CN101586198B - A process for preparing aluminum oxide dispersion strengthened copper with high strength and high conductivity - Google Patents
A process for preparing aluminum oxide dispersion strengthened copper with high strength and high conductivity Download PDFInfo
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- CN101586198B CN101586198B CN2009103036998A CN200910303699A CN101586198B CN 101586198 B CN101586198 B CN 101586198B CN 2009103036998 A CN2009103036998 A CN 2009103036998A CN 200910303699 A CN200910303699 A CN 200910303699A CN 101586198 B CN101586198 B CN 101586198B
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Abstract
The invention provides a process for preparing aluminum oxide dispersion strengthened copper with high strength and high conductivity, wherein the Cu-Al alloy powder contains 0.1-0.6 wt% of Al and less than 0.5 wt% of impurity, and cuprous oxide is used as an oxidizing agent. The alloy is directly executed cold deformation after sintered and densification treatment, which avoids thermal deformation process in traditional preparation technique. The prepared aluminum oxide dispersion strengthened copper composite material has performances of high strength, high conductivity and excellent high temperature anti-softening, wherein the tensile strength is larger than 500N/mm<2>, the electric conductivity is larger than 80% IACS, and the softening temperature is higher than 600 DEG C; and the tensile strength is larger than 400N/mm<2> after annealing at 950 DEG C for 30min. The aluminum oxide dispersion strengthened copper is ideal material for making a lead frame of an integrate circuit, aerial extension of high speed electrified railroad, a resistance welding electrode, large thrust rocket engine inside lining, etc.
Description
Technical field
The present invention relates to a kind of preparation technology of aluminum oxide dispersion strengthened copper with high strength and high conductivity.
Background technology
Alumina dispersion-strenghtened copper-base composite material is because have good physicals and mechanical property and high temperature softening resistance energy, being widely used in the high-technology fields such as resistance welding electrode, high-thrust rocket liner in circuit lead frame, high-speed electric railway pole line, automobile and the colored picture tube industry, is the critical material of hyundai electronics information, energy industry development.Particularly over past ten years along with the fast development of automobile industry, information industry and microelectronic industry, alumina dispersion-strenghtened copper has also obtained significant progress, and demonstrate its irreplaceability, thereby caused the extensive concern of lot of domestic and foreign enterprises and scientific research institutions with its good performance.Copper and copper alloy have the favorable conductive thermal conductivity, but its room temperature strength and hot strength are all lower and wear resistance is relatively poor, in order to improve its this shortcoming, by in copper-based material, adding oxide particle as wild phase, and its tiny disperse equably is distributed in the copper matrix, thereby improve the mechanical property and the anti-softening power of high temperature of Cu-base composites, do not reduce its electroconductibility or reduction simultaneously again seldom, this is the research focus in present copper alloy with high strength and high conductivity material field and the direction of industrialization
[1,2,3]Alumina dispersion-strenghtened copper is to introduce the alumina particle of tiny even dispersion distribution as wild phase in the copper matrix, strengthens the matrix material of copper matrix.This alloy system is the intensity height not only, and electric conductivity and thermal conductivity are all very high, more attractive is, almost any copper alloy works long hours being higher than under the 1/3-1/2 melting temperature, its intensity and electrical and thermal conductivity all will reduce significantly, and alumina dispersion-strenghtened copper-base composite material is increased to its softening temperature near the fusing point of copper, thereby can at high temperature work long hours.The alumina particle that this premium properties mainly distributes from disperse in the copper matrix.
