CN103331451A - Method for preparing aluminum oxide (Al2O3) dispersed and strengthened copper alloy powder - Google Patents

Abstract

The invention provides a method for preparing aluminum oxide (Al2O3) dispersed and strengthened copper alloy powder, and the method comprises the following steps that a certain amount of copper (Cu) powder, aluminum (Al) powder, cupric oxide (CuO) powder or cuprous oxide (Cu2O) powder and grinding aid are weighed, mixed by a certain proportion, added into a high-energy horizontal stirring ball mill, and ball milling is performed under the protection of inert gas; then the mixed powder after ball milling is added into an energy-saving program-controlled tube furnace; vacuumizing is carried out; hydrogen-argon mixed gas is fed in, heated for a period of time and cooled down, and the Al2O3 dispersed and strengthened copper alloy powder is obtained. The Al2O3 dispersed and strengthened copper alloy powder which is prepared through a reaction ball milling method has the advantages of simple process, short time of ball milling, good dispersion effect of the obtained alloy powder and the like, the grinding aid stearic acid is added during the preparation process, so that the problem that the powder is cured during the ball milling process can be effectively solved.

Description

A kind of production Al 2O 3The method of dispersion strengthening copper alloy powder

Technical field

The present invention relates to a kind of production Al₂O₃The method of dispersion strengthening copper alloy powder especially relates to a kind of reaction ball milling method and produces Al₂O₃The method of dispersion strengthening copper alloy powder.

Background technology

Al₂O₃The dispersion-strengtherning carbon/carbon-copper composite material is present most widely used dispersion-strengtherning carbon/carbon-copper composite material, intensity height not only, electrical and thermal conductivity and fine copper approach, and have that good high temperature resistance is softening, anti electric arc corrosion, high conductivity and antiwear property.Al₂O₃The dispersion-strengtherning carbon/carbon-copper composite material is faced with vast market at home, now has been applied in aspects such as replacing silver based contact material, continuous casting steel machine crystallizer, high strength power line, resistance welding electrode.And Al₂O₃The dispersion strengthening copper alloy powder is preparation Al₂O₃The necessary raw material of dispersion-strengtherning carbon/carbon-copper composite material, the quality of its disperse effect directly affects Al₂O₃The dispersion-strengthened Cu performance of composites.Dispersion-strengtherning refers to a kind of by add the reinforcement means of a kind of material of hard particles in homogeneous material.Thereby the essence of dispersion-strengtherning is to utilize the motion of the ultrafine dust obstruction dislocation of even dispersion to improve the mechanical property of material under hot conditions, the invigoration effect of second phase of its even dispersion had both improved elevated temperature strength and the hardness of material, can obviously not reduce the electric conductivity of alloy again, thereby make this material have good comprehensive performances.

At present, preparation Al₂O₃Dispersion strengthening copper alloy powder technology mainly contains mechanical alloying method, internal oxidation, nitrate fusion method, coprecipitation etc.Mechanical alloying method is a kind of solid state powder treatment process, adopts this method to can be used to prepare ceramic particle and strengthens metal-base composites.This method was at first proposed by Benjamin in 1970.Its basic principle is that required powder is placed the high energy ball mill ball milling, and powder is subjected to intense plastic strain, cold welding and fragmentation repeatedly in the mechanical milling process, forms the comparatively average particle of size.Mechanical alloying method prepares Al₂O₃The method of dispersion strengthening copper alloy powder is Cu powder and Al₂O₃Powder joins ball milling a period of time in the high energy ball mill, and powder is subjected to intense plastic strain, cold welding and fragmentation repeatedly in the mechanical milling process, forms second powder that is evenly distributed mutually, can get Al again behind hydrogen reducing₂O₃The dispersion strengthening copper alloy powder.It is simple that the method has technology, low cost and other advantages, but have certain defective, namely in mechanical milling process, keep away unavoidable Al₂O₃The reunion of powder exists the bigger Al of particle₂O₃Powder; Internal oxidation is to commercially produce Al at present₂O₃One of main method of dispersion strengthening copper alloy powder, interior oxidation refer to that oxygen is dissolved in the alloy phase in the alloy oxidation process, and spread in alloy phase, and constituent element and oxygen more active in the alloy react, in the inner process that generates oxide particle of alloy.The preparation technology of internal oxidation is: melting Cu-Al alloy melt, powder by atomization then; With powder and oxidant (CuO or the Cu that makes₂The O attritive powder) mix mutually, under the high temperature of 1073～1223K, compound is carried out interior oxidation processes then, in this course, oxidant decomposes, and the oxygen of generation is diffused in the particle of Cu-Al alloy powder, and wherein Al is by preferential oxidation; After treating that the Al oxidation is intact, powder heat in reducing atmosphere remove wherein unnecessary oxygen, thereby obtain even distribution Al on the Cu matrix₂O₃The composite granule of particle.The method can obtain the Al that small and dispersed distributes₂O₃Particle, the Al of generation₂O₃Particle has higher thermodynamic stability, the gained material property is higher, but adopt the method to exist oxidization time length, complex process, cost than problems such as height, and interior oxidizing process is that oxygen is to the process of metal inside diffusion, when if Al content surpasses 1wt% in the Cu-Al alloy, the aluminium oxide that forms is fine and close continuously film, continues to cause oxidation not thorough to the granule interior diffusion thereby hinder oxygen atom.

