CN115652174B - Aluminum oxide dispersion strengthening copper alloy and preparation method and application thereof - Google Patents
Aluminum oxide dispersion strengthening copper alloy and preparation method and application thereof Download PDFInfo
- Publication number
- CN115652174B CN115652174B CN202211408646.4A CN202211408646A CN115652174B CN 115652174 B CN115652174 B CN 115652174B CN 202211408646 A CN202211408646 A CN 202211408646A CN 115652174 B CN115652174 B CN 115652174B
- Authority
- CN
- China
- Prior art keywords
- copper alloy
- equal
- aluminum oxide
- particles
- oxide dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 49
- 239000006185 dispersion Substances 0.000 title claims abstract description 36
- 238000005728 strengthening Methods 0.000 title claims abstract description 27
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000010949 copper Substances 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 238000003466 welding Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 48
- 238000009694 cold isostatic pressing Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000137 annealing 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
- 238000012545 processing Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000005482 strain hardening Methods 0.000 claims description 9
- 238000001192 hot extrusion Methods 0.000 claims description 8
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003746 surface roughness Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 22
- 229910045601 alloy Inorganic materials 0.000 description 18
- 239000000956 alloy Substances 0.000 description 18
- 229910017767 Cu—Al Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000003723 Smelting Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 238000012360 testing method Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000009849 vacuum degassing Methods 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000010998 test method 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
- 238000007599 discharging Methods 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000007546 Brinell hardness test Methods 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
Abstract
The aluminum oxide dispersion strengthening copper alloy disclosed by the invention comprises 0.45-1.5wt% of Al 2 O 3 The balance of Cu; the average grain size of the alumina dispersion strengthening copper alloy is 10-50 mu m, and Al contained in 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) multiplied by 10 9 Individual/mm 2 . The invention is realized by the method that Al in copper alloy 2 O 3 The size, distribution and standard deviation of the particles are controlled to obtain a fine and uniform distribution microstructure. The aluminum oxide dispersion strengthening 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%, the area shrinkage of more than or equal to 35%, the conductivity of 75-90% IACS, and excellent cold heading processability, higher strength and conductivity, and can be used as an automobile welding material.
Description
Technical Field
The invention relates to the technical field of copper alloy, in particular to a high-strength high-conductivity aluminum oxide dispersion strengthening 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 automobile body welding. In order to meet the requirements of the current automobile body welding and the development trend of the future aluminum automobile body welding, the aluminum oxide dispersion strengthening 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, subgrain boundaries, and inhibiting movement of dislocations. The dispersion strengthening copper has higher strength and high softening temperature because fine and uniform oxide particles are dispersed in the copper matrix; meanwhile, the tiny dispersed oxide particles do not have adverse effect on the electric conductivity and the thermal conductivity of the copper alloy, so that the dispersion strengthening copper can maintain the excellent electric conductivity and the thermal conductivity while improving the strength. The aluminum oxide dispersion copper material has great advantages in the field of welding of aluminum plates and galvanized steel plates, the material not only has good current conductivity, but also can effectively avoid adhesion with a base material, and meanwhile, the service life of an electrode is prolonged by more than 5 times.
The dispersed copper welding material mainly comprises electrode caps, conductive nozzles and other component materials, and has excellent high strength, high conductivity and high-temperature softening resistance because of being in a high-temperature and high-current environment. Meanwhile, since parts such as an electrode cap are generally formed by cold heading, excellent cold heading workability is required. The cold heading requires that the material have a uniform texture and a suitable strength. At present, aluminum oxide dispersion strengthening copper alloy bars for preparing electrode cap materials form large-particle Al due to the growth of crystal grains of the materials after heat treatment and the back diffusion action of aluminum element 2 O 3 Particles, leading to Al 2 O 3 The dispersion distribution of the particles is uneven, and the problems of large deformation resistance and irregular deformation easily occur in the subsequent cold working and cold heading process, so that stress concentration is caused, and cracking is caused.
