CN109055806A - A kind of multiple dimensioned granule reinforced copper base composite material and preparation method thereof - Google Patents
A kind of multiple dimensioned granule reinforced copper base composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0073—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only borides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
- B22F2003/208—Warm or hot extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The present invention relates to a kind of multiple dimensioned granule reinforced copper base composite materials and preparation method thereof, belong to Cu-base composites technical field.Multiple dimensioned particle Cu-base composites of the invention are by copper and copper facing TiB2Particle is made；The copper facing TiB2Particle includes the first copper facing TiB2Particle and the second copper facing TiB2Particle, the first copper facing TiB2The partial size of particle is greater than the second copper facing TiB2The partial size of particle.Copper, the first copper facing TiB2Particle and the second copper facing TiB2Particle is uniformly mixed, and then multiple dimensioned particle Cu-base composites are made in progress isostatic cool pressing, vacuum-sintering, hot-working.The Cu-base composites use the copper facing TiB of two kinds of different-grain diameters2Particle carries out Copper substrate to mix modification, and using the two, pattern and occupy-place are different in Copper substrate, and mutual supplement with each other's advantages and coupling effect between two kinds of reinforcements may be implemented to reach collaboration enhancing matrix, improve the comprehensive performance of Cu-base composites.
Description
Technical field
The present invention relates to a kind of multiple dimensioned granule reinforced copper base composite materials and preparation method thereof, belong to Cu-base composites
Technical field.
Background technique
Copper and copper alloy is traditional highly conductive, Heat Conduction Material, there is critically important use in industrial departments such as electric appliance, electronics
On the way.With the fast development of electronic technology, computer and information technology, welding electrode, contact wire, bearing shell, electronic communication device
The variety of components such as the contact element in part increase, and demand sharply increases, and device is to high density integrated circuit, highly dense actual load
Etc. direction changes, it is desirable that the Cu alloy material used not only has good conductive property, heating conduction, elastic limit and tough
Property, but also should have good wear-resisting property and higher tensile strength.Traditional copper alloy since intensity and heat resistance are insufficient,
It is limited by very large in the application.Currently, introducing the ceramics of chemical thermal stability and better heat stability in Copper substrate
Particle is one of the effective means for preparing high-strength and high-conductivity copper-based alloy material.TiB2Particle have high-melting-point, high rigidity,
Outstanding advantages of high-wearing feature and high-temperature electric conduction is to prepare one of common reinforced phase of high-performance copper based composites.
A kind of copper-plating titanium diboride particle increasing is disclosed in the Chinese patent application that application publication number is CN101928854A
Strong Cu-base composites and preparation method thereof.The Cu-base composites are by 70%~99% pure copper powder or copper alloy powder and 1%
Two boronation of~30% copper facing is made by mixing, sintering.Technical solution disclosed in this application is solved since copper is to titanium diboride
Wetability it is poor, it is difficult to prepare the TiB of densification2/ Cu composite material；Due to titanium diboride particle and copper thermal expansion coefficient and
Elasticity modulus differs larger the problem of being also easy to produce crackle in cooling procedure.But the enhancing of this single constituent element, single form
Cu-base composites are difficult to solve the contradictions such as Cu-base composites conductibility, intensity and plasticity and toughness, intensity and wearability to ask
Topic, therefore limit the promotion of Cu-base composites comprehensive performance.
Summary of the invention
The purpose of the present invention is to provide a kind of multiple dimensioned granule reinforced copper base composite materials, pass through various sizes of copper facing
TiB2The comprehensive performance of confusion raising Cu-base composites.
The object of the invention is also to provide a kind of preparation methods of above-mentioned multiple dimensioned granule reinforced copper base composite material.
To achieve the above object, the technical scheme is that
A kind of multiple dimensioned granule reinforced copper base composite material, the multiple dimensioned granule reinforced copper base composite material is by copper and copper facing
TiB2Particle is made；Copper facing TiB2Particle includes the first copper facing TiB2Particle and the second copper facing TiB2Particle, first copper facing
TiB2The partial size of particle is greater than the second copper facing TiB2The partial size of particle.
Using the copper facing TiB of two kinds of partial sizes2Particle can make smaller particle be filled into the space that larger particles can not occupy,
To improve the bulk density of material, the relative density of the composite material of raising, to improve the mechanical property of composite material.
Copper facing TiB2Volume fraction of the particle in multi-scale enhancement Cu-base composites is not more than 10%.If copper facing TiB
The volume fraction of particle is higher than 10%, and the conductive performance of Cu-base composites can be made to decline.
