CN101709401B - Cu-Cr in-situ composite with boron, silver and rare earth elements added and preparation method thereof - Google Patents
Cu-Cr in-situ composite with boron, silver and rare earth elements added and preparation method thereof Download PDFInfo
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- CN101709401B CN101709401B CN2009101866941A CN200910186694A CN101709401B CN 101709401 B CN101709401 B CN 101709401B CN 2009101866941 A CN2009101866941 A CN 2009101866941A CN 200910186694 A CN200910186694 A CN 200910186694A CN 101709401 B CN101709401 B CN 101709401B
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Abstract
The invention discloses a Cu-Cr in-situ composite with boron, silver and rare earth elements added and a preparation method thereof. The invention is characterized by adopting multimode comprehensive strengthening technology such as multi-micro alloying, solid solution strengthening, aging strengthening, fine grain strengthening, distortion strengthening, fiber strengthening and the like, using Cu as the base and adding a little Cr and trace Ag and B, rare earth or rare earth compounds to prepare the high performance copper alloy in-situ composite through smelting, casting, hot forging or hot rolling, solid solution treatment, cold rolling or cold drawing, aging and the like. The prepared material has the advantages of high strength, good electric and thermal conductivity, simple preparation process and low cost, thus realizing industrial application in the aspects such as electrician switches, contact materials, resistance electrodes, rotor conductors of large electrical high speed turbine generators, overhead conductors of electric cars and electric trains, lead frames of very large scale integrated circuits and the like.
Description
Technical field
The present invention relates to a kind of by boron, silver, rare earth element interpolation Cu-Cr in-situ composite and preparation method thereof, genus nonferrous materials technical field.
Background technology
Along with the fast development of high-tech sectors such as electronics, communication, traffic, electric power, space flight, precision instrument, more and more high for the requirement of copper alloy.Require used Cu alloy material not only to possess outside high strength, the electric-conductivity heat-conductivity high performance, higher softening temperature, non-oxidizability, creep resistant, characteristic such as high pressure resistant also must be arranged, traditional copper alloy with high strength and high conductivity has been difficult to reach requirement.In recent decades, countries in the world have been carried out the research and development of high property copper alloy in succession, have obtained application on some industries.Because China starts late in the research work in this field, the main dependence on import of high-performance electrolytic copper alloy material that industry is required, and China is copper resource big country, have numerous copper processing enterprises, therefore, high-performance copper alloy material is researched and developed, and it is significant progressively to set up the Cu alloy material system that has independent intellectual property right.
The conductivity of Cu alloy material and intensity are a pair of contradiction that is difficult to take into account, i.e. well intensity difference then of conductivity, and intensity improves then that conductance reduces.It is a kind of reliable method that obtains best intensity and conductivity combination that the deformation in-situ composite material legal system is equipped with the high strength and high conductivity Cu alloy material, also is the hot topic and the forward position of present Cu alloy material research field.Deformation copper base was that composite study mainly concentrates on Cu-Nb and Cu-Ag in-situ composite originally at present, but because Nb and Ag are noble metals, and the fusing point of Nb is up to 2648 ℃, there are bigger non-miscible gap again in liquid Cu and Nb, have therefore limited the preparation and the application of this class new material.Because the solid solubility of Cr in Cu is very low, the solid solubility of Cu in Cr is littler, so the Cu-Cr alloy combines high rigidity and the Cu favorable conductive thermal conductivity of Cr, at aspects such as preparation iec switch, contact material, resistance electrode, TV university type high-speed turbine generator amature lead, electric car and electric power train aerial condutor, very lagre scale integrated circuit (VLSIC) lead frames, especially in high-power vacuum high-voltage switch, demonstrate wide application prospect.
Notification number CN1233492 discloses a kind of W-Cu or the powder deformed combination electrode material preparation method of Cu-Cr, and it adopts Cu and Cr or W and Cu simple substance powder is raw material, and the first step is carried out mechanical ball milling powder process; Second goes on foot the base of colding pressing; The 3rd step was carried out the vacuum solid-phase sintering, and the 4th step was hot quiet liquid extruding.Publication number CN101384739 discloses a kind of Cr-Cu alloy, its manufacture method, semiconductor heating panel and semiconductor thermal component, described Cr-Cu alloy obtains with flat Cr powder metallurgy mutually by comprising the Cu matrix, wherein, make Cr content in the Cr-Cu alloy surpass 30% and below 80%.
