CN114192788B - Alumina dispersion strengthening copper-tin alloy powder and preparation method thereof - Google Patents
Alumina dispersion strengthening copper-tin alloy powder and preparation method thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 119
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000006185 dispersion Substances 0.000 title claims abstract description 76
- 238000005728 strengthening Methods 0.000 title claims abstract description 76
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000003647 oxidation Effects 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims description 49
- 230000009467 reduction Effects 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 36
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 32
- 238000009792 diffusion process Methods 0.000 claims description 26
- 238000005275 alloying Methods 0.000 claims description 25
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000011362 coarse particle Substances 0.000 abstract description 3
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 229910003460 diamond Inorganic materials 0.000 description 13
- 239000010432 diamond Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
- C22C32/001—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 only oxides
- C22C32/0015—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 only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
-
- 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
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/045—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention discloses alumina dispersion strengthening copper-tin alloy powder and a preparation method thereof, belonging to the field of powder metallurgy. Aiming at the problems of high preparation difficulty, low yield, high cost and the like of the existing alumina dispersion strengthening copper matrix fine powder, the invention provides the alumina dispersion strengthening copper-tin alloy powder with small powder particle size, low apparent density and small hydrogen loss by taking coarse particles of alumina dispersion strengthening copper prepared by an internal oxidation method as raw materials and a preparation method thereof.
Description
Technical Field
The invention relates to alumina dispersion strengthening copper-tin alloy powder and a preparation method thereof, belonging to the field of powder metallurgy.
Background
Diamond is the highest-hardness substance found in nature, and thus is an indispensable tool material for processing various hard materials. Diamond is generally in the form of fine particles which need to be formed into shaped and mechanically strong articles using matrix materials for use. In diamond tools, diamond is the cutting element and the matrix is an integral component, which is decisive for the adequate and efficient operation of the diamond. The carcass has two main functions: firstly, the cutting elements are "coated" to determine the service life of the diamond tool; secondly, "matching" wear with the cutting element (diamond) determines the sharpness (or working efficiency) of the diamond tool. The quality of a diamond article depends to a large extent on the properties of its carcass, which are primarily dependent on the carcass material.
A large number of application tests show that the strength, hardness, elastic modulus, proper wear characteristics and high-temperature softening resistance of the matrix are key to ensuring the sharpness and the service life of the diamond tool. The common strengthening mode of the existing metal matrix is mostly to add alloy elements, and the strength and hardness of the matrix are improved through the solid solution strengthening or precipitation strengthening effect. With these methods, on the one hand, it is difficult to strike a balance between strength, hardness, elastic modulus and proper wear properties; on the other hand, the alloy phase is softened at high temperature, resulting in insufficient high temperature softening resistance of the carcass.
Dispersion strengthening is a method for improving the performance of copper-based matrix. The reinforced phase alumina particles in the alumina dispersion reinforced copper alloy are uniformly dispersed and distributed in the copper matrix in a nano-scale size, and are not dissolved or coarsened at a high temperature close to the melting point of the copper matrix, so that the movement of dislocation, grain boundary and subgrain boundary can be strongly blocked, the matrix can be reinforced, the matrix has good high-temperature softening resistance, the abrasion characteristic of the matrix is changed, and finally the performance of the tool is obviously improved. However, alumina particles have a significant impediment to sinter densification, and thus alumina dispersion strengthened copper matrix powders typically require higher pressures and temperatures during hot press sintering. The hot press sintering pressure of the nano aluminum oxide dispersion strengthening copper-nickel-tin matrix disclosed by ZL 201910616893.5 is required to exceed 35MPa, and the optimal sintering temperature is required to reach 880 ℃. This increases the difficulty of manufacturing the diamond tool and reduces the useful life of the graphite mold.
