CN111378867A - High-conductivity and high-strength copper-chromium-magnesium alloy and preparation method thereof - Google Patents
High-conductivity and high-strength copper-chromium-magnesium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-conductivity high-strength copper-chromium-magnesium alloy and a preparation method thereof, wherein the content of Cr in the alloy is 0.05-10 wt.%, the content of Mg in the alloy is 0.10-0.50 wt.%, and the balance is Cu and inevitable impurities. The method for preparing the high-conductivity high-strength copper chromium magnesium alloy can solve the problem of uneven distribution of Cr precipitated phases in the high-strength high-conductivity copper chromium magnesium alloy, and can realize the nanoscale even distribution of the Cr precipitated phases in the copper matrix. Compared with the traditional casting-cold deformation process and the powder metallurgy-cold deformation process without Mg, on the premise of maintaining high conductivity unchanged basically, the tensile strength of the copper-chromium-magnesium alloy is obviously improved, the lifting amount is up to 50%, and the high-temperature service performance is also improved.
Description
Technical Field
The invention belongs to the field of copper-chromium-magnesium alloy, and particularly relates to a preparation method of high-conductivity and high-strength copper-chromium-magnesium alloy.
Background
The traditional high-strength high-conductivity copper-chromium alloy is prepared by continuously combining methods such as cold rolling, heat treatment and the like after casting. Due to the problems of large size, uneven distribution and the like of Cr precipitated phases in the casting process, the mechanical property of the alloy after deformation processing is difficult to realize the optimum, and the problem of insufficient mechanical property still exists.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology and provide a high-conductivity high-strength copper-chromium-magnesium alloy and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the high-conductivity high-strength copper-chromium-magnesium alloy is made up by using alloy powder prepared by atomizing process and making it undergo the processes of sintering, cold working and ageing treatment, and its Cr content is 0.05-10 wt.%, Mg content is 0.10-0.50 wt.%, and the rest is Cu and inevitable impurities.
Furthermore, the electrical conductivity of the alloy is 70-90% IACS, and the tensile strength is 550-1030 MPa.
Further, the Cr content is 6.0-8.0 wt.%, and the Mg content is 0.10-0.20 wt.%.
The invention provides a preparation method of a high-conductivity high-strength copper chromium magnesium alloy, which comprises the following steps:
(1) preparing alloy raw materials into alloy powder by adopting an atomization method according to the content of each alloy element;
(2) sintering the alloy powder to obtain a sintered blank;
(3) carrying out cold working deformation treatment on the sintered blank to obtain a deformed Cu-Cr-Mg material;
(4) and carrying out aging treatment on the variable-form Cu-Cr-Mg material to obtain the high-conductivity high-strength copper-chromium-magnesium alloy.
Further, the atomization method in the step (1) is an air atomization method or a water atomization method.
Further, the gas atomization method adopts nitrogen or argon atomization, and the gas flow is 0.02-0.24m3The gas pressure is 0.5-0.9MPa, and the temperature of atomized melt is 1050-; the water atomization method has the water flow of 110-.
Further, the granularity of the alloy powder obtained in the step (1) is 10-100 μm.
Further, the sintering treatment in the step (2) comprises: firstly, pressing alloy powder under the pressure of 30-300MPa to obtain a powder compact; then sintering the powder pressed compact under the conditions of 900-1100 ℃ and 0-10MPa for 0.5-2h in a reducing atmosphere, or sintering the alloy powder by adopting an electric spark activation sintering method in a reducing atmosphere or an inert atmosphere at the sintering temperature of 800-950 ℃ and the pressure maintaining time of 10-45 min; the reducing atmosphere refers to more than one atmosphere of hydrogen, decomposed ammonia or carbon monoxide.
Further, the cold working deformation treatment comprises cold rolling, drawing or cold forging, and is carried out at room temperature, wherein the deformation amount of the material in the process is 0-80%.
Further, the temperature of the aging treatment in the step (4) is 200-.
Compared with the prior art, the invention has the beneficial effects that:
the method for preparing the high-conductivity high-strength copper chromium magnesium alloy can solve the problem of uneven distribution of Cr precipitated phases in the high-strength high-conductivity copper chromium magnesium alloy, and can realize the nanoscale even distribution of the Cr precipitated phases in the copper matrix. Compared with the traditional casting-cold deformation process and the powder metallurgy-cold deformation process without Mg, on the premise of maintaining high conductivity unchanged basically, the tensile strength of the copper-chromium-magnesium alloy is obviously improved, the lifting amount is up to 50%, and the high-temperature service performance is also improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a topographical view of the tissue of the sample of example 18.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In one embodiment, the preparation method of the high-conductivity high-strength copper-chromium-magnesium alloy comprises the following steps: (1) firstly, preparing alloy powder by adopting an atomization method; (2) sintering the alloy powder to obtain a sintered blank; (3) carrying out cold machining (cold rolling/drawing/cold forging and the like) deformation treatment on the sintered blank to obtain a deformed Cu-Cr-Mg material; (4) the deformation Cu-Cr-Mg material can realize synchronous improvement of strength and electrical conductivity after aging treatment, and finally the Cu-Cr-Mg alloy is obtained.
Preferably, the atomization method in the step (1) is an air atomization method or a water atomization method. The gas atomization method adopts nitrogen or argon atomization, and the gas flow is 0.02-0.24m3The gas pressure is 0.5-0.9MPa, and the temperature of the atomized melt is 1050-. Or adopting a water atomization mode, wherein the water flow is 110-380kg/min, the water pressure is 5.5-20MPa, and the temperature of the atomized melt is 1050-1350 ℃. The preparation method adopts an atomization method to prepare the alloy powder, and because the cooling speed of alloy liquid drops is high, Cr in a copper matrix in the obtained alloy powder is in a supersaturated solid solution state and is uniformly dispersed and distributed in a nanoscale state, so that the problems of difficult alloy processing caused by macrosegregation of chromium in the traditional casting process, low alloy mechanical property caused by large Cr phase and the like can be solved.
Preferably, the particle size of the alloy powder in the step (1) is 10-100 μm. Controlling the particle size within the range of the present invention can improve the sintering properties of the powder because, when the particle size is too small, the oxygen content of the powder is high, which deteriorates the plastic workability of the sintered product, and