CN116397128A - Rare earth copper chromium alloy material and preparation method thereof - Google Patents
Rare earth copper chromium alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN116397128A CN116397128A CN202310414060.7A CN202310414060A CN116397128A CN 116397128 A CN116397128 A CN 116397128A CN 202310414060 A CN202310414060 A CN 202310414060A CN 116397128 A CN116397128 A CN 116397128A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- treatment
- alloy material
- chromium alloy
- temperature
- 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.)
- Pending
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 131
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 103
- 229910000599 Cr alloy Inorganic materials 0.000 title claims abstract description 83
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000788 chromium alloy Substances 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 84
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 75
- 239000011651 chromium Substances 0.000 claims abstract description 38
- 238000005242 forging Methods 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000000265 homogenisation Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000007670 refining Methods 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 229910017813 Cu—Cr Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 30
- 238000001816 cooling Methods 0.000 description 24
- 230000008569 process Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 238000010586 diagram Methods 0.000 description 14
- 238000003801 milling Methods 0.000 description 14
- 238000009826 distribution Methods 0.000 description 9
- 238000004321 preservation Methods 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000005097 cold rolling Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 230000006698 induction Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910001093 Zr alloy Inorganic materials 0.000 description 4
- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 2
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 2
- 229910017985 Cu—Zr Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a rare earth copper chromium alloy material and a preparation method thereof, which mainly adopts the following technical scheme: the rare earth copper chromium alloy material comprises the following chemical components in percentage by weight: 0.1-2.0wt% of Cr, more than 0 and less than or equal to 200ppm of rare earth elements, not more than 0.005wt% of unavoidable impurity elements, and the balance of copper; the preparation method of the rare earth copper chromium alloy material comprises the following steps: 1) Smelting and casting the raw materials to obtain an ingot; 2) Homogenizing the cast ingot to obtain an alloy ingot after homogenization; 3) Sequentially carrying out hot forging treatment, solution treatment, primary cold deformation treatment and aging treatment on the alloy ingot subjected to the homogenization treatment to obtain a rare earth copper chromium alloy material; wherein the cold deformation amount of one cold deformation treatment is 50-90%. The invention is mainly used for improving the conductivity and the high-temperature thermal stability of the copper-chromium alloy by adding ultra-trace rare earth elements and introducing a large-deformation cold-heat treatment system.
Description
Technical Field
The invention relates to the technical field of nonferrous metals, in particular to a rare earth copper-chromium alloy material and a preparation method thereof.
Background
Copper and copper alloys have been increasingly used in many high and new technical fields, especially cu—cr series alloys, due to their good combination properties, and have been widely used in electrical contacts, contact wires, lead frames, aerospace technical fields, etc.
Besides a certain strength, the alloy also needs to have better conductivity and high-temperature thermal stability. However, the surface structure of the existing Cu-Cr alloy is coarse, the precipitated Cr phase is unstable, and Cu grains are easy to grow abnormally at high temperature, so that the comprehensive performance of the material is greatly reduced. In the prior art, the structural performance is usually improved by adding an alloy element, such as Zr element to inhibit recrystallization and Cr phase growth, thereby achieving the effect of grain refinement and improving the strength. Compared with Zr element, rare earth has higher chemical activity, can be interacted with all elements except inert gas, has the capability of absorbing gas, has the name of industrial monosodium glutamate, and just can lead the material performance to be better by adding a small amount of rare earth.
The following related art is related preparation and performance report of rare earth copper chromium alloy.
The first related technology prepares a rare earth copper alloy with high conductivity, high strength and high extensibility (the rare earth content is 0.02-0.15%), the tensile strength is more than 630Mpa, the conductivity is more than 80% IACS, the extensibility is more than 10%, and the softening temperature is more than 520 ℃. The technology mainly improves the strength, the conductivity and the softening temperature resistance of the alloy by limiting the alloy components and the proportion and regulating and controlling the conventional preparation process, but the technology does not relate to the structural stability of the alloy material under the high-temperature condition.
The second related technology prepares an alloy with the components Cu-Cr (0.1-2.0) -Y (0.1-1.0) by a powder metallurgy method, has the tensile strength higher than 480MPa, the electric conductivity higher than 85 percent IACS, the softening temperature higher than 800 ℃, and has better electric conductivity and softening temperature resistance. However, this powder metallurgy method has a limit for mass production.
The third related art discloses a method for preparing rare earth copper chromium zirconium alloy (the rare earth content is 0.05-0.1%) by adopting a Cu-La intermediate alloy through an arc melting method, and the method does not need solution treatment, thereby saving the production cost. However, this method cannot be prepared on a large scale and the difficulty of the smelting process is high.
In summary, in the prior art, the strength and the conductivity of the alloy and the softening resistance temperature of the alloy are improved mainly by adding elements and changing a preparation method, but synchronous improvement of all performances is difficult to realize, and in general, the softening resistance temperature is improved very limited on the premise of maintaining certain alloy strength and conductivity. In particular, there are few reports on improving the structure and properties of alloys at high temperatures (e.g., above 900 ℃). In addition, the existing microalloying method is complex in component types of common added elements, increases process difficulty and increases cost. Although the softening temperature resistance is remarkably improved by methods such as powder metallurgy, the method is limited in mass production.
Disclosure of Invention
In view of the above, the invention provides a rare earth copper chromium alloy material and a preparation method thereof, which mainly aims to improve the conductivity and high-temperature thermal stability of copper chromium alloy by adding ultra-trace rare earth elements and introducing a large deformation cold and heat treatment system.
In order to achieve the above purpose, the present invention mainly provides the following technical solutions:
in one aspect, an embodiment of the present invention provides a method for preparing a rare earth copper chromium alloy material, wherein the rare earth copper chromium alloy material comprises the following chemical components in percentage by weight: 0.1-2.0wt% of Cr, more than 0 and less than or equal to 200ppm of rare earth element (RE), not more than 0.005wt% of unavoidable impurity elements, and the balance of copper; the preparation method of the rare earth copper chromium alloy material comprises the following steps:
1) Smelting and casting the raw materials to obtain an ingot;
2) Homogenizing the cast ingot to obtain a homogenized alloy ingot;
3) Sequentially carrying out hot forging treatment, solution treatment, primary cold deformation treatment and aging treatment on the alloy ingot subjected to the homogenization treatment to obtain a rare earth copper chromium alloy material; wherein the cold deformation amount of the primary cold deformation treatment is 50-90%.
Preferably, the rare earth element (RE) is one or more of La, ce and Y.
Preferably, the ratio of the content of the rare earth element to the content of the Cr element is 0.005-0.01.
Preferably, in the step 1): the raw materials include raw materials for providing rare earth elements; wherein the raw material for providing rare earth elements comprises a Cu-xRE intermediate alloy; wherein x is 15-25%, and the oxygen content in the Cu-xRE intermediate alloy is lower than 5ppm; and/or smelting the raw materials under the conditions of 1200-1400 ℃ and protective atmosphere.
Preferably, in the step 1): the protective atmosphere is nitrogen or argon;
preferably, in the step 1): loading Cu and Cr into a crucible, putting the Cu-xRE intermediate alloy into a secondary feeding disc, and wrapping the Cu-xRE intermediate alloy by using copper foil to prevent the Cu-xRE intermediate alloy from being oxidized at high temperature; vacuumizing, regulating power, heating to 1200-1250 deg.c, raising power after Cu and Cr are completely melted, refining at 1300-1400 deg.c to eliminate gas, charging argon gas, adding Cu-xRE intermediate alloy into crucible, and smelting and casting.
In the step 1): the casting temperature is 1100-1150 ℃.
Preferably, in said step 2): the homogenization treatment temperature is 900-1000 ℃; preferably, the temperature is kept for 1-10h at the homogenization treatment temperature.
Preferably, in the hot forging process of step 3): the initial forging temperature is 750-950 ℃ and the final forging temperature is 700-800 ℃; and/or a forging ratio of 2 to 6.
Preferably, in the solid solution treatment of step 3): the temperature of the solid solution treatment is 880-980 ℃; preferably, the temperature is kept for 0.5 to 10 hours at the temperature of solution treatment; preferably, after the solution treatment is finished, water quenching treatment is required; preferably, the temperature error of the solution treatment is not more than ±5°.
Preferably, in the primary cold deformation treatment of step 3), multiple passes of cold deformation are included; wherein, the deformation of each pass is not more than 20% compared with the deformation of the last pass. Preferably, in the aging treatment of step 3): the temperature of the aging treatment is 350-500 ℃; the aging treatment time is 0.5-8h.
In one aspect, the embodiment of the invention provides a rare earth copper chromium alloy material, wherein the rare earth copper chromium alloy material comprises the following chemical components in percentage by weight: 0.1-2.0wt% of Cr, more than 0 and less than or equal to 200ppm of rare earth RE, not more than 0.005wt% of unavoidable impurity elements, and the balance of copper; preferably, the rare earth copper chromium alloy material is insulated for 1-4 hours at 900-980 ℃, and after being cooled along with a furnace, the average grain size is smaller than 25 mu m, the electric rate is larger than 80% IACS, the hardness is larger than 50HV, and the volume percentage of an annealing twin crystal is 40-80%; preferably, the rare earth copper chromium alloy material is prepared by the preparation method of any one of the rare earth copper chromium alloy materials.
Compared with the prior art, the rare earth copper chromium alloy material and the preparation method thereof have at least the following beneficial effects:
the preparation method of the rare earth copper chromium alloy material provided by the invention adjusts the content distribution of a phase at a grain boundary of a matrix by adding the ultra-trace rare earth element and combining a reasonable large-deformation cold and hot treatment system on the basis of not reducing the conductivity of the alloy, and the grain boundary is pinned, so that the growth of crystal grains is inhibited, the high-temperature thermal stability is improved, and in addition, the ultra-trace rare earth can purify the matrix and the conductivity is improved. Finally, the effect of substituting zirconium element in the copper-chromium alloy is achieved, so that the cost is reduced. The rare earth copper chromium alloy material prepared by the invention is realized after high-temperature treatment: (1) fine grains; specifically, the grain size of the rare earth copper chromium alloy material prepared by the invention is finer than that of Cu-Cr alloy and Cu-Cr-Zr alloy; (2) conductivity and hardness are also better.
In summary, the preparation method of the rare earth copper chromium alloy material provided by the invention obtains the rare earth copper chromium alloy material with high conductivity and high thermal stability by adding ultra-trace rare earth elements and combining a reasonable large-deformation cold-heat treatment system, can be used for the use requirement of a high-temperature service environment, and still maintains good structure and performance state after high-temperature sintering treatment for 3 hours at 980 ℃, wherein the average grain size is smaller than 25 mu m, the conductivity is larger than 80% IACS, and the hardness is larger than 50HV.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is an IPF diagram of an alloy material after high temperature heat treatment (heat preservation at a high temperature of 900-980 ℃ for 1-4h and furnace cooling); wherein, graph a in FIG. 1 is an IPF diagram of the rare earth copper chromium alloy material (Cu-1 Cr-100 ppmLa) prepared in example 1; panel b is an IPF plot of Cu-1Cr prepared in comparative example 1; FIG. c is an IPF diagram of Cu-1Cr-0.1Zr prepared in comparative example 2.
FIG. 2 is a grain distribution diagram of an alloy material after high temperature heat treatment (heat preservation at a high temperature of 900-980 ℃ for 1-4h and furnace cooling); wherein, a graph in FIG. 1 is a grain distribution diagram of the rare earth copper chromium alloy material (Cu-1 Cr-100 ppmLa) prepared in example 1; panel b shows the grain distribution diagram of Cu-1Cr prepared in comparative example 1; FIG. c is a grain distribution diagram of Cu-1Cr-0.1Zr prepared in comparative example 2.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the invention, the following detailed description refers to the specific implementation, structure, characteristics and effects according to the application of the invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The invention mainly prepares the ultra-trace rare earth alloying alloy material with high conductivity and high thermal stability by a conventional method, and has the advantages of simple components, simple and convenient process and cost saving. Specifically, the Cu-Cr alloy is prepared by adding ultra-trace rare earth and simultaneously reducing or not adding Zr element, so that a better performance effect can be achieved, and the cost is reduced. The invention improves the conductivity and high-temperature heat stability of the alloy by reasonably configuring the rare earth elements and the content and introducing a large deformation cold and hot treatment system.
On one hand, the embodiment of the invention provides a preparation method of a rare earth copper chromium alloy material, wherein the rare earth copper chromium alloy material comprises the following chemical components in percentage by weight: 0.1-2.0wt% of Cr, more than 0 and less than or equal to 200ppm of rare earth elements, not more than 0.005wt% of unavoidable impurity elements, and the balance of copper; the preparation method of the rare earth copper chromium alloy material comprises the following steps:
1) Smelting and casting the raw materials to obtain an ingot.
The raw materials include raw materials for providing rare earth elements; wherein the raw material for providing rare earth elements comprises a Cu-xRE intermediate alloy; wherein x is 15-25%, and the oxygen content in the Cu-xRE intermediate alloy is lower than 5ppm. Here, the addition of rare earth in the form of a master alloy has the following advantages: 1) The rare earth oxidation burning loss in the smelting process is reduced, so that the rare earth components in the cast ingot can be accurately controlled; 2) The rare earth is more uniformly distributed in the melt, so that segregation phenomenon is reduced; 3) Can reduce the oxygen content in pure rare earth metal and reduce the introduction of impurities. The proportion range of rare earth in the intermediate alloy can ensure that the intermediate alloy is easy to prepare, uniform in components and convenient to process.
Smelting raw materials under the conditions of 1200-1400 ℃ and protective atmosphere; preferably, the protective atmosphere is nitrogen or argon.
2) Homogenizing the cast ingot to obtain an alloy ingot after homogenization treatment.
The homogenization treatment temperature is 900-1000 ℃; preferably, the temperature of the homogenization treatment is maintained for 1-10 hours. Preferably, the homogenizing cooling mode is air cooling.
3) Sequentially carrying out hot forging treatment, solution treatment, primary cold deformation treatment and aging treatment on the alloy ingot subjected to the homogenization treatment to obtain a rare earth copper chromium alloy material; wherein the cold deformation amount of one cold deformation treatment is 50-90%.
Preferably, double milling is performed after the solution treatment to remove defects on the surface of the plate after the solution treatment.
Wherein, in the hot forging process: the initial forging temperature is 750-950 ℃, the final forging temperature is 700-800 ℃, and the forging ratio is 2-6.
In the solid solution treatment: the temperature of the solution treatment is 880-980 ℃; preferably, the temperature is kept for 0.5 to 10 hours at the temperature of solution treatment; after the solution treatment is finished, water quenching treatment is required; the temperature error of the solution treatment is not more than + -5 deg..
In the primary cold deformation treatment: including multiple passes of cold deformation; preferably, the deformation per pass is not more than 20% compared to the deformation of the previous pass.
In the aging treatment: the temperature of the aging treatment is 350-500 ℃; the aging treatment time is 0.5-8h.
Preferably, in the above step, the rare earth element is one or more of La, ce, and Y. The ratio of the content of the rare earth element to the content of the Cr element is 0.005-0.01.
Here, regarding the preparation method of the rare earth copper chromium alloy material provided by the embodiment of the invention, the following needs to be described:
1. the invention realizes the preparation of Cu-Cr-rare earth alloy, and the alloy still maintains finer and uniform structure and better strength and conductivity after high-temperature heat treatment. The alloy compositions (including Cr, zr, rare earth) and the process conditions involved in the related art mentioned in the background art are different from those of the present invention. In addition, the prior art does not mention the tissue properties after high temperature heat treatment.
2. The invention firstly reasonably controls the addition amount of rare earth, in particular strictly requires the proportion of Cr content to rare earth content, so that the excessive rare earth content is lower, excessive chemical reaction can not be generated on Cr element, and the action effect of the Cr element is reserved.
By combining a large deformation cold and hot treatment system process, the excessive rare earth primary phases are uniformly and finely distributed, and the effect of refining the matrix structure and pinning the grain boundary can be achieved in the thermal deformation process. The rare earth primary phase can be reserved at the grain boundary, and can induce Cr phase to be separated out nearby the grain boundary in the subsequent cold deformation and heat treatment processes, so that the effect of regulating and controlling the content of the separated-out phase at the grain boundary is realized, and the separated-out phase plays a strong pinning role relative to the growth of a recrystallization tissue in the high-temperature heat treatment process, so that the high-temperature stability is improved.
3. The large deformation cold-hot treatment system comprises hot forging treatment, primary cold deformation treatment and aging treatment. The method comprises the following steps: 1) Through the hot forging treatment of "large deformation": because the added rare earth elements form hard granular primary phases with larger sizes in the alloy matrix, the rare earth hard granular primary phases have the effect of crushing matrix tissues in the hot forging treatment process, and the primary phases are crushed and uniformly distributed under the action of large deformation, so that the growth of dynamic recrystallization grains is inhibited; after hot forging treatment, the alloy has uniform components and uniform and fine structure. 2) By the "one-time cold deformation" process: the recrystallized tissue is subjected to severe plastic deformation to meet the required size requirement, and enough deformation energy storage is accumulated; in addition, a fibrous structure is formed in the alloy, and the rare earth phase is distributed along the deformation direction. 3) By "heat treatment" immediate effect treatment: the solid solubility of solute atoms changes, and second-phase particles which are dispersed and fine are easier to separate out in an alloy matrix under the drive of deformation energy storage, so that the second-phase particles are attracted to separate out nearby due to the elastic deformation energy effect around the primary rare earth phase.
4. The prior art processes generally comprise two types: (1) sheet strip: hot forging-solid solution-hot rolling-1 cold rolling-heat treatment-2 cold rolling (or no 2 cold rolling); (2) wire material: hot extrusion-1 cold drawing-solid solution-2 cold drawing-aging. Compared with the prior art, the method has fewer working procedures, and the introduced rare earth primary phase particles have an improvement effect on deformed tissues.
On the other hand, the embodiment of the invention provides a rare earth copper chromium alloy material, wherein the rare earth copper chromium alloy material comprises the following chemical components in percentage by weight: 0.1-2.0wt% of Cr, more than 0 and less than or equal to 200ppm of rare earth RE, not more than 0.005wt% of unavoidable impurity elements, and the balance of copper; preferably, the rare earth copper chromium alloy material is insulated for 1-4 hours at 900-980 ℃, the average grain size after furnace cooling is smaller than 25 mu m, the electric rate is larger than 80% IACS, the hardness is larger than 50HV, and the volume percentage of an annealing twin crystal is 40-80%; the rare earth copper chromium alloy material is prepared by the preparation method of any one of the rare earth copper chromium alloy materials.
The following is further detailed by the specific examples:
example 1
The rare earth copper chromium alloy material is prepared in the embodiment; wherein, the rare earth copper chromium alloy material of the embodiment contains, by weight: 1wt% Cr, 100PPmLa, not more than 0.005wt% of unavoidable impurity elements, and the balance copper.
The preparation method mainly comprises the following steps:
1) Vacuum induction melting: weighing the raw materials according to the weight percentage, loading an electrolytic copper plate and a pure Cr block into a crucible, putting a Cu-20RE intermediate alloy into a secondary feeding disc, wrapping the copper plate by using a copper foil to prevent the copper plate and the pure Cr block from being oxidized at a high temperature, vacuumizing to about 10Pa, adjusting the power, starting heating, and completely melting the Cu block and the Cr block after 20min at the temperature of about 1200 ℃; raising power, regulating the temperature to 1300-1400 ℃ for refining, mainly removing gas in the alloy, after about 30min, charging argon into the solution, adding Cu-La intermediate alloy in a secondary disc into a crucible, then carrying out in-furnace melting, casting, and cooling to room temperature at about 1150 ℃ to obtain an ingot.
2) Homogenizing: the ingot is insulated for 2 hours at the temperature of 920+/-10 ℃; wherein, the cooling mode after the homogenization treatment is air cooling.
3) Hot forging of cast ingots: carrying out hot forging treatment on the alloy ingot subjected to homogenization treatment; wherein, the initial forging temperature is 900 ℃, the final forging temperature is more than or equal to 700 ℃ (specifically 750 ℃), and the alloy with the width of 100mm and the thickness of 20mm is obtained by forging; wherein the forging ratio was 5.
4) Solution treatment: carrying out solution treatment on the alloy after the hot forging treatment; wherein the solution treatment temperature is 880+/-10 ℃, the total heat preservation time is 1h, and then water quenching treatment is carried out.
5) Double milling face: and removing the defects on the surface of the plate subjected to solution treatment, wherein the milling depth is 0.2mm.
6) Primary cold deformation: carrying out primary cold deformation treatment on the alloy after milling; wherein, the cold deformation amount is 80 percent (the cold deformation is performed for 4 times, and the cold deformation amount is sequentially 30 percent, 20 percent, 15 percent and 15 percent);
7) Aging the alloy subjected to primary cold deformation treatment; wherein the aging treatment temperature is 430 ℃, and the heat preservation time is 2 hours, so that the rare earth copper chromium alloy material is obtained.
The rare earth copper chromium alloy material prepared in the embodiment is kept at a high temperature of 980 ℃ for 3 hours, the average grain size after furnace cooling is 23.1 mu m, the conductivity is 80.21% IACS, and the hardness is 50.14HV.
Example 2
The rare earth copper chromium alloy material is prepared in the embodiment; wherein, the rare earth copper chromium alloy material of the embodiment contains, by weight: 1.5wt% Cr, 150PPmLa, not more than 0.005wt% of unavoidable impurity elements, and the balance being copper.
The preparation method mainly comprises the following steps:
1) Vacuum induction melting: weighing the raw materials according to the weight percentage, loading an electrolytic copper plate and a pure Cr block into a crucible, putting a Cu-15RE intermediate alloy into a secondary feeding disc, wrapping the copper plate by using a copper foil to prevent the copper plate and the pure Cr block from being oxidized at a high temperature, vacuumizing to about 10Pa, adjusting the power, starting heating, and completely melting the Cu block and the Cr block after 20min at the temperature of about 1200 ℃; raising power, regulating the temperature to 1300-1400 ℃ for refining, mainly removing gas in the alloy, after about 30min, charging argon into the solution, adding Cu-La intermediate alloy in a secondary disc into a crucible, then carrying out in-furnace melting, casting, and cooling to room temperature at about 1150 ℃ to obtain an ingot.
2) Homogenizing: the ingot is insulated for 2 hours at the temperature of 920+/-10 ℃; wherein, the cooling mode after the homogenization treatment is air cooling.
3) Hot forging of cast ingots: carrying out hot forging treatment on the alloy ingot subjected to homogenization treatment; wherein, the initial forging temperature is 900 ℃, the final forging temperature is more than or equal to 700 ℃ (specifically 750 ℃), and the alloy with the width of 100mm and the thickness of 20mm is obtained by forging; wherein the forging ratio was 5.
4) Solution treatment: carrying out solution treatment on the alloy after the hot forging treatment; wherein the solution treatment temperature is 880+/-10 ℃, the total heat preservation time is 1h, and then water quenching treatment is carried out.
5) Double milling face: and removing the defects on the surface of the plate subjected to solution treatment, wherein the milling depth is 0.2mm.
6) Primary cold deformation: carrying out primary cold deformation treatment on the alloy after milling; wherein, the cold deformation amount is 80 percent (the cold deformation is performed for 4 times, and the cold deformation amount is sequentially 30 percent, 20 percent, 15 percent and 15 percent);
7) Aging the alloy subjected to primary cold deformation treatment; wherein the aging treatment temperature is 440 ℃, and the heat preservation time is 2 hours, thus obtaining the rare earth copper chromium alloy material.
The rare earth copper chromium alloy material prepared in the embodiment is kept at the high temperature of 980 ℃ for 3 hours, the average grain size after furnace cooling is 20.5 mu m, the conductivity is 78.45% IACS, and the hardness is 55.60HV.
Comparative example 1
Comparative example 1 a copper chromium alloy material was prepared; wherein, the copper-chromium alloy material of comparative example 1 comprises the following components in percentage by weight: 1wt% Cr, not more than 0.005wt% total of unavoidable impurity elements, and the balance copper.
The main preparation method comprises the following steps:
vacuum induction melting: weighing the raw materials according to the weight percentage, loading an electrolytic copper plate and a pure Cr block into a crucible, vacuumizing to about 10Pa, adjusting power, starting heating, and melting the Cu block and the Cr block completely after 20min at the temperature of about 1200 ℃; raising power, regulating the temperature to 1300-1400 deg.c, refining, eliminating gas for 30min, casting in furnace at 1200 deg.c and cooling to room temperature to obtain cast ingot.
And carrying out homogenization treatment, hot forging treatment, solution treatment, double milling surface treatment, primary cold rolling deformation treatment and aging treatment on the cast ingot to obtain the copper-chromium alloy material. Among them, the processes of homogenization treatment, hot forging treatment, solution treatment, double milling treatment, primary cold rolling deformation treatment and aging treatment are described in example 1.
The copper-chromium alloy material prepared in comparative example 1 was kept at a high temperature of 980 ℃ for 3 hours, and after furnace cooling, the average grain size was 36.2 μm, the conductivity was 72.43% IACS, and the hardness was 46.87HV.
Comparative example 2
Comparative example 2 a copper chromium zirconium alloy material was prepared; wherein, the copper-chromium-zirconium alloy material of the comparative example 2 comprises the following components in percentage by weight: 1wt% Cr,0.1wt% Zr, the total of unavoidable impurity elements not exceeding 0.005wt%, the balance being copper.
The main preparation method comprises the following steps:
vacuum induction melting: weighing the raw materials according to the weight percentage, loading an electrolytic copper plate and a pure Cr block into a crucible, putting pure Zr or Cu-Zr intermediate alloy wrapped by copper foil into a secondary feeding disc, vacuumizing to about 10Pa, adjusting power, starting heating, and completely melting the Cu block and the Cr block after 20min at the temperature of about 1200 ℃; raising power, regulating the temperature to 1300-1400 ℃ for refining, mainly removing gas, after about 30min, charging argon gas into the solution surface without boiling, adding pure Zr or Cu-Zr intermediate alloy wrapped by copper foil in a secondary disc into a crucible, then carrying out in-furnace melting, casting, and cooling to room temperature at the casting temperature of about 1200 ℃ to obtain cast ingots.
And carrying out homogenization treatment, hot forging treatment, solution treatment, double milling surface treatment, primary cold rolling deformation treatment and aging treatment on the cast ingot to obtain the copper-chromium alloy material. Among them, the processes of homogenization treatment, hot forging treatment, solution treatment, double milling treatment, primary cold rolling deformation treatment and aging treatment are described in example 1.
The copper-chromium-zirconium alloy material prepared in comparative example 2 was kept at a high temperature of 980 ℃ for 3 hours, and the average grain size after furnace cooling was 59.4 μm, the conductivity was 66.10% IACS, and the hardness was 49.98HV.
Comparative example 3
Comparative example 3 a rare earth copper chromium alloy material was prepared; here, the chemical composition of the rare earth copper chromium alloy material of comparative example 3 is the same as in example 1, but the preparation method is different.
The preparation method of comparative example 3 mainly comprises the following steps:
1) Vacuum induction melting: weighing the raw materials according to the weight percentage, loading an electrolytic copper plate and a pure Cr block into a crucible, putting metal La into a secondary charging tray, wrapping the metal La by copper foil to prevent the metal La from being oxidized at a high temperature, vacuumizing to about 10Pa, adjusting the power, starting heating, and completely melting the Cu block and the Cr block after 20min at the temperature of about 1200 ℃; raising power, regulating the temperature to 1300-1400 ℃ for refining, mainly removing gas, after about 30min, charging argon gas into the solution surface without boiling, adding La metal in a secondary disc into a crucible, then carrying out in-furnace melting, casting, and cooling to room temperature at the casting temperature of about 1200 ℃ to obtain an ingot.
2) Homogenizing: the ingot is insulated for 2 hours at the temperature of 920+/-10 ℃; wherein, the cooling mode after the homogenization treatment is air cooling.
3) Solution treatment: carrying out solution treatment on the homogenized alloy; wherein the solution treatment temperature is 880+/-10 ℃, the total heat preservation time is 1h, and then water quenching treatment is carried out.
4) Double milling face: and removing the defects on the surface of the plate subjected to solution treatment, wherein the milling depth is 0.2mm.
5) Primary cold deformation: carrying out primary cold deformation treatment on the alloy after milling; wherein, the cold deformation amount is 80%;
6) Aging the alloy subjected to primary cold deformation treatment; wherein the aging treatment temperature is 430 ℃, and the heat preservation time is 2 hours, so that the rare earth copper chromium alloy material is obtained.
The rare earth copper chromium alloy material prepared in comparative example 3 is kept at a high temperature of 980 ℃ for 3 hours, the average grain size after furnace cooling is 45.2 mu m, the conductivity is 77.6% IACS, and the hardness is 45.50HV.
Comparative example 4
Comparative example 4 a rare earth copper chromium alloy material was prepared; the rare earth copper chromium alloy material prepared in comparative example 4 contains, in weight percent: 1wt% Cr,0.1wt% La, the total of unavoidable impurity elements not exceeding 0.005wt%, and the balance copper.
The preparation method of the rare earth copper chromium alloy material in comparative example 4 is identical to that in example 1.
The rare earth copper chromium alloy material prepared in comparative example 4 is kept at a high temperature of 980 ℃ for 3 hours, the average grain size after furnace cooling is 55.4 mu m, the conductivity is 70.10% IACS, and the hardness is 50.20HV.
The overall performance data of examples 1-2 and comparative examples 1-4 are shown in Table 1.
TABLE 1
In addition, FIG. 1 is an IPF diagram of an alloy material after high temperature heat treatment (heat preservation for 3h at a high temperature of 980 ℃ and furnace cooling); wherein, graph a in FIG. 1 is an IPF diagram of the rare earth copper chromium alloy material (Cu-1 Cr-100 ppmLa) prepared in example 1; panel b is an IPF plot of Cu-1Cr prepared in comparative example 1; FIG. c is an IPF diagram of Cu-1Cr-0.1Zr prepared in comparative example 2.
FIG. 2 is a grain distribution diagram of an alloy material after high temperature heat treatment (3 h at 980 ℃ C., furnace cooling); wherein, a graph in FIG. 1 is a grain distribution diagram of the rare earth copper chromium alloy material (Cu-1 Cr-100 ppmLa) prepared in example 1; panel b shows the grain distribution diagram of Cu-1Cr prepared in comparative example 1; FIG. c is a grain distribution diagram of Cu-1Cr-0.1Zr prepared in comparative example 2.
Here, as can be seen from table 1 and fig. 1 and 2:
(1) As is evident from table 1, fig. 1 and fig. 2: compared with comparative examples 1 and 2, the rare earth copper chromium alloy materials prepared by the examples of the invention have finer crystal grains than Cu-Cr alloy and Cu-Cr-Zr alloy after high temperature heat treatment. Compared with the similar alloy, the rare earth copper chromium alloy material prepared by the embodiment of the invention has obvious grain refinement effect after high-temperature heat treatment. The rare earth copper chromium alloy material prepared by the embodiment of the invention also has better strength and higher conductivity after high-temperature heat treatment.
What should be stated here is: other similar alloys and other similar rare earth alloys in the prior art cannot achieve the comprehensive effects of fine crystals, high conductivity and good strength after high temperature heat treatment.
(2) The rare earth copper chromium alloy materials prepared in the examples of the present invention have fine grain size and excellent conductivity, compared with comparative examples 3 and 4. The chemical composition design and the preparation process design of the rare earth copper chromium alloy material have synergistic effect, and the synergistic effect of the chemical composition design and the preparation process design improves the microscopic property and the macroscopic property of the rare earth copper chromium alloy material.
(3) Compared with the comparative example, the rare earth copper chromium alloy material prepared by the embodiment of the invention has high annealing twin crystal content after high temperature heat treatment, which is beneficial to tissue stabilization and strength improvement.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the rare earth copper chromium alloy material is characterized by comprising the following chemical components in percentage by weight: 0.1-2.0wt% of Cr, more than 0 and less than or equal to 200ppm of rare earth elements, not more than 0.005wt% of unavoidable impurity elements, and the balance of copper; the preparation method of the rare earth copper chromium alloy material comprises the following steps:
1) Smelting and casting the raw materials to obtain an ingot;
2) Homogenizing the cast ingot to obtain a homogenized alloy ingot;
3) Sequentially carrying out hot forging treatment, solution treatment, primary cold deformation treatment and aging treatment on the alloy ingot subjected to the homogenization treatment to obtain a rare earth copper chromium alloy material; wherein the cold deformation amount of the primary cold deformation treatment is 50-90%.
2. The method for preparing a rare earth copper chromium alloy material according to claim 1, wherein the rare earth element is one or more of La, ce and Y.
3. The method for producing a rare earth copper chromium alloy material according to claim 1 or 2, wherein the ratio of the content of the rare earth element to the content of the Cr element is 0.005 to 0.01.
4. A method of producing a rare earth copper chromium alloy material according to any one of claims 1 to 3, wherein in said step 1):
the raw materials include raw materials for providing rare earth elements; wherein the raw material for providing rare earth elements comprises a Cu-xRE intermediate alloy; wherein x is 15-25%, and the oxygen content in the Cu-xRE intermediate alloy is lower than 5ppm; and/or
Smelting raw materials under the conditions of 1200-1400 ℃ and protective atmosphere; preferably, the protective atmosphere is nitrogen or argon; and/or
Loading Cu and Cr into a crucible, putting the Cu-xRE intermediate alloy into a secondary feeding disc, and wrapping the Cu-xRE intermediate alloy by using copper foil to prevent the Cu-xRE intermediate alloy from being oxidized at high temperature; vacuumizing, adjusting power, starting heating to 1200-1250 ℃, after Cu and Cr are completely melted, increasing power, adjusting the temperature to 1300-1400 ℃ for refining, removing gas in the Cu-Cr, charging argon when the surface of the solution is not boiled, adding Cu-xRE intermediate alloy in a secondary disc into a crucible, and then carrying out furnace flushing and melting and casting; and/or
The casting temperature is 1100-1150 ℃.
5. The method for producing a rare earth copper chromium alloy material according to any one of claims 1 to 4, wherein in said step 2):
the homogenization treatment temperature is 900-1000 ℃; preferably, the temperature is kept for 1-10h at the homogenization treatment temperature.
6. The method for producing a rare earth copper chromium alloy material according to any one of claims 1 to 5, wherein in the hot forging treatment of step 3):
the initial forging temperature is 750-950 ℃ and the final forging temperature is 700-800 ℃; and/or
The forging ratio is 2-6.
7. The method for producing a rare earth copper chromium alloy material according to any one of claims 1 to 6, wherein, in the solid solution treatment of step 3):
the temperature of the solid solution treatment is 880-980 ℃;
preferably, the temperature is kept for 0.5 to 10 hours at the temperature of solution treatment;
preferably, after the solution treatment is finished, water quenching treatment is required;
preferably, the temperature error of the solution treatment is not more than ±5°.
8. The method according to any one of claims 1 to 7, wherein the single cold deformation treatment in the step 3) includes multiple cold deformation steps;
preferably, the deformation per pass is not more than 20% compared to the deformation of the previous pass.
9. The method for producing a rare earth copper chromium alloy material according to any one of claims 1 to 8, wherein in the aging treatment of step 3):
the temperature of the aging treatment is 350-500 ℃; the aging treatment time is 0.5-8h.
10. The rare earth copper chromium alloy material is characterized by comprising the following chemical components in percentage by weight: 0.1-2.0wt% of Cr, more than 0 and less than or equal to 200ppm of rare earth elements, not more than 0.005wt% of unavoidable impurity elements, and the balance of copper;
preferably, the rare earth copper chromium alloy material is insulated for 1-4 hours at 900-980 ℃, and after being cooled along with a furnace, the average grain size is smaller than 25 mu m, the electric rate is larger than 80% IACS, the hardness is larger than 50HV, and the volume percentage of an annealing twin crystal is 40-80%;
preferably, the rare earth copper chromium alloy material is prepared by the preparation method of the rare earth copper chromium alloy material according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310414060.7A CN116397128A (en) | 2023-04-18 | 2023-04-18 | Rare earth copper chromium alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310414060.7A CN116397128A (en) | 2023-04-18 | 2023-04-18 | Rare earth copper chromium alloy material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116397128A true CN116397128A (en) | 2023-07-07 |
Family
ID=87010328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310414060.7A Pending CN116397128A (en) | 2023-04-18 | 2023-04-18 | Rare earth copper chromium alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116397128A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116875842A (en) * | 2023-07-19 | 2023-10-13 | 中国科学院金属研究所 | Rare earth copper-tin-phosphorus alloy material and preparation method thereof |
-
2023
- 2023-04-18 CN CN202310414060.7A patent/CN116397128A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116875842A (en) * | 2023-07-19 | 2023-10-13 | 中国科学院金属研究所 | Rare earth copper-tin-phosphorus alloy material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2511397B1 (en) | Magnetic material sputtering target | |
| EP2692879B1 (en) | Cu-co-si-based copper alloy strip for electron material, and method for manufacturing same | |
| KR101802009B1 (en) | Cu-si-co-base copper alloy for electronic materials and method for producing same | |
| CN113564408B (en) | High-strength high-conductivity rare earth copper alloy Cu-Cr-Zr-Y and preparation method thereof | |
| WO2023065942A1 (en) | Copper alloy material for 5g base station power connector, and preparation method therefor | |
| CN115652132B (en) | Copper alloy material and application and preparation method thereof | |
| CN116397128A (en) | Rare earth copper chromium alloy material and preparation method thereof | |
| CN109295346B (en) | High-conductivity soft aluminum alloy and preparation method and application thereof | |
| CN114318032B (en) | Preparation method of high-strength high-conductivity copper alloy Cu-Cr-Zr-Nb | |
| CN110872659A (en) | High-performance copper alloy | |
| JP2012077346A (en) | Boron-containing pure titanium material, and method of manufacturing the same | |
| CN112210703B (en) | High-recrystallization-resistance and high-toughness aluminum lithium alloy and preparation method thereof | |
| CN114150179B (en) | Oxygen-free copper material, oxygen-free copper material product and preparation method thereof | |
| CN113897567B (en) | Homogenization thermomechanical treatment method for rapidly refining and homogenizing cast aluminum-lithium alloy | |
| CN114277280B (en) | Precipitation strengthening type tin brass alloy and preparation method thereof | |
| CN113005324B (en) | Copper-titanium alloy and preparation method thereof | |
| CN114427046A (en) | Short-process preparation device and preparation method of alloy | |
| CN114672689B (en) | Rare earth copper alloy material with electromagnetic shielding function and preparation method thereof | |
| CN114657410B (en) | High-strength high-conductivity copper-iron alloy and preparation method thereof | |
| US9437405B2 (en) | Hot rolled plate made of copper alloy used for a sputtering target and sputtering target | |
| CN114540663B (en) | Cu-Ni-Si-Fe alloy and preparation method and application thereof | |
| KR102362668B1 (en) | High stength and high conductivity copper alloys and manufacturing method of the same | |
| CN112962069B (en) | Intermetallic compound-containing aluminum alloy target and preparation method thereof | |
| CN113981272B (en) | Ti-6Al-4V-xFe-yMo titanium alloy and preparation method thereof | |
| JPH04210438A (en) | Continuous casting mold material made of high strength cu 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 |