Reducing the particle size of the matrix powder can increase the sintering activity of the powder. For example, one of the wet chemical methods available from Umicore, belgium is named CobaliteIs a powder of (1) comprisingHas a mass content of 0.6% of nano-scale Y 2 O 3 . The powder has a Fisher size of 2.2 μm and D 50 Is 12 μm. The powder can reach 99.3% density after hot pressing sintering at 800 ℃ and 35 MPa. However, the chemical method for preparing the nano oxide dispersion strengthening powder has high raw material cost and high energy consumption, and the generated waste water and waste gas (such as NO) 2 、NH 3 Etc.) require further processing, etc. Compared with a wet chemical method, the cost for preparing the nano aluminum oxide dispersion strengthening copper powder by an internal oxidation method is lower. However, as disclosed in chinese patent ZL 201410132717.1, in the process of preparing nano-alumina dispersion-strengthened copper powder based on the internal oxidation method, in order to ensure that the internal oxidation can be sufficiently performed, the internal oxidation temperature generally needs to reach 900-950 ℃. Under such high temperature conditions, sintering between powders inevitably occurs. Meanwhile, the oxidation of Al is an exothermic process, which results in that the actual temperature of the powder during the internal oxidation exceeds the internal oxidation temperature and increases as the Al content increases. Theoretical calculations indicate (LIANG S H, FANG L, XU L, et al Effect of Al content on the properties and microstructure of Al) 2 O 3 -Cu composite prepared by internal oxidation[J]Journal of Composite Materials,2004, 38:1495-1504.), the actual temperature of the internal oxidation will reach the melting point of Cu when the Al content in the powder reaches 0.5 wt. -% at 950 ℃. This causes the powder to undergo very severe agglomeration during internal oxidation, which makes crushing of the powder very difficult. Therefore, in general, the nano-alumina dispersion-strengthened copper powder prepared by the internal oxidation method has a relatively coarse particle size, and the yield of fine powder with a particle size of less than or equal to 45 μm is not more than 15%.
Disclosure of Invention
Aiming at the problems of high preparation difficulty, low yield, high cost and the like of the existing nano aluminum oxide dispersion strengthening copper matrix fine powder, the invention provides the aluminum oxide dispersion strengthening copper-tin alloy powder with small powder particle size, low apparent density and small hydrogen loss and the preparation method thereof by taking coarse particles of aluminum oxide dispersion strengthening copper prepared by internal oxidation as raw materials.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the preparation method of the alumina dispersion strengthening copper-tin alloy powder comprises the following steps:
(1) Oxidizing: placing the alumina dispersion-strengthened copper particles in a box-type sintering furnace for oxidation to obtain oxidized alumina dispersion-strengthened copper particles;
(2) Crushing: sealing the oxidized alumina dispersion strengthening copper particles and grinding balls in a ball milling tank, ball milling the mixture on a ball mill according to a certain process, taking out the mixture, and sieving the mixture to obtain fine powder;
(3) And (3) reduction: placing the fine powder into a hydrogen reduction furnace, and reducing the fine powder in a hydrogen atmosphere to obtain reduced fine powder;
(4) Diffusion alloying: mixing the reduced fine powder with tin powder to obtain mixed powder; placing the mixed powder into a hydrogen reduction furnace, and performing diffusion alloying treatment under the hydrogen atmosphere;
(5) Sealing the material obtained in the step (4) and grinding balls in a ball milling tank, ball milling the materials on a ball mill according to a certain process, taking out the materials, and sieving the materials to obtain the alumina dispersion strengthening copper-tin alloy powder.
According to the invention, the alumina dispersion-strengthened copper particles prepared by an internal oxidation method are used as raw materials, and the oxygen content of the alumina dispersion-strengthened copper particles is increased by oxidation in air, so that the grindability of the alumina dispersion-strengthened copper particles is improved; by reduction, the oxygen content of the reduced fine powder is reduced, and meanwhile, serious agglomeration among the reduced fine powder is avoided; at a temperature higher than the reduction temperature, the reduced powder and the tin powder are subjected to diffusion alloying, so that the oxygen content of the aluminum oxide dispersion strengthening copper-tin alloy powder can be further reduced, the deagglomeration effect can be realized through the diffusion of tin, and the granularity and the apparent density of the aluminum oxide dispersion strengthening copper-tin alloy powder can be further reduced. The process conditions of the steps of the preparation method are mutually influenced and complemented, and the prepared alumina dispersion strengthening copper-tin alloy powder has a porous structure, so that the preparation method has the characteristics of good compression performance, high sintering activity and the like when in use, and can meet the preparation requirements of diamond tools; compared with the wet chemical method for preparing the alumina dispersion strengthening copper-tin alloy powder, the preparation method has the advantages of low cost, less pollution and the like.