In view of the above, a high-strength high-conductivity aluminum oxide dispersion-strengthened copper alloy with excellent cold heading workability, and a preparation method and application thereof have been proposed.
Disclosure of Invention
The invention aims to solve the first technical problem of providing a high-strength high-conductivity aluminum oxide dispersion-strengthened copper alloy with excellent cold heading processability aiming at the current requirement 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 alumina dispersion strengthening copper alloy comprises 0.45-1.5wt% of Al 2 O 3 The balance of Cu; the average grain size of the alumina dispersion strengthening copper alloy is 10-50 mu m, and Al contained in 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 Individual/mm 2 。
Preferably, the aluminum oxide dispersion-strengthened copper alloy comprises Al in a microstructure 2 O 3 The standard deviation of the particle size is less than or equal to 10nm.
Preferably, in the microstructure of the alumina dispersion strengthened copper alloy, al having a 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 Individual/mm 2 。
Al in the aluminum oxide dispersion strengthening copper alloy 2 O 3 The shape of the particles is mainly spherical and triangular, wherein Al with particle size of more than 50nm 2 O 3 Large particles are mainly distributed at the grain boundary, and Al with a particle size of less than 50nm 2 O 3 The fine particles are uniformly distributed in the copper matrix (i.e., within the grains). Al in the copper alloy of the invention 2 O 3 The fine and uniform distribution of the particles ensures the cutting efficiency of the alloy during the cutting process. The finer the grains, the higher the grain boundary volume fraction, when Al having a grain size of less than 50nm 2 O 3 The particles are uniformly distributed in the copper matrix, and the average grain size of the copper alloy is 10-50 mu m, and the Al contained in the microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, al in unit area 2 O 3 The number of the particles is (5-103). Times.10 9 Individual/mm 2 Can promote the rheological uniformity of the alloy in the pressure processing process, therebyThe cracking phenomenon of the part during cold heading is effectively avoided. In addition, the fine and uniform grain size is beneficial to improving the finish of cold heading products and avoiding the occurrence of orange peel.
Preferably, after the radial cold heading coarseness is 10%, the surface roughness Ra of the aluminum oxide dispersion strengthening copper alloy is less than or equal to 2.5 mu m.
Preferably, the hardness of the aluminum oxide dispersion strengthening copper alloy is 70-85 HRB, the yield strength is 400-520 MPa, the tensile strength is 450-580 MPa, the elongation after fracture is more than or equal to 16%, the area shrinkage is more than or equal to 35%, and the conductivity is 75-90% IACS.
The second technical problem to be solved by the invention is to provide a preparation method of high-strength high-conductivity aluminum oxide dispersion strengthening copper alloy with excellent cold heading processability, which comprises the following steps: high-purity nitrogen atomization pulverizing, oxygen source preparation, powder mixing, cold isostatic pressing processing, short-flow integrated heat treatment, water seal hot extrusion, cold processing, step-type stress relief annealing, straightening and finishing, wherein the specific steps comprise the following parameters:
1) Atomizing and pulverizing high-purity nitrogen: the invention adopts a vacuum medium frequency induction smelting furnace to smelt, firstly heats high-purity red copper to smelt for 30-80 min, continuously vacuumizes a smelting chamber in the heating process, closes a vacuum system when copper liquid begins to appear at the bottom of a crucible, and fills N 2 After the red copper added is completely melted for 5-20 min to normal pressure, adding an aluminum ingot through a secondary feeding bin, stirring, smelting for 1-10 min, pouring at 1150-1300 ℃, and then carrying out gas atomization powder preparation by using high-purity nitrogen pressure of 3-10 MPa to obtain Cu-Al powder, wherein 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 is controlled to effectively control the thickness of an oxide layer on the surface of the powder, so that the powder can be used for oxidizing Al element in the powder more effectively during the subsequent short-flow integrated heat treatment, and the oxidation ratio of the Al element is increased; finally sieving the obtained Cu-Al powder to obtain 100-300 meshes of Cu-Al alloyGold powder and Cu-Al alloy powder with the particle size of more than or equal to 300 meshes;