Summary of the invention

Prepare Al in order to solve the mechanical alloying method that exists in the prior art₂O₃Unavoidably there is the bigger Al of particle during the dispersion strengthening copper alloy powder₂O₃Powder; Internal oxidation then exist complex process, cost higher, be difficult to prepare high Al₂O₃Problems such as content dispersion strengthening copper alloy powder the invention provides a kind of production Al₂O₃The method of dispersion strengthening copper alloy powder takes by weighing a certain amount of Cu powder, Al powder, CuO powder (or Cu₂The O powder), after grinding aid mixes in proportion; add in the horizontal agitating ball mill of high energy, ball milling under the protection of inert gas atmospheres such as argon gas or nitrogen, ratio of grinding media to material is 10:1～15:1; drum's speed of rotation is 400rpm～500rpm; the ball milling time is 8h～10h, and then that ball milling is good mixed-powder adds in the energy-conservation program control tube furnace, vacuumizes; feeding hydrogen when temperature is 450 ℃～600 ℃-argon-mixed; the feeding time is 30min～60min, treats can take out after the tube furnace cooling, obtains Al₂O₃The dispersion strengthening copper alloy powder.

Wherein, in the ratio of grinding media to material, the ball of employing is that diameter is the stainless steel ball of 2mm to 5mm; In the described hydrogen-argon-mixed, by volume, the hydrogen by 10% and 90% argon gas are formed.

The present invention adopts above technical scheme, and its advantage is, provides a kind of reaction ball milling legal system to be equipped with Al₂O₃The method of dispersion strengthening copper alloy powder.Know-why is: the reaction ball milling legal system is equipped with Al₂O₃The dispersion strengthening copper alloy powder is the process that stirring-type high-energy ball milling method and chemical reaction combine, have that technology is simple, steady quality, easy to operate, be convenient to advantage such as large-scale production.The stirring-type high energy ball mill stirs abrasive media by agitator and produces impact, friction and shear action, and material is pulverized.In the stirring-type high energy ball mill, puddler stirring ball on the shaft produces sizable speed and passes to powder, powder is produced stronger abrasive action, the high speed rotary motion of ball produces swirling action the strong circulation of powder generation is made the powder grinding evenly around axle simultaneously, and its mechanical energy is delivered to powder by the high-speed rotation of agitator and ball.When rotational speed of ball-mill higher, along with the prolongation of ball milling time, when the ball milling energy increases gradually, Al powder and CuO powder (or Cu₂The O powder) each other chemical reaction can take place, will obtain Al₂O₃Particle, effects such as the particle of these generations and original powder mix in mechanical milling process, fragmentation, seam, plastic deformation, Al₂O₃Particle will be evenly distributed in the Cu matrix.After the mixed-powder of gained passed through hydrogen reducing at a certain temperature, residual CuO powder (or Cu in the mixed-powder₂The O powder) the Cu powder will be reduced to, Al can be obtained₂O₃The dispersion strengthening copper alloy powder.

Preferably, the purity of described Cu powder is not less than 99.8%, and powder size is not more than 74 μ m.

Preferably, the purity that described Al powder is pure aluminium powder is for being not less than 99.8%, and powder size is not more than 44 μ m.

