CN1544673A - Process for preparing W-Cu alloy by mechanical activation and chemical activation method - Google Patents
Process for preparing W-Cu alloy by mechanical activation and chemical activation method Download PDFInfo
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- CN1544673A CN1544673A CNA200310113507XA CN200310113507A CN1544673A CN 1544673 A CN1544673 A CN 1544673A CN A200310113507X A CNA200310113507X A CN A200310113507XA CN 200310113507 A CN200310113507 A CN 200310113507A CN 1544673 A CN1544673 A CN 1544673A
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Abstract
The invention provides a technique of preparing W-Cu alloy by mechanical and chemical activating methods, and its technical characteristic: the mass ratio of W powder to Cu powder is (95-60) : (5-40); using inert gas as protective gas to make high-energy ball milling; adopting high-energy ball milling for 2-50 hours; adding in 0.01%-0.5% activating element before forming; forming and sintering to obtain W-Cu alloy. Its advantages: the mechanical activating technique can regulate tissue and structure of W-Cu alloy, break through limitation of traditional techniques and expands the alloy component range; promotes W solubility in Cu, and provides beneficial conditions for liquid-phase sintering and compacting; further fines W/Cu crystal particles in mechanical activation, enhances property of W-Cu alloy; it has the characters of concise preparing technique, easy operation, simple device, and low cost, suitable to industrialized popularization.
Description
Technical field
The invention belongs to the powder metallurgy preparing technical field, particularly provide a kind of method of using mechanical activation and chemical activation to prepare the method for W-Cu alloy.
Background technology
The W-Cu alloy has good heat conductivility, and the programmable coefficient of expansion and arc ablation resistance performance are commonly used for the contact material and the electrode materials of electrical alloy, comprise each electric appliances, high speed steering switch, oil circulation current breaker etc.Since the eighties, the W-Cu alloy is chosen as electronic package material again, with the stupalith soldering together, can not only guarantee heat coupling, be again good passage of heat simultaneously, therefore can be used as the heat sink substrate of CPU, IC, the contour air-tight packaging device of solid state microwave pipe.
The preparation method commonly used of W-Cu alloy has: the infiltration method, ultra-high voltage solidifies, oxide compound coreduction sintering process and mechanical activation etc.The infiltration method is meant the briquet that earlier the W powder is pressed into certain density, arrives certain density through the high temperature sintering post shrinkage, and then Cu is penetrated in the skeleton of W under being higher than the temperature of its fusing point, thereby makes the W-Cu alloy.Because the hardness ratio of tungsten powder is higher, and then compactibility is lower, so add the copper powder of 1-2.5% usually in advance at the formative stage of tungsten powder.General using infiltration method can obtain the W-Cu alloy of higher relative density, but need carry out strict control to sintering process.Ultra-high voltage solidifies and can obtain relative density up to 99% W-Cu alloy, but microtexture shows Cu phase skewness, and there is overflowing of copper on the surface, and individual areas also has the phenomenon of grain growth.Oxide powder coreduction sintering is meant WO
3With the roasting formation CuWO in air of CuO mixed powder elder generation
4, then at H
2Middle reduction, that is roasting-reduction method.The oxide powder of tungsten and copper is carried out the coreduction sintering, in solid phase and liquid phase sintering process, all present the intensive densification, and then can obtain relative density and surpass 99% W-Cu alloy.Mechanical alloying method (Mechanical Alloying, be called for short MA) adopt high-energy ball milling processing tungsten, copper powder to make the thermodynamics and kinetics performance of powder systems have the feature that departs from equilibrium state, thereby improve the sintering character of powder, finally obtain high performance W-Cu alloy.
Mechanical alloying is that the American I NCO Benjamin of company in 1970 strengthens the type material preparation technology that Ni base alloy is succeeded in developing for the preparation oxide particle dispersion.Nineteen eighty-three Koch etc. utilize the MA method to form Ni with the pure element powder first
60Nb
40Amorphous powdered alloy, thus propose and might prepare bulk amorphous material with the compacting sintering of the non-crystalline flour of MA, and the research of Koch etc. makes the research of mechanical alloying enter into a new developmental stage.Subsequently, countries in the world material supplier author studies MA and has poured into great enthusiasm, and the MA method is synthesized novel material, and the MA method is newly used, and the mechanism of MA method, and the new report of technical study continues to bring out.At present, the range of application of mechanical alloying expands to the every field of investigation of materials day by day.
Mechanical alloying is to pass through high-energy ball milling, the powder of desiring alloying is hunted down in frequent collision process, intensive viscous deformation, cold welding formation composite powder take place, this composite powder is cracked because of work hardening again, and seam very easily takes place again under the effect of mechanical force the fresh atomic surface that cracked back powder exposes.So powder is by constantly repeating cold welding, cracked, the process of seam again, and it organizes continuous refinement, finally reaches atom level and mixes and realize alloying.Owing in the high-energy ball milling process, produce a large amount of strain, defective and nano level microtexture, thereby make material away from equilibrium state, make ma process be different from common solid state reaction process, can obtain the special heterogeneous microstructure that other technology is difficult to obtain.The mechanical alloying technology has enlarged the performance range of material, and the tissue of material, controllable structure; Broken through the limitation of fusion casting and flash set technology, expanded the alloy ingredient scope, brought out solid-state phase changes, can prepare accurate crystalline substance, amorphous material and a series of nanocrystalline material and satiety and close metastable materials such as sosoloid.
It is generally acknowledged that powder produces in ma process physics and chemical transformation have: (1) powder particle refinement also produces unsalted surface, interface.The powder energy has been improved at the surface, the interface that increase, and atom is active big on the high-energy of fine powder and the fresh interface, and foreign peoples's material atom mixes mutually, boning has system to be different from the partial potential of equilibrium state.(2) atomic diffusion is easier carries out.Mechanical force makes particle deformation, cold welding, fracture, causes partial temperature rise, and the temperature rising can increase spread coefficient; On the other hand, the interface of powder Forced Mixing, adhesion and interatomic distance is in conjunction with all making foreign atom that quick mutual diffusion takes place.(3) powder strong deformation cold welding, cold working hardening, embrittlement, fracture make lattice distortion and store lot of energy; Simultaneously, microdefects such as room, dislocation are bred in a large number, have reduced the thermodynamic stability of powder systems.This just makes that the thermodynamics and kinetics process of mechanical alloying is different with conventional solid state reaction, and its special mechanism is arranged.
Think that at present the mechanism that exists has in ma process: (1) vitrifying mechanism; (2) supersaturated solid solution forms mechanism; (3) nanocrystalline formation mechanism; (4) reaction ball milling mechanism.
Summary of the invention
The object of the present invention is to provide a kind of method of using mechanical activation and chemical activation to prepare the method for W-Cu alloy.Make the processing condition simple economy, the W-Cu alloy product superior performance of preparing is suitable for industrialization promotion.
Technology of the present invention is: with tungsten powder and copper powder by (95～60): (5～40) quality is packed into after than uniform mixing in the ball grinder of the high energy ball mill that cleaned, with inert gas as protective gas ball milling 2～100 hours totally.Add a certain amount of magnesium-yttrium-transition metal salt in the W-Cu composite powder behind ball milling, as NiSO
4, FeSO
4, CoSO
4The aqueous solution, make the mass percent of magnesium-yttrium-transition metal account for 0.01～0.5% of total system, natural then airing.Add 1-7% caking agent (glycerine, alcohol etc.) in the W-Cu composite powder behind airing, grind and made powder and caking agent uniform mixing in 10-20 minute.Take by weighing the 3-5g mixed powder at every turn and pack in the compacting tool set, adopt unidirectional or two-way compacting, pressing pressure is 100～500MPa, and in 1～20 second of pressurize, mold removal is deviate from pressed compact then.Adopt when normal pressure-sintered, pressed compact is placed on burns in the boat, and imbed AL
2O
3In the powder.Load then and burn boat, the sealing sintering oven feeds H
2, carry out detonating experiment after the combustion.Light H
2, logical water coolant powers up intensification, and heats up by regulating voltage control, and voltage rising speed is 1～20V/10min.When temperature rises to 1100～1400 ℃ of sintering temperatures, be incubated 1～20 minute.Insulation finishes the back with the 10-40V/10min step-down, afterwards outage.When being cooled to 200 ℃, close water coolant and stop H
2, come out of the stove after naturally cooling to room temperature.
High-energy ball milling of the present invention can adopt vibromill, agitating ball mill, planetary ball mill; During high-energy ball milling, ratio of grinding media to material is (5～50): 1, and charge amount is 30～50%; The integrating sphere time consuming is 2～50 hours.Add the solution of magnesium-yttrium-transition metal salt, make the mass percent of magnesium-yttrium-transition metal account for 0.01～0.5% of W-Cu powdered alloy.The mode that is shaped can adopt unidirectional or two-way press forming, hydrostatic pressing, injection forming, roll forming, extrusion molding, warm-pressing formation, powder forging etc.When adopting unidirectional or two-way press forming, pressing pressure is 100～500MPa, 1～20 second of pressurize.Sintering can adopt normal pressure-sintered (reducing gas protection), vacuum sintering, SPS sintering, forge hot or isostatic sintering.
The invention has the advantages that:
1. mechanical activating technique can be regulated W-Cu alloy organizing, structure, has broken through the limitation of traditional fusion casting and flash set technology, has expanded alloy component range.
2. adopt mechanical activation and chemical activation to promote the solubleness of W in Cu, for liquid phase sintering and densification provide favourable condition.
In the mechanical activation process further refinement tungsten copper crystal grain, finally improved the performance of W-Cu alloy.
3. preparation technology of the present invention is simple, easy handling, equipment are simple, with low cost.
Description of drawings
Fig. 1 is a kind of sintering process graphic representation of the present invention, and X-coordinate t is the time, and ordinate zou T is a temperature.T
0＝1613
0K
Embodiment
Example 1: mechanical activation W-15wt%Cu powder is normal pressure-sintered down at 1340 ℃.
Raw material: W powder, 59.5g, granularity 1.5 μ m; The Cu powder, 10.5g, granularity is less than 74.0 μ m.
Powder process:
(1) dehydrated alcohol that takes by weighing 20-30g is poured in the ball grinder, sealing back ball milling 10-20 minute.Open ball grinder then, pour out dirty liquid, clean repeatedly several times with dehydrated alcohol again, with jar and ball oven dry.
(2) medical balance takes by weighing tungsten (59.5g), copper (10.5g) powder of certain mass respectively, pours into behind the uniform mixing in the ball grinder, seals up cover, is fixed in then on the ball mill, and the logical argon shield atmosphere that goes up is carried out the high energy vibration ball milling.
(3) after 50 minutes, shut down heat radiation 10 minutes at ball milling.Powder is shut down and is taken out in total integrating sphere time consuming after 28 hours.
Be shaped:
(1) for the metal Ni that introduces about 0.2wt% as activating element, earlier with a certain amount of Ni
2SO
4The aqueous solution soaking ball milling after the W-Cu composite powder, dry;
(2) the W-Cu composite powder after will drying is poured in the mortar porphyrize into.Adding 3g glycerine, 4g alcohol mix as granule agglomerant.Ground 10-20 minute, it is comparatively even that powder is mixed with binding agent;
(3) take by weighing the 4g mixed powder, it is placed mould, to be pressed.The experiment mould therefor is the cylindrical punching block of φ 8mm;
(4) mould (behind the charged) is placed on the press, carry out unidirectional compacting.The pressing pressure that powder is subjected to is 300MPa, keep-ups pressure for 5 seconds;
(5) compacting finishes the back mold removal, and pressed compact is ejected from mould, preserves with to be sintered or its usefulness.
Normal pressure-sintered:
(1) adopts the sintering boat, contain the Al that goes up calcination in the boat
2O
3Powder.Pressed compact is imbedded Al
2O
3In the powder.
(2) extract the boiler tube plug, boat is pushed soaking zone, boiler tube middle part, make it near thermopair.Boiler tube plug beyond the Great Wall then.Open the gas circuit valve, feed the dry hydrogen of crossing.After 20 minutes, carry out the detonation test, guarantee the purity of hydrogen atmosphere in boiler tube, the furnace wall, prevent mishap.
(3) light hydrogen at the place, air outlet, open water coolant, closing a main switch begins to heat up.Heat-up rate is difficult for too fast, heats up by regulating voltage (transformer control), and the control rate of rise is about 10V/10min; With W-Re 3-W-Re 25 thermocouple temperature measurements.After temperature reaches 1340 ℃ of preset values, be incubated, soaking time is 10 minutes.
(4) after insulation finishes, begin cooling, with the speed step-down of 20V/10min, outage after 1 hour.When stove is as cold as below 200 ℃ then, closes water coolant and stop ventilation.To be cooledly can take out sample to room temperature.The sintering process curve as shown in Figure 1.
The W-Cu alloy density 15.886g/cm of preparation
3(relative density 96.7%), thermal expansivity 7.18ppm/ ℃, thermal conductivity 182.00W/mK.
Example 2: mechanical activation W-20wt%Cu powder is normal pressure-sintered down at 1340 ℃.
Raw material: W powder, 56.0g, granularity 1.5 μ m; The Cu powder, 14.0g, granularity is less than 74.0 μ m.
Powder process:
(1) dehydrated alcohol that takes by weighing 20-30g is poured in the ball grinder, sealing back ball milling 10-20 minute.Open ball grinder then, pour out dirty liquid, clean repeatedly several times with dehydrated alcohol again, with jar and ball oven dry.
(2) medical balance takes by weighing tungsten (56.0g), copper (14.0g) powder of certain mass respectively, pours into behind the uniform mixing in the ball grinder, seals up cover, is fixed in then on the ball mill, and the logical argon shield atmosphere that goes up is carried out the high energy vibration ball milling.
(3) after 50 minutes, shut down heat radiation 10 minutes at ball milling.Powder is shut down and is taken out in total integrating sphere time consuming after 28 hours.
Be shaped:
(1) for the metal Ni that introduces about 0.2wt% as activating element, earlier with a certain amount of Ni
2SO
4The aqueous solution soaking ball milling after the W-Cu composite powder, dry;
(2) the W-Cu composite powder after will drying is poured in the mortar porphyrize into.Adding 3g glycerine, 4g alcohol mix as granule agglomerant.Ground 10-20 minute, it is comparatively even that powder is mixed with binding agent;
(3) take by weighing the 4g mixed powder, it is placed mould, to be pressed.The experiment mould therefor is the cylindrical punching block of φ 8mm;
(4) mould (behind the charged) is placed on the press, carry out unidirectional compacting.The pressing pressure that powder is subjected to is 300MPa, keep-ups pressure for 5 seconds;
(5) compacting finishes the back mold removal, and pressed compact is ejected from mould, preserves with to be sintered or its usefulness.
Normal pressure-sintered:
(1) adopts the sintering boat, contain the Al that goes up calcination in the boat
2O
3Powder.Pressed compact is imbedded Al
2O
3In the powder.
(2) extract the boiler tube plug, boat is pushed soaking zone, boiler tube middle part, make it near thermopair.Boiler tube plug beyond the Great Wall then.Open the gas circuit valve, feed the dry hydrogen of crossing.After 20 minutes, carry out the detonation test, guarantee the purity of hydrogen atmosphere in boiler tube, the furnace wall, prevent mishap.
(3) light hydrogen at the place, air outlet, open water coolant, closing a main switch begins to heat up.Heat-up rate is difficult for too fast, heats up by regulating voltage (transformer control), and the control rate of rise is about 10V/10min; With W-Re 3-W-Re 25 thermocouple temperature measurements.After temperature reaches 1340 ℃ of preset values, be incubated, soaking time is 10 minutes.
(4) after insulation finishes, begin cooling, with the speed step-down of 30V/10min, outage after 1 hour.When stove is as cold as below 200 ℃ then, closes water coolant and stop ventilation.To be cooledly can take out sample to room temperature.
The W-Cu alloy density 15.148g/cm of preparation
3(relative density 96.6%), thermal expansivity 7.19ppm/ ℃, thermal conductivity 181.97W/mK.
Example 3: mechanical activation W-15wt%Cu powder is at 1200 ℃ of following SPS sintering.
Raw material: W powder, 59.5g, granularity 1.5 μ m; The Cu powder, 10.5g, granularity is less than 74.0 μ m.
Powder process:
(1) dehydrated alcohol that takes by weighing 20-30g is poured in the ball grinder, sealing back ball milling 10-20 minute.Open ball grinder then, pour out dirty liquid, clean repeatedly several times with dehydrated alcohol again, with jar and ball oven dry.
(2) medical balance takes by weighing tungsten (59.5g), copper (10.5g) powder of certain mass respectively, pours into behind the uniform mixing in the ball grinder, seals up cover, is fixed in then on the ball mill, and the logical argon shield atmosphere that goes up is carried out the high energy vibration ball milling.
(3) after 50 minutes, shut down heat radiation 10 minutes at ball milling.Powder is shut down and is taken out in total integrating sphere time consuming after 28 hours.
The SPS sintering:
(1) for the metal Ni that introduces about 0.2wt% as activating element, earlier with a certain amount of Ni
2SO
4The aqueous solution soaking ball milling after the W-Cu composite powder, dry;
(2) the W-Cu composite powder after will drying is poured in the mortar porphyrize into.Adding 3g glycerine, 4g alcohol mix as granule agglomerant.Ground 10-20 minute, it is comparatively even that powder is mixed with binding agent;
(3) take by weighing the 5g mixed powder at every turn, it is placed sintering mold, then mould is inserted in the sintering oven by SPS working specification sintering 5 minutes;
The W-Cu alloy density 15.632g/cm of preparation
3(relative density 95.03%), thermal expansivity 7.20ppm/ ℃, thermal conductivity 182.16W/mK.
Claims (6)
1, a kind of method of using mechanical activation and chemical activation prepares the method for W-Cu alloy, it is characterized in that: with tungsten powder and copper powder by (95～60): (5～40) quality is packed into after than uniform mixing in the ball grinder of the high energy ball mill that cleaned, carries out ball milling with inert gas as protective gas; The solution that adds magnesium-yttrium-transition metal salt in the W-Cu composite powder behind ball milling, natural air drying then; Add 1～7g glycerine, alcohol caking agent in the W-Cu composite powder behind airing, grind uniform mixing; Take by weighing mixed powder and pack into and be shaped in the compacting tool set, pressed compact is placed on burns in the boat then, and imbed AL
2O
3In the powder; Load then and burn boat, the sealing sintering oven feeds H
2, carry out detonating experiment after the combustion, light H
2, logical water coolant powers up intensification, and heats up by regulating voltage control, and voltage rising speed is 1～20V/10min; When temperature rises to 1100～1400 ℃ of sintering temperatures, be incubated 1～20 minute; Insulation finishes the back with the 10-40V/10min step-down, afterwards outage; When being cooled to 200 ℃, close water coolant and stop H
2, naturally cool to the shaping of coming out of the stove after the room temperature, obtain the W-Cu alloy.
2, in accordance with the method for claim 1, it is characterized in that: described high-energy ball milling can adopt vibromill, agitating ball mill, planetary ball mill; During high-energy ball milling, ratio of grinding media to material is (5～50): 1, and charge amount is 30～50%; The integrating sphere time consuming is 2～50 hours.
3, in accordance with the method for claim 1, it is characterized in that: add the solution of magnesium-yttrium-transition metal salt, make the mass percent of magnesium-yttrium-transition metal account for 0.01～0.5% of W-Cu powdered alloy.
4, in accordance with the method for claim 1, it is characterized in that: the mode of shaping adopts unidirectional or two-way press forming, hydrostatic pressing, injection forming, roll forming, extrusion molding, warm-pressing formation, powder forging.
5, according to claim 1 or 4 described methods, it is characterized in that: when adopting unidirectional or two-way press forming, pressing pressure is 100～500MPa, 1～20 second of pressurize
6, in accordance with the method for claim 1, it is characterized in that: sintering adopts normal pressure-sintered, vacuum sintering, SPS sintering, forge hot or isostatic sintering.
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| 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 |
| CN105256159A (en) * | 2015-10-22 | 2016-01-20 | 清华大学 | Tungsten and copper composite material and application thereof |
| CN105364075A (en) * | 2014-08-29 | 2016-03-02 | 优美科科技材料（苏州）有限公司 | Manufacturing method for long-bar-shaped fine-grain copper-tungsten contact |
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2003
- 2003-11-13 CN CN 200310113507 patent/CN1236090C/en not_active Expired - Fee Related
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| 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 |
| CN105256159A (en) * | 2015-10-22 | 2016-01-20 | 清华大学 | Tungsten and copper composite material and application thereof |
| CN105671411A (en) * | 2016-01-24 | 2016-06-15 | 中南大学 | Carbide-reinforced iron base composite material and powder metallurgy in-situ synthesis method thereof |
| CN106148794B (en) * | 2016-08-19 | 2017-11-28 | 北京尚华扬电子技术开发有限公司 | A kind of copper-tungsten of dopen Nano iron powder and preparation method thereof |
| CN106148794A (en) * | 2016-08-19 | 2016-11-23 | 北京尚华扬电子技术开发有限公司 | A kind of copper-tungsten of dopen Nano iron powder and preparation method thereof |
| CN109355541A (en) * | 2018-12-17 | 2019-02-19 | 东北大学 | A method of preparing high density tungsten copper alloy |
| CN109355541B (en) * | 2018-12-17 | 2020-01-17 | 东北大学 | Method for preparing high-density tungsten-copper alloy |
| CN112687787A (en) * | 2020-12-29 | 2021-04-20 | 南昌航空大学 | Manufacturing method of polycrystal series LED copper alloy bonding wire |
| CN112687787B (en) * | 2020-12-29 | 2022-08-16 | 南昌航空大学 | Manufacturing method of polycrystal series LED copper alloy bonding wire |
| CN114932222A (en) * | 2022-06-17 | 2022-08-23 | 合肥工业大学智能制造技术研究院 | Method for improving density of tungsten-copper alloy |
| CN114932222B (en) * | 2022-06-17 | 2023-11-07 | 合肥工业大学智能制造技术研究院 | Method for improving density of tungsten-copper alloy |
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