2) Preparing an oxygen source: oxidizing Cu-Al powder with the particle size of more than or equal to 300 meshes for 6-10 hours under the condition of compressed air with micro positive pressure at 150-300 ℃, then decomposing into solid oxygen source of cuprous oxide with the particle size of more than or equal to 300 meshes at 600-950 ℃ under the condition of nitrogen protection, 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 is 1.5-2.5 wt%, and controlling the oxygen content of the oxygen source to be within the range can effectively control Al in the alumina dispersed copper 2 O 3 The particle size of the aluminum alloy can effectively increase the oxidation rate of the Al element;
3) Mixing powder: mixing the oxygen source with the particle size of more than or equal to 300 and the Cu-Al alloy powder with the particle size of 100-300 according to a proportion, wherein the mixing time is 1-3 hours, and obtaining the dispersed copper alloy powder after mixing, wherein the uniformity of the dispersed copper alloy powder directly influences the Al in the alumina dispersion strengthening copper 2 O 3 Uniformity of particle distribution;
4) Cold isostatic pressing: sealing the mixed dispersed copper alloy powder with cold isostatic pressing rubber sleeve, vibrating in vibrator for 1-3 min to make the bulk density homogeneous and compact density homogeneous and tap density of 5.0-6.5 g/cm 3 Then sealing the mouth with a rubber cap; putting the rubber sleeve packaged with the dispersed copper alloy powder into a cold isostatic pressing cylinder for cold isostatic pressing treatment to prepare a cold isostatic pressing powder ingot, and pressing the powder ingot under the following pressure: 180-300 MPa, and boosting speed: 10-20 MPa/min, and the dwell time is 30-300 s; preferably, step-type boosting is adopted, namely pressure is maintained for 30-300 s under 50MPa and 150MPa respectively;
5) Short-flow integrated heat treatment: putting the cold isostatic pressing powder ingot into a furnace liner of a heat treatment furnace, and carrying out short-flow integrated heat treatment according to the internal oxidation and reduction sequence, 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 purpose of the reduction treatment is to reduce and treat redundant O element 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 normally-on state,maintaining the pressure of 0.2-1 MPa in the furnace;
6) Carrying out vacuum sheathing treatment on the cold isostatic pressing powder ingot after heat treatment, wherein the specific contents are as follows: filling the cold isostatic pressing powder ingot after heat treatment into an oxygen-free copper sheath, and then sheathing the oxygen-free copper sheath filled with the cold isostatic pressing powder ingot at the temperature of less than or equal to 10 -1 Heating in Pa high vacuum environment at 100-600 deg.c for 1-3 hr; then the gas in the inter-powder gaps of the cold isostatic pressing powder ingot is thoroughly removed by 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) And (3) 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 extrusion rod blank, wherein the extrusion heating temperature is 800-950 ℃, the heating time is 1-3 hours, and the extrusion ratio is 10-30;
8) Large deformation cold working: removing head and tail of an extruded rod blank obtained after water seal hot extrusion, straightening, and carrying out cold working to obtain a straight rod, wherein the pass processing rate of cold working is controlled to be 5-30%, the total processing rate before step-type stress relief annealing is more than or equal to 40%, and the high pass processing rate and the high total processing rate can enable large-particle Al to be obtained 2 O 3 Further crushing during cold deformation processing to obtain dispersed and fine Al 2 O 3 A grain and grain structure;
9) Step-type stress relief annealing: putting the cold-processed straight rod into an annealing furnace for step-type stress relief annealing, wherein the step-type stress relief annealing process comprises the following steps: the temperature is kept for 2-8 h at 880-950 ℃, 1-3 h at 550-650 ℃, 1-3 h at 450-550 ℃, 1-3 h at 350-450 ℃, and cooling to Room Temperature (RT), the step annealing process can effectively remove the internal stress of the material after cold deformation processing, and further promote the finer and uniform distribution of alloy tissues and dispersed particles;