Summary of the invention
The objective of the invention is to, provide a kind of and have high strength and high conductivity, thermal conductivity, and preparation technology is simple, cost is low Cu-Cr in-situ composite and preparation technology thereof.
Technical scheme of the present invention is, Cu-Cr in-situ composite of the present invention is the copper material by batching, melting, casting, forge hot or hot rolling, cold rolling, the last moulding of cold-drawn.
The formula components of Cu-Cr in-situ composite of the present invention consists of (by mass percentage):
Cr:5~28;
Ag:0.01~1.00;
B:0.001~0.500;
Rare earth metal or lucium: 0.001~1.000;
Cu: surplus;
Rare earth in the Cu-Cr in-situ composite prescription of the present invention is meant metal or alloy or the oxide that contains cerium or yttrium or lanthanum element, and lucium is meant alloy or the oxide mixture that contains two kinds or three kinds elements in cerium or yttrium or the lanthanum.
Cu-Cr in-situ composite of the present invention is to prepare by following steps:
1, batching:
Requirement according to chemical composition will meet cathode copper, the pure Cr of prescription quality percentage or contain Cr alloy, pure Ag or contain the Ag alloy, contain B alloy, rare earth metal or lucium or contain rare earth alloy and mix, and obtain batching;
2, melting:
The batching for preparing is put into intermediate frequency electromagnetic induction furnace or other smelting furnaces, copper alloy smelting process fusing routinely;
3, casting:
The molten metal that has melted poured in water-cooled punching block, graphite mo(u)ld or other moulds obtain ingot casting;
4, forge hot or hot rolling:
Above-mentioned cast article is put into heat-treatment furnace, be heated to a certain temperature in 800 ℃~1000 ℃ of intervals, be incubated 1~5 hour, forge hot or hot rolling on conventional hot-rolling mill then makes it reach distortion more than 20%;
5, solution treatment:
Alloy after forge hot or the hot rolling is packed in the heat-treatment furnace, be heated to a certain temperature in 950 ℃~1100 ℃ of intervals, be incubated 0.2~5 hour, carry out Quenching Treatment then;
6, cold rolling: the alloy after will quenching carries out the deformation process more than 20%;
7, annealing: with a certain temperature of the alloy after cold rolling between 400 ℃~700 ℃, be incubated 0.1~3 hour, cold with stove;
8, cold-drawn: the alloy after will handling carries out the deformation process of multi-pass more than 30%;
9, Ageing Treatment: alloy in 250 ℃~650 ℃ a certain intervals, is incubated 1~24 hour.
The present invention passes through to add the Ag of certain content in the Cu-Cr alloy, the mainly effect of its three aspect, and the one, reduced the solid solubility of Cr in Cu under the high temperature, promote that Cr separates out from the Cu matrix under the low temperature, be that the electric conductivity of material improves; The 2nd, refinement Cr dendrite, make it to become ball shape, be that the intensity of material is significantly improved; The 3rd, improve the plasticity of material, improve the cold deformation performance of material extremely significantly, thereby increased substantially the lumber recovery of material.
The present invention mainly plays two aspects by adding the B element of certain content, and the one, the evolution effect reduces gas and impurity content in the material, is that the electric conductivity of material improves; The 2nd, the recrystallization temperature of raising material helps improving timeliness and annealing temperature, promotes the Cr particle to separate out, and is that material obtains best intensity and conducts electricity combination property.
The present invention has improved the degree of purity of metal bath by adding proper amount of rare-earth metal or lucium, simultaneously important function has also been played in the material grains refinement, helps improving simultaneously the intensity and the electric conductivity of material.
The present invention becomes Cr simple substance by multi-pass deformation fibrous, and being arranged in the copper base of rule makes the dislocation motion resistance of material increase, thereby the strength of materials is strengthened.
The present invention's beneficial effect compared with the prior art is, the present invention purifies the Cu alloy material matrix, structure refinement combines with working hardening, utilize Cr fiber reinforcement and Cr particle dispersion to strengthen combination, make the intensity and the electric conductivity of material reach best combination, the intensity of stretching of material reaches 800~1300MPa, conductance reaches 70~85%IACS, and the preparation method is simple, the cost of raw material is low can to realize that it is at iec switch, contact material, resistance electrode, TV university type high-speed turbine generator amature lead, electric car and electric power train aerial condutor, the very lagre scale integrated circuit (VLSIC) lead frame, aspect extensive uses such as high-power vacuum high-voltage switch.
Description of drawings
Accompanying drawing is a process chart of the present invention
Embodiment
Embodiment 1
(1) batching: requirement according to chemical composition, will meet prescription quality percentage pure Cr 8%, pure Ag 0.05%, to contain B alloy 0.05%, rare earth metal Ce 0.01%, cathode copper be surplus, obtains batching;
(2) melting: the batching that will prepare is put into the intermediate frequency electromagnetic induction furnace, copper alloy smelting process fusing routinely 25 minutes;
(3) casting: the molten metal that will melt pours into and obtains ingot casting in the graphite mo(u)ld;
(4) forge hot or hot rolling: above-mentioned cast article is put into heat-treatment furnace, be heated to 900 ℃, be incubated 3 hours, hot rolling on conventional hot-rolling mill then makes it reach 40% distortion;
(5) solution treatment: the alloy after the hot rolling is packed in the heat-treatment furnace, be heated to 980 ℃, be incubated 1 hour, cooling fast in the cold water of quenching then;
(6) cold rolling: the alloy after will quenching carries out 80% deformation process;
(7) annealing: with the alloy after cold rolling, be heated to 450 ℃, be incubated 0.5 hour, cold with stove;
(8) cold-drawn: the alloy after will handling carries out the deformation process of multi-pass 80%;
(9) Ageing Treatment: alloy at 480 ℃, is incubated 1 hour.
The Cu alloy material that makes at last
Tensile strength: 〉=800MPa
Conductivity: 〉=80%IACS
Embodiment 2
(1) batching: requirement according to chemical composition, will meet the containing Cr alloy 10%, pure Ag 0.05%, contain B alloy 0.05% of prescription quality percentage, rare earth element y 0.01%, cathode copper is surplus, obtains batching;
(2) melting: the batching that will prepare is put into the intermediate frequency electromagnetic induction furnace, copper alloy smelting process fusing routinely 25 minutes;
(3) casting: the molten metal that will melt pours in the water-cooled punching block and to obtain ingot casting;
(4) forge hot or hot rolling: above-mentioned cast article is put into heat-treatment furnace, be heated to 900 ℃, be incubated 3 hours, hot rolling on conventional hot-rolling mill then makes it reach 40% distortion;
(5) solution treatment: the alloy after the hot rolling is packed in the heat-treatment furnace, be heated to 980 ℃, be incubated 1 hour, cooling fast in the cold water of quenching then;
(6) cold rolling: the alloy after will quenching carries out 80% deformation process;
(7) annealing: with the alloy after cold rolling, be heated to 470 ℃, be incubated 0.5 hour, cold with stove;
(8) cold-drawn: the alloy after will handling carries out the deformation process of multi-pass 80%.
(9) Ageing Treatment: alloy at 480 ℃, is incubated 4 hours;
The Cu alloy material that makes at last
Tensile strength: 〉=900MPa
Conductivity: 〉=75%IACS
Embodiment 3
(1) batching: requirement according to chemical composition, will meet prescription quality percentage pure Cr 12%, contain Ag alloy 0.1%, contain B alloy 0.05%, rare-earth elements La 0.01%, cathode copper be surplus, obtains batching;
(2) melting: the batching that will prepare is put into the intermediate frequency electromagnetic induction furnace, copper alloy smelting process fusing routinely 25 minutes;
(3) casting: the molten metal that will melt pours into and obtains ingot casting in the graphite mo(u)ld;
(4) forge hot or hot rolling: above-mentioned cast article is put into heat-treatment furnace, be heated to 930 ℃, be incubated 3 hours, hot rolling on conventional hot-rolling mill then makes it reach 40% distortion;
(5) solution treatment: the alloy after the hot rolling is packed in the heat-treatment furnace, be heated to 1000 ℃, be incubated 1 hour, cooling fast in the cold water of quenching then;
(6) cold rolling: the alloy after will quenching carries out 80% deformation process;
(7) annealing: with the alloy after cold rolling, be heated to 490 ℃, be incubated 0.5 hour, cold with stove;
(8) cold-drawn: the alloy after will handling carries out the deformation process of multi-pass 80%;
(9) Ageing Treatment: alloy at 480 ℃, is incubated 4 hours.
