of wolfram steel - Google Patents
Method for preparing high diffusive composite powder of wolfram steel Download PDFInfo
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- CN1539579A CN1539579A CNA03118328XA CN03118328A CN1539579A CN 1539579 A CN1539579 A CN 1539579A CN A03118328X A CNA03118328X A CN A03118328XA CN 03118328 A CN03118328 A CN 03118328A CN 1539579 A CN1539579 A CN 1539579A
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Abstract
A high-dispersity composite W-Cu particles, that is, Cu phase is wrapped by W phase, is prepared through preparing the composite oxide of W and Cu, high-energy ball grinding for co-reduction, and sintering. Its advantages are high density (99%) and high thermal and electric conductivities.
Description
[technical field] the present invention relates to the high heat conduction of a kind of preparation near theoretical density, the method of the tungsten-copper composite material of low bulk, this matrix material are mainly used in large-scale integrated circuit and the HIGH-POWERED MICROWAVES device as substrate, abaculus, web member and heat dissipation element.
[background technology] tungsten-copper composite material produce electrical contact and as thermal control element such as heat sink, heat abstractor in obtained using widely.The high density tungsten carbon/carbon-copper composite material can make the finished product except having certain mechanical property, and more importantly being can increase the thermal conductivity of product to adapt to as heat sink material.The main method for preparing nearly fully dense tungsten-copper composite material comprises: infiltration method, pressure sintering, Aeroform method and other technology such as lqiuid phase sintering method and mechanical alloying method.
Infiltration method is the traditional method of preparation tungsten-copper composite material, because infiltration needs the hole of connection in the base substrate, so general final material internal has the residual porosity rate of 1%-3%, finally influences every performance of product.The lqiuid phase sintering method of tungsten-copper composite material generally need add sintering activator, to strengthen the mutual solubility between the tungsten copper, this sintering process can make the final sintered density of material reach near complete fine and close, and still Fe, the Ni that adds, Co etc. have very adverse influence to the thermal conductivity of final material; It is long that mechanical alloying method also has technology, and shortcomings such as foreign matter content height have certain limitation to producing high heat conduction tungsten-copper composite material.Other method such as pressure sintering, Aeroform method are higher to equipment requirements, and the product cost costliness generally only limits to the research of scientific research aspect.Usual way prepares tungsten-copper composite material and also has tungsten copper two-phase skewness and cause degradation shortcoming under the material mechanical performance in addition.The sintering general requirement of tungsten-copper composite material is carried out being higher than under the copper fusing point (1084 ℃), and elevated temperature helps the sintering densification process, but (greater than 1300 ℃ time) can cause the volatilization of copper phase under the very high situation of temperature, is difficult to the composition of control material.Also have by coated layer of copper on tungsten particle and reach the homogeneity that increases tungsten copper sintering phase, but these coat copper is volatilization very easily in the agglomerating process or scatters and disappears, so the loss that reduces the copper phase in the agglomerating process is very favorable to the performance of end article as far as possible.
[summary of the invention] the present invention seeks to prepare a kind of ultra-fine disperse W-Cu composite powder with high sintering character, and each particle is that wherein tungsten exists with the form that coats the copper phase by copper phase and tungsten phase composite in this body of powder.
The present invention mainly comprises the preparation of tungsten copper composite oxides precursor, the coreduction of high-energy ball milling oxide powder, the steps such as sintering of W-Cu composite powder, and concrete technical process is as follows:
1. the preparation of tungsten copper composite oxides precursor
Adopt reduction tungsten powder or other comparatively purified tungsten powder, electrolytic copper or copper reduction are raw material, wherein copper content be changed to 2wt%-30wt%, raw material is the tungsten powder and the copper powder of any granularity shape in theory, as long as the purity of powder does not influence the heat-conductivity conducting performance of the finished product.Tungsten powder and the copper powder ratio according to W-2-30Cu wt% is mixed in mixer, take in the stove in air atmosphere 650 ℃ of-700 ℃ of oxidations, obtain by CuWO horse
4And WO
3The mixture of forming.Mixed powder after the oxidation is ball milling 0-12h in high energy ball mill, and ball-milling medium adopts air or alcohol, and different ball-milling mediums see Table 1, table 2 to the influence of oxide powder granularity and specific surface.When alcohol as the ball milling agent than the dry grinding effect more obvious.
The different ball milling agent of table 1 ball milling rear oxidation thing powder size changes (W-20Cu (wt%))
Ball milling time (h) alcohol air
0???????????????3.99?????????3.99
4???????????????1.28?????????1.71
8???????????????0.93?????????1.65
12??????????????0.33?????????1.8
The different ball milling agent of table 2 ball milling rear oxidation thing specific surface area changes (W-20Cu (wt%))
Ball milling time (h) alcohol air
0???????????????0.33?????????0.33
4???????????????5.32?????????0.71
8???????????????10.45????????0.8
12??????????????18.98????????0.9
2. the coreduction of high-energy ball milling oxide powder
Powder is at H
2Atmosphere reduction, reduction temperature is 650 ℃-750 ℃, the powder after reduction presents irregularly shaped, and is to exist with the form that tungsten coats the copper phase mutually.Composite powder granularity, oxygen level are as shown in table 3 with the variation of oxide powder ball milling time.
Table 3 composite powder granularity, oxygen level are with the variation (alcohol ball milling 10h, 700 ℃ of reduction temperatures) of oxide powder ball milling time
(W-20Cu(wt％))
| The ball milling time (h) | Composite powder granularity (μ m) | Specific surface m 2/g | Composite powder oxygen level ppm |
| ????0 | ??????1.51 | ??????0.65 | ?????????450 |
| ????4 | ??????0.82 | ??????2.35 | ?????????300 |
| ????8 | ??????0.50 | ??????8.56 | ?????????250 |
| ????12 | ??????0.47 | ??????12.35 | ?????????200 |
3. the sintering of W-Cu composite powder
The powder repressed pressed compact that gets the 50%-55% relative density in reduction back is at 1150 ℃ of-1600 ℃ of sintering.The present invention reduces heat-up rate in the solid state sintering stage and can obtain high sintered density and almost can eliminate overflowing of copper fully.Concrete final sintering temperature changes with the variation of copper content in the composite powder.As shown in table 4 is its sintering temperature and final sintered density.
The composite powder optimal sintering temperature of table 4 different Cu content and final densities (oxide compound alcohol wet-milling 10h, sintering time 1h)
| Copper content wt% | Sintering temperature ℃ | Final sintering relative density % |
| ????20-25 | ????1150-1200 | ??＞99.4 |
| ????15-20 | ????1200-1250 | ??＞99.1 |
| ????10-15 | ????1250-1300 | ??＞98.6 |
| ????5-10 | ????1300-1350 | ??＞98.4 |
| ????2-5 | ????1350-1600 | ??＞98.1 |
Each particle is by copper phase and tungsten phase composite in the ultra-fine disperse W-Cu composite powder of the present invention's preparation, wherein tungsten exists with the form that coats the copper phase, this tungsten coating copper particulate body of powder has uniform tungsten and distributes mutually with copper mutually behind compacting sintering, in sintering, can reduce the volatilization and the loss of copper phase, can reach near fully dense tungsten copper composite product with high heat-conductivity conducting performance.The present invention improves powder sintered density to obtain the final performance of product in the content of various impurity in reducing the finished product.Oxide powder is carried out high-energy ball milling in short-term, and rapid refinement oxide powder granularity is prepared the superfine W-Cu cladding powder of high dispersive, has uniform tungsten through sintering and distributes mutually with copper mutually, and can reduce the volatilization and the loss of copper phase in sintering.The final sintered density of goods is not less than 99% of theoretical density.This powder compact can reach behind sintering near fully dense tungsten-copper composition with high heat-conductivity conducting performance.Another advantage of the present invention is that the tungsten copper-clad powder that is generated can be avoided the volatilization of copper and leakage in high-temperature liquid-phase sintering process subsequently and the composition organizational controls that causes is inaccurate, avoids the reduction of the finished product performance.