Referring to Fig. 1, internal oxidation process is the main method for preparing the alumina dispersion-strenghtened copper matrix material at present, this therewith the matrix material that makes of method to have remarkable performance be inseparable.The traditional technology process that adopts internal oxidation to prepare the alumina dispersion-strenghtened copper matrix material is: the melting X alloy, adopt single-stage atomizations such as water atomization, nitrogen atomization then, or rotation multistage atomizing method atomizing melt, the preparation powder, centrifugal drying, screening then closed and criticized.The powdered alloy that makes is mixed with oxygenant (normally cuprous oxide powder), mixed powder is heated to high temperature more than 800 ℃, under nitrogen atmosphere or the high vacuum atmosphere, Red copper oxide decomposes, the oxygen that generates is diffused in the particle of copper aluminium solid solution alloy, because aluminum ratio copper easily generates oxide compound, so the aluminium in the alloy preferentially is oxidized to aluminum oxide.Aluminium in the X alloy is added thermal reduction by after all oxidation generates aluminum oxide in hydrogen or cracked ammonium atmosphere, become water vapour to overflow hydrogen reduction unnecessary in the powdered alloy, thereby make the alumina dispersion-strenghtened copper powder.Adopt unidirectional compacting, two-way compacting or isostatic cool pressing to become ingot blank powdered alloy, the cold compaction ingot blank is carried out sintering in vacuum sintering stove fire protective atmosphere sintering oven, sintering temperature is 850-1050 ℃, and soaking time is 1-4 hour.According to purposes the densified sintering product body heat is squeezed into needed round bar or plate etc. then, hot-pressed dispersion-strengthened Cu processing material has good process industrial art performance, can carry out various machinings
[4]
Existing internal oxidation process has following shortcoming: because goods adopt powder metallurgy process to make, having a certain amount of hole in the goods exists, the easier oxygen intake of hole at high temperature, so adopt hot extrusion to make the goods shaping can cause the oxidation of goods in the existing internal oxidation process, make the tissue of the finished product, performance not good; And if adopt atmosphere protection or under vacuum, carry out operation such as hot extrusion and need increase extra equipment, thereby cost is significantly increased and operation numerous and diverse.
Reference:
[1] Ning Ailin, Shen lofty ideal, Lei Xianming, Peng Beishan etc. the development status and prospects [J] of dispersion-strengthened Cu. the journal .2001.vol.14:165 of Shaoyang higher junior college～166.
[2] Ning Ailin, Shen lofty ideal, Peng Beishan, Mo Yawu etc. the electroconductibility of different wild phase dispersion-strengthened Cus [J]. Hunan non-ferrous metal .2002.vol.18:34～36.
[3] Peng Maogong, high if paddy is counted Chinese appearance etc. Chinese .CN 1915562A.2007.2.21.
[4] Liu Ping, Zhao Dongmei, Tian Baohong etc. high property copper alloy and processing technology thereof. Beijing: metallurgical industry press .2005:128～129.
Summary of the invention
Technical problem to be solved by this invention provides the preparation technology of the low aluminum oxide dispersion strengthened copper with high strength and high conductivity of a kind of production cost.
In order to solve the problems of the technologies described above, the preparation technology of aluminum oxide dispersion strengthened copper with high strength and high conductivity provided by the invention, adopting aluminium content is 0.1-0.6wt%, all the other make body material for copper, foreign matter content is a raw material less than the copper-aluminum alloy powder of 0.5wt%, and preparation technology comprises:
(1), copper-aluminum alloy powder is mixed with oxygenant: copper-aluminum alloy powder was mixed 0.5-3 hour in planetary ball mill or drum-type mixer etc. with the mixed powder of oxygenant (being generally Red copper oxide), oxygenant is uniformly distributed in the copper-aluminum alloy powder, in the oxygenant in oxygen level and the powdered alloy aluminium content atomic ratio be 3: 2-4: between 2;
(2), oxidation in the powder: mixed powder is heated to 800-1000 ℃, under nitrogen atmosphere or the high vacuum atmosphere, Red copper oxide decomposes, the oxygen that generates is diffused in the particle of copper aluminium solid solution alloy, because aluminum ratio copper easily generates oxide compound, therefore the aluminium in the alloy preferentially is oxidized to aluminum oxide, promptly interior oxidation, and interior oxidization time is 1-3 hour;
