CN115652174A - Aluminum oxide dispersion strengthened copper alloy and preparation method and application thereof - Google Patents
Aluminum oxide dispersion strengthened copper alloy and preparation method and application thereof Download PDFInfo
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 54
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims abstract description 26
- 238000003466 welding Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 53
- 238000009694 cold isostatic pressing Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000001192 hot extrusion Methods 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 23
- 229910052802 copper Inorganic materials 0.000 description 23
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000000956 alloy Substances 0.000 description 19
- 229910017767 Cu—Al Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000003754 machining Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000009849 vacuum degassing Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 238000012216 screening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
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- 238000007546 Brinell hardness test Methods 0.000 description 1
- 241000669069 Chrysomphalus aonidum Species 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
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Abstract
The invention discloses an aluminum oxide dispersion strengthened copper alloy, which comprises 0.45 to 1.5wt% of Al in percentage by mass 2 O 3 The balance being Cu; the average grain size of the aluminum oxide dispersion strengthened copper alloy is 10 to 50 mu m, and Al contained in a microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, and Al in unit area 2 O 3 The number of the granules is (5 to 103). Times.10 9 Per mm 2 . The invention is realized by adding Al into the copper alloy 2 O 3 The size, distribution and standard deviation of the particles are controlled to obtain a fine and uniformly distributed microstructure. The aluminum oxide dispersion strengthened copper alloy has the hardness of 70-85HRB, the yield strength of 400-520MPa, the tensile strength of 450-580 MPa, the elongation after fracture of more than or equal to 16 percent, the reduction of area of more than or equal to 35 percent and the electric conductivity of 75-90 IACS, has excellent cold heading processability and higher strength and electric conductivity, and can be used as automobile welding materials.
Description
Technical Field
The invention relates to the technical field of copper alloy, in particular to a high-strength high-conductivity aluminum oxide dispersion strengthened copper alloy with excellent cold heading processability and a preparation method and application thereof.
Background
With the development of new energy automobiles, higher requirements are put forward on electrode materials for welding automobile bodies. In order to meet the requirements of current automobile body welding and the development trend of future aluminum body welding, the aluminum oxide dispersion strengthened copper welding material is a key material meeting the conditions.
Dispersion strengthening is a method of strengthening a material by introducing stable, uniform, fine oxide particles into a metal matrix, pinning dislocations, grain boundaries, and subgrain boundaries, and hindering the movement of dislocations. Because fine and uniform oxide particles are dispersed in the copper matrix, the dispersion strengthened copper has higher strength and high softening temperature; meanwhile, the oxide particles distributed in a fine dispersion manner can not cause adverse effects on the electric and thermal conductivity of the copper alloy, so that the dispersion strengthened copper can keep excellent electric and thermal conductivity while the strength is improved. Aluminum oxide dispersion copper material has great advantage in aluminum plate and galvanized steel sheet welding field, and the material not only has better current conductivity, can also effectually avoid with the bonding of parent metal, and the life-span of electrode promotes more than 5 times simultaneously.
The dispersed copper welding material mainly comprises electrode caps, contact tips and other component materials, and has excellent high strength, high conductivity and high temperature resistance due to being in a high-temperature and high-current environmentSoftening performance. Meanwhile, since parts such as electrode caps are generally formed by cold heading, excellent cold heading property is required. The cold heading requires that the material has a uniform structure and appropriate strength. At present, aluminum oxide diffusion strengthened copper alloy bars for preparing electrode cap materials are formed by large-particle Al due to growth of crystal grains of the materials after heat treatment and reverse diffusion of aluminum elements 2 O 3 Particles of lead to Al 2 O 3 The particles are not uniformly dispersed and distributed, and the problems of large deformation resistance and irregular deformation are easily caused in the subsequent cold processing and cold heading processes, so that stress concentration is caused, and cracking is caused.
In view of the above, a high-strength and high-conductivity alumina dispersion-strengthened copper alloy having excellent cold heading workability, and a method for producing and using the same are provided.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a high-strength high-conductivity aluminum oxide dispersion strengthened copper alloy with excellent cold heading processability aiming at the current requirements of automobile body welding and the development trend of future aluminum body welding.