The grain diameter of copper is 50~200 μm.It is preferred that the copper raw material of this specification, is conducive to raw material and is uniformly mixed.
The first copper facing TiB2Particle and the second copper facing TiB2The partial size of particle is no more than 100 μm.If grain diameter is too
Greatly, then it is unobvious to promote effect.
Above-mentioned first copper facing TiB2Particle and the second copper facing TiB2The partial size ratio of particle is 2~10:10~50.
First copper facing TiB2Particle and the second copper facing TiB2Particle volume ratio is 1~7:1~7.In this volume ratio range,
The synergistic action effect of the two is best.
Copper facing TiB2Particle is by TiB2Particle is successively obtained through sensitization plays, activation, copper plating treatment.
Sensitizing solution used in the sensitized treatment is mixed by stannous chloride, hydrochloric acid and water.Wherein stannous chloride with
SnCl2·2H2O meter, mass concentration are 20~30g/L；Hydrochloric acid is the concentrated hydrochloric acid that mass fraction is 36~38%, additional amount 20
~30mL/L.Preferably, sensitized treatment temperature is 40~50 DEG C, and the time is 30~40min.
Activating solution used in the activation processing the preparation method comprises the following steps: into the silver nitrate solution of 8~12g/L be added ammonium hydroxide it is straight
It is transparent to get activating solution to system.Color change is Transparent color-brown-Transparent color in above-mentioned activating solution process for preparation.It is preferred that
, activation temperature is 40~50 DEG C, and the time is 30~40min.
Copper plating bath used in the copper plating treatment is the aqueous solution of sulfur acid copper.Basic ingredient in 1L copper plating bath is 6~
12gCuSO4·5H2O, 10mL formalin, 6~10gNa2CO3, 5~7gNaOH, 15~25g C4H4O6KNa·4H2O, 40mg
2,2- bipyridyls, solvent are water；The mass fraction of formaldehyde is 36~38% in the formalin.When copper plating treatment, plating is adjusted
The pH to 11~12.5 of copper liquid, copper facing temperature are 60~70 DEG C, and the copper facing time is 60~80min.
TiB2Particle passes through purification process, then carries out sensitized treatment.
The refined solution of purification process is mixed by the concentrated sulfuric acid and concentrated nitric acid.The mass fraction of the concentrated sulfuric acid be 95%~
98%, the mass fraction of concentrated nitric acid is 65%~68%.Preferably, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
Technical solution used by the preparation method of multiple dimensioned granule reinforced copper base composite material of the invention includes as follows
Step: by the first copper facing TiB2Particle, the second copper facing TiB2Particle and copper are uniformly mixed, isostatic cool pressing, vacuum-sintering, hot-working,
To obtain the final product.
Described to be mixed into ball milling mixing, ratio of grinding media to material 5:1, Ball-milling Time is 8~16h.
The isostatic cool pressing is that the mixed-powder after ball milling is packed into elastic packing grinding tool made of rubber, using cold etc.
Static pressure machine applies the pressure of all directions equalization using hydraulic oil as medium to it.During isostatic cool pressing pressure be 280~
320MPa, dwell time are 20~40min.
The temperature of the vacuum-sintering is 900~950 DEG C, and sintering time is 1~2h.Under this sintering parameter, sintering temperature
Spend it is low, sintering it is high-efficient.
The hot-working is hot extrusion, and hot extrusion is to be heated to 850~950 DEG C and keep the temperature 50~70min, to be not less than 5:
1 extrusion ratio squeezes.The bar being squeezed under this squeezing parameter, intensity are higher.
The present invention is by multiple dimensioned TiB2Particle introduces Cu-base composites, utilizes multi-scale reinforcing body physical parameter itself
It is different with occupy-place, it realizes mutual supplement with each other's advantages and coupling effect between them, improves Cu alloy material comprehensive performance to reach
Purpose.Cu-base composites prepared by the present invention, for consistency up to 98%, conductivity can reach 80%IACS or more, and hardness can
Reach 65HBW or more.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
The multiple dimensioned granule reinforced copper base composite material of the present embodiment is by pure copper powder, the first copper facing TiB2Particle and the second plating
Copper TiB2Particle is made.Wherein the second copper facing TiB2Grain diameter is 2 μm, the first copper facing TiB2Grain diameter is 50 μm.