(3), reduction: the aluminium in the X alloy is heated 750-1000 ℃ of reduction by after all oxidation generates aluminum oxide in hydrogen or cracked ammonium atmosphere, become water vapour to overflow hydrogen reduction unnecessary in the powdered alloy, thereby make the alumina dispersion-strenghtened copper powder;
(4), compacting: the powdered alloy after will reducing adopts unidirectional compacting, two-way compacting or isostatic cool pressing to become ingot blank then to carry out high temperature solid-phase sintering; Or carry out hot-isostatic pressing and directly become fine and close ingot blank;
(5), sintering: the cold compaction ingot blank is carried out sintering in vacuum sintering furnace or protective atmosphere sintering oven, sintering temperature is 850-1050 ℃, and soaking time is 1-4/ hour;
(6) densification: adopt modes such as mold pressing, isostatic cool pressing, forging to improve the density of sintered compact, make its relative density reach 97%-99%, in reducing atmospheres such as hydrogen, carry out 500-600 ℃ of annealing then to eliminate stress;
(7), cold machine-shaping: will carry out cold rolling, cold working such as swage through the material of densification, deflection is 30%-40%, further improves density, improves performance, makes material profile, size conforms service requirements simultaneously; As thin sheet material of needs preparations or thinner wire rod, deflection is big, needs to increase annealing process, promptly in protective atmosphere, anneal under the 600-900 ℃ temperature, and then material is carried out cold working, up to obtaining desired product size.
Adopt the preparation technology of the aluminum oxide dispersion strengthened copper with high strength and high conductivity of technique scheme, compare with traditional inner oxidation method, the invention has the advantages that and adopted cold rolling, cold machine-shaping such as swage, need when shaping, not carry out heat treated to goods, do not need it is carried out atmosphere protection yet, thereby avoided adding extra equipment, thereby can reduce cost, improved income; And resulting product tissue, functional, constant product quality.
The tensile strength of the dispersion strengthening copper alloy of employing prepared of the present invention is greater than 500N/mm
2, softening temperature is higher than 600 ℃, and electric conductivity is greater than 80%IACS; Behind 950 ℃ of annealing 30min, the tensile strength of material is higher than 400N/mm
2Has higher mechanical property, good high temperature resistance softening performance and favorable conductive, heat conductivility.Adopt the alumina dispersion-strenghtened copper matrix material of above-mentioned technology manufacturing can be applied to make circuit lead frame, high-speed electric railway pole line, resistance welding electrode, high-thrust rocket liner etc., can obviously improve use properties and life-span.
Description of drawings
Fig. 1 is the conventional process flow figure that internal oxidation prepares alumina dispersion-strenghtened copper.
Fig. 2 is the process flow sheet that the present invention prepares alumina dispersion-strenghtened copper.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment 1:
Referring to Fig. 2, adopting aluminium content is 0.1wt%, and all the other make body material for copper, and foreign matter content is a raw material less than the copper-aluminum alloy powder of 0.5wt%.
(1), the Cu-Al powdered alloy mixes with oxygenant: the Cu-Al powdered alloy was mixed 0.5 hour with 200 rev/mins in planetary ball mill with the mixed powder of oxygenant, in the oxygenant in oxygen level and the powdered alloy aluminium content atomic ratio be 3: 2;
(2), interior oxidation: mixed powder is heated to 800 ℃, under nitrogen atmosphere in oxidation 3 hours;
(3), reduction: reduction is 1 hour in 750 ℃ of hydrogen atmospheres;
(4), the compacting: with powder at 600N/mm
2Pressure under die forming;
(5), sintering: sintering is 1 hour in 1050 ℃ of hydrogen atmospheres;
(6), densification: directly on hydropress, sintered compact is depressed 40% distortion, make its relative density reach 98%, in 600 ℃ of hydrogen atmospheres, annealed 1 hour then with bigger pressure;
(7), cold roll forming: will carry out cold rollingly for the first time through the material of densification, deflection is 30%, anneals 1 hour in 600 ℃ of hydrogen atmospheres afterwards; And then with material carry out deflection be 50% cold rolling.
Dispersion-strengthened Cu composite property after above operation processing is: tensile strength 576N/mm
2, yield strength 536N/mm
2, electric conductivity is 82%IACS; Behind 950 ℃ of annealing 30min, the tensile strength 462N/mm of material
2
Embodiment 2:
Referring to Fig. 2, adopting aluminium content is 0.6wt%, and all the other make body material for copper, and foreign matter content is a raw material less than the copper-aluminum alloy powder of 0.5wt%;
(1), the Cu-Al powdered alloy mixes with oxygenant: the Cu-Al powdered alloy was mixed in the drum-type mixer 3 hours with the mixed powder of oxygenant, in the oxygenant in oxygen level and the powdered alloy aluminium content atomic ratio be 4: 2;
(2), interior oxidation: mixed powder is heated to 1000 ℃, under nitrogen atmosphere in oxidation 1 hour;
(3), reduction: reduction is 1 hour in 1000 ℃ of hydrogen atmospheres;
(4), the compacting: with powder at 600N/mm
2Pressure under die forming;
(5), sintering: sintering is 4 hours in 850 ℃ of hydrogen atmospheres;
(6), densification: sintered compact is suppressed distortion once more in mould, make its relative density reach 98%, in 500 ℃ of hydrogen atmospheres, annealed 1 hour then;
(7), cold roll forming: will swage for the first time through the material of densification, deflection is 30%, anneals 1 hour in 900 ℃ of hydrogen atmospheres afterwards; And then material is carried out deflection is 40% swage.
Dispersion-strengthened Cu composite property after above operation processing is: tensile strength 538N/mm
2, yield strength 503N/mm
2, electric conductivity is 80.5%IACS; Behind 950 ℃ of annealing 30min, the tensile strength 450N/mm of material
2
Claims (1)
1. the preparation technology of an aluminum oxide dispersion strengthened copper with high strength and high conductivity, adopting aluminium content is 0.1-0.6wt%, all the other make body material for copper, foreign matter content is a raw material less than the copper-aluminum alloy powder of 0.5wt%, adopt copper-aluminum alloy powder to mix with oxygenant-Nei oxidation-reduction-compacting-sintering-densification-cold machine-shaping technology making high-strength highly-conductive and have the dispersed and strengthened copper-based composite material of high temperature resistance softening performance, it is characterized in that: preparation technology comprises:
(1), with the mixed powder mixing of copper-aluminum alloy powder and oxygenant 0.5-3 hour, in the oxygenant in oxygen level and the powdered alloy aluminium content atomic ratio be 3: 2-4: between 2;
(2), interior oxidation: mixed powder is heated to 800-1000 ℃, under nitrogen atmosphere or the high vacuum atmosphere, mixed powder is carried out interior oxidation, interior oxidization time is 1-3 hour;
(3), reduction: the aluminium in the X alloy is by after all oxidation generates aluminum oxide, and 750-1000 ℃ of reduction under hydrogen or cracked ammonium atmosphere is with hydrogen reduction unnecessary in the powdered alloy;
(4), compacting: adopt unidirectional compacting, two-way compacting or isostatic cool pressing to become ingot blank then to carry out high temperature solid-phase sintering powdered alloy; Or carry out hot-isostatic pressing and directly become fine and close ingot blank;
(5), sintering: the cold compaction ingot blank is carried out sintering in vacuum sintering stove fire protective atmosphere sintering oven, sintering temperature is 850-1050 ℃, and soaking time is 1-4 hour;
(6), densification: adopt mold pressing, isostatic cool pressing, forging mode to improve the density of sintered compact, make its relative density reach 97%-99%, in reducing atmosphere, carry out 500-600 ℃ of annealing then to eliminate stress;
(7), cold machine-shaping: will carry out cold working through the material of densification, deflection is 30%-40%, further improves density, improves performance, makes material profile, size conforms service requirements simultaneously; As thin sheet material of needs preparations or thinner wire rod, deflection is big, needs to increase annealing process, promptly in protective atmosphere, anneal under the 600-900 ℃ temperature, and then material is carried out cold working, up to obtaining desired product size.
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