[embodiment]
Embodiment 1: composition W-5wt%Cu, and 650 ℃ of oxidizing temperatures, the ball milling time 0,4,8,12h (alcohol), 700 ℃ of reduction temperatures, 1350 ℃ of sintering temperatures, the time is 60min, and each performance of sintered sample sees Table 5:
Table 5 tungsten-copper composite material performance
| The ball milling time | ????0 | ????4 | ????8 | ????12 |
| Sintered density g/cm 3-relative theory density T D% | ????17.34-95.0 | ????17.43-95.5 | ????17.52-96 | ????17.55- ????96.2 |
| Specific conductivity (%IACS) | ????30 | ????31.5 | ????32 | ????32 |
| Thermal conductivity (W/m.K) | ????155.6 | ????165.3 | ????171.2 | ????171.2 |
| 50 ℃ of thermal expansivity CTE at (ppm/ ℃) | ????5.1 | ????5.1 | ????5.1 | ????5.1 |
| Young's modulus (GPa) | ????285.3 | ????298.4 | ????309.3 | ????312.5 |
| Shearing modulus (GPa) | ????112.3 | ????118.5 | ????121.2 | ????122.5 |
| Hardness (RC) | ????33.8 | ????34.6 | ????34.6 | ????34.6 |
| Cross-breaking strength (Mpa) | ????980 | ????1000 | ????1100 | ????1150 |
Embodiment 2: composition is W-5wt%Cu, 400 ℃ of W-20wt%Cu oxidizing temperatures, and ball milling time 8h (alcohol), 1350 ℃ of sintering temperatures, each performance of 15 ℃/min of heat-up rate sintered sample sees Table 6.
Table 6 tungsten-copper composite material performance
| W-5wt％Cu | ?W-20wt％Cu | |
| Sintered density g/cm 3-relative theory density T D% | 16.35-89.6 | ?14.47-92.3 |
| Specific conductivity (%IACS) | 25 | ?38 |
| Thermal conductivity (W/m.K) | 125.2 | ?175.3 |
| 50 ℃ of thermal expansivity CTE (ppm/ ℃) | 5.3 | ?7.2 |
| Young's modulus (GPa) | 256.3 | ?185.6 |
| Shearing modulus (GPa) | 85.6 | ?68.3 |
| Hardness (RC) | 30.2 | ?19.5 |
| Cross-breaking strength (Mpa) | 650 | ?1325 |
Embodiment 3: composition W-10wt%Cu, and 650 ℃ of oxidizing temperatures, the ball milling time 0,4,8,12h (alcohol is medium), 700 ℃ of reduction temperatures, 1300 ℃ of sintering temperatures, each performance of sintered sample sees Table 7:
Table 7 tungsten-copper composite material performance
| The ball milling time | ????0 | ????4 | ????8 | ????12 |
| Sintered density g/cm 3-relative theory density T D% | ????16.58-95.8 | ????16.95-98 | ????17.1-98.8- | ????17.2-99.2 |
| Specific conductivity (%IACS) | ????33 | ????38 | ????41 | ????45 |
| Thermal conductivity (W/m.K) | ????170.5 | ????188.1 | ????198.5 | ????202.3 |
| 50 ℃ of thermal expansivity CTE at (ppm/ ℃) | ????5.9 | ????5.8 | ????5.8 | ????5.8 |
| Young's modulus (GPa) | ????287.6 | ????291.8 | ????305.4 | ????315.1 |
| Shearing modulus (GPa) | ????109.5 | ????113.4 | ????123.5 | ????131.7 |
| Hardness (RC) | ????33.6 | ????34.5 | ????34.5 | ????34.5 |
| Cross-breaking strength (MPa) | ????1200 | ????1250 | ????1300 | ????1300 |
Embodiment 4:W-20wt%Cu, 650 ℃ of oxidizing temperatures, the ball milling time 0,4,8,12h (alcohol is medium), 700 ℃ of reduction temperatures, 1250 ℃ of sintering temperatures, each performance of sintered sample sees Table 8:
Table 8 tungsten-copper composite material performance
| The ball milling time | ????0 | ????2 | ????4 | ????8 | ????10 |
| Sintered density g/cm 3-relative theory density T D% | ????15.54-92.5 | ????14.99-95.6 | ????16.58-98.7 | ????16.71-99.5 | ????16.75-99.7 |
| Specific conductivity (%IACS) | ????44 | ????46 | ????48 | ????50 | ????51 |
| Thermal conductivity (W/m.K) | ????190.5 | ????210.4 | ????215.8 | ????220.3 | ????220.5 |
| 50 ℃ of thermal expansivity CTE at (ppm/ ℃) | ????7.1 | ????7.0 | ????7.0 | ????7.0 | ????7.0 |
| Young's modulus (GPa) | ????195.4 | ????210.9 | ????220.8 | ????225.3 | ????230.6 |
| Shearing modulus (GPa) | ????75.8 | ????81.7 | ????90.5 | ????90.9 | ????91.0 |
| Hardness (RC) | ????19.0 | ????21.0 | ????22.5 | ????22.5 | ????22.6 |
| Cross-breaking strength (MPa) | ????1400 | ????1460 | ????1500 | ????1520 | ????1550 |
Embodiment 5:W-20wt%Cu, 650 ℃ of oxidizing temperatures, the ball milling time 0,4,8,12h (alcohol is medium), 800 ℃ of reduction temperatures, 1250 ℃ of sintering temperatures, each performance of sintered sample sees Table 9:
Table 9 tungsten-copper composite material performance
| The ball milling time | ????0 | ????4 | ????8 | ????12 |
| Sintered density g/cm 3-relative theory density T D % | ????15.88-94.5 | ????16.43-97.8 | ????16.56-98.6 | ????16.65-99.1 |
| Specific conductivity (%IACS) | ????45 | ????45 | ????46 | ????49 |
| Thermal conductivity (W/m.K) | ????201.5 | ????210.4 | ????212.6 | ????218.5 |
| 50 ℃ of thermal expansivity CTE at (ppm/ ℃) | ????7.1 | ????7.1 | ????7.1 | ????7.1 |
| Young's modulus (GPa) | ????205.6 | ????215.3 | ????220.0 | ????223.4 |
| Shearing modulus (GPa) | ????79.5 | ????86.4 | ????90.2 | ????90.6 |
| Hardness (RC) | ????20.2 | ????22.3 | ????22.6 | ????22.6 |
| Cross-breaking strength (MPa) | ????1460 | ????1480 | ????1500 | ????1530 |
Embodiment 6:W-20wt%Cu, 650 ℃ of oxidizing temperatures, the ball milling time 0,4,8,12h (dry grinding), 800 ℃ of reduction temperatures, 1250 ℃ of sintering temperatures, each performance of sintered sample sees Table 10:
Table 10 tungsten-copper composite material performance
| The ball milling time | ????0 | ????4 | ????8 | ????12 |
| Sintered density g/cm 3-relative theory density T D % | ????15.88-94.5 | ????16.33-97.2 | ????16.51-98.3 | ????16.60-98.8 |
| Specific conductivity (%IACS) | ????45 | ????45 | ????45 | ????48 |
| Thermal conductivity (W/m.K) | ????201.5 | ????208.3 | ????210.5 | ????215.3 |
| 50 ℃ of thermal expansivity CTE at (ppm/ ℃) | ????7.1 | ????7.1 | ????7.1 | ????7.1 |
| Young's modulus (GPa) | ????205.6 | ????210.5 | ????218.7 | ????220.5 |
| Shearing modulus (GPa) | ????79.5 | ????84.4 | ????88.8 | ????90.0 |
| Hardness (RC) | ????20.2 | ????21.8 | ????22.2 | ????22.4 |
| Cross-breaking strength (MPa) | ????1460 | ????1465 | ????1486 | ????1510 |
Claims (3)
1. the preparation method of high diffusive W-Cu composite powder, it is characterized in that: the present invention mainly comprises the preparation of tungsten copper composite oxides precursor, the coreduction of high-energy ball milling oxide powder, the steps such as sintering of W-Cu composite powder, concrete technical process is as follows:
A〉preparation of tungsten copper composite oxides precursor
Tungsten powder and copper powder are mixed in mixer according to W-2-30Cu wt%, take in the stove in air atmosphere 650 ℃ of-700 ℃ of oxidations, obtain by CuWO horse
4And WO
3The mixture of forming, the mixed powder after the oxidation is ball milling 0-12h in high energy ball mill;
B〉coreduction of high-energy ball milling oxide powder
Powder is at H behind the ball milling
2The atmosphere reduction, reduction temperature is 650 ℃-750 ℃;
C〉sintering of W-Cu composite powder
The powder repressed pressed compact that gets the 50%-55% relative density in reduction back is at 1150 ℃ of-1600 ℃ of sintering.
2. method according to claim 1 is characterized in that: used tungsten powder is reduction tungsten powder or other comparatively purified tungsten powder, and used copper powder is electrolytic copper or copper reduction.
3. method according to claim 1 is characterized in that: adopt alcohol as ball-milling medium.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101850420A (en) * | 2010-06-25 | 2010-10-06 | 西安理工大学 | Preparation method of tungsten-cladding-copper nanometer composite powder with controllable thickness of cladding coating |
| CN101628338B (en) * | 2009-08-07 | 2012-08-22 | 深圳市新宏泰粉末冶金有限公司 | Superfine iron-copper alloy powder and preparation method thereof |
| CN103981389A (en) * | 2014-05-15 | 2014-08-13 | 厦门理工学院 | Method for preparing tungsten-copper alloy by low-temperature sintering of tungsten skeleton |
| CN106756376A (en) * | 2016-11-24 | 2017-05-31 | 深圳市圆梦精密技术研究院 | tungsten-copper alloy and its processing method and application |
| CN108213762A (en) * | 2018-01-17 | 2018-06-29 | 宁国市顺鑫金属制品有限公司 | A kind of high rigidity mash welder soldering tip and preparation method thereof |
| CN112391551A (en) * | 2020-12-07 | 2021-02-23 | 西安稀有金属材料研究院有限公司 | Preparation method of biomedical titanium-copper alloy |
-
2003
- 2003-04-22 CN CNA03118328XA patent/CN1539579A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628338B (en) * | 2009-08-07 | 2012-08-22 | 深圳市新宏泰粉末冶金有限公司 | Superfine iron-copper alloy powder and preparation method thereof |
| CN101850420A (en) * | 2010-06-25 | 2010-10-06 | 西安理工大学 | Preparation method of tungsten-cladding-copper nanometer composite powder with controllable thickness of cladding coating |
| CN101850420B (en) * | 2010-06-25 | 2012-02-08 | 西安理工大学 | Preparation method of tungsten-cladding-copper nanometer composite powder with controllable thickness of cladding coating |
| CN103981389A (en) * | 2014-05-15 | 2014-08-13 | 厦门理工学院 | Method for preparing tungsten-copper alloy by low-temperature sintering of tungsten skeleton |
| CN103981389B (en) * | 2014-05-15 | 2016-06-15 | 厦门理工学院 | A kind of method that low-temperature sintering W skeleton prepares tungsten-copper alloy |
| CN106756376A (en) * | 2016-11-24 | 2017-05-31 | 深圳市圆梦精密技术研究院 | tungsten-copper alloy and its processing method and application |
| CN106756376B (en) * | 2016-11-24 | 2019-02-22 | 深圳市圆梦精密技术研究院 | Tungsten-copper alloy and its processing method and application |
| CN108213762A (en) * | 2018-01-17 | 2018-06-29 | 宁国市顺鑫金属制品有限公司 | A kind of high rigidity mash welder soldering tip and preparation method thereof |
| CN108213762B (en) * | 2018-01-17 | 2020-03-31 | 宁国市顺鑫金属制品有限公司 | Welding head for high-hardness spot welding machine and preparation method thereof |
| CN112391551A (en) * | 2020-12-07 | 2021-02-23 | 西安稀有金属材料研究院有限公司 | Preparation method of biomedical titanium-copper alloy |
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