Wherein the quality of pure copper powder is 962.68g, and the partial size of copper powder is 75 μm.2 μm of copper facing TiB2The quality of particle is
8.52g, 50 μm of copper facing TiB2The quality of particle is 17.04g, copper facing TiB2Total volume fraction of the particle in Cu-base composites
It is 5%.2 μm of copper facing TiB2Particle and 50 μm of copper facing TiB2Particle volume ratio is 1:2.
The copper facing TiB of the present embodiment2Particle is made by the preparation method included the following steps:
(1)TiB2The purifying of particle: by mass fraction be 95% the concentrated sulfuric acid and mass fraction be 65% concentrated nitric acid by
Volume ratio 3:1 is configured to mixed acid solution, by TiB2Particle is added in mixed acid solution, revolving speed is 400r/min, temperature is 60 DEG C
Under conditions of purify 3h, filter, be washed with deionized to neutrality after standing, obtain purifying TiB2Particle.
(2)TiB2The sensitization of particle: by the TiB of purifying2Particle, which is added in dispersant solution, carries out ultrasonic disperse；Then
TiB is purified to 200mL2200mL sensitizing solution is added in particle dispersion, in the condition that revolving speed is 400r/min, temperature is 40 DEG C
Lower sensitized treatment 40min is filtered after standing, is washed with deionized to neutrality, obtains sensitization TiB2Particle；Wherein dispersing agent is molten
Liquid is the TNWDIS solution of mass concentration 0.6g/L, purifies TiB2The additional amount of particle is 0.6g/L；In sensitizing solution, SnCl2·
2H2The mass concentration of O is 20g/L, and the addition concentration of concentrated hydrochloric acid is 25mL/L, and the mass fraction of concentrated hydrochloric acid is 37%.
(3)TiB2The activation of particle: TiB will be sensitized2Particle is added to progress ultrasonic wave dispersion in dispersant solution, obtains
It is sensitized TiB2Particle dispersion；TiB is sensitized to 200mL2200mL activating solution is added in particle dispersion, is 400r/ in revolving speed
Min, temperature are activated 40min under conditions of being 40 DEG C, filter after standing, are washed with deionized to neutrality, are activated
TiB2Particle；Wherein dispersant solution is the TNWDIS solution of mass concentration 0.6g/L, is sensitized TiB2The additional amount of particle is
0.6g/L；Activating solution becomes transparent from brown to system from dropwise addition ammonium hydroxide in the silver nitrate solution to 8g/L and is made.
(4) TiB will copper plating treatment: be activated2Particle is added to progress ultrasonic wave dispersion in dispersant solution, is activated
TiB2Particle dispersion；TiB is activated to 500mL2Addition 500mL copper plating bath in particle dispersion, adjustment system pH to 11.5,
70min is handled under conditions of revolving speed is 400r/min, temperature is 65 DEG C, is stood to TiB2Particle precipitating after filter, spend from
Sub- water washing obtains copper facing TiB to neutrality2Particle；Wherein dispersant solution is the TNWDIS solution of mass concentration 0.6g/L, living
Change TiB2The additional amount of particle is 0.6g/L；The basic ingredient of 1L copper plating bath are as follows: 6g CuSO4·5H2O, 10mL formalin
(37%), 6g Na2CO3, 5g NaOH, 15g C4H4O6KNa·4H2O, 40mg 2,2- bipyridyl, solvent are deionized water.
Embodiment 2
The present embodiment is the preparation method of the multiple dimensioned granule reinforced copper base composite material of embodiment 1, comprising the following steps:
1) by 2 μm of copper facing TiB2Particle, 50 μm of copper facing TiB2Particle and the mixing of 100g pure copper powder, are added mixed-powder volume 2
Ethyl alcohol again, the then wet mixing in magnetic stirring apparatus, temperature are 60 DEG C, revolving speed 600r/min, mixing time 2.5h；It is added
Then copper powder needed for residue carries out ball milling, Ball-milling Time 16h in the ball mill, ball material mass ratio is 5:1, revolving speed 100r/
Min obtains mixed-powder；
2) isostatic cool pressing, pressure maintaining 20min are carried out to mixed-powder with pressure 280MPa using cold isostatic press；
3) the raw material powder that step 2) obtains is sintered in vacuum sintering funace, sintering temperature is 950 DEG C, sintering
Time is 1.5h；
4) sintered sample is heated to 900 DEG C and keeps the temperature 60min, sample is squeezed by bar with the extrusion ratio of 5:1.