As a preferred embodiment of the method for preparing aluminum oxide dispersion-strengthened copper-tin alloy powder of the present invention, the oxidation conditions in the step (1) are as follows: the oxidation temperature is 400-600 ℃, and the oxidation time is 2-4h.
The oxidation temperature can influence the subsequent treatment of the alumina dispersion strengthening copper particles, and the excessive oxidation temperature can lead to hardening of the alumina dispersion strengthening copper particles, increase the difficulty of crushing and reduce the yield of the superfine powder; too low an oxidation temperature may result in a low oxidation level of the alumina dispersion strengthened copper particles, which may also increase the difficulty of comminution.
In alternative embodiments, the oxidation temperature may be 400 ℃, 500 ℃, 600 ℃, and any value between 400-600 ℃, and the oxidation time may be any value between 2h, 3h, 4h, and 2-4h.
As a preferred embodiment of the method for preparing aluminum oxide dispersion strengthening copper-tin alloy powder of the present invention, the reduction conditions in the step (3) are as follows: the reduction temperature is 400-450 ℃, and the reduction time is 3-6h.
The reduction temperature can influence the performance of the aluminum oxide dispersion strengthening copper-tin alloy powder, the reduction temperature is too high, and the agglomeration of the fine powder is serious in the reduction process, so that the granularity of the aluminum oxide dispersion strengthening copper-tin alloy powder is increased, and the apparent density is increased; the reduction temperature is too low, the reduction degree of the fine powder is low, and tin is easily oxidized during alloying, thereby resulting in an increase in the oxygen content of the final powder.
In alternative embodiments, the reduction temperature may be 400 ℃, 430 ℃, 450 ℃, and any value between 400-450 ℃, and the reduction time may be any value between 3h, 4h, 6h, and 3-6h.
As a preferred embodiment of the method for preparing aluminum oxide dispersion-strengthened copper-tin alloy powder of the present invention, the conditions for the diffusion alloying treatment in the step (4) are as follows: the temperature is 450-500 ℃, and the reduction time is 3-6h.
The temperature of diffusion alloying treatment can influence the performance of the aluminum oxide dispersion strengthening copper-tin alloy powder, and the reduction temperature is too high, so that the deagglomeration effect of tin in the diffusion alloying process is weakened, the particle size of the aluminum oxide dispersion strengthening copper-tin alloy powder is increased, and the technical effect of the invention can not be achieved; too low a temperature of the diffusion alloying treatment may reduce the reduction effect at this stage and increase the oxygen content of the powder.
In alternative embodiments, the temperature of the diffusion alloying process may be 450 ℃, 480 ℃, 500 ℃ and any value between 450-500 ℃, and the time of the diffusion alloying process may be any value between 3h, 4h, 6h and 3-6h.
The mixing time of the reduced fine powder and the tin powder may be determined according to the situation, and the main purpose is to uniformly mix the reduced fine powder and the tin powder, and in an alternative embodiment, the mixing time may be any value between 1h, 1.5h, 2h and 1-2 h.
As a preferred embodiment of the preparation method of the alumina dispersion strengthening copper-tin alloy powder, the ball milling conditions in the step (2) are as follows: ball-material ratio is 1:1-1:5, ball milling rotating speed is 40-80rpm, and ball milling time is 2-4h.
The ball-material ratio can influence the crushing efficiency of the oxidized alumina dispersion strengthening copper particles, the powder treated for a single time is reduced due to too high ball-material ratio, the ball-milling time is correspondingly prolonged due to too low ball-material ratio, and the crushing efficiency of the alumina dispersion strengthening copper particles can be reduced due to too high ball-material ratio or too low ball-material ratio.
As a preferred embodiment of the preparation method of the alumina dispersion strengthening copper-tin alloy powder, the ball milling condition in the step (5) is as follows: ball-material ratio is 1:1-1:5, ball milling rotating speed is 40-80rpm, and ball milling time is 20-30min.
In a second aspect, the invention provides alumina dispersion strengthening copper-tin alloy powder, which is prepared by the preparation method.