Preferably, described CuO powder or Cu₂The purity of O powder is not less than 99.0%, and powder size is not more than 74 μ m.

Preferably, CuO powder or Cu₂The ratio of the amount of substance of O powder and Al powder is between 3:2～2:1.

Preferably, described stearic quality is 2% Cu opaque amount.

Preferably, described inert gas adopts argon gas or nitrogen.

Preferably, described grinding aid adopts stearic acid.

Beneficial effect of the present invention comprises:

1, the present invention adopts the Al of reaction ball milling method preparation₂O₃The dispersion strengthening copper alloy powder can prepare different al by the amount ratio that changes raw material₂O₃The Al of content₂O₃The dispersion strengthening copper alloy powder, and increased the grinding aid stearic acid in process of production, can prevent that effectively agglomeration appears in powder in the mechanical milling process.

2, adopt the horizontal agitating ball mill high-energy ball milling of high energy, can realize temperature programmed control, the energy input is ground in programme-control, omnidistance real-time data record, and full-automatic programme-control can guarantee operating personnel's safety, and equipment failure rate is low, is convenient to large-scale production Al₂O₃The dispersion strengthening copper alloy powder.Can mate not isometric ball grinder according to the needs of producing, the ball grinder volume is more big, producible Al₂O₃The amount of dispersion strengthening copper alloy powder is more big, can effectively improve preparation Al₂O₃The problem that dispersion strengthening copper alloy powder output is little, can not mass production.

3, than traditional handicrafts such as mechanical alloying methods, under the prerequisite of ensuring the quality of products, method of the present invention has shortened the ball milling time, has improved production efficiency.

Description of drawings

Fig. 1 is that mass fraction is 0.4% Al₂O₃Dispersion strengthening copper alloy powder SEM figure.

Fig. 2 is that mass fraction is 0.6% Al₂O₃Dispersion strengthening copper alloy powder SEM figure.

Fig. 3 is the Al of embodiment 3 gained₂O₃Dispersion strengthening copper alloy powder SEM figure.

The specific embodiment

Below in conjunction with accompanying drawing, more excellent embodiment of the present invention is described in further detail:

The invention discloses the horizontal agitating ball mill reaction ball milling of a kind of employing high energy and be convenient to suitability for industrialized production Al₂O₃The method of dispersion strengthening copper alloy powder the steps include: to take by weighing a certain amount of Cu powder, Al powder, CuO powder or Cu₂The O powder; mix the back and add in the horizontal agitating ball mill of high energy, ball milling under the protection of inert gas atmospheres such as argon gas or nitrogen, ratio of grinding media to material is 10:1～15:1; drum's speed of rotation is 400rpm～500rpm; the ball milling time is 8h～10h, and then that ball milling is good mixed-powder adds in the energy-conservation program control tube furnace, vacuumizes; feeding hydrogen when temperature is 450 ℃～600 ℃-argon-mixed; through hydrogen reducing 30min～60min, treat can take out after the tube furnace cooling, obtain Al₂O₃The dispersion strengthening copper alloy powder.

Method one: take by weighing a certain amount of Cu powder, Al powder, CuO powder, wherein the Cu powder is that pure copper powder (purity 〉=99.8%, powder size≤74 μ m), Al powder are pure aluminium powder (purity is 〉=99.8%, powder size≤44 μ m), CuO powder (purity 〉=99.0%, powder size≤74 μ m), Al₂O₃Disperse phase mass fraction in copper alloy powder is that 0.4%～2.5%, Al opaque amount is according to required preparation Al₂O₃Al in the dispersion strengthening copper alloy powder₂O₃Amount determine; the ratio of the amount of substance of CuO powder and Al powder is between 3:2～2:1; and the stearic quality of grinding aid of adding is about 2% Cu opaque amount; after this ratio mixing; add in the horizontal agitating ball mill of high energy; ball milling under the protection of inert gas atmospheres such as argon gas or nitrogen; ratio of grinding media to material is 10:1～15:1, and drum's speed of rotation is 400rpm～500rpm, and the ball milling time is 8h～10h; then that ball milling is good mixed-powder adds in the energy-conservation program control tube furnace; vacuumize, feeding hydrogen when temperature is 450 ℃～600 ℃-argon-mixed is through hydrogen reducing 30min～60min; treat to take out after the tube furnace cooling, obtain Al₂O₃The dispersion strengthening copper alloy powder.

