CN105543535B - Al4SiC4With Cr cooperative reinforcings net/spherical copper product and preparation method - Google Patents

Al4SiC4With Cr cooperative reinforcings net/spherical copper product and preparation method Download PDF

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CN105543535B
CN105543535B CN201510952589.XA CN201510952589A CN105543535B CN 105543535 B CN105543535 B CN 105543535B CN 201510952589 A CN201510952589 A CN 201510952589A CN 105543535 B CN105543535 B CN 105543535B
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CN105543535A (en
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倪俊杰
王永康
刘瑞环
张昊
贾正锋
黄宝旭
马杰
王长征
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Liaocheng University
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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
    • 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
    • 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
    • C22C32/0052—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 carbides
    • 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 invention belongs to nonferrous materials field, it is related to a kind of Al4SiC4With Cr cooperative reinforcings net/spherical copper product and preparation method thereof.The present invention utilizes hard phase dispersion-strengtherning and alloying element solution strengthening principle, using mechanical ball mill and synchronous hot pressing and sintering technique, has prepared high rigidity and high conductive Cu-base composites.The preparation method of material is：First by Cu and Al4SiC4Reactant powder carries out mechanical ball mill and obtains nanometer crystal powder in proportion, then is ground with Cr powder and the remaining Cu spheres of powder, finally with synchronous hot pressing and sintering technique, obtains Al4SiC4Enhanced copper chromium composite.Main feature of the present invention：Al4SiC4With Cr even dispersions in Copper substrate, hard phase is high with copper-titanium alloy basal body interface bond strength, and the hardness high conductivity of material is good.

Description

Al4SiC4With Cr cooperative reinforcings net/spherical copper product and preparation method
Technical field
The invention belongs to nonferrous materials field, it is related to a kind of Al4SiC4With Cr cooperative reinforcings net/spherical copper product and Its preparation method.
Background technology
The chemical stability of copper is strong, nonmagnetic, attractive and durable, conductive and heat-conductive, it is easy to welding, is widely used in electronics, leads to The fields such as news, household electrical appliances, traffic and mechanical engineering, can be used as such as automobile synchronizer tooth ring, circuit lead frame, air-conditioning cold The raw material of solidifying pipe, naval vessel and desalinization device.But, copper is but because its face-centered cubic (fcc) crystal structure and slip system are more Characteristic, and with low strong/hardness, shortcoming easy to wear.Which has limited copper component answering under big load working condition With.So, on the premise of sufficiently conductive property is ensured, the hardness and intensity for improving copper product are significant.
The Composite of copper product is the important channel for improving its intensity and hardness, and this method is usually through melting or powder smelting Gold process adds with high rigidity, dystectic hard phase to realize into copper.Hard phase mainly include metal oxide, Nitride and carbide, such as Al2O3、SiO2, AlN, WC, SiC, NbC, VC etc., the mechanism of these hard phases enhancing copper product and its Dislocation pinning effect to Cu is closely related, and in general, the distribution of hard phase is more uniform, then its dispersion-strengthened effect is better； Meanwhile, the reinforcing effect of hard phase is also relevant with its physicochemical characteristic.At present, powder metallurgical technique is to realize hard phase and copper product After the effective way of Composite, i.e. copper powder are fully mixed with additive, link is prepared according to " pressed compact-sintering ", block material is obtained Material.This method can be such that hard phase is evenly distributed among Copper substrate, however, hard phase is but difficult to soak with Copper substrate, cause Hard phase and the interfacial bonding property of matrix phase are poor, and this is unfavorable for the electric conductivity of material.Therefore, from suitable hard phase, improve Wetability between reinforcement and Copper substrate, is the important channel for improving copper product combination property.
In addition, adding the transition group alloying elements such as Cr, Zr, Fe, Ti in copper, the hardness and intensity of material can be also improved, because Play a part of solid solution aging for these elements.Strengthen effect and depend on the solid solution quantity of alloying element and distribution shape in Copper substrate Condition.Alloying element is difficult to solid solution in Cu in the state of the equilibrium, and reinforcing effect is restricted.It can be seen that, alloying element is improved in copper Solid solution quantity in matrix, be strengthen copper product it is strong/important channel of hardness.
The content of the invention
For problem present in the above-mentioned state of the art, it is contemplated that Al4SiC4Excellent anti-oxidant and hydration resistance, be based on Dispersion-strengtherning and the cooperative effect of solid solution aging strengthening mechanism, alloying element solid solubility in copper can be improved using high-energy ball milling And the characteristics of dispersed reinforcement, present invention comprehensive utilization multi-step mechanical ball mill and synchronous hot pressing and sintering technique there is provided A kind of Al4SiC4With Cr cooperative reinforcings net/spherical copper product and preparation method thereof.
The technical scheme is that：Al4SiC4With Cr cooperative reinforcing copper products, consisting of：(Cu100-xCrx)100-y (Al4SiC4)y；X is Cr elements in Cu100-xCrxAtomic percent in alloy, the at% of 1at%≤x≤10, y is Al4SiC4 Percent by volume in the composite, the vol % of 1 vol%≤y≤30.
Described Al4SiC4With Cr cooperative reinforcings net/spherical copper product, the at% of preferably 2at%≤x≤7 is (preferably , the at% of 3at%≤x≤6).
Described Al4SiC4With Cr cooperative reinforcings net/spherical copper product, the vol % of preferably 5 vol%≤y≤25 (preferably, 8 vol%≤x≤16 vol%).
Present invention also offers described Al4SiC4With the preparation method of Cr cooperative reinforcings net/spherical copper product, its step It is as follows：
Step 1：According to (Cu100-xCrx)100-y(Al4SiC4)yComposition proportion, weigh Cu, Cr and Al4SiC4Powder, and Stearic acid is weighed, ethanol is measured according to every 100 grams 0.5 ~ 5 milliliter of ratio, modulates the ball milling mistake that stearic acid is mixed with ethanol Program control preparation；
Step 2：The Al that step 1 is prepared4SiC4Controlled with the Cu raw material, steel ball and Mechanical Milling Process of half quality Agent, loads vacuum ball grinder, rear seal-cover, vacuumize, be filled with high-purity argon, carry out high-energy mechanical ball milling, Ball-milling Time 30 ~ 150 Hour, 250 ~ 500 revs/min of rotational speed of ball-mill obtains Cu bags Al4SiC4High-activity nano crystalline flour body；, will in oxygen-free environment Cu/Al4SiC4Nanometer crystal powder loads with mechanical milling process control together with Cr powder and the Cu powder of second half quality that step 1 prepares In the vacuum tank of agent, vacuumize and be filled with afterwards high-purity argon, and carry out on ball mill short time ball milling, ratio of grinding media to material now and Rotating speed, with above-mentioned ball milling Cu/Al4SiC4Parameter area it is identical, Ball-milling Time be 5 ~ 25 hours, obtain Cu, Cr and Al4SiC4 The powder being evenly distributed；
Step 3：The powder that step 2 is prepared into, is put into the mould of vacuum sintering funace, and vacuum in stove is evacuated to 10-3~10-4The pa orders of magnitude, carry out hot pressed sintering, heating and the asynchronous progress of pressure process, are warming up to after 420 DEG C and start to apply afterwards Plus-pressure, is furnace-cooled to room temperature after terminating, obtain that hardness is high and Cu-base composites with good conductivity.
Described preparation method, it is preferred that step 1：Cu, Cr and Al4SiC4The average grain diameter of powder is 10 microns, pure Degree is more than 99%.
Described preparation method, it is preferred that step 1：Stearic consumption is Cu, Cr and Al4SiC4Powder gross mass 0.1 ~ 5% (preferably, stearic consumption be Cu, Cr and Al4SiC4The 0.5 of powder gross mass ~ 2%).
Described preparation method, it is preferred that step 2：The Cu and Al that step 1 is prepared4SiC4Raw material, steel ball and machine Tool mechanical milling process controlling agent, loads vacuum ball grinder, ratio of grinding media to material 9：1~35：1（It is preferred that, 10：1~20：1）.
Described preparation method, it is preferred that step 3：Sintering temperature is 600-1000 DEG C, and sintering time is that 0.5-5 is small When（It is preferred that, sintering temperature 850-950, sintering time 2-4 hours）.
Described preparation method, it is preferred that step 3：Pressure reaches 30-200 MPa during sintered heat insulating（It is preferred that, burn Pressure reaches 80-150 MPa during knot insulation）.
The invention belongs to nonferrous materials field, it is related to a kind of Al4SiC4With Cr cooperative reinforcings net/spherical copper product and Its preparation method.The present invention utilizes hard phase dispersion-strengtherning and alloying element solution strengthening principle, using mechanical ball mill and synchronization Hot pressing and sintering technique, has prepared high rigidity and high conductive Cu-base composites.The preparation method of material is：First by Cu And Al4SiC4Reactant powder carries out mechanical ball mill and obtains nanometer crystal powder in proportion, then is ground with Cr powder and the remaining Cu spheres of powder, most Afterwards with synchronous hot pressing and sintering technique, Al is obtained4SiC4Enhanced copper chromium composite.Main feature of the present invention：Al4SiC4With Cr even dispersions are in Copper substrate, and hard phase is high with copper-titanium alloy basal body interface bond strength, and the hardness high conductivity of material is good It is good.
The excellent effect of the present invention is that, due to using above-mentioned technical proposal, Cu-base composites produced by the present invention are with adding Plus the Cu-base composites of other single hardening constituents are compared, with more excellent hardness and electric conductivity；Meanwhile, reality of the invention Apply and employ common equipment, be easy to Technique Popularizing and large-scale production.
Brief description of the drawings
Fig. 1 is the Al of the embodiment of the present invention 14SiC4With Cr cooperative reinforcings net/spherical copper product tissue and distribution diagram of element.
Embodiment
Below with reference to embodiment, the present invention will be further described, and embodiments of the invention are merely to illustrate the present invention's Technical scheme, and the non-limiting present invention.
Cu and Cr raw materials used can be bought from market in embodiment.Al4SiC4For fabricated material, its preparation method is as follows：
Step 1：According to Al4SiC4Composition proportion, weigh Al, Si and C more than 99% of 10 microns of purity of average grain diameter Powder, weighs stearic acid according to every 100 grams of powders, 1 gram of stearic acid ratio, is used as mechanical milling process controlling agent；
Step 2：Raw material powder that step 1 is prepared, stearic acid and steel ball load vacuum ball grinder, rear seal-cover, vacuumize, High-purity argon is filled with, high-energy mechanical ball milling is carried out, Ball-milling Time 20 hours, 380 revs/min of rotational speed of ball-mill obtains mixed powder；
Step 3：The powder that step 2 is prepared into, is put into vacuum sintering furnace, and vacuum in stove is evacuated to 2 × 10-3Pa it After be sintered, sintering temperature be 1800 DEG C, sintering time be 3 hours, be furnace-cooled to room temperature after terminating, Al can be obtained4SiC4 Powder.
The present invention has net/spherical characteristics (Cu100-xCrx)100-y(Al4SiC4)yThe preparation method of material, conventional steps are such as Under：
Step 1：According to (Cu100-xCrx)100-y(Al4SiC4)yComposition proportion, it is 10 microns of purity to weigh average grain diameter Cu, Cr and Al more than 99%4SiC4Powder, and the stearic acid suitable with Cu, Ti and C powder gross mass 0.1 ~ 5% is weighed, press Ratio according to every 100 grams 0.5 ~ 5 milliliter measures ethanol, modulates the mechanical milling process controlling agent that stearic acid is mixed with ethanol.
Step 2：The Al that step 1 is prepared4SiC4With the Cu powder, steel ball and Mechanical Milling Process controlling agent of half quality, dress Enter vacuum ball grinder, ratio of grinding media to material 8：1~40：1, rear seal-cover, vacuumize, be filled with high-purity argon, carry out high-energy mechanical ball milling, ball milling 30 ~ 150 hours time, 250 ~ 500 revs/min of rotational speed of ball-mill obtains Cu bags Al4SiC4High-activity nano crystalline flour body；In anaerobic In environment, by Al4SiC4/ Cu nanometer crystal powders load with ball milling together with Cr powder and the Cu powder of second half quality that step 1 prepares In the vacuum tank of process control agent, high-purity argon is vacuumized and be filled with afterwards, and short time ball milling is carried out on ball mill, now Ratio of grinding media to material and rotating speed, with above-mentioned ball milling Al4SiC4/ Cu parameter area is identical, Ball-milling Time be 5 ~ 20 hours, obtain Cu, Cr and Al4SiC4The powder being evenly distributed.
Step 3：The powder that step 2 is prepared into, is put into the mould of vacuum sintering funace, and vacuum in stove is evacuated to 10-3~10-4The pa orders of magnitude, carry out hot pressed sintering afterwards, heat progress synchronous with pressure process, sintering temperature is 600-1000 DEG C, sintering time is 0.5-5 hours, and pressure reaches 30-150 MPa during sintered heat insulating, and room temperature is furnace-cooled to after terminating, and is obtained Hardness is high and Cu-base composites with good conductivity.
Embodiment 1：
(1) Cu bags Al4SiC4The preparation of nanometer crystal powder：Based on (Cu95Cr5)91(Al4SiC4)9Composition proportion, weigh flat Cu, Ti and the Al of equal 10 microns of particle diameter and purity 99.5%4SiC4Powder, and with the stearic acid suitable with powder gross mass 1.5% and 3 milliliters/100 grams of alcohol mixture is mechanical milling process controlling agent；Al4SiC4Cu powder and mechanical milling process control with half quality Preparation is fitted into vacuum ball grinder, ratio of grinding media to material 15：1, rear seal-cover, vacuumize, be filled with high-purity argon, carry out high-energy mechanical ball milling, Ball-milling Time 100 hours, 400 revs/min of rotational speed of ball-mill obtains Cu bags Al4SiC4High-activity nano crystalline flour body.
(2) preparation of uniform powder：The Cu bags Al that step 1 is prepared4SiC4Nanometer crystal powder is expected as forerunner, and and Cr Powder, second half Cu powder, steel ball, Mechanical Milling Process controlling agent together, in oxygen-free environment, are put into vacuum tank, take out true afterwards It is empty and be filled with high-purity argon, and carry out on ball mill mechanical ball mill, ratio of grinding media to material now and rotating speed, the ball milling parameter expected with forerunner Scope is identical, and Ball-milling Time is shorten to 8 hours, obtains the powder that Cu, Ti and C are evenly distributed.
(3) synchronous hot pressed sintering：The powder that step 2 is prepared into, is put into the mould of vacuum sintering funace, stove Interior vacuum is evacuated to 3 × 10-3Pa, is heated afterwards, starts simultaneously at application pressure, and when temperature is increased to 900 DEG C, pressure reaches To 90MPa, heat-insulation pressure keeping sintering 2 hours, subsequent material furnace cooling to room temperature, obtain hardness high and with good conductivity afterwards Cu-base composites.
Comparative example 1：
Using ball powder-grinding-hot-pressing sintering technique, by add SiC (10 microns of grain size average out to) prepare with Strengthen powder ball milling parameter and sintering parameter and implementation in phase volume fraction identical Cu-base composites, comparative example in example 1 Example 1 it is identical.
Hardness is measured using THV-100XS Vickers hardnesses Standard Machine, on-load pressure is 1.96N during test, and the retention time is 15S；The electric conductivity that conductivity apparatus measures material is vortexed using FQR7501A, as a result as shown in table 1.
The example 1 of table 1. and the hardness and conductivity test data of comparative example 1
Knowable to the data of contrast table 1, Al4SiC4It is higher than with the hardness and conductance of Cr cooperative reinforcing copper products in comparative example The respective value of material, compared with comparative example 1, the material hardness of embodiment 1 improves 17.6%, and conductance is improved 27.7%。
Fig. 1 is the Al of the embodiment of the present invention 14SiC4With Cr cooperative reinforcings net/spherical copper product tissue and distribution diagram of element. As seen from Figure 1 in fine and close acid bronze alloy, mesh-like area is rich in Cu, and Al4SiC4It is evenly distributed on Cr among material.
(1) Cu bags Al4SiC4The preparation of nanometer crystal powder：Based on (Cu93Cr7)87(Al4SiC4)13Composition proportion, weigh flat Cu, Cr and the Al of equal 10 microns of particle diameter and purity on 99.5%4SiC4Powder, and with the stearic acid suitable with powder gross mass 1.0% Alcohol mixture with 2 milliliters/100 grams is mechanical milling process controlling agent；Al4SiC4With the Cu powder and mechanical milling process of half quality Controlling agent is fitted into vacuum ball grinder, ratio of grinding media to material 10：1, rear seal-cover, vacuumize, be filled with high-purity argon, carry out high energy mechanical ball Mill, Ball-milling Time 84 hours, 380 revs/min of rotational speed of ball-mill obtains Cu bags Al4SiC4High-activity nano crystalline flour body.
(2) preparation of uniform powder：The Cu bags Al that step 1 is prepared4SiC4Nanometer crystal powder is expected as forerunner, and and Cr Powder, second half Cu powder, steel ball, Mechanical Milling Process controlling agent together, in oxygen-free environment, are put into vacuum tank, take out true afterwards It is empty and be filled with high-purity argon, and carry out on ball mill mechanical ball mill, ratio of grinding media to material now and rotating speed, the ball milling parameter expected with forerunner Scope is identical, and Ball-milling Time is shorten to 6 hours, obtains Cu, Cr and Al4SiC4The powder being evenly distributed.
(3) synchronous hot pressed sintering：The powder that step 2 is prepared into, is put into the mould of vacuum sintering funace, stove Interior vacuum is evacuated to 2.5 × 10-3Pa, is heated afterwards, starts simultaneously at application pressure, when temperature is increased to 920 DEG C, pressure 100MPa is reached, heat-insulation pressure keeping is sintered 3 hours afterwards, subsequent material furnace cooling to room temperature, obtain hardness height and electric conductivity is good Good Cu-base composites.
Comparative example 2：
Using ball powder-grinding-hot-pressing sintering technique, by add SiC (10 microns of grain size average out to) prepare with Strengthen powder ball milling parameter and sintering parameter and implementation in phase volume fraction identical Cu-base composites, comparative example in example 2 Example 2 it is identical.
Hardness is measured using THV-100XS Vickers hardnesses Standard Machine, on-load pressure is 1.96N during test, and the retention time is 15S；The electric conductivity that conductivity apparatus measures material is vortexed using FQR7501A, as a result as shown in table 1.
The example 2 of table 2. and the hardness and conductivity test data of comparative example 2
Knowable to the data of contrast table 2, Al4SiC4It is higher than with the hardness and conductance of Cr cooperative reinforcing copper products in comparative example The respective value of material, compared with comparative example 2, the material hardness of embodiment 2 improves 25.7%, and conductance is improved 28.3%。
Embodiment 3：
(1) Cu bags Al4SiC4The preparation of nanometer crystal powder：Based on (Cu95Cr5)84(Al4SiC4)16Composition proportion, weigh flat Cu, Ti and the Al of equal 10 microns of particle diameter and purity 99.5%4SiC4Powder, and with the stearic acid suitable with powder gross mass 1.0% and 1 milliliter/100 grams of alcohol mixture is mechanical milling process controlling agent；Al4SiC4Cu powder and mechanical milling process control with half quality Preparation is fitted into vacuum ball grinder, ratio of grinding media to material 10：1, rear seal-cover, vacuumize, be filled with high-purity argon, carry out high-energy mechanical ball milling, Ball-milling Time 72 hours, 350 revs/min of rotational speed of ball-mill obtains Cu bags Al4SiC4High-activity nano crystalline flour body.
(2) preparation of uniform powder：The Cu bags Al that step 1 is prepared4SiC4Nanometer crystal powder is expected as forerunner, and and Cr Powder, second half Cu powder, steel ball, Mechanical Milling Process controlling agent together, in oxygen-free environment, are put into vacuum tank, take out true afterwards It is empty and be filled with high-purity argon, and carry out on ball mill mechanical ball mill, ratio of grinding media to material now and rotating speed, the ball milling parameter expected with forerunner Scope is identical, and Ball-milling Time is shorten to 8 hours, obtains Cu, Cr and Al4SiC4The powder being evenly distributed.
(3) synchronous hot pressed sintering：The powder that step 2 is prepared into, is put into the mould of vacuum sintering funace, stove Interior vacuum is evacuated to 1 × 10-3Pa, is heated afterwards, starts simultaneously at application pressure, and when temperature is increased to 950 DEG C, pressure reaches To after 80MPa, heat-insulation pressure keeping is sintered 2 hours, subsequent material furnace cooling to room temperature, and acquisition hardness is high and copper with good conductivity Based composites.
Comparative example 3：
Using ball powder-grinding-hot-pressing sintering technique, by add SiC (10 microns of grain size average out to) prepare with Strengthen powder ball milling parameter and sintering parameter and implementation in phase volume fraction identical Cu-base composites, comparative example in example 3 Example 3 it is identical.
Hardness is measured using THV-100XS Vickers hardnesses Standard Machine, on-load pressure is 1.96N during test, and the retention time is 15S；The electric conductivity that conductivity apparatus measures material is vortexed using FQR7501A, as a result as shown in table 3.
The example 3 of table 3. and the hardness and conductivity test data of comparative example 3
Knowable to the data of contrast table 3, Al4SiC4It is higher than with the hardness and conductance of Cr cooperative reinforcing copper products in comparative example The respective value of material, compared with comparative example 3, the material hardness of embodiment 3 improves 13.1%, and conductance is improved 43.5%。
The application is based on Shandong Province's development in science and technology planning item (numbering：2014GGX102016) with natural section of Shandong Province NSF National Science Foundation (numbering：ZR2013EMM010) subsidize.

Claims (9)

1.Al4SiC4With Cr cooperative reinforcings net/spherical copper product, it is characterized in that, constitute and be：(Cu100-xCrx)100-y(Al4SiC4)y； X is Cr elements in Cu100-xCrxAtomic percent in alloy, the at% of 1at%≤x≤10, y is Al4SiC4In composite In percent by volume, the vol % of 1 vol%≤y≤30.
2. the Al described in claim 14SiC4With Cr cooperative reinforcings net/spherical copper product, it is characterized in that, 2at%≤x≤7 at%。
3. the Al described in claim 14SiC4With Cr cooperative reinforcings net/spherical copper product, it is characterized in that, 5 vol%≤y≤ 25 vol %。
4. any one of the claim 1-3 Al4SiC4With the preparation method of Cr cooperative reinforcings net/spherical copper product, its feature It is that step is as follows：
Step 1：According to (Cu100-xCrx)100-y(Al4SiC4)yComposition proportion, weigh Cu, Cr and Al4SiC4Powder, and weigh hard Resin acid, ethanol is measured according to every 100 grams 0.5 ~ 5 milliliter of ratio, modulates the mechanical milling process control that stearic acid is mixed with ethanol Agent；
Step 2：The Al that step 1 is prepared4SiC4With the Cu raw material, steel ball and Mechanical Milling Process controlling agent of half quality, dress Enter vacuum ball grinder, rear seal-cover, vacuumize, be filled with high-purity argon, carry out high-energy mechanical ball milling, Ball-milling Time 30 ~ 150 hours, 250 ~ 500 revs/min of rotational speed of ball-mill, obtains Cu bags Al4SiC4High-activity nano crystalline flour body；In oxygen-free environment, by Cu/ Al4SiC4Nanometer crystal powder loads with mechanical milling process controlling agent together with Cr powder and the Cu powder of second half quality that step 1 prepares In vacuum tank, high-purity argon is vacuumized and be filled with afterwards, and carry out on ball mill short time ball milling, ratio of grinding media to material now and turn Speed, with above-mentioned ball milling Cu/Al4SiC4Parameter area it is identical, Ball-milling Time be 5 ~ 25 hours, obtain Cu, Cr and Al4SiC4Point The uniform powder of cloth；
Step 3：The powder that step 2 is prepared into, is put into the mould of vacuum sintering funace, and vacuum in stove is evacuated to 10-3~ 10-4The pa orders of magnitude, carry out hot pressed sintering, heating and the asynchronous progress of pressure process, are warming up to after 420 DEG C and start to apply pressure afterwards Power, is furnace-cooled to room temperature after terminating, obtain that hardness is high and Cu-base composites with good conductivity.
5. the preparation method described in claim 4, it is characterized in that, step 1：Cu, Cr and Al4SiC4The average grain diameter of powder is 10 Micron, purity is more than 99%.
6. the preparation method described in claim 4, it is characterized in that, step 1：Stearic consumption is Cu, Cr and Al4SiC4Powder The 0.1 ~ 5% of gross mass.
7. the preparation method described in claim 4, it is characterized in that, step 2：The Cu and Al that step 1 is prepared4SiC4Raw material, steel Ball and Mechanical Milling Process controlling agent, load vacuum ball grinder, ratio of grinding media to material 9：1~35：1.
8. the preparation method described in claim 4, it is characterized in that, step 3：Sintering temperature is 600-1000 DEG C, and sintering time is 0.5-5 hours.
9. the preparation method described in claim 4, it is characterized in that, step 3：Pressure reaches 30-200 MPa during sintered heat insulating.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1188158A (en) * 1997-01-13 1998-07-22 中国科学院金属研究所 Method for preparing metal-base composite material reinforced by non-continuous ceramics reinforcing agent
CN1995436A (en) * 2006-11-03 2007-07-11 大连交通大学 Copper base particle reinforced friction material
CN102367526A (en) * 2011-10-20 2012-03-07 北京科技大学 Method for preparing evenly dispersed metal matrix composite friction material through mechanical alloying

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5891065A (en) * 1981-11-27 1983-05-30 旭硝子株式会社 Manufacture of silicon carbide ceramic sintered body

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1188158A (en) * 1997-01-13 1998-07-22 中国科学院金属研究所 Method for preparing metal-base composite material reinforced by non-continuous ceramics reinforcing agent
CN1995436A (en) * 2006-11-03 2007-07-11 大连交通大学 Copper base particle reinforced friction material
CN102367526A (en) * 2011-10-20 2012-03-07 北京科技大学 Method for preparing evenly dispersed metal matrix composite friction material through mechanical alloying

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