10 Straightening and finishing: straightening the aluminum oxide dispersion strengthening copper alloy bar subjected to the step-type stress relief annealing, and cutting 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 average grain size of the alumina dispersion strengthening copper alloy is controlled to be 10-50 mu m, and Al contained in microstructure is controlled to be 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 (5-103). Times.10 9 Individual/mm 2 Obtaining Al 2 O 3 Copper alloy with fine dispersion distribution of particles, and further, al contained in microstructure of the aluminum oxide dispersion-strengthened copper alloy 2 O 3 The standard deviation of the particle size is controlled within 10nm, al with the particle size of more than 50nm in unit area is controlled 2 O 3 The number of the particles is less than or equal to 2 multiplied by 10 7 Individual/mm 2 The aluminum oxide dispersion copper alloy with fine and uniform distribution can be further obtained. The small grain size means that the alloy has higher grain boundary volume fraction, 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 remarkably improved, the cracking phenomenon of parts during cold heading is effectively avoided, the smoothness of cold heading products can be improved, and the orange peel phenomenon is avoided.
(2) The hardness of the aluminum oxide dispersion strengthening copper alloy is 70-85 HRB, the yield strength is 400-520 MPa, the tensile strength is 450-580 MPa, the elongation after fracture is more than or equal to 16%, the area shrinkage is more than or equal to 35%, the conductivity is 75-90% IACS, and the surface roughness Ra after the radial cold heading coarseness is 10% is less than or equal to 2.5 mu m.
(3) The invention adopts the mode of large deformation cold working and stepped stress relief annealing to obtain the finished product straight bar, and the method controls the pass working rate and the total working rate of the cold working to carry out forming processing, thus obtaining more uniform and fine grain structure, and leading coarse grains and large grain Al formed in heat treatment and hot extrusion 2 O 3 Is uniformly crushed in the large-deformation cold working process, and meanwhile, due to the influence of three-dimensional compressive stress on the material during cold working, the grain sizes of the center and the edge of the processed material are uniform, and the material has proper hardness, strength and plasticity by being matched with step-type stress relief annealing, so that the flatness of the section after cutting and blanking is ensured, the deformation resistance of the material is reduced, and the uniform deformation of the material is increasedThe shape performance capability has positive effect on the smooth forming of cold heading.
Drawings
Fig. 1 is a TEM photograph of the alumina dispersion strengthened copper alloy of example 1.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
The method for producing the alumina dispersion strengthened copper alloy in examples 1 to 11 and comparative examples 1 to 2 comprises the steps of:
firstly, heating a vacuum intermediate frequency induction smelting furnace to smelt high-purity red copper for 30-80 min, smelting, continuously vacuumizing a smelting chamber in the heating process, closing a vacuum system when copper liquid begins to appear at the bottom of a crucible, and filling N 2 After the red copper added is completely melted for 5-20 min to normal pressure, adding an aluminum ingot through a secondary charging bin, stirring, smelting for 1-10 min, casting at 1150-1300 ℃, then performing gas atomization powder preparation by using high-purity nitrogen pressure of 3-10 MPa to obtain Cu-Al powder, and screening out Cu-Al alloy powder with 100-300 meshes and Cu-Al alloy powder with the granularity of more than or equal to 300 meshes;
secondly, oxidizing Cu-Al powder with the particle size of more than or equal to 300 meshes for 6-10 hours under the condition of micro-positive pressure compressed air at 150-300 ℃, then decomposing the Cu-Al powder into a cuprous oxide solid oxygen source with the particle size of more than or equal to 300 meshes at 600-950 ℃ under the condition of nitrogen protection, and calculating the hydrogen loss value of the oxygen source through a hydrogen burning test after discharging, namely obtaining the oxygen content A of the oxygen source;
thirdly, mixing the prepared oxygen source with the particle size of more than or equal to 300 meshes and Cu-Al alloy powder with the particle size of 100-300 meshes in proportion for 1-3 hours;
fourthly, sealing the mixed dispersed copper alloy powder in proportion by using a cold isostatic pressing rubber sleeve, and vibrating on a vibrator for 1-3 minutes to ensure that the loose density is uniform, the pressed compact density is uniform, and the tap density is 5.0-6.5 g/cm 3 Then sealing the mouth with a rubber cap; putting the rubber sleeve packaged with the dispersed copper alloy powder into a cold isostatic pressing cylinder for cold isostatic pressing treatment to prepare a cold isostatic pressing powder ingot, and pressing the powder ingot under the following pressure: 180-300 MPa, and boosting speed: 10 to20 MPa/min, and the pressure maintaining time is 30-300 s;
fifthly, placing the cold isostatic pressing powder ingot into a furnace liner of a heat treatment furnace, and carrying out short-flow integrated heat treatment according to the internal oxidation and reduction sequence, 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-on state, and the pressure in the furnace is kept at 0.2-1 MPa;
sixthly, carrying out vacuum sheathing treatment on the cold isostatic pressing powder ingot after heat treatment, wherein the specific contents are as follows: filling the cold isostatic pressing powder ingot after heat treatment into an oxygen-free copper sheath, and then sheathing the oxygen-free copper sheath filled with the cold isostatic pressing powder ingot at the temperature of less than or equal to 10 -1 Heating in Pa high vacuum environment at 100-600 deg.c for 1-3 hr; then, thoroughly removing gas in inter-powder gaps of the cold isostatic pressing powder ingot through high vacuum degassing;
seventhly, carrying out 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;
eighth, removing heads and tails, straightening and carrying out large-deformation cold processing on the extruded rod blank obtained after water seal hot extrusion to obtain a straight rod, wherein the pass processing rate of cold processing is controlled to be 5-30%, and the total processing rate before step-type stress relief annealing is more than or equal to 40%;
ninth, putting the cold-processed straight rod into an annealing furnace for step-type stress relief annealing, wherein the step-type 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, and cooling to Room Temperature (RT);
and tenth, straightening the aluminum oxide dispersion strengthening copper alloy bar subjected to step stress relief annealing, and cutting the head and the tail to obtain a finished product straight bar.
For bar samples of the prepared example alloy and comparative example alloy, tensile strength, yield strength, elongation, reduction of area, hardness, conductivity, surface roughness after cold heading, and the like were respectively tested.
Room temperature tensile test according to GB/T228.1-2010 section 1 of metallic materials tensile test: the room temperature test method was carried out on an electronic universal tester using a round scale sample (d 0 =8mm, sample No. R5), the stretching speed was 2mm/min.
Hardness test according to GB/T231.1-2009 section 1 of Brinell hardness test for Metal materials: test methods HBW2.5/187.5 was measured.
Conductivity test according to GB/T3048-2007 part 2 of the wire and cable Electrical test method: metal material resistivity test, expressed in% IACS.
Al 2 O 3 Standard deviation of mean size and particle size of particles: taking a cross section perpendicular to the machining direction, grinding, thinning ions, observing through TEM imaging, and counting each Al in the picture through imageJ software 2 O 3 Particle size. TEM photograph of alumina dispersion strengthened copper alloy in 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 2 O 3 The particles are dispersed and uniformly distributed in the copper matrix.
After the radial cold heading roughness was analyzed by a laser confocal microscope by 10%, the surface roughness Ra of each of the example alloy and the comparative example alloy was measured.
Al was measured by ICP spectrometer for each of the example alloys and the comparative example alloys 2 O 3 The content was tested.
The composition and structure of the alloys of examples 1 to 11 and comparative examples 1 to 2 are shown in Table 1, and the performance test results are shown in Table 2.
As can be seen from tables 1 and 2, the average grain size of the alumina dispersion-strengthened copper alloy of the present invention is 10 to 50. Mu.m, and Al is contained in the microstructure 2 O 3 The average size of the particles is less than or equal to 50nm, and the Al is contained 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 is higherBut the strength is lower, and the target requirement is not met; although the strength of comparative example 2 was excellent, the conductivity was poor, and the use requirement could not be met even with 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 extents, and the use requirement could not be met.
Table 1 examples, comparative example compositions and tissue test results
Table 2 results of performance tests of examples, comparative examples
Claims (5)
1. An alumina dispersion strengthening copper alloy is characterized in that the alumina dispersion strengthening copper alloy comprises 0.45 to 1.5 weight percent of Al 2 O 3 The balance of Cu; the average grain size of the alumina dispersion strengthening copper alloy is 10-50 mu m, and Al contained in 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 Individual/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the Al contained in 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, and Al with the particle size of more than 50nm in unit area 2 O 3 The number of the particles is less than or equal to 2 multiplied by 10 7 Individual/mm 2 The method comprises the steps of carrying out a first treatment on the surface of the The hardness of the aluminum oxide dispersion strengthening copper alloy is 70-85 HRB, the yield strength is 400-520 MPa, the tensile strength is 450-580 MPa, the elongation after fracture is more than or equal to 16%, the area shrinkage is more than or equal to 35%, and the conductivity is 75-90% IACS.
2. The aluminum oxide dispersion strengthened copper alloy according to claim 1, wherein 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 coarseness is 10%.
3. The method for producing an alumina dispersion strengthened copper alloy according to any one of claims 1 to 2, comprising the steps of: high-purity nitrogen atomization pulverizing, 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.
4. The method for preparing aluminum oxide dispersion strengthened copper alloy according to claim 3, wherein the cold working pass working rate is 5-30%, the total working rate before step-type stress relief annealing is more than or equal to 40%, and the step-type stress relief annealing process is as follows: the temperature is kept for 2 to 8 hours at 880 to 950 ℃, 1 to 3 hours at 550 to 650 ℃, 1 to 3 hours at 450 to 550 ℃, 1 to 3 hours at 350 to 450 ℃ and 1 to 3 hours at 350 to cooling to room temperature.
5. Use of an alumina dispersion strengthened copper alloy according to any one of claims 1 to 2 in the welding of automotive body parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211408646.4A CN115652174B (en) | 2022-11-11 | 2022-11-11 | Aluminum oxide dispersion strengthening copper alloy and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211408646.4A CN115652174B (en) | 2022-11-11 | 2022-11-11 | Aluminum oxide dispersion strengthening copper alloy and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115652174A CN115652174A (en) | 2023-01-31 |
| CN115652174B true CN115652174B (en) | 2024-02-02 |
Family
ID=85021731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211408646.4A Active CN115652174B (en) | 2022-11-11 | 2022-11-11 | Aluminum oxide dispersion strengthening copper alloy and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115652174B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276230A (en) * | 2013-04-27 | 2013-09-04 | 苏州金江铜业有限公司 | Preparation method of Al2O3 dispersion strengthened copper |
| CN107557609A (en) * | 2017-09-15 | 2018-01-09 | 北京有色金属研究总院 | A kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof |
| CN109536771A (en) * | 2018-11-23 | 2019-03-29 | 中铝洛阳铜加工有限公司 | A kind of preparation method of dispersion strengthened copper oxygen sheet alloy |
| CN110508816A (en) * | 2019-09-04 | 2019-11-29 | 陕西斯瑞新材料股份有限公司 | A kind of preparation method of high voltage direct current contact for relay material |
| CN110625126A (en) * | 2019-10-14 | 2019-12-31 | 中铝洛阳铜加工有限公司 | Preparation method of high-conductivity high-heat-resistance dispersion oxygen-free copper |
| 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 |
-
2022
- 2022-11-11 CN CN202211408646.4A patent/CN115652174B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276230A (en) * | 2013-04-27 | 2013-09-04 | 苏州金江铜业有限公司 | Preparation method of Al2O3 dispersion strengthened copper |
| CN107557609A (en) * | 2017-09-15 | 2018-01-09 | 北京有色金属研究总院 | A kind of copper alloy of single phase nano alumina particle dispersion-strengtherning and preparation method thereof |
| CN109536771A (en) * | 2018-11-23 | 2019-03-29 | 中铝洛阳铜加工有限公司 | A kind of preparation method of dispersion strengthened copper oxygen sheet alloy |
| CN110508816A (en) * | 2019-09-04 | 2019-11-29 | 陕西斯瑞新材料股份有限公司 | A kind of preparation method of high voltage direct current contact for relay material |
| CN110625126A (en) * | 2019-10-14 | 2019-12-31 | 中铝洛阳铜加工有限公司 | Preparation method of high-conductivity high-heat-resistance dispersion oxygen-free copper |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115652174A (en) | 2023-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Microstructure evolution and tensile properties of as-rolled TiB/TA15 composites with network microstructure | |
| CN106756319A (en) | A kind of aluminium alloy and aluminum matrix composite for preparing high-strength high-plastic aluminum matrix composite | |
| CN110923499B (en) | Ce and B-containing titanium bronze alloy strip and preparation method thereof | |
| WO2019153953A1 (en) | Copper material and preparation method therefor | |
| CN110819873B (en) | High Nb-TiAl alloy added with nano yttrium oxide and preparation method thereof | |
| WO2021148054A1 (en) | Copper alloy wire for connector and method for manufacture thereof | |
| CN112458349A (en) | Low-rare earth high-strength wrought magnesium alloy containing neodymium and yttrium and preparation method thereof | |
| EP4364871A1 (en) | Tantalum-tungsten alloy powder and preparation method therefor | |
| CN113373329A (en) | Preparation method of nano gradient magnesium alloy | |
| CN109207766A (en) | A kind of controllable high aluminium content Cu-Al of tissue2O3Nano-diffusion copper alloy preparation process | |
| CN110586824A (en) | Multidirectional isothermal forging method for refining titanium alloy grains by utilizing alpha' hexagonal martensite phase transformation | |
| CN110592510A (en) | Method for electromagnetic impact reinforcement of titanium alloy | |
| CN112593100A (en) | Preparation method of large-size 6061 aluminum alloy plate for semiconductor equipment | |
| Lebo et al. | Structure and properties of a splat cooled 2024 aluminum alloy | |
| CN110438422B (en) | Heat treatment method for additive manufacturing of 2219 aluminum alloy | |
| CN113481405B (en) | Preparation method of copper-iron alloy | |
| CN114438385B (en) | Preparation method of metal titanium particle reinforced magnesium-based composite material | |
| CN110373583A (en) | A kind of quality oxide effect high strength alumin ium alloy and preparation method thereof | |
| CN115011894A (en) | Production method of TB3 titanium alloy cold-rolled wire for fastener | |
| CN113462911B (en) | Preparation method of tough corrosion-resistant AZ80 magnesium alloy | |
| CN102586655B (en) | Process for strengthening Al-Sc-Zr conduction alloy and optimizing conductivity | |
| CN115652174B (en) | Aluminum oxide dispersion strengthening copper alloy and preparation method and application thereof | |
| CN111593227B (en) | High-conductivity high-strength copper-iron-calcium alloy and preparation method thereof | |
| CN111378867A (en) | High-conductivity and high-strength copper-chromium-magnesium alloy and preparation method thereof | |
| CN114540688B (en) | Ultrahigh-pressure heat treatment method for Mg-Zn-Zr-Gd alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |