CN104928551B - A kind of tungsten-copper composite material and preparation method thereof - Google Patents
A kind of tungsten-copper composite material and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of tungsten-copper composite material and preparation method thereof, specifically, this tungsten-copper composite material is made up of following raw material by weight: 60 68 parts of tungsten powders, 28 32 parts of copper powders, 13 parts of nikel powders, 13 parts of cobalt powders, 0.2 1 parts of metal-oxides, 80 100 parts of adhesives；Described metal-oxide at least one, the metal in described metal-oxide is aluminum, calcium, chromium, manganese, molybdenum, tantalum or rhenium.The compactness of this tungsten-copper composite material is high, thermal conductivity is high, thermal expansivity is little.The preparation method of this tungsten-copper composite material includes mixing, injection, defat, sintering and heat treatment process, and the method is suitable for large-scale industrial production, and the compactness of prepared product is high, thermal expansivity is little.
Description
Technical field
The present invention relates to a kind of tungsten-copper composite material and preparation method thereof.
Background technology
Tungsten-copper composite material is with a kind of two phase structure pseudo-alloy that tungsten, copper are main composition, is Metal Substrate
Composite.Owing to metallic copper and tungsten physical difference are relatively big, fusion casting therefore can not be used to produce, one
As use powder metallurgy technology produce.
Tungsten-copper composite material uniformity prepared by powder metallurgic method is bad, there is more space of closing, and consistency is led to
Often less than 98%, but by adding the activated sintering method of a small amount of nickel, mechanical alloying method or oxide for also
Former method is prepared ultra-fine, nanometer powder and can be improved sintering activity, thus improve the consistency of tungsten copper, molybdenum-copper.
But nickel activated sintering can make the conduction of material, heat conductivility significantly reduce, mechanical alloying introduces impurity and also can
Reduce conduct performance；Oxide co-reducing process prepares powder, and technical process is loaded down with trivial details, and production efficiency is low,
It is difficult to produce in batches.
Powder injection forming (PIM) is a kind of developing rapidly and up-and-coming new near-net-shape technique.It
Maximum feature be exactly mobility and the rheological characteristic utilizing organic binder, variously-shaped complexity, chi can be shaped
The powder metallurgy parts that very little precision is high and performance is high.
About the preparation method of tungsten-copper alloy, patent CN200610136919.9 discloses one and prepares tungsten copper conjunction
The method of gold, copper powder and tungsten powder are first carried out the molded rear sintering of hybrid guided mode, obtain tungsten-copper alloy bone by the method
Frame, then ooze copper by aluminium oxide landfill intensification, it is thus achieved that high copper content tungsten-copper alloy.Patent
CN200910259935.0 discloses the preparation method of a kind of nano tungsten-copper-rare earth composite powder, and the method uses molten
Glue-spray drying, high temperature moment decomposition technique, and by adding rare earth element, crystal grain thinning, suppresses crystal grain
Grow up.The method, with the form of precursor powder, first prepares tungsten copper oxide composite end, then through reducing
To nano tungsten-copper-rare earth composite powder.
By powder injection forming tungsten-copper alloy, it is suitable for the production of alloy on a large scale, there is higher answering
Use prospect.But tungsten and the poor compatibility of copper, prepared composite easily occurs that compactness is poor, electrical conductivity or
The problem of thermal conductance rate variance, preparation process, because heat transfer is uneven or thermal expansion coefficient difference, also easily occurs lacking
Fall into.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of compactness height, thermal conductivity
The tungsten-copper composite material high, thermal coefficient of expansion is little.
For solving the problems referred to above, the technical solution adopted in the present invention is as follows:
A kind of tungsten-copper composite material, is made up of following raw material by weight: 60-68 part tungsten powder, 28-32
Part copper powder, 1-3 part nikel powder, 1-3 part cobalt powder, 0.2-1 part metal-oxide, 80-100 part adhesive；
Described metal-oxide at least one, the metal of described metal-oxide be aluminum, calcium, chromium, manganese,
Molybdenum, tantalum or rhenium.
As preferably, described metal-oxide includes the aluminum of following components by weight percentage: 20-30%
Oxide, the oxide of chromium of 30-40% and complement to the oxide of 100% molybdenum.
As preferably, described metal-oxide includes the aluminum of following components by weight percentage: 20-30%
Oxide, the oxide of calcium of 30-40% and complement to the oxide of 100% molybdenum.
As preferably, described adhesive is made up of by weight percentage following components: the low molecule of 60-74% has
Machine thing, the macromolecular scaffold of 25-39% and complement to 100% couplant；Described low molecule organic matter is paraffin
Or oils and fats, described high-molecular bone frame material is EVA, HDPE, PB, PP or PS.
As preferably, the particle diameter of described tungsten powder, copper powder, nikel powder, cobalt powder and metal-oxide is 2-8 μm.
Another object of the present invention is to provide the method preparing above-mentioned tungsten-copper composite material, including following step
Rapid:
1) mixing: to weigh tungsten powder, copper powder, nikel powder, cobalt powder, metal-oxide and adhesive successively, feed intake
Mixing must mix feeding；
2) injection: mixed feeding is granulation into the powder that particle diameter is 2-8 μm, notes machine injection moulding altogether through powder；
3) defat: with the speed defat of 0.5-2mm/h, removes adhesive；
4) sintering: sinter 60-90min at 1048-1073 DEG C；
5) heat treatment: use the speed of 40-50 DEG C/min to be cooled to 950 DEG C, carries out quenching, rapid cooling, gas
Atmosphere Dehydroepiandrosterone derivative, Surface hardening treatment.
As preferably, described powder is noted machine altogether and is provided with material pipe and the nozzle of binder pipe, and described material pipe includes one
Pipe and an outside material pipe for formation of parts surface is expected for the center in formation of parts heart portion.
Compared to existing technology, the beneficial effects of the present invention is:
1. the tungsten-copper composite material that the present invention provides is added what nickel, cobalt and metal-oxide were made by tungsten copper,
This metal-oxide energy effective activation tungsten and copper, reduce tungsten and the interface energy level difference of copper, this tungsten copper composite wood
The compactness of material is high, thermal conductivity is high, thermal expansivity is little；
2. this metal-oxide that the present invention provides can be effectively increased corrosion resistance and the electric conductivity of tungsten-copper alloy；
3. the invention provides the preparation method of this tungsten-copper composite material, use powder injection-molded mode,
By mixing to tungsten powder, copper powder, nikel powder, cobalt powder and metal-oxide and adhesive, the compatibility between each component
Improving, nikel powder, cobalt powder and metal-oxide play preferably activation and the effect of catalysis, decrease tungsten copper
Between interface energy level difference, accelerate the transfer of electronics so that formed fine and close, thermal conductivity high, heat is swollen
The tungsten-copper alloy that swollen coefficient is little.
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
Detailed description of the invention
The present invention provides a kind of tungsten-copper composite material, is made up of following raw material by weight: 60-68 part tungsten
Powder, 28-32 part copper powder, 1-3 part nikel powder, 1-3 part cobalt powder, 1-2 part metal-oxide, 80-100 part are cohered
Agent；
Described metal-oxide at least one, the metal of described metal-oxide be aluminum, calcium, chromium, manganese, molybdenum,
Tantalum or rhenium.
In following example, the raw material powder of use is 2-8 μm.
The method preparing above-mentioned tungsten-copper composite material, comprises the following steps:
1) mixing: to weigh tungsten powder, copper powder, nikel powder, cobalt powder, metal-oxide and adhesive successively, feed intake
Mixing must mix feeding；
The rheological characteristic of mixed feeding is a critically important physical property, the flow regime pair of material in injection process
The impact of mould filling process and quality of item has highly important meaning.Viscosity be one of rheological characteristic very
Important aspect, it is feeding rheological characteristic and the important indicator of formability quality, and viscosity is suitably conducive to avoiding
Two-phase laminated flow and injection defect, beneficially injection moulding；
2) injection: mixed feeding is granulation into the powder that particle diameter is 2-8 μm, notes machine injection moulding altogether through powder；
Injection process is likely to result in the defect of product, if crackle, hole, weld seam, layering, powder are with glutinous
The problems such as knot agent separation；
3) defat: with the speed defat of 0.5-2mm/h, removes adhesive；
Defat primarily to removing organic binder, to reduce in later stage sintering process generation defect；De-
The mode of fat is mainly thermal debinding and catalysis degreasing two kinds, and thermal debinding is relatively slow, is suitable for the defat of finding,
And catalysis degreasing is relatively fast, for 1-2mm/h, the thickness < part of 40mm can be produced；
4) sintering: sinter 60-90min at 1048-1073 DEG C；
After defat, the intensity of blank is extremely low, therefore, shrinks the biggest, it is easy to cave in sintering process,
Deformation and bending.The performance of alloy is had a significant impact by the height of sintering temperature, at 1048 DEG C-1073 DEG C sintering,
Sintered density reaches theoretical sintered density.Sintering time also has certain impact to the performance of alloy, the most optimal
Temperature retention time is 60-90min, and when more than 120min, performance is decreased obviously；
5) heat treatment: use the speed of 40-50 DEG C/min to be cooled to 950 DEG C, carries out quenching, rapid cooling, gas
Atmosphere Dehydroepiandrosterone derivative, Surface hardening treatment；
Heat treatment can be effectively improved the performance of sintered state alloy.
Embodiment 1:
A kind of tungsten-copper composite material, is made up of following raw material by weight: 65 parts of tungsten powders, 30 parts of copper powders,
2 parts of nikel powders, 2 parts of cobalt powders, 1 part of metal-oxide, 100 parts of adhesives；
Described metal-oxide is by the Al of 20wt%2O3, the MoO of CaO, 40wt% of 40wt%3Composition,
Described adhesive is by the paraffin of 70wt%, the stearic acid of HDPE and 5wt% of EVA, 15wt% of 10wt%
Composition.
The method preparing this tungsten-copper composite material, comprises the following steps:
1) mixing: to weigh tungsten powder, copper powder, nikel powder, cobalt powder, metal-oxide and adhesive successively, feed intake
Mixing must mix feeding；
2) injection: mixed feeding is granulation into the powder that particle diameter is below 5 μm, notes machine injection moulding altogether through powder；
Powder is noted machine altogether and is provided with material pipe and the nozzle of binder pipe, and described material pipe includes one for formation of parts heart portion
Center material pipe and an outside material pipe for formation of parts surface；Use this mode to inject, effectively reduce
Piece surface and internal flatulence of heat type difference, thus form the composite of compactness；
3) defat: use catalysis degreasing, with the speed defat of 2mm/h；
4) sintering: sinter 90min at 1058-1068 DEG C, removes adhesive；
5) heat treatment: use the speed of 50 DEG C/min to be cooled to 950 DEG C, carry out quenching, rapid cooling, atmosphere de-
Hydrogen processes, Surface hardening treatment, obtains tungsten-copper composite material.
Because the fusing point of tungsten is higher, at the tungsten-copper composite material that the present embodiment obtains, nickel and cobalt serve activation and make
With, significantly reduce the boundary energy level difference of tungsten and copper so that tungsten and copper can preferably sinter；Al2O3
It is effectively improved electronics transfer ability in the composite, improves conductance and the thermal conductance of composite,
CaO is effectively improved the corrosion resistance of composite, MoO3It is doped between tungsten, copper, makes composite
There are good photoelectric properties；
Wherein tungsten powder, copper powder, nikel powder, cobalt powder and metal-oxide are effectively disperseed by adhesive, reduce
Interfacial tension between material powder, especially the interfacial tension between tungsten powder and copper powder, effectively promotes
The compatibility that tungsten is biphase with copper.
Comparative example 1
Comparative example is with the difference of embodiment 1, without metal-oxide.
Embodiment 2
A kind of tungsten-copper composite material, is made up of following raw material by weight: 68 parts of tungsten powders, 28 parts of copper powders,
1 part of nikel powder, 2 parts of cobalt powders, 1 part of metal-oxide, 90 parts of adhesives；
Described metal-oxide is by the Al of 30wt%2O3, the CrO of 30wt%3, the MoO of 40wt%3Composition,
Described adhesive is by the paraffin of 74wt%, the stearic acid of HDPE and 1wt% of EVA, 15wt% of 10wt%
Composition.
The method preparing this tungsten-copper composite material, comprises the following steps:
1) mixing: to weigh tungsten powder, copper powder, nikel powder, cobalt powder, metal-oxide and adhesive successively, feed intake
Mixing must mix feeding；
2) injection: mixed feeding is granulation into the powder that particle diameter is below 5 μm, notes machine injection moulding altogether through powder；
Described powder is noted machine altogether and is provided with material pipe and the nozzle of binder pipe, and described material pipe includes one for the formation of parts heart
The center material pipe in portion and an outside material pipe for formation of parts surface；Use this mode to inject, effectively subtract
Lack piece surface and internal flatulence of heat type difference, thus form the composite of compactness；
3) defat: use catalysis degreasing, with the speed defat of 2mm/h；
4) sintering: sinter 120min at 1048-1055 DEG C, removes adhesive；
5) heat treatment: use the speed of 40 DEG C/min to be cooled to 950 DEG C, carry out quenching, rapid cooling, atmosphere de-
Hydrogen processes, Surface hardening treatment, obtains tungsten-copper composite material.
CrO in the present embodiment3Can effectively reduce the boundary repulsion of tungsten and copper, thus promote to form fine and close tungsten
Carbon/carbon-copper composite material.
Comparative example 2:
Comparative example 2 is with the difference of embodiment 2, and the mode that comparative example 2 uses single material pipe to connect nozzle is noted
Penetrate.
Embodiment 3:
A kind of tungsten-copper composite material, is made up of following raw material by weight: 65 parts of tungsten powders, 30 parts of copper powders,
2 parts of nikel powders, 2 parts of cobalt powders, 0.5 part of metal-oxide, 80 parts of adhesives；
Described metal-oxide is by the Al of 30wt%2O3, the CrO of 30wt%3, the MoO of 40wt%3Composition,
Described adhesive is made up of the DOP of the oil of 33wt%, PP and 1wt% of PS, 33wt% of 33wt%.
The method preparing this tungsten-copper composite material, comprises the following steps:
1) mixing: to weigh tungsten powder, copper powder, nikel powder, cobalt powder, metal-oxide and adhesive successively, feed intake
Mixing must mix feeding；
2) injection: mixed feeding is granulation into the powder that particle diameter is below 5 μm, notes machine injection moulding altogether through powder；
Wherein powder note altogether machine include two material pipe, including one center material pipe and outer material pipe, outer material pipe box is located at center
On material pipe, center material pipe and outer material pipe are both connected on same nozzle, and center material pipe is for forming part
Heart portion, outer material pipe is for forming the surface of part；Use this mode to inject, effectively reduce piece surface
With internal flatulence of heat type difference, thus form the composite of compactness；
3) defat: use catalysis degreasing, with the speed defat of 2mm/h；
4) sintering: sinter 90min at 1065-1073 DEG C, removes adhesive；
5) heat treatment: use the speed of 40 DEG C/min to be cooled to 950 DEG C, carry out quenching, rapid cooling, atmosphere de-
Hydrogen processes, Surface hardening treatment, obtains tungsten-copper composite material.
CrO in the present embodiment3Can effectively reduce the boundary repulsion of tungsten and copper, thus promote to form fine and close tungsten
Carbon/carbon-copper composite material.
Comparative example 3:
Comparative example 3 is with the difference of embodiment 3, is not added with cobalt powder in comparative example 3.
Embodiment 4:
Embodiment 4 is with the difference of embodiment 1, and described metal-oxide is by the Al of 30wt%2O3, 30wt%
CrO3, the Ta of 40wt%2O3Composition.
Embodiment 5:
Embodiment 5 is with the difference of embodiment 1, and described metal-oxide is by CaO, 30wt% of 20wt%
MnO2, the Re of 40wt%2O3Composition.
Performance detects
The tungsten-copper composite material that embodiment 1-3 obtains carries out proportion, thermal conductivity, electrical conductivity, thermal coefficient of expansion
Detection, result is as shown in table 1；
The physical and chemical index of table 1 tungsten-copper composite material
In Table 1, from the comparative result of comparative example 1 with embodiment 1, it is not added with metal-oxide and obtains
The tungsten-copper composite material arrived, its proportion is relatively low, and thermal conductivity and electrical conductivity will be little, thermal coefficient of expansion phase
To height, the physicochemical property of composite can be effectively improved with the metal-oxide that the present invention provides；By
Embodiment 2 understands with comparative example 2, uses thin material pipe to connect the mode of nozzle injection, the heat of the product obtained
The coefficient of expansion is apparently higher than the mode using two material pipes to connect nozzle injection；By embodiment 3 and comparative example 3
Understanding, be not added with cobalt powder, the compactness of tungsten-copper composite material declines；Can from embodiment 1,2,3,4 and 5
Knowing, the compactness of the tungsten-copper composite material that the present invention provides is good, has preferably thermal conductance and conductivity, and
Thermal coefficient of expansion is less.
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit present invention protection with this
Scope, the change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement
Belong to scope of the present invention.
Claims (7)
1. a tungsten-copper composite material, it is characterised in that be made up of following raw material by weight: 60-68
Part tungsten powder, 28-32 part copper powder, 1-3 part nikel powder, 1-3 part cobalt powder, 0.2-1 part metal-oxide, 80-100
Part adhesive；
Described metal-oxide at least one, the metal of described metal-oxide be aluminum, calcium, chromium, manganese,
Molybdenum, tantalum or rhenium；
This tungsten-copper composite material is through the following steps that prepare:
1) mixing: to weigh tungsten powder, copper powder, nikel powder, cobalt powder, metal-oxide and adhesive successively, feed intake
Mixing must mix feeding；
2) injection: mixed feeding is granulation into the powder that particle diameter is 2-8 μm, notes machine injection moulding altogether through powder；
3) defat: with the speed defat of 0.5-2mm/h, removes adhesive；
4) sintering: sinter 60-90min at 1048-1073 DEG C；
5) heat treatment: use the speed of 40-50 DEG C/min to be cooled to 950 DEG C, carries out quenching, rapid cooling, gas
Atmosphere Dehydroepiandrosterone derivative, Surface hardening treatment.
2. tungsten-copper composite material as claimed in claim 1, it is characterised in that described metal-oxide includes
The oxide of the aluminum of following components by weight percentage: 20-30%, the oxide of chromium of 30-40% and benefit
The sufficient oxide to 100% molybdenum.
3. tungsten-copper composite material as claimed in claim 1, it is characterised in that described metal-oxide includes
The oxide of the aluminum of following components by weight percentage: 20-30%, the oxide of calcium of 30-40% and benefit
The sufficient oxide to 100% molybdenum.
4. tungsten-copper composite material as claimed in claim 1, it is characterised in that described adhesive is by following group
Point by weight percentage composition: the low molecule organic matter of 60-74%, the macromolecular scaffold of 25-39% and complement to
The couplant of 100%；Described low molecule organic matter is paraffin or oils and fats, described high-molecular bone frame material be EVA,
HDPE, PB, PP or PS.
5. tungsten-copper composite material as claimed in claim 1, it is characterised in that described tungsten powder, copper powder, nickel
The particle diameter of powder, cobalt powder and metal-oxide is 2-8 μm.
6. the method preparing tungsten-copper composite material as claimed in claim 1, it is characterised in that include following
Step:
1) mixing: to weigh tungsten powder, copper powder, nikel powder, cobalt powder, metal-oxide and adhesive successively, feed intake
Mixing must mix feeding；
2) injection: mixed feeding is granulation into the powder that particle diameter is 2-8 μm, notes machine injection moulding altogether through powder；
3) defat: with the speed defat of 0.5-2mm/h, removes adhesive；
4) sintering: sinter 60-90min at 1048-1073 DEG C；
5) heat treatment: use the speed of 40-50 DEG C/min to be cooled to 950 DEG C, carries out quenching, rapid cooling, gas
Atmosphere Dehydroepiandrosterone derivative, Surface hardening treatment.
7. method as claimed in claim 6, it is characterised in that described powder is noted machine altogether and is provided with material pipe and connects
The nozzle of material receiving tube, described material pipe includes that one expects that for the center in the formation of parts heart portion pipe and is for shaping zero
The outside material pipe on part surface.
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| CN110527886A (en) * | 2019-09-02 | 2019-12-03 | 广州市华司特合金制品有限公司 | A kind of clock and watch are again vertical and preparation method thereof |
| CN113070474A (en) * | 2021-03-29 | 2021-07-06 | 深圳市注成科技股份有限公司 | Preparation and forming method of nano tungsten-copper alloy radiating fin |
| CN113136515B (en) * | 2021-04-10 | 2022-03-25 | 广州市华司特合金制品有限公司 | High-thermal-conductivity tungsten-copper alloy material and preparation method and application thereof |
| CN117568687B (en) * | 2024-01-15 | 2024-03-29 | 西安稀有金属材料研究院有限公司 | Nanometer second-phase reinforced superfine crystal tungsten copper composite material and preparation method thereof |
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| CN101875134A (en) * | 2009-12-23 | 2010-11-03 | 云泰硬质合金(赣州)有限公司 | Method for preparing nano tungsten-copper-rare earth composite powder |
| CN102162055A (en) * | 2011-04-08 | 2011-08-24 | 福州博力达机电有限公司 | Method for preparing a tungsten-copper composite material with high arc ablation resistance |
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| CN101875134A (en) * | 2009-12-23 | 2010-11-03 | 云泰硬质合金(赣州)有限公司 | Method for preparing nano tungsten-copper-rare earth composite powder |
| CN102162055A (en) * | 2011-04-08 | 2011-08-24 | 福州博力达机电有限公司 | Method for preparing a tungsten-copper composite material with high arc ablation resistance |
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