Embodiment 3
The multiple dimensioned granule reinforced copper base composite material of the present embodiment is by pure copper powder, the first copper facing TiB2Particle and the second plating
Copper TiB2Particle is made.Wherein the second copper facing TiB2Grain diameter is 2 μm, the first copper facing TiB2Grain diameter is 10 μm.
Wherein the quality of pure copper powder is 962.68g, and the partial size of copper powder is 200 μm.2 μm of copper facing TiB2The quality of particle is
8.52g, 10 μm of copper facing TiB2The quality of particle is 17.04g, copper facing TiB2Total volume fraction of the particle in Cu-base composites
It is 5%.2 μm of copper facing TiB2Particle and 10 μm of copper facing TiB2Particle volume ratio is 1:2.
The copper facing TiB of the present embodiment2Particle is made by the preparation method included the following steps:
(1)TiB2The purifying of particle: by mass fraction be 97% the concentrated sulfuric acid and mass fraction be 67% concentrated nitric acid by
Volume ratio 3:1 is configured to mixed acid solution, by TiB2Particle is added in mixed acid solution, revolving speed is 450r/min, temperature is 65 DEG C
Under conditions of purify 2.5h, filter, be washed with deionized to neutrality after standing, obtain purifying TiB2Particle.
(2)TiB2The sensitization of particle: by the TiB of purifying2Particle, which is added in dispersant solution, carries out ultrasonic disperse；Then
TiB is purified to 200mL2200mL sensitizing solution is added in particle dispersion, in the condition that revolving speed is 400r/min, temperature is 45 DEG C
Lower sensitized treatment 40min is filtered after standing, is washed with deionized to neutrality, obtains sensitization TiB2Particle；Wherein dispersing agent is molten
Liquid is the TNWDIS solution of mass concentration 0.8g/L, purifies TiB2The additional amount of particle is 0.8g/L；In sensitizing solution, SnCl2·
2H2The mass concentration of O is 25g/L, and the addition concentration of concentrated hydrochloric acid is 25mL/L, and the mass fraction of concentrated hydrochloric acid is 37%.
(3)TiB2The activation of particle: TiB will be sensitized2Particle is added to progress ultrasonic wave dispersion in dispersant solution, obtains
It is sensitized TiB2Particle dispersion；TiB is sensitized to 200mL2200mL activating solution is added in particle dispersion, is 400r/ in revolving speed
Min, temperature are activated 45min under conditions of being 45 DEG C, filter after standing, are washed with deionized to neutrality, are activated
TiB2Particle；Wherein dispersant solution is the TNWDIS solution of mass concentration 0.8g/L, is sensitized TiB2The additional amount of particle is
0.8g/L；Activating solution becomes transparent from brown to system from dropwise addition ammonium hydroxide in the silver nitrate solution to 10g/L and is made.
(4) TiB will copper plating treatment: be activated2Particle is added to progress ultrasonic wave dispersion in dispersant solution, is activated
TiB2Particle dispersion；TiB is activated to 500mL2Addition 500mL copper plating bath in particle dispersion, adjustment system pH to 11.5,
60min is handled under conditions of revolving speed is 450r/min, temperature is 60 DEG C, is stood to TiB2Particle precipitating after filter, spend from
Sub- water washing obtains copper facing TiB to neutrality2Particle；Wherein dispersant solution is the TNWDIS solution of mass concentration 0.8g/L, living
Change TiB2The additional amount of particle is 0.8g/L；The basic ingredient of 1L copper plating bath are as follows: 9g CuSO4·5H2O, 10mL formalin
(37%), 7g Na2CO3, 6g NaOH, 20g C4H4O6KNa·4H2O, 40mg 2,2- bipyridyl, solvent are deionized water.
Embodiment 4
The present embodiment is the preparation method of the multiple dimensioned granule reinforced copper base composite material of embodiment 3, comprising the following steps:
1) by 2 μm of copper facing TiB2Particle, 10 μm of copper facing TiB2Particle and the mixing of 100g pure copper powder, are added mixed-powder volume 2
Ethyl alcohol again, the then wet mixing in magnetic stirring apparatus, temperature are 60 DEG C, revolving speed 600r/min, mixing time 2.5h；It is added
Then copper powder needed for residue carries out ball milling, Ball-milling Time 16h in the ball mill, ball material mass ratio is 5:1, revolving speed 100r/
Min obtains mixed-powder；
2) isostatic cool pressing, pressure maintaining 20min are carried out to mixed-powder with pressure 280MPa using cold isostatic press；
3) the raw material powder that step 2) obtains is sintered in vacuum sintering funace, sintering temperature is 950 DEG C, sintering
Time is 1.5h；
4) sintered sample is heated to 900 DEG C and keeps the temperature 60min, sample is squeezed by bar with the extrusion ratio of 5:1.
Embodiment 5
The multiple dimensioned granule reinforced copper base composite material of the present embodiment is by pure copper powder, the first copper facing TiB2Particle and the second plating
Copper TiB2Particle is made.Wherein the second copper facing TiB2Grain diameter is 10 μm, the first copper facing TiB2Grain diameter is 50 μm.
Wherein the quality of pure copper powder is 962.68g, and the partial size of copper powder is 100 μm.10 μm of copper facing TiB2The quality of particle is
8.52g, 50 μm of copper facing TiB2The quality of particle is 17.04g, copper facing TiB2Total volume fraction of the particle in Cu-base composites
It is 5%.10 μm of copper facing TiB2Particle and 50 μm of copper facing TiB2Particle volume ratio is 1:2.
The present embodiment copper facing TiB particle is made by the preparation method included the following steps:
(1)TiB2The purifying of particle: by mass fraction be 98% the concentrated sulfuric acid and mass fraction be 68% concentrated nitric acid by
Volume ratio 3:1 is configured to mixed acid solution, by TiB2Particle is added in mixed acid solution, revolving speed is 450r/min, temperature is 60 DEG C
Under conditions of purify 3h, filter, be washed with deionized to neutrality after standing, obtain purifying TiB2Particle.
(2)TiB2The sensitization of particle: by the TiB of purifying2Particle, which is added in dispersant solution, carries out ultrasonic disperse；Then
TiB is purified to 200mL2200mL sensitizing solution is added in particle dispersion, in the condition that revolving speed is 450r/min, temperature is 50 DEG C
Lower sensitized treatment 30min is filtered after standing, is washed with deionized to neutrality, obtains sensitization TiB2Particle；Wherein dispersing agent is molten
Liquid is the TNWDIS solution of mass concentration 1.0g/L, purifies TiB2The additional amount of particle is 1.0g/L；In sensitizing solution, SnCl2·
2H2The mass concentration of O is 30g/L, and the addition concentration of concentrated hydrochloric acid is 25mL/L, and the mass fraction of concentrated hydrochloric acid is 37%.
(3)TiB2The activation of particle: TiB will be sensitized2Particle is added to progress ultrasonic wave dispersion in dispersant solution, obtains
It is sensitized TiB2Particle dispersion；TiB is sensitized to 200mL2200mL activating solution is added in particle dispersion, is 450r/ in revolving speed
Min, temperature are activated 40min under conditions of being 50 DEG C, filter after standing, are washed with deionized to neutrality, are activated
TiB2Particle；Wherein dispersant solution is the TNWDIS solution of mass concentration 1g/L, is sensitized TiB2The additional amount of particle is 1g/L；
Activating solution becomes transparent from brown to system from dropwise addition ammonium hydroxide in the silver nitrate solution to 12g/L and is made.
(4) TiB will copper plating treatment: be activated2Particle is added to progress ultrasonic wave dispersion in dispersant solution, is activated
TiB2Particle dispersion；TiB is activated to 500mL2Addition 500mL copper plating bath in particle dispersion, adjustment system pH to 12.5,
50min is handled under conditions of revolving speed is 450r/min, temperature is 60 DEG C, is stood to TiB2Particle precipitating after filter, spend from
Sub- water washing obtains copper facing TiB to neutrality2Particle；Wherein dispersant solution is the TNWDIS solution of mass concentration 1g/L, activation
TiB2The additional amount of particle is 1g/L；The basic ingredient of 1L copper plating bath are as follows: 6g CuSO4·5H2O, 10mL formalin (37%),
8g Na2CO3, 6g NaOH, 25g C4H4O6KNa·4H2O, 40mg 2,2- bipyridyl, solvent are deionized water.
Embodiment 6
The present embodiment is the preparation method of the multiple dimensioned granule reinforced copper base composite material of embodiment 5, comprising the following steps:
1) by 10 μm of copper facing TiB2Particle, 50 μm of copper facing TiB2Particle and the mixing of 100g pure copper powder, are added mixed-powder volume
2 times of ethyl alcohol, the then wet mixing in magnetic stirring apparatus, temperature are 60 DEG C, revolving speed 600r/min, mixing time 2.5h；Add
Enter copper powder needed for residue and then carry out ball milling in the ball mill, Ball-milling Time 16h, ball material mass ratio is 5:1, and revolving speed is
100r/min obtains mixed-powder；
2) isostatic cool pressing, pressure maintaining 20min are carried out to mixed-powder with pressure 280MPa using cold isostatic press；
3) the raw material powder that step 2) obtains is sintered in vacuum sintering funace, sintering temperature is 950 DEG C, sintering
Time is 1.5h；
4) sintered sample is heated to 900 DEG C and keeps the temperature 60min, sample is squeezed by bar with the extrusion ratio of 5:1.
Embodiment 7
The multiple dimensioned granule reinforced copper base composite material of the present embodiment is by pure copper powder, the first copper facing TiB2Particle and the second plating
Copper TiB2Particle is made.Wherein the second copper facing TiB2Grain diameter is 2 μm, the first copper facing TiB2Grain diameter is 50 μm.
Wherein the quality of pure copper powder is 912.01g, and the partial size of copper powder is 45 μm.2 μm of copper facing TiB2The quality of particle is
44.73g, 50 μm of copper facing TiB2The quality of particle is 6.39g, copper facing TiB2Total volume fraction of the particle in Cu-base composites
It is 10%.2 μm of copper facing TiB2Particle and 50 copper facing μm TiB2Particle volume ratio is 7:1.
The copper facing TiB of the present embodiment2Particle referring to the preparation method in embodiment 1 by being made.
Embodiment 8
The present embodiment is the preparation method of the multiple dimensioned granule reinforced copper base composite material of embodiment 7, comprising the following steps:
1) by 2 μm of copper facing TiB2Particle, 50 μm of copper facing TiB2Particle and the mixing of 100g pure copper powder, are added mixed-powder volume 2
Ethyl alcohol again, the then wet mixing in magnetic stirring apparatus, temperature are 60 DEG C, revolving speed 600r/min, mixing time 2.5h；It is added
Then copper powder needed for residue carries out ball milling, Ball-milling Time 16h in the ball mill, ball material mass ratio is 5:1, revolving speed 100r/
Min obtains mixed-powder；
2) isostatic cool pressing, pressure maintaining 40min are carried out to mixed-powder with pressure 300MPa using cold isostatic press；
3) the raw material powder that step 2) obtains is sintered in vacuum sintering funace, sintering temperature is 900 DEG C, sintering
Time is 1h；
4) sintered sample is heated to 850 DEG C and keeps the temperature 50min, sample is squeezed by bar with the extrusion ratio of 5:1.
Embodiment 9
The multiple dimensioned granule reinforced copper base composite material of the present embodiment is by copper powder, the first copper facing TiB2Particle and the second copper facing
TiB2Particle is made.Wherein the second copper facing TiB2Grain diameter is 10 μm, the first copper facing TiB2Grain diameter is 50 μm.
Wherein the quality of pure copper powder is 1003.22g, and the partial size of copper powder is 45 μm.10 μm of copper facing TiB2The quality of particle is
0.64g, 50 μm of copper facing TiB2The quality of particle is 4.47g, copper facing TiB2Volume fraction of the particle in Cu-base composites be
1%.10μmTiB2Particle and 50 μm of TiB2Particle volume ratio is 1:7.
The copper facing TiB of the present embodiment2Particle referring to the preparation method in embodiment 1 by being made.
Embodiment 10
The present embodiment is the preparation method of the multiple dimensioned granule reinforced copper base composite material of embodiment 9, comprising the following steps:
1) by 10 μm of copper facing TiB2Particle, 50 μm of copper facing TiB2Particle and the mixing of 100g pure copper powder, are added mixed-powder volume
2 times of ethyl alcohol, the then wet mixing in magnetic stirring apparatus, temperature are 60 DEG C, revolving speed 600r/min, mixing time 2.5h；Add
Enter copper powder needed for residue and then carry out ball milling in the ball mill, Ball-milling Time 16h, ball material mass ratio is 5:1, and revolving speed is
100r/min obtains mixed-powder；
2) isostatic cool pressing, pressure maintaining 30min are carried out to mixed-powder with pressure 320MPa using cold isostatic press；
3) the raw material powder that step 2) obtains is sintered in vacuum sintering funace, sintering temperature is 890 DEG C, sintering
Time is 2h；
4) sintered sample is heated to 880 DEG C and keeps the temperature 70min, sample is squeezed by bar with the extrusion ratio of 6:1.
Embodiment 11
The multiple dimensioned granule reinforced copper base composite material of the present embodiment is by copper powder, the first copper facing TiB2Particle and the second copper facing
TiB2Particle is made.Wherein the second copper facing TiB2Grain diameter is 2 μm, the first copper facing TiB2Grain diameter is 30 μm.
Wherein the quality of pure copper powder is 962.68g, and the partial size of copper powder is 75 μm.2 μm of copper facing TiB2The quality of particle is
2.12g, 30 μm of copper facing TiB2The quality of particle is 22.37g, copper facing TiB2Volume fraction of the particle in Cu-base composites be
5%.2μmTiB2Particle and 30 μm of TiB2Particle volume ratio is 1:7.
The copper facing TiB of the present embodiment2Particle referring to the preparation method in embodiment 1 by being made.
Embodiment 12
The present embodiment is the preparation method of the multiple dimensioned granule reinforced copper base composite material of embodiment 11, specific preparation process
Referring to embodiment 1.
Comparative example 1
This comparative example uses the copper facing TiB of single particle size2Enhance Cu-base composites, copper facing TiB2Grain diameter size is 2
μm.Copper facing TiB2Volume fraction in Cu-base composites is 5%, and surplus is pure copper powder, and copper powder size is 75 μm.Wherein plate
Copper TiB2Particle is made by the preparation method referring to embodiment 1.
The copper facing TiB of the single particle size of this comparative example2Enhance the preparation method of Cu-base composites referring to embodiment 2.
Comparative example 2
This comparative example uses the copper facing TiB of single particle size2Enhance Cu-base composites, copper facing TiB2Grain diameter size is
10μm.Copper facing TiB2Volume fraction in Cu-base composites is 5%, and surplus is copper powder, and copper powder size is 45 μm.Wherein plate
Copper TiB2Particle is made by the preparation method referring to embodiment 1.
The copper facing TiB of the single particle size of this comparative example2Enhance the preparation method of Cu-base composites referring to embodiment 2.
Comparative example 3
This comparative example uses the copper facing TiB of single particle size2Enhance Cu-base composites, copper facing TiB2Grain diameter size is
50μm.Copper facing TiB2Volume fraction in Cu-base composites is 1%, and surplus is copper powder, and copper powder size is 45 μm.Wherein plate
Copper TiB2Particle is made by the preparation method referring to embodiment 1.
The copper facing TiB of the single particle size of this comparative example2Enhance the preparation method of Cu-base composites referring to embodiment 2.
Test example
To the 1~3 of multiple dimensioned granule reinforced copper base composite material described in embodiment 1,3,5,7,9 and 11 and comparative example
Single particle size copper facing TiB2Consistency, conductivity and the hardness of enhancing Cu-base composites are tested.Using A Ji meter
The consistency of moral drainage survey Cu-base composites；Its conductivity is surveyed using Sigma 2008B1 digital conductivity meter；Using
320HBS-3000 type digital brinell hardness tester tests its hardness.Test result is as shown in table 1.
1 Cu-base composites the performance test results of table
| Project | Consistency/% | Conductivity/%IACS | Hardness/HBW |
| Embodiment 1 | 98.5 | 85.3 | 69 |
| Embodiment 3 | 98.1 | 84.2 | 67.5 |
| Embodiment 5 | 98 | 84.9 | 67.7 |
| Embodiment 7 | 95.5 | 75.2 | 81 |
| Embodiment 9 | 99.1 | 91 | 56.2 |
| Embodiment 11 | 98.2 | 84.6 | 68.1 |
| Comparative example 1 | 96.9 | 81.4 | 61.5 |
| Comparative example 2 | 94 | 70.6 | 72 |
| Comparative example 3 | 98.2 | 88.1 | 53 |
By the above testing result it is found that of the invention mixes partial size copper facing TiB2The Cu-base composites of particle enhancing have
Good consistency, conductivity and hardness, comprehensive performance is compared with single particle size TiB2Granule reinforced copper base composite material has larger amplitude
Degree improves.
Test example 2
By 1 result of test example it is found that the comprehensive performance of the multiple dimensioned granule reinforced copper base composite material of embodiment 1 is preferable.
The single particle size copper facing TiB of 1 multi-scale enhancement Cu-base composites and comparative example 1 to embodiment2Enhance copper-based composite wood
Material tests its current-carrier friction coefficient and wear rate using pin disc type HST100 type current-carrying high-speed tester (HST).Test condition are as follows: electric current
25A, speed 10m/s, load 0.63MPa.Test result is shown in Table 2.
2 test result of table
| Project | Coefficient of friction | Wear rate (mg/m) |
| Embodiment 1 | 0.38 | 1.2 |
| Comparative example 1 | 0.42 | 2.4 |
As shown in Table 2, the intensity of multiple dimensioned granule reinforced copper base composite material of the invention is higher.
Claims (10)
1. a kind of multiple dimensioned granule reinforced copper base composite material, it is characterised in that: the Cu-base composites are by copper and copper facing TiB2
Particle is made；The copper facing TiB2Particle includes the first copper facing TiB2Particle and the second copper facing TiB2Particle, first copper facing
TiB2The partial size of particle is greater than the second copper facing TiB2The partial size of particle.
2. multiple dimensioned granule reinforced copper base composite material according to claim 1, it is characterised in that: the copper facing TiB2?
Volume fraction of the grain in Cu-base composites is not more than 10%.
3. multiple dimensioned granule reinforced copper base composite material according to claim 1, it is characterised in that: the particle of the copper
Diameter size is 45 μm~200 μm.
4. multiple dimensioned granule reinforced copper base composite material according to claim 1, it is characterised in that: first copper facing
TiB2Particle and the second copper facing TiB2The partial size of particle is no more than 100 μm.
5. multiple dimensioned granule reinforced copper base composite material according to claim 4, it is characterised in that: first copper facing
TiB2Particle and the second copper facing TiB2The partial size ratio of particle is 2~10:10~50.
6. multiple dimensioned granule reinforced copper base composite material according to claim 4 or 5, it is characterised in that: first plating
Copper TiB2Particle and the second copper facing TiB2Particle volume ratio is 1~7:1~7.
7. multiple dimensioned granule reinforced copper base composite material according to claim 1, it is characterised in that: the copper facing TiB2?
Grain is by TiB2Particle is successively obtained through sensitization plays, activation, copper plating treatment.
8. a kind of preparation method of multiple dimensioned granule reinforced copper base composite material according to claim 1, which is characterized in that
Include the following steps: the first copper facing TiB2Particle, the second copper facing TiB2Particle and copper are uniformly mixed, and isostatic cool pressing, vacuum is burnt
Knot, hot-working to get.
9. the preparation method of multiple dimensioned granule reinforced copper base composite material according to claim 8, it is characterised in that: described
The temperature of vacuum-sintering is 890~950 DEG C, and sintering time is 1~2h.
10. the preparation method of multiple dimensioned granule reinforced copper base composite material according to claim 8, it is characterised in that: institute
Stating hot-working is hot extrusion, and the hot extrusion is to be heated to 850~900 DEG C and keep the temperature 50~70min, with squeezing not less than 5:1
Pressure ratio squeezes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358990A (en) * | 2019-07-04 | 2019-10-22 | 西安理工大学 | A kind of post-processing approach of hot pressed sintering titanium diboride enhancing Cu-base composites |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928854A (en) * | 2010-04-13 | 2010-12-29 | 哈尔滨工业大学 | Copper-plating titanium diboride particle enhanced copper-based composite material and preparation method thereof |
| CN107177839A (en) * | 2017-05-17 | 2017-09-19 | 河南科技大学 | One kind is in TiB2Particle surface copper coating |
-
2018
- 2018-09-05 CN CN201811033509.0A patent/CN109055806A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928854A (en) * | 2010-04-13 | 2010-12-29 | 哈尔滨工业大学 | Copper-plating titanium diboride particle enhanced copper-based composite material and preparation method thereof |
| CN107177839A (en) * | 2017-05-17 | 2017-09-19 | 河南科技大学 | One kind is in TiB2Particle surface copper coating |
Non-Patent Citations (1)
| Title |
|---|
| 张胜利 等: "TiB2颗粒混杂对TiB2/Cu复合材料微观组织和性能的影响", 《材料热处理学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358990A (en) * | 2019-07-04 | 2019-10-22 | 西安理工大学 | A kind of post-processing approach of hot pressed sintering titanium diboride enhancing Cu-base composites |
| CN110358990B (en) * | 2019-07-04 | 2020-07-28 | 西安理工大学 | Post-treatment method for hot-pressed sintering of titanium diboride reinforced copper-based composite material |
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