Method two: take by weighing a certain amount of Cu powder, Al powder, Cu₂The O powder, wherein the Cu powder is that pure copper powder (purity 〉=99.8%, powder size≤74 μ m), Al powder are pure aluminium powder (purity is 〉=99.8%, powder size≤44 μ m), CuO powder (purity 〉=99.0%, powder size≤74 μ m), Al₂O₃Disperse phase mass fraction in copper alloy powder is that 0.3%～2.5%, Al opaque amount is according to required preparation Al₂O₃Al in the dispersion strengthening copper alloy powder₂O₃Amount determine Cu₂The ratio of the amount of substance of O powder and Al powder is between 3:2～2:1; and the stearic quality of grinding aid of adding is about 2% Cu opaque amount; after this ratio mixing; add in the horizontal agitating ball mill of high energy; ball milling under the protection of inert gas atmospheres such as argon gas or nitrogen; ratio of grinding media to material is 10:1～15:1; drum's speed of rotation is 400rpm～500rpm; the ball milling time is 8h～10h, and then that ball milling is good mixed-powder adds in the energy-conservation program control tube furnace, vacuumizes; feeding hydrogen when temperature is 450 ℃～600 ℃-argon-mixed; through hydrogen reducing 30min～60min, treat can take out after the tube furnace cooling, obtain Al₂O₃The dispersion strengthening copper alloy powder.

Embodiment 1:

Be the Al of feedstock production 0.4% with Cu powder, Al powder, CuO powder₂O₃The dispersion strengthening copper alloy powder

Test raw materials used: the Cu powder is that pure copper powder (purity 〉=99.8%, powder size≤74 μ m), Al powder are pure aluminium powder (purity is 〉=99.8%, powder size≤44 μ m), CuO powder (purity 〉=99.0%, powder size≤74 μ m), stearic acid

Accurate weighing Cu powder 1500g; Al powder 4.76g; CuO powder 28.09g; stearic acid 30g; join in the horizontal agitating ball mill of high energy after fully mixing; ratio of grinding media to material is 10:1; after the ball grinder sealing; vacuumize twice of logical argon gas, and continuous repetitive operation more earlier; mechanical milling process is in the argon shield atmosphere; before the ball mill start, earlier recirculated cooling water is opened, prevented that the ball mill temperature is too high, damage ball mill; it is 150rpm trial run 10 minutes that rotational speed of ball-mill is set; rotating speed is 460rpm operation 10 hours,, after the ball mill startup; ball mill moves automatically by set program. and ball milling finished after 3 hours; powder can be taken out, again the powder behind the ball milling be added in the energy-conservation program control tube furnace, vacuumize the back and heat up; in the time of 480 ℃, feed hydrogen-argon-mixed 40 minutes, behind hydrogen reducing, obtain Al₂O₃The dispersion strengthening copper alloy powder is 0.4% Al as Fig. 1₂O₃The SEM figure of dispersion strengthening copper alloy powder.

Embodiment 2

Be the Al of feedstock production 0.6% with Cu powder, Al powder, CuO powder₂O₃The dispersion strengthening copper alloy powder

Test raw materials used: the Cu powder is that pure copper powder (purity 〉=99.8%, powder size≤74 μ m), Al powder are pure aluminium powder (purity is 〉=99.8%, powder size≤44 μ m), CuO powder (purity 〉=99.0%, powder size≤74 μ m), stearic acid

Accurate weighing Cu powder 1500g; Al powder 6.78g; CuO powder 40g; stearic acid 30g; fully mixing the back adds in the horizontal agitating ball mill of high energy; ratio of grinding media to material is 11:1; after the ball grinder sealing; vacuumize twice of logical argon gas, and continuous repetitive operation more earlier; mechanical milling process is in the argon shield atmosphere; before the ball mill start, earlier recirculated cooling water is opened, prevented that the ball mill temperature is too high, damage ball mill; it is 150rpm trial run 10 minutes that rotational speed of ball-mill is set; rotating speed is 460rpm operation 10 hours,, after the ball mill startup; ball mill moves automatically by set program. and ball milling finished after 3 hours; powder can be taken out, again the powder behind the ball milling be added in the energy-conservation program control tube furnace, vacuumize the back and heat up; in the time of 480 ℃, feed hydrogen-argon-mixed 40 minutes, behind hydrogen reducing, obtain Al₂O₃The dispersion strengthening copper alloy powder.Be 0.6% Al as Fig. 2₂O₃The SEM figure of dispersion strengthening copper alloy powder.

Embodiment 3

With Cu powder, Al powder, Cu₂The O powder is the Al of feedstock production 0.6%₂O₃The dispersion strengthening copper alloy powder

Test raw materials used: the Cu powder is that pure copper powder (purity 〉=99.8%, powder size≤74 μ m), Al powder are pure aluminium powder (purity is 〉=99.8%, powder size≤44 μ m), Cu₂O powder (purity 〉=99.0%, powder size≤74 μ m), stearic acid

Accurate weighing Cu powder 1500g, Al powder 6.78g, Cu₂O powder 53.95g; stearic acid 30g; fully mixing the back adds in the horizontal agitating ball mill of high energy; ratio of grinding media to material is 11:1; after the ball grinder sealing; vacuumize twice of logical argon gas, and continuous repetitive operation more earlier; mechanical milling process is in the argon shield atmosphere; before the ball mill start, earlier recirculated cooling water is opened, prevented that the ball mill temperature is too high, damage ball mill; it is 150rpm trial run 10 minutes that rotational speed of ball-mill is set; rotating speed is 460rpm operation 10 hours,, after the ball mill startup; ball mill moves automatically by set program. and ball milling finished after 3 hours; powder can be taken out, again the powder behind the ball milling be added in the energy-conservation program control tube furnace, vacuumize the back and heat up; in the time of 480 ℃, feed hydrogen-argon-mixed 40 minutes, behind hydrogen reducing, obtain Al as shown in Figure 3₂O₃The dispersion strengthening copper alloy powder.

Reaction ball milling legal system provided by the present invention is equipped with Al₂O₃The dispersion strengthening copper alloy powder has been inherited the advantage of mechanical alloying method and internal oxidation simultaneously, not only tiny, the even dispersion distribution of alumina particle in the gained alloy powder, can reach the requirement of high-quality powder, and solve and have the bigger Al of particle in the mechanical alloying method preparation process₂O₃The problem of powder, internal oxidation can not prepare high Al₂O₃Problems such as the alloy powder of content, the matrix grain size of reaction ball milling method gained alloyed powder is littler, Al₂O₃Distribution of particles is more even.

Above content be in conjunction with concrete preferred embodiment to further describing that the present invention does, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.

Claims (10)

1. produce Al for one kind₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, comprising: take by weighing a certain amount of Cu powder, Al powder, CuO powder or Cu₂After O powder, grinding aid mix in proportion, add in the horizontal agitating ball mill of high energy ball milling under the inert gas atmosphere protection; then that ball milling is good mixed-powder adds in the energy-conservation program control tube furnace, vacuumizes feeding hydrogen-argon-mixed; heating a period of time, obtain Al after the cooling again₂O₃The dispersion strengthening copper alloy powder.

2. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, the purity of described Cu powder is not less than 99.8%, and powder size is not more than 74 μ m, and described Al powder is pure aluminium powder, and purity is for being not less than 99.8%, and powder size is not more than 44 μ m.

3. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, described CuO powder or Cu₂The purity of O powder is not less than 99.0%, and powder size is not more than 74 μ m.

4. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, Al₂O₃Disperse phase mass fraction in copper alloy powder is 0.3%～2.5%.

5. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, CuO powder or Cu₂The ratio of the amount of substance of O powder and Al powder is between 3:2～2:1.

6. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, described grinding aid adopts stearic acid, and stearic quality is 2% Cu opaque amount.

7. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, described inert gas adopts argon gas or nitrogen.

8. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, ratio of grinding media to material is 10:1～15:1, and drum's speed of rotation is 400rpm～500rpm, and the ball milling time is 8h～10h.

9. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, the temperature when feeding hydrogen-argon-mixed is 450 ℃～600 ℃, by the time be 30min～60min.

10. production Al as claimed in claim 1₂O₃The method of dispersion strengthening copper alloy powder is characterized in that, in the described hydrogen-argon-mixed, by volume, the hydrogen by 10% and 90% argon gas are formed.

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