CN1180907C - Tungsten-copper gradient heat sink material and its preparing method - Google Patents
Tungsten-copper gradient heat sink material and its preparing method Download PDFInfo
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- CN1180907C CN1180907C CNB031426786A CN03142678A CN1180907C CN 1180907 C CN1180907 C CN 1180907C CN B031426786 A CNB031426786 A CN B031426786A CN 03142678 A CN03142678 A CN 03142678A CN 1180907 C CN1180907 C CN 1180907C
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Abstract
The present invention provides a tungsten-copper gradient heat sink material and a preparing method thereof. The tungsten-copper gradient heat sink material is composed of a sealing surface layer containing 10 to 20 wt% of Cu, a heat radiating layer containing 40 to 60 wt% of Cu, and 1 to 3 transition layers which are positioned between the sealing surface and the heat radiating layer and contain 15 to 45 wt% of Cu; the preparation method comprises: adopting a multi-blank extrusion method for single forming; milling tungsten-copper materials of different ingredients in the layers, and preparing a W-Cu ultrafine powder of 5 to 100 nm; mixing the milled tungsten-copper ultrafine powder with a multi-component thermoplastic adhesive; extruding the tungsten-copper ultrafine powder and the adhesive to obtain W-Cu gradient material workblanks after complete mixing; degreasing the obtained workblanks by heating; sintering the degreased blank bodies in a hydrogen atmosphere. The present invention has the advantages of simplified preparation process, continuous change of the performance of the tungsten-copper gradient material along the thickness direction, and good consistency.
Description
Technical field
The invention belongs to the Tungsten-copper Composites technical field, a kind of tungsten copper (W/Cu) gradient heat sink material and preparation method thereof particularly is provided.
Background technology
Along with the development of device for switching to high pressure, high power capacity, and electronic device is constantly to miniaturization, high-power, high reliability and low-cost development, the raising of semiconductor power device integrated level and cause high heat generation rate, the heat conductivility of typical heat sink material-tungsten-copper alloy that an urgent demand is widely used high as far as possible (thermal conductivity 〉=300W/ (mK), low (leak rate≤5 * 10 of air content
-9Pam
3/ s), and have lower thermal coefficient of expansion (thermal coefficient of expansion (6～7) * 10
-6℃
-1), can be complementary with ceramic substrate (the following face that will contact with ceramic substrate is called sealing surface).Traditional homogeneous tungsten-copper alloy is difficult to satisfy simultaneously the requirement of high heat conductance and low thermal coefficient of expansion.Therefore, need ward off the small stream footpath in addition at the process aspect of preparation Tungsten-copper Composites.As the present tungsten copper FGM that proposes is that address the above problem a kind of more preferably selects.This functionally gradient material (FGM), simultaneously (radiating surface) is high-load copper (assurance high heat conductance), simultaneously (sealing surface) is high-load tungsten (assurance low-expansion coefficient), the centre is the tungsten copper gradient layer of transition gradually, it can relax the thermal stress that tungsten, copper hot property do not match and causes well, has kept tungsten, copper advantage separately again.The performance of tungsten copper functionally gradient material (FGM) is apparently higher than the Tungsten-copper Composites of homogeneous.
At present the technology of preparation functionally gradient material (FGM) mainly contains a layer shop hot pressed sintering, infiltration copper, and technology such as plasma spraying.But all there is certain shortcoming in these methods, as back, layer shop hot pressed sintering, and complex process, interface shape and bed thickness change greatly.If sintering temperature height (more than 1400 ℃), copper overflows easily, " sweating " phenomenon occurs and cause composition to be offset, and size distortion is serious under the high temperature.Activation forced fluid phase sintering causes the thermal conductivity of composite to descend owing to add micro-active element, is limited to for the demanding electronic material of thermal conductivity.The complex process of infiltration copper method, yield rate is low, can only prepare the material of low copper content.Defectives such as there is the porosity height in the tungsten copper functionally gradient material (FGM) of plasma spraying method preparation, and the interlayer adhesion is low do not satisfy above-mentioned high-air-tightness requirement.
China is the required whole dependence on import of high tungsten tungsten-copper product at present, and price is expensive, the annual a large amount of foreign exchanges of cost that need.Therefore the DOMESTICATION PROBLEM that solves high tungsten tungsten-carbon/carbon-copper composite material have great significance (see Jiang Guosheng, Wang Zhifa, Liu Zhengchun. the present Research of high tungsten tungsten-carbon/carbon-copper composite material. rare metal and carbide alloy, 1999,136:39.).
Summary of the invention
The objective of the invention is to: a kind of tungsten copper (W/Cu) gradient heat sink material and preparation method thereof is provided, and to simplify technology, processability is stablized, can be changed the tungsten copper functionally gradient material (FGM) of high conformity continuously.
The present invention adopts multi-blank extrusion once-forming to have 3～5 layers tungsten copper functionally gradient material (FGM).The basic principle of multi-blank extrusion as shown in drawings, in recipient 1, offer 3～5 blank holes 2 (being the situation in 3 blank holes shown in the figure), put into the pre-extruded stock A of tungsten copper, B, the C of heterogeneity in each base hole, (fusing point that depends on the multicomponent binding agent) pushes simultaneously to it at a certain temperature.Flowing of the extrusion die 3 control blanks of special construction, the blank of heterogeneity finally is pressed into one and is extruded in nib 4, obtain the multi-gradient material.The bond strength of each base interlayer is guaranteed that by binding agent the number of plies of gradient base substrate is correspondingly determined by the quantity in blank hole.The thickness of each base layer, width are determined by the outlet of extrusion die 3 and nib 4.Adopt the multi-blank extrusion can accurately control the content of tungsten copper composition in each layer, can adjust component as requested and reach mitigation thermal stress purpose.
Tungsten copper functionally gradient material (FGM) of the present invention is formed and preparation technology is:
1. according to the instructions for use of tungsten copper functionally gradient material (FGM), sealing surface needs consistent with the thermal coefficient of expansion of ceramic substrate, to guarantee matched seal.Cu content in this layer can be chosen in 10～20wt% scope, and then thermal coefficient of expansion is 5.83～7.24 * 10
-6℃
-1The content of heat dissipating layer Cu can correspondingly improve, and guarantees to have high thermal.The content of Cu can be chosen between 35～60wt% (wt is a quality), and the thermal conductivity that can guarantee radiating surface is greater than 265W/ (mK), to satisfy the requirement of HIGH-POWERED MICROWAVES device.The centre can add 1～3 layer of transition zone, designs the content of each interlayer Cu in the scope of 15～45wt%Cu less than 25% requirement according to the thermal expansion mismatch of each layer.
2. according to the different tungsten copper compositions in each layer, utilize the mechanical alloying technology to prepare the tungsten copper nanometer crystal powder of different proportion, the superfine powder of this nanoscale has higher sintering activity, can be issued to high-compactness being lower than conventional tungsten copper powder sintering temperature.In the ball milling parameter is ratio of grinding media to material (5～50): 1 (mass ratio), and under the condition of rotating speed 150～300rpm, utilize the planetary ball mill high-energy ball milling after 10～40 hours, can prepare the W-Cu superfine powder of 5～100nm.
3. tungsten copper superfine powder behind the ball milling and multicomponent thermoplastic adhesive are mixing.This binding agent is the modified wax-based binder, and it had both had excellent conformality, can be easier to again thoroughly remove.The main component of multicomponent binding agent is: polypropylene, stearic acid, paraffin, peanut oil and dioctyl phthalate modifier.The melting range of binding agent is 150～170 ℃, can carry out in wider temperature range when guaranteeing extruding.The W-Cu composite powder of different proportion need add the binding agent of different content, under the prerequisite that guarantees forming property, should reduce the content of binding agent as far as possible.The content of binding agent can change in 5～20wt% scope.
Tungsten copper superfine powder and binding agent through fully mixing evenly after, between 60～80 ℃, be pressed into bar-shaped base in advance.The effect of precompressed and characteristics are reinforced fast, accurately do not have dust; Reduce compression ratio, can reduce mold charge chamber and mold height; Pre-binder is tight, and air content is few, and it is fast to conduct heat, and shortens the time of preheating and curing, and goods are not prone to bubble yet.The bar-shaped base of heterogeneity is put into each blank hole 2 respectively, then the mould outside heated, and extruding between 140～170 ℃, extrusion speed 1～50mm/min can obtain the good multilayer W-Cu gradient blank of surface quality.
5. the gradient blank that obtains needs to carry out hot degreasing under specific degreasing process.According to the pyrolysis temperature of the different constituent elements in the multicomponent binding agent, take following degreasing process:
After being warmed up to 70 ℃ with 3～5 ℃/minute programming rates, be warmed up to 150 ℃, be incubated 0.5～3 hour with 1～3 ℃/minute programming rate; After being warmed up to 300 ℃ with 1～3 ℃/minute programming rate again, be warmed up to 450 ℃, be incubated 1～3 hour with 1～5 ℃/minute programming rate; Be warmed up to 900 ℃ with 3～6 ℃/minute programming rate again, be incubated 0.5～2 hour.Fig. 2 is seen in technological process.
6. the base substrate after the degreasing carries out once sintered under hydrogen atmosphere in 1050～1350 ℃ of temperature ranges.Adopting hydrogen is in order to restore the oxygen of nanometer powder surface absorption, to guarantee the purity of material.Also can adopt hot pressing to carry out double sintering as required, also can carry out gas pressure sintering, further promote densifiedly, can effectively prevent the later stage sintering warpage problem of functionally gradient material (FGM).
Key problem in technology of the present invention is: 1. utilize multi-blank extrusion once-forming multilayer W-Cu functionally gradient material (FGM), need the extrusion die of correct design processing sandwich construction, accurately control flowing of blank; 2. the number of plies of multi-gradient material is many more, the thickness of each layer is just more little, when each layer thickness during less than 1mm, guarantee the continuity that every layer of base is shaped, thickness evenness, and between layer and the layer enough bond strengths are arranged, the binding agent that needs development and exploitation to have conformality and can thoroughly remove, and the suitable addition of definite binding agent; 3. because W and Cu two metal not solid solutions mutually, so complex densified be subjected to very big influence, and the control of its densified speed, institutional framework distribution and composition and size is the key issue of the densification process of this composite.Adopt the high-energy ball milling processing method can increase densified process effectively, improve densified speed, and can reduce sintering temperature, be beneficial to effective control of composition and size.
Major advantage of the present invention is that each layer thickness of tungsten copper functionally gradient material (FGM) is adjustable, and each composition of layer can change arbitrarily, finally adjusts the thermal coefficient of expansion behind the sintering, and it is minimum that thermal stress is dropped to.That the gradient base substrate can obtain behind sintering is high fine and close, composition is the function-graded material that continuous gradient changes.By sintering, utilize element diffusion at high temperature, realize the continuous transition of composition between layer and the layer, the composition at interface and continuous tissue are changed, the thermal stress of material is greatly relaxed.Prepared tungsten copper functionally gradient material (FGM), it is lower to have a sealing surface thermal coefficient of expansion, can with the ceramic substrate matched seal, the thermal conductivity of radiating surface is near the characteristics of fine copper thermal conductivity.This functionally gradient material (FGM) can improve the thermal diffusivity of electric substrate effectively, satisfies the requirement of big electric current, and the while can guarantee the reliable sealing-in with ceramic substrate again, significantly improves the performance of HIGH-POWERED MICROWAVES device.Compare with the technology of traditional preparation process functionally gradient material (FGM), it is simple relatively to have technology, and finished product uniformity consistency height is beneficial to the realization mass production.
Description of drawings
Fig. 1 is a multi-blank extrusion schematic diagram of the present invention.Wherein can offer 3～5 blank holes 2, extrusion die 3 and 4 in the recipient 1.The pre-extruded stock A of tungsten copper, B, C.
Fig. 2 is a degreasing process flow chart of the present invention.
The specific embodiment
Adopt multi-blank extrusion preparation 3 layers of tungsten copper (W/Cu) functionally gradient material (FGM): selecting the sealing layer composition for use is W-15wt%Cu, and the transition zone composition is W-25wt%Cu, and the heat dissipating layer composition is W-35wt%Cu.Bright through theoretical computational chart, the thermal coefficient of expansion of sealing layer W-15wt%Cu is low approaching with ceramic substrate, can guarantee the reliable sealing-in with ceramic substrate; Heat dissipating layer is that W-35wt%Cu has high thermal, and its theoretical thermal conductivity is 265W/ (mK), can improve the thermal diffusivity of electric substrate effectively, improves the performance of semiconductor power device; Coefficient of thermal expansion differences between transition zone W-25wt%Cu mitigation is two-layer up and down.The thermal mismatching of each layer is less, makes thermal stress obtain relaxing.
The WCu composite powder of above-mentioned three kinds of compositions is 10: 1 (mass ratio) in ratio of grinding media to material, and drum's speed of rotation is under the condition of 300rpm, and crystallite dimension reaches 40nm behind 10 hours high-energy ball milling.W-15wt%Cu, three kinds of nanometer crystal powders of W-25wt%Cu and W-35wt%Cu respectively with 8wt%, the binding agent of 10wt% and 13wt% fully mixing evenly after, be pressed into the blank hole that bar-shaped base substrate is put into Fig. 1 respectively in advance, to mold heated.When temperature rose to 140 ℃, with the speed extruding of 10mm/min, it was good to have obtained surface quality, and the interface is in conjunction with firm gradient base substrate.Base substrate after the degreasing process degreasing of Fig. 2 behind 1250 ℃ of temperature sintering, records the base substrate density and reach 98%, and composition changes continuously at the interface under hydrogen atmosphere.The microscopic structure of each layer is all the uniform tungsten particle of a kind of disperse and forms continuous skeleton in the gradient base substrate of sintering, and copper is the contiguous network distributed architecture around the tungsten particle gap.The variation of the W skeleton decision thermal coefficient of expansion that forms, network copper helps the raising of thermal conductivity.
Claims (3)
1. tungsten copper gradient heat sink material, it is characterized in that: the Cu content in the sealing-in surface layer is 10～20wt%, and the content of Cu is 35～60wt% in the heat dissipating layer, is 1～3 layer of transition zone in the middle of sealing surface and the heat dissipating layer, and the content of Cu is 15～45wt% in the transition zone.
2, a kind of according to the described tungsten copper gradient of claim 1 heat sink material preparation method, it is characterized in that: adopt multi-blank extrusion once-forming by 3～5 layers of multi-gradient blanks of forming; Concrete preparation method is as follows:
A. with the tungsten material of the heterogeneity in each layer, be that ball material mass ratio is (5～50) in the ball milling parameter: 1, under the condition of rotating speed 150～300rpm, utilized the planetary ball mill high-energy ball milling 10～40 hours, the W-Cu superfine powder of preparation 5～100nm;
B. tungsten copper superfine powder behind the ball milling and multicomponent thermoplastic adhesive are mixing: binding agent is a wax-based binder, and composition is: polypropylene, stearic acid, paraffin, peanut oil and dioctyl phthalate modifier; The melting range of binding agent is 150～170 ℃, and the content of binding agent is 5～20wt%;
C. tungsten copper superfine powder and binding agent through fully mixing evenly after, between 60～80 ℃, be pressed into bar-shaped base in advance, the bar-shaped base of heterogeneity is put into each blank hole respectively, then the mould outside is heated, extruding between 140～170 ℃, extrusion speed 1～50mm/min can obtain the good multilayer W-Cu gradient blank of surface quality;
D. the gradient blank that obtains is carried out hot degreasing, degreasing process is:
After being warmed up to 70 ℃ with 3～5 ℃/minute programming rates, be warmed up to 150 ℃, be incubated 0.5～3 hour with 1～3 ℃/minute programming rate; After being warmed up to 300 ℃ with 1～3 ℃/minute programming rate again, be warmed up to 450 ℃, be incubated 1～3 hour with 1～5 ℃/minute programming rate; Be warmed up to 900 ℃ with 3～6 ℃/minute programming rate again, be incubated 0.5～2 hour;
Base substrate after the e degreasing carries out sintering in 1050～1350 ℃ of temperature ranges under hydrogen atmosphere.
3, according to the described tungsten copper gradient of claim 2 heat sink material preparation method, it is characterized in that: the base substrate after the degreasing under hydrogen atmosphere in 1050～1350 ℃ of temperature ranges once sintered after, adopt the mode of hot pressing or air pressure to carry out double sintering, to improve product density.
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