As a preferred embodiment of the aluminum oxide dispersion-strengthened copper-tin alloy powder of the invention, the Fisher size of the aluminum oxide dispersion-strengthened copper-tin alloy powder is less than or equal to 2 mu m and D 50 15 μm or less and the loose density or less than 1.5g/cm 3 The oxygen content is less than or equal to 1.0wt%
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the alumina dispersion-strengthened copper particles prepared by an internal oxidation method are used as raw materials, and the oxygen content of the alumina dispersion-strengthened copper particles is increased by oxidation in air, so that the grindability of the alumina dispersion-strengthened copper particles is improved; by reduction, the oxygen content of the reduced fine powder is reduced, and meanwhile, serious agglomeration among the reduced fine powder is avoided; at a temperature higher than the reduction temperature, the reduced powder and the tin powder are subjected to diffusion alloying, so that the oxygen content of the aluminum oxide dispersion strengthening copper-tin alloy powder can be further reduced, the deagglomeration effect can be realized through the diffusion of tin, and the granularity and the apparent density of the aluminum oxide dispersion strengthening copper-tin alloy powder can be further reduced.
2. The alumina dispersion strengthening copper-tin alloy powder prepared by the invention has a porous structure, so that the alumina dispersion strengthening copper-tin alloy powder has the characteristics of good compression performance, high sintering activity and the like when in use, and can meet the preparation requirements of diamond tools.
3. Compared with the wet chemical method for preparing the alumina dispersion strengthening copper-tin alloy powder, the preparation method has the advantages of low cost, less pollution and the like.
Drawings
FIG. 1 is an SEM image (500 times) of the alumina dispersion-strengthened copper-tin alloy powder obtained in example 1;
FIG. 2 is an SEM image (magnification of 5000) of an alumina dispersion-strengthened copper-tin alloy powder obtained in example 1.
Detailed Description
In the context of the present invention, the alumina dispersion strengthened copper particles are prepared, without any particular explanation, using methods known in the art, for example, the following steps may be employed: (1) Copper-aluminum alloy powder with the aluminum content of 0.5-5% and stearic acid with the aluminum content of 0.2-0.3% are ball-milled for 5-10 hours at the ambient temperature of 2-10 ℃ according to the ball-to-material ratio (8-10) of 1, 300-400rpm, and air can freely enter and exit in the whole ball milling process; (2) Adding Cu with the mass of 1-1.5% into the ball-milled copper-aluminum alloy powder 2 O powder, mixing for 4-8h; (3) Placing the mixed powder into a vacuum furnace, vacuumizing to 0.08-0.1MPa, charging nitrogen to 0.03-0.02MPa, heating to 900-950 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 1-2h, and cooling to room temperature along with the furnace; (4) Crushing step (3)Sieving the obtained material with a 80-mesh sieve, placing the sieved powder in a tube furnace, heating to 700-900 ℃ at a heating rate of 5-10 ℃/min in a hydrogen atmosphere, preserving heat for 1-4h, and cooling to room temperature along with the furnace to obtain the alumina dispersion strengthening copper particles.
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples and the accompanying drawings.
Example 1
The embodiment provides a preparation method of aluminum oxide dispersion strengthening copper-tin alloy powder, which comprises the following steps:
(1) Oxidizing: loading the alumina dispersion strengthening copper particles into an alumina sintering boat, paving powder with the thickness of less than or equal to 20mm, placing the sintering boat into an open muffle furnace, heating to 400 ℃, preserving heat for 4 hours, and cooling to room temperature to obtain oxidized alumina dispersion strengthening copper particles, wherein the particle size of the alumina dispersion strengthening copper particles is less than or equal to 3mm, and the mass content of alumina is 0.5%;
(2) Crushing: sealing oxidized alumina dispersion strengthening copper particles and grinding balls in a ball milling tank, and taking out the ball milling tank after ball milling according to a certain process on a ball mill, wherein the ball milling conditions are as follows: ball-material ratio is 1:1, ball milling rotation speed is 40rpm, ball milling time is 2 hours, and the alumina dispersion strengthening copper fine powder after oxidation is obtained through a 100-mesh sieve;
(3) And (3) reduction: placing the oxidized aluminum oxide dispersion strengthening copper fine powder into a hydrogen reduction furnace, and reducing the aluminum oxide dispersion strengthening copper fine powder in the hydrogen atmosphere at the reduction temperature of 400 ℃ for 6 hours to obtain reduced aluminum oxide dispersion strengthening copper fine powder;
(4) Diffusion alloying: detecting the content of alumina dispersion strengthening copper in the partially reduced alumina dispersion strengthening copper micro powder by a hydrogen loss method, and then dispersing strengthening copper according to alumina: respectively weighing reduced alumina dispersion-strengthened copper micro-powder and tin powder according to the mass percentage of tin=90:10, and filling the aluminum oxide dispersion-strengthened copper micro-powder and the tin powder into a double-cone mixer for mixing for 2 hours, wherein the particle size of the tin powder is less than or equal to 45 mu m, so as to obtain mixed powder; placing the mixed powder into a hydrogen reduction furnace, and performing diffusion alloying treatment under the hydrogen atmosphere, wherein the conditions of the diffusion alloying treatment are as follows: the temperature is 450 ℃, the reduction time is 6 hours, and the mixture is cooled to room temperature;
(5) Sealing the materials and grinding balls obtained in the step (4) in a ball milling tank, ball milling the materials and the grinding balls on a ball mill according to a certain process, and taking out the materials and the grinding balls under the following ball milling conditions: ball-material ratio is 1:1, ball milling rotation speed is 40rpm, ball milling time is 20min, and the aluminum oxide dispersion strengthening copper-tin alloy powder is obtained through 100 mesh screening.
Example 2
The embodiment provides a preparation method of aluminum oxide dispersion strengthening copper-tin alloy powder, which comprises the following steps:
(1) Oxidizing: loading the alumina dispersion strengthening copper particles into an alumina sintering boat, paving powder with the thickness of less than or equal to 20mm, placing the sintering boat into an open muffle furnace, heating to 600 ℃, preserving heat for 2h, and cooling to room temperature to obtain oxidized alumina dispersion strengthening copper particles, wherein the particle size of the alumina dispersion strengthening copper particles is less than or equal to 3mm, and the mass content of alumina is 1.2%;
(2) Crushing: sealing oxidized alumina dispersion strengthening copper particles and grinding balls in a ball milling tank, and taking out the ball milling tank after ball milling according to a certain process on a ball mill, wherein the ball milling conditions are as follows: ball-material ratio is 1:5, ball milling rotation speed is 80rpm, ball milling time is 4 hours, and the alumina dispersion strengthening copper fine powder after oxidation is obtained through a 100-mesh sieve;
(3) And (3) reduction: placing the oxidized aluminum oxide dispersion strengthening copper fine powder into a hydrogen reduction furnace, and reducing the aluminum oxide dispersion strengthening copper fine powder in the hydrogen atmosphere at the reduction temperature of 450 ℃ for 3 hours to obtain reduced aluminum oxide dispersion strengthening copper fine powder;
(4) Diffusion alloying: detecting the content of alumina dispersion strengthening copper in the reduced alumina dispersion strengthening copper micro powder by a hydrogen loss method, and then dispersing strengthening copper according to alumina: respectively weighing reduced alumina dispersion-strengthened copper micro-powder and tin powder according to the mass percentage of tin=80:20, and filling the aluminum oxide dispersion-strengthened copper micro-powder and the tin powder into a double-cone mixer for mixing for 2 hours, wherein the particle size of the tin powder is less than or equal to 45 mu m, so as to obtain mixed powder; placing the mixed powder into a hydrogen reduction furnace, and performing diffusion alloying treatment under the hydrogen atmosphere, wherein the conditions of the diffusion alloying treatment are as follows: the temperature is 500 ℃, the reduction time is 3 hours, and the mixture is cooled to room temperature;
(5) Sealing the materials and grinding balls obtained in the step (4) in a ball milling tank, ball milling the materials and the grinding balls on a ball mill according to a certain process, and taking out the materials and the grinding balls under the following ball milling conditions: ball-material ratio is 1:5, ball milling rotation speed is 80rpm, ball milling time is 30min, and the aluminum oxide dispersion strengthening copper-tin alloy powder is obtained through 100 mesh screening.
Comparative example 1
Comparative example 1 is Cobalite produced by Belgium, calif. by wet chemistry (B.J.Kamphuis, J.Peersman.Pre-allowed bond pores. US Patent 7077883,2006)
Comparative example 2
The comparative example provides a preparation method of aluminum oxide dispersion strengthening copper-tin alloy powder, which comprises the following steps:
(1) Mixing: alumina dispersion strengthening copper particles (Al) with particle diameter less than or equal to 3mm 2 O 3 1.2% of mass content) and tin powder with the grain diameter less than or equal to 45 mu m are used as raw materials, and copper is strengthened according to alumina dispersion: respectively weighing the powder according to the ratio of tin=80:20, and filling the powder into a double-cone mixer for mixing for 1h to obtain mixed powder;
(2) Diffusion alloying: placing the mixed powder into a hydrogen reduction furnace, and performing diffusion alloying treatment under the hydrogen atmosphere, wherein the conditions of the diffusion alloying treatment are as follows: the temperature is 500 ℃, the reduction time is 3 hours, and the mixture is cooled to room temperature;
(3) Sealing the materials and grinding balls obtained in the step (2) in a ball milling tank, ball milling the materials and the grinding balls on a ball mill according to a certain process, and taking out the materials and the grinding balls under the following ball milling conditions: ball-material ratio is 1:5, ball milling rotation speed is 80rpm, ball milling time is 60min, and the aluminum oxide dispersion strengthening copper-tin alloy powder is obtained through sieving with a 200-mesh sieve.
Comparative example 3
As a comparative example of the preparation method of the alumina dispersion-strengthened copper-tin alloy powder of the present invention, the present comparative example is different from example 2 only in that the reduction temperature of the step (3) is 500 ℃.
Comparative example 4
As a comparative example of the method for producing the alumina dispersion-strengthened copper-tin alloy powder of the present invention, the present comparative example is different from example 2 only in that the step (3) is reduced.
Comparative example 5
As a comparative example of the method for producing the alumina dispersion-strengthened copper-tin alloy powder of the present invention, the present comparative example is different from example 2 only in that the step (4) is reduced.
Comparative example 6
As a comparative example of the method for producing the alumina dispersion-strengthened copper-tin alloy powder of the present invention, this comparative example is different from example 2 in that the step (3) is reduced and the diffusion alloying temperature of the step (4) is increased to 550 ℃.
Comparative example 7
As a comparative example of the method for producing the alumina dispersion-strengthened copper-tin alloy powder of the present invention, this comparative example is different from example 2 in that the step (3) is reduced and the diffusion alloying temperature of the step (4) is increased to 750 ℃.
The properties of the alumina dispersion-strengthened copper-tin alloy powders of examples 1 to 2 and comparative examples 1 to 7 were tested, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the Fisher size of the alumina dispersion-strengthened copper-tin alloy powder prepared by the preparation method of the invention is less than or equal to 2 mu m, D 50 15 μm or less and the loose density or less than 1.5g/cm 3 The oxygen content is less than or equal to 1.0 weight percent. Because the oxygen content of the alumina dispersion strengthening copper-tin alloy powder in the comparative examples 4 to 6 is not less than 1.0wt%, the requirements of the alumina dispersion strengthening copper-tin alloy powder of the invention are not met, and therefore, other performances are not tested.
Fig. 1 and 2 are SEM images of the alumina dispersion-strengthened copper-tin alloy powder obtained in example 1, and it can be seen from the figures that the alumina dispersion-strengthened copper-tin alloy powder obtained in the invention is fine in size and has a porous structure.
Finally, it should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, and that those skilled in the art will understand that the technical scheme of the invention may be modified or equally substituted without departing from the spirit and scope of the technical scheme of the invention.