The Cu alloy material that makes at last
Tensile strength: 〉=1000MPa
Conductivity: 〉=70%IACS
Embodiment 4
(1) batching: requirement according to chemical composition, will meet prescription quality percentage pure Cr 13%, pure Ag0.1%, contain B alloy 0.05%, rare-earth elements La 0.01% and Ce0.01%, cathode copper is a surplus, obtain the batching;
(2) melting: the batching that will prepare is put into the intermediate frequency electromagnetic induction furnace, copper alloy smelting process fusing routinely 25 minutes;
(3) casting: the molten metal that will melt pours into and obtains ingot casting in the graphite mo(u)ld;
(4) forge hot or hot rolling: above-mentioned cast article is put into heat-treatment furnace, be heated to 950 ℃, be incubated 3 hours, hot rolling on conventional hot-rolling mill then makes it reach 40% distortion;
(5) solution treatment: the alloy after the hot rolling is packed in the heat-treatment furnace, be heated to 1000 ℃, be incubated 1 hour, cooling fast in the cold water of quenching then;
(6) cold rolling: the alloy after will quenching carries out 80% deformation process;
(7) annealing: with the alloy after cold rolling, be heated to 500 ℃, be incubated 0.5 hour, cold with stove;
(8) cold-drawn: the alloy after will handling carries out the deformation process of multi-pass 80%;
(9) Ageing Treatment: alloy at 500 ℃, is incubated 4 hours.
The Cu alloy material that makes at last
Tensile strength: 〉=1050MPa
Conductivity: 〉=70%IACS
Claims (2)
1. a boron, silver, rare earth element add the preparation method of Cu-Cr in-situ composite, it is characterized in that the formula components of Cu-Cr in-situ composite consists of (by mass percentage): Cr:5~28 in the described method; Ag:0.01~1.00; B:0.001~0.500; Rare earth metal or lucium: 0.001~1.000; Cu: surplus;
The Cu-Cr in-situ composite is that its step of preparation process is as follows by the copper material of batching, melting, casting, forge hot or hot rolling, cold rolling, the last moulding of cold-drawn in the described method:
(1) batching: requirement according to chemical composition, will meet cathode copper, the pure Cr of prescription quality percentage or contain Cr alloy, pure Ag or contain the Ag alloy, contain B alloy, rare earth metal or lucium or contain rare earth alloy and mix, obtain batching;
(2) melting: the batching that will prepare is put into intermediate frequency electromagnetic induction furnace or other smelting furnaces, copper alloy smelting process fusing routinely;
(3) casting: the molten metal that will melt pours in water-cooled punching block, graphite mo(u)ld or other moulds and to obtain ingot casting;
(4) forge hot or hot rolling: above-mentioned cast article is put into heat-treatment furnace, be heated to a certain temperature in 800 ℃~1000 ℃ of intervals, be incubated 1~5 hour, forge hot or hot rolling on conventional hot-rolling mill then makes it reach distortion more than 20%;
(5) solution treatment: the alloy after forge hot or the hot rolling is packed in the heat-treatment furnace, be heated to a certain temperature in 950 ℃~1100 ℃ of intervals, be incubated 0.2~5 hour, carry out Quenching Treatment then;
(6) cold rolling: the alloy after will quenching carries out the deformation process more than 20%;
(7) annealing: with a certain temperature of the alloy after cold rolling between 400 ℃~700 ℃, be incubated 0.1~3 hour, cold with stove;
(8) cold-drawn: the alloy after will handling carries out the deformation process of multi-pass more than 30%;
(9) Ageing Treatment: alloy in 250 ℃~650 ℃ a certain intervals, is incubated 1~24 hour.
2. a kind of boron according to claim 1, silver, rare earth element add the preparation method of Cu-Cr in-situ composite, it is characterized in that, rare earth in the described method in the Cu-Cr in-situ composite prescription is meant metal or alloy or the oxide that contains cerium or yttrium or lanthanum element, and lucium is meant alloy or the oxide mixture that contains two kinds or three kinds elements in cerium or yttrium or the lanthanum.
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CN107805734A (en) * | 2017-12-13 | 2018-03-16 | 柳州智臻智能机械有限公司 | A kind of copper alloy for electronic material and preparation method thereof |
CN114606414B (en) * | 2022-03-11 | 2022-12-02 | 北京理工大学 | High-conductivity regenerated aluminum alloy conductor and preparation method thereof |
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