The technical scheme adopted by the invention for solving the first technical problem is as follows: an aluminum oxide dispersion strengthened copper alloy, the aluminum oxide dispersion strengthened copper alloy comprises 0.45-1.5 wt% of Al 2 O 3 The balance being Cu; the average grain size of the aluminum oxide dispersion strengthened copper alloy is 10-50 mu m, and Al contained in a microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, and Al in unit area 2 O 3 The number of the particles is (5-103). Times.10 9 Per mm 2 。
Preferably, al contained in the microstructure of the aluminum oxide dispersion-strengthened copper alloy 2 O 3 The standard deviation of the particle size is less than or equal to 10nm.
Preferably, in the microstructure of the aluminum oxide dispersion-strengthened copper alloy, al has a particle size per unit area of 50nm or more 2 O 3 The number of the particles is less than or equal to 2 multiplied by 10 7 Per mm 2 。
Hair brushAl in bright alumina dispersion strengthened copper alloy 2 O 3 The shape of the particles is mainly spherical and triangular, wherein the particle size of Al is more than 50nm 2 O 3 Large particles are mainly distributed at the grain boundary, and the particle size of Al is less than 50nm 2 O 3 The fine particles are uniformly distributed in the copper matrix (i.e., within the crystal). Al in the copper alloy of the invention 2 O 3 The fine and uniform distribution of the particles can ensure the cutting efficiency of the alloy in the cutting process. The finer the crystal grain, the higher the volume fraction of the grain boundary, when the particle size is less than 50nm of Al 2 O 3 The particles are uniformly distributed in the copper matrix, the average grain size of the copper alloy is 10-50 μm, and Al contained in the microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, and Al in unit area 2 O 3 The number of the particles is (5 to 103). Times.10 9 Per mm 2 During the process, the rheological uniformity of the alloy in the pressure processing process can be promoted, and the cracking phenomenon of parts during cold heading processing can be effectively avoided. In addition, the fine and uniform grain size is beneficial to improving the smoothness of a cold heading product and avoiding the occurrence of orange peel phenomenon.
Preferably, the surface roughness Ra of the aluminum oxide dispersion strengthened copper alloy is less than or equal to 2.5 μm after the radial cold heading rate is 10%.
Preferably, the alumina dispersion strengthened copper alloy has a hardness of 70 to 85HRB, a yield strength of 400 to 520MPa, a tensile strength of 450 to 580MPa, an elongation after fracture of not less than 16%, a reduction of area of not less than 35%, and an electric conductivity of 75 to 90% IACS.
The second technical problem to be solved by the invention is to provide a preparation method of a high-strength and high-conductivity aluminum oxide dispersion strengthened copper alloy with excellent cold heading processability, which comprises the following steps: high-purity nitrogen atomization powder making → oxygen source preparation → powder mixing → cold isostatic pressing processing → short-flow integrated heat treatment → water seal hot extrusion → cold processing → stepped stress relief annealing → straightening and finishing, and the specific steps have the following parameters:
1) High-purity nitrogen atomization powder preparation: the component control level, the surface quality and the uniformity of the internal structure of the Cu-Al powder can ensure that the alloy can be smoothly processed toThe invention adopts a vacuum medium-frequency induction smelting furnace for smelting, firstly, high-purity red copper is heated and smelted for 30-80 min, the smelting chamber is continuously vacuumized in the temperature rise process, a vacuum system is closed when copper liquid begins to appear at the bottom of a crucible, and N is charged 2 When the temperature is normal pressure, after the first added red copper is completely melted for 5-20 min, adding an aluminum ingot through a secondary feeding bin, stirring and then melting for 1-10 min, pouring at 1150-1300 ℃, then carrying out gas atomization powder making by using high-purity nitrogen pressure of 3-10 MPa, and obtaining Cu-Al powder, wherein preferably, the median diameter (D50) of the obtained Cu-Al powder is controlled to be less than or equal to 65 mu m, the oxygen content is controlled to be less than or equal to 300ppm, and the oxygen content of the Cu-Al powder can be controlled to effectively control the thickness of an oxidation layer on the surface of the powder, so that the powder can more effectively oxidize Al elements in the powder during the later short-process integrated heat treatment, and the oxidation ratio of the Al elements is increased; finally, screening the obtained Cu-Al powder to obtain 100-300 meshes of Cu-Al alloy powder and more than or equal to 300 meshes of Cu-Al alloy powder;
2) Preparing an oxygen source: oxidizing Cu-Al powder with a particle size of more than or equal to 300 meshes for 6-10 hours at the temperature of 150-300 ℃ under the condition of micro-positive pressure compressed air, decomposing the Cu-Al powder into a cuprous oxide solid oxygen source with a particle size of more than or equal to 300 meshes at the temperature of 600-950 ℃ under the protection of nitrogen, calculating the hydrogen loss value of the oxygen source through a hydrogen burning test after discharging, namely the oxygen content A of the oxygen source, wherein the range of A is 1.5-2.5 wt%, and the oxygen content of the oxygen source can be controlled within the range to effectively control the Al in the aluminum oxide dispersed copper 2 O 3 The particle size of (2) and the oxidation rate of Al element can be effectively increased;
3) Mixing powder: the prepared oxygen source with the mesh size of more than or equal to 300 and the Cu-Al alloy powder with the mesh size of 100-300 are proportioned and mixed for 1-3 hours to obtain dispersed copper alloy powder, and the uniformity of the dispersed copper alloy powder directly influences Al in aluminum oxide dispersion strengthened copper 2 O 3 The distribution uniformity of the particles;
4) Cold isostatic pressing: sealing the dispersed copper alloy powder mixed in proportion by using a cold isostatic pressing rubber sleeve, and vibrating on a vibrator for 1-3 minutes to ensure that the loose packing density is uniform, the compact density is consistent, and the tap density is 5.0-6.5 g/cm 3 Then, howeverSealing the opening with a rubber cap; placing the rubber sleeve with the dispersed copper alloy powder packaged in a cold isostatic pressing cylinder body for cold isostatic pressing treatment to obtain a cold isostatic pressing powder ingot, and pressing the cold isostatic pressing powder ingot under the pressure: 180-300 MPa, pressure increasing speed: 10-20 MPa/min, and the pressure maintaining time is 30-300 s; preferably, the pressure is increased in a stepped manner, namely the pressure is respectively maintained at 50MPa and 150MPa for 30-300 s;
5) Short-process integrated heat treatment: putting the cold isostatic pressing powder ingot into a furnace pipe of a heat treatment furnace, and carrying out short-flow integrated heat treatment according to the sequence of internal oxidation and reduction, wherein the purpose of the internal oxidation treatment is to convert Al in the cold isostatic pressing powder ingot into Al 2 O 3 The internal oxidation temperature is 850-950 ℃, the internal oxidation time is 4-8 hours, and the protective atmosphere is nitrogen; the reduction treatment aims to reduce redundant O elements by hydrogen, the reduction temperature is 900-950 ℃, the reduction time is 4-8 h, the reduction treatment is carried out under high-purity hydrogen or ammonia decomposition gas, the gas is in a normal open state, and the pressure in the furnace is kept at 0.2-1 MPa;
6) And (3) carrying out vacuum sheath treatment on the cold isostatic pressing powder ingot after heat treatment, wherein the specific contents are as follows: placing the cold isostatic pressing powder ingot after heat treatment into an oxygen-free copper sheath, and then sleeving the oxygen-free copper sheath filled with the cold isostatic pressing powder ingot into a position which is less than or equal to 10 DEG C -1 Heating in a high vacuum environment of Pa at the temperature of 100-600 ℃ for 1-3 hours; then, the gas in the gaps between the powders of the cold isostatic pressing powder ingot is thoroughly removed through high vacuum degassing, thereby improving the conductivity of the dispersed copper and reducing Al 2 O 3 The large particle number plays a good role;
7) Water seal hot extrusion: carrying out water-seal hot extrusion on the cold isostatic pressing powder ingot subjected to high vacuum degassing to obtain an extruded bar blank, wherein the heating temperature of the extrusion is 800-950 ℃, the heating time is 1-3 hours, and the extrusion ratio is 10-30;
8) Large deformation cold working: removing the head and the tail of an extruded rod blank obtained after water seal hot extrusion, straightening and carrying out cold machining to obtain a straight rod, wherein the pass machining rate of the cold machining is controlled to be 5-30%, the total machining rate before stepped stress relief annealing is more than or equal to 40%, and the high pass machining rate and the total machining rate can enable large-particle Al to be large 2 O 3 Further crushing in the cold deformation process to obtain dispersed and fine Al 2 O 3 Grain and grain structure;
9) Step-type stress relief annealing: putting the cold-processed straight rod into an annealing furnace for stepped stress relief annealing, wherein the stepped stress relief annealing process comprises the following steps: preserving heat at 880-950 ℃ for 2-8 h → preserving heat at 550-650 ℃ for 1-3 h → preserving heat at 450-550 ℃ for 1-3 h → preserving heat at 350-450 ℃ for 1-3 h → cooling to Room Temperature (RT), wherein the step annealing process can effectively remove the internal stress of the material after cold deformation processing, and further promote the finer and more uniform distribution of alloy tissues and dispersed particles;
10 Straightening and finishing: straightening the aluminum oxide dispersion strengthened copper alloy bar subjected to the step-type stress relief annealing, and cutting off the head and the tail to obtain a finished product straight bar.
Compared with the prior art, the invention has the following advantages:
(1) The invention controls the average grain size of the aluminum oxide dispersion strengthened copper alloy to be 10-50 mu m, and Al contained in the microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, and Al in unit area 2 O 3 The number of particles (5 to 103). Times.10 9 Per mm 2 Obtaining Al 2 O 3 A copper alloy having fine particles dispersed therein, and further, al contained in the microstructure of the aluminum oxide dispersion-strengthened copper alloy 2 O 3 Standard deviation of particle size controlled to 10nm or less, al having particle size of 50nm or more per unit area 2 O 3 The number of the particles is less than or equal to 2 multiplied by 10 7 Per mm 2 Can further obtain the fine and evenly distributed aluminum oxide dispersion copper alloy. The fine grain size means that the grain boundary volume fraction is higher, and the grain boundary structure is relatively loose, so that the movement of grains during cold heading is facilitated, the cold heading performance of the alloy can be obviously improved, the generation of cracking phenomena of parts during cold heading processing is effectively avoided, in addition, the smoothness of a cold heading product can be improved, and the generation of orange peel phenomena is avoided.
(2) The aluminum oxide dispersion strengthened copper alloy has the hardness of 70-85 HRB, the yield strength of 400-520 MPa, the tensile strength of 450-580 MPa, the elongation after fracture of more than or equal to 16 percent, the reduction of area of more than or equal to 35 percent, the electric conductivity of 75-90 percent IACS, and the surface roughness Ra of 10 percent of radial cold heading of less than or equal to 2.5 mu m.
(3) The invention adopts the modes of large-deformation cold processing and stepped stress relief annealing to obtain the finished straight bar, and the forming processing is carried out by controlling the pass processing rate and the total processing rate of the cold processing, so that more uniform and fine grain structures can be obtained, and coarse grains and large-grain Al formed in the heat treatment and hot extrusion are enabled to be in large grain structure 2 O 3 The material is uniformly crushed in the large-deformation cold machining process, meanwhile, the material is influenced by three-dimensional compressive stress during cold machining, the grain sizes of the center and the edge of the machined material are uniform, and the material is matched with stepped stress relief annealing to have proper hardness, strength and plasticity, so that the flatness of the section after shearing and blanking is ensured, the deformation resistance of the material is reduced, the uniform deformation performance capability of the material is improved, and the material has a positive effect on smooth cold heading forming.
Drawings
FIG. 1 is a TEM photograph of an alumina dispersion-strengthened copper alloy of example 1.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
The method for producing the alumina dispersion strengthened copper alloy in the embodiments 1 to 11 and the comparative examples 1 to 2 includes the steps of:
firstly, heating high-purity red copper by adopting a vacuum intermediate frequency induction smelting furnace for smelting for 30-80 min, continuously vacuumizing the smelting chamber in the temperature rise process, closing a vacuum system when copper liquid begins to appear at the bottom of a crucible, and filling N 2 When the pressure is normal, after the red copper added firstly is completely melted for 5-20 min, adding an aluminum ingot through a secondary feeding bin, stirring and then melting for 1-10 min, casting at 1150-1300 ℃, then carrying out gas atomization powder preparation by using high-purity nitrogen pressure of 3-10 MPa to obtain Cu-Al powder, and screening out 100-300 meshes of Cu-Al alloy powder and Cu-Al alloy powder of more than or equal to 300 meshes;
secondly, oxidizing Cu-Al powder with a particle size of more than or equal to 300 meshes for 6 to 10 hours at the temperature of between 150 and 300 ℃ under the condition of micro-positive pressure compressed air, decomposing the powder into a cuprous oxide solid oxygen source with a particle size of more than or equal to 300 meshes at the temperature of between 600 and 950 ℃ under the protection of nitrogen, and calculating the hydrogen loss value of the oxygen source through a hydrogen burning test after the powder is discharged, wherein the hydrogen loss value is the oxygen content A of the oxygen source;
thirdly, the prepared oxygen source with the mesh size of more than or equal to 300 and the Cu-Al alloy powder with the mesh size of 100-300 are proportioned and mixed for 1-3 hours;
fourthly, sealing the dispersed copper alloy powder mixed in proportion by using a cold isostatic pressing rubber sleeve, and vibrating on a vibrator for 1 to 3 minutes to ensure that the loose packing density is uniform, the compact density is consistent, and the tap density is 5.0 to 6.5g/cm 3 Then sealing the opening with a rubber cap; placing the rubber sleeve packaged with the dispersed copper alloy powder into a cold isostatic pressing cylinder body for cold isostatic pressing treatment to prepare a cold isostatic pressing powder ingot, and pressing the pressure: 180-300 MPa, pressure increasing speed: 10-20 MPa/min, and the pressure maintaining time is 30-300 s;
fifthly, placing the cold isostatic pressing powder ingot into a furnace pipe of a heat treatment furnace, and carrying out short-flow integrated heat treatment according to the sequence of internal oxidation and reduction, wherein the internal oxidation treatment aims at converting Al in the cold isostatic pressing powder ingot into Al 2 O 3 The internal oxidation temperature is 850-950 ℃, the internal oxidation time is 4-8 hours, and the protective atmosphere is nitrogen; the reduction temperature is 900-950 ℃, the reduction time is 4-8 h, the reduction treatment is carried out under high-purity hydrogen or ammonia decomposition gas, the gas is in a normally open state, and the pressure in the furnace is kept at 0.2-1 MPa;
sixthly, carrying out vacuum sheath treatment on the cold isostatic pressing powder ingot after heat treatment, wherein the specific contents are as follows: the cold isostatic pressing powder ingot after heat treatment is arranged in an oxygen-free copper sheath, and then the oxygen-free copper sheath filled with the cold isostatic pressing powder ingot is sleeved in the oxygen-free copper sheath with the thickness less than or equal to 10 DEG -1 Heating in a high vacuum environment of Pa, wherein the heating temperature is 100-600 ℃, and the heat preservation time is 1-3 hours; then, degassing through high vacuum to completely remove gas in the powder gap of the cold isostatic pressing powder ingot;
seventhly, performing water seal hot extrusion on the cold isostatic pressing powder ingot subjected to high vacuum degassing to obtain an extruded rod blank, wherein the extrusion heating temperature is 800-950 ℃, the heating time is 1-3 hours, and the extrusion ratio is 10-30;
eighthly, removing the head and the tail of the extruded rod blank obtained after water seal hot extrusion, straightening, and carrying out large-deformation cold machining to obtain a straight rod, wherein the pass machining rate of cold machining is controlled to be 5-30%, and the total machining rate before stepped stress relief annealing is more than or equal to 40%;
and step nine, putting the cold-processed straight rod into an annealing furnace for stepped stress relief annealing, wherein the stepped stress relief annealing process comprises the following steps: keeping the temperature at 880-950 ℃ for 2-8 h → 550-650 ℃ for 1-3 h → 450-550 ℃ for 1-3 h → 350-450 ℃ for 1-3 h → cooling to Room Temperature (RT);
and step ten, straightening the aluminum oxide dispersion strengthened copper alloy bar subjected to the step-type stress relief annealing, and cutting off the head and the tail to obtain a finished product straight bar.
For the bar samples of the prepared example alloy and comparative example alloy, tensile strength, yield strength, elongation, reduction of area, hardness, electric conductivity, surface roughness after cold heading, and the like were measured, respectively.
Tensile test at room temperature according to GB/T228.1-2010 part 1 of tensile test for metallic materials: room temperature test method is carried out on an electronic universal tester using a circular scale specimen (d) 0 =8mm, sample No. R5), and the drawing speed was 2mm/min.
Hardness test according to GB/T231.1-2009 Brinell hardness test for Metal materials part 1: test method "to determine HBW2.5/187.5.
Conductivity test according to GB/T3048-2007 electric wire and cable electric performance test method part 2: resistivity test of metallic material, expressed in% IACS.