Claims (4)
1. The preparation method of the aluminum oxide dispersion strengthening copper-tin alloy powder is characterized by comprising the following steps of:
(1) Oxidizing: placing the alumina dispersion-strengthened copper particles in a box-type sintering furnace for oxidation to obtain oxidized alumina dispersion-strengthened copper particles;
(2) Crushing: sealing the oxidized alumina dispersion strengthening copper particles and grinding balls in a ball milling tank, ball milling the mixture on a ball mill according to a certain process, taking out the mixture, and sieving the mixture with a 100-mesh sieve to obtain fine powder;
(3) And (3) reduction: placing the fine powder into a hydrogen reduction furnace, and reducing the fine powder in a hydrogen atmosphere to obtain reduced fine powder;
(4) Diffusion alloying: mixing the reduced fine powder with tin powder to obtain mixed powder; placing the mixed powder into a hydrogen reduction furnace, and performing diffusion alloying treatment under the hydrogen atmosphere;
(5) Sealing the material obtained in the step (4) and grinding balls in a ball milling tank, ball milling the materials on a ball mill according to a certain process, taking out the materials, and sieving the materials to obtain alumina dispersion strengthening copper-tin alloy powder;
the oxidation conditions of the step (1) are as follows: the oxidation temperature is 400-600 ℃ and the oxidation time is 2-4 h;
the ball milling conditions in the step (2) are as follows: ball-material ratio is 1:1-1:5, ball milling rotating speed is 40-80rpm, and ball milling time is 2-4 h;
the reduction conditions of the step (3) are as follows: the reduction temperature is 400-450 ℃, and the reduction time is 3-6 h;
the conditions of the diffusion alloying treatment in the step (4) are as follows: the temperature is 450-500 ℃, and the reduction time is 3-6 h;
the ball milling conditions in the step (5) are as follows: ball-material ratio is 1:1-1:5, ball milling rotating speed is 40-80rpm, and ball milling time is 20-30min.
2. An alumina dispersion-strengthened copper-tin alloy powder, characterized by being prepared by the method for preparing the alumina dispersion-strengthened copper-tin alloy powder according to claim 1.
3. The aluminum oxide dispersion strengthened copper-tin alloy powder according to claim 2, wherein the aluminum oxide dispersion strengthened copper-tin alloy powder has a Fisher size of 2 μm or less and D 50 15 μm or less and the apparent density or less than 1.5. 1.5g/cm 3 The oxygen content is less than or equal to 1.0 and wt percent.
4. The alumina dispersion-strengthened copper-tin alloy powder according to claim 2, wherein the mass content of alumina in the alumina dispersion-strengthened copper-tin alloy powder is more than or equal to 0.3%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2218529A1 (en) * | 2009-01-29 | 2010-08-18 | Bodycote European Holdings GmbH Deutschland | Method for the diffusion alloying of metal powders |
| CN103934451A (en) * | 2014-04-03 | 2014-07-23 | 广东省工业技术研究院(广州有色金属研究院) | Method for preparing aluminum oxide dispersion strengthening copper alloy powder |
| CN107282932A (en) * | 2017-05-20 | 2017-10-24 | 广东省材料与加工研究所 | A kind of Al2O3The preparation method of dispersion-strengthened Cu base oil containing bearing |
| CN109530705A (en) * | 2019-01-02 | 2019-03-29 | 广东省材料与加工研究所 | A kind of preparation method of alumina dispersion-strenghtened copper-base diffusion alloy powder |
| CN110340345A (en) * | 2019-07-09 | 2019-10-18 | 广东省材料与加工研究所 | A kind of nanometer mutually enhances Cu-based diamond tools carcass powder and carcass preparation method |
Family Cites Families (1)
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2218529A1 (en) * | 2009-01-29 | 2010-08-18 | Bodycote European Holdings GmbH Deutschland | Method for the diffusion alloying of metal powders |
| CN103934451A (en) * | 2014-04-03 | 2014-07-23 | 广东省工业技术研究院(广州有色金属研究院) | Method for preparing aluminum oxide dispersion strengthening copper alloy powder |
| CN107282932A (en) * | 2017-05-20 | 2017-10-24 | 广东省材料与加工研究所 | A kind of Al2O3The preparation method of dispersion-strengthened Cu base oil containing bearing |
| CN109530705A (en) * | 2019-01-02 | 2019-03-29 | 广东省材料与加工研究所 | A kind of preparation method of alumina dispersion-strenghtened copper-base diffusion alloy powder |
| CN110340345A (en) * | 2019-07-09 | 2019-10-18 | 广东省材料与加工研究所 | A kind of nanometer mutually enhances Cu-based diamond tools carcass powder and carcass preparation method |
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