Al 2 O 3 Mean size of particles and standard deviation of particle size: taking a section vertical to the processing direction, grinding, ion thinning, observing by TEM imaging, and counting Al in the picture by ImageJ software 2 O 3 The size of the particles. A TEM photograph of the aluminum oxide dispersion-strengthened copper alloy of example 1 is shown in FIG. 1, and it can be seen from FIG. 1 that fine Al having a particle size of less than 50nm is present 2 O 3 The particles are dispersed and uniformly distributed in the copper matrix.
The surface roughness Ra of each of the example alloys and the comparative example alloys was analyzed by laser confocal microscopy after 10% of the radial cold heading.
Al of each example alloy and comparative example alloy by ICP spectrometer 2 O 3 The content was tested.
The compositions and the results of the structure test of the alloys of examples 1 to 11 and comparative examples 1 to 2 are shown in Table 1, and the results of the performance test are shown in Table 2.
As can be seen from tables 1 and 2, the average grain size of the aluminum oxide dispersion-strengthened copper alloy of the present invention is 10 to 50 μm, and Al contained in the microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, and the contained Al 2 O 3 The standard deviation of the particle size is less than or equal to 10nm, and the particles are fine and uniform and are obviously superior to the alloy of the comparative example. Although the conductivity of comparative example 1 was high, the strength was low, and the target requirement was not satisfied; although the strength of comparative example 2 was excellent, the conductivity was poor, and the use requirement could not be met only by 61% iacs, and the elongation, the reduction of area, the surface roughness after cold heading, and the like of comparative example 1 and comparative example 2 were affected to different degrees, and the use requirement could not be met.
TABLE 1 Components of examples and comparative examples and results of tissue testing
TABLE 2 results of performance test of examples and comparative examples
Claims (8)
1. An aluminum oxide dispersion strengthened copper alloy is characterized in that the aluminum oxide dispersion strengthened copper alloy comprises 0.45-1.5 wt% of Al in percentage by mass 2 O 3 The balance being Cu; the alumina oxideThe average grain size of the dispersion strengthened copper alloy is 10-50 mu m, and Al contained in the microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, and Al in unit area 2 O 3 The number of the particles is (5-103). Times.10 9 Per mm 2 。
2. The alumina dispersion strengthened copper alloy according to claim 1, wherein Al contained in the microstructure of the alumina dispersion strengthened copper alloy 2 O 3 The standard deviation of the particle size is less than or equal to 10nm.
3. The alumina dispersion strengthened copper alloy according to claim 1, wherein the microstructure of the alumina dispersion strengthened copper alloy contains Al having a particle size per unit area of 50nm or more 2 O 3 The number of the particles is less than or equal to 2 multiplied by 10 7 Per mm 2 。
4. The alumina dispersion strengthened copper alloy according to claim 1, wherein the surface roughness Ra of the alumina dispersion strengthened copper alloy is less than or equal to 2.5 μm after the radial cold heading rate is 10%.
5. The aluminum oxide dispersion-strengthened copper alloy as claimed in claim 1, wherein the aluminum oxide dispersion-strengthened copper alloy has a hardness of 70-85 HRB, a yield strength of 400-520 MPa, a tensile strength of 450-580 MPa, a post-fracture elongation of 16% or more, a reduction of area of 35% or more, and an electrical conductivity of 75-90% IACS.
6. The method for producing the aluminum oxide dispersion-strengthened copper alloy according to any one of claims 1 to 5, characterized by comprising the steps of: high-purity nitrogen atomization powder making → oxygen source preparation → powder mixing → cold isostatic pressing processing → short-flow integrated heat treatment → water seal hot extrusion → cold processing → stepped stress relief annealing → straightening and finishing.
7. The method for preparing the aluminum oxide dispersion strengthened copper alloy according to claim 6, wherein the pass processing rate of cold processing is 5-30%, the total processing rate before the step-type stress relief annealing is not less than 40%, and the step-type stress relief annealing process is as follows: keeping the temperature of 880-950 ℃ for 2-8 h → 550-650 ℃ for 1-3 h → 450-550 ℃ for 1-3 h → 350-450 ℃ for 1-3 h → cooling to room temperature.
8. Use of the aluminum oxide dispersion strengthened copper alloy according to any one of claims 1 to 5 for welding automobile body parts.
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| CN114592138A (en) * | 2022-03-09 | 2022-06-07 | 西部金属材料股份有限公司 | Nano alumina particle reinforced copper-based composite material and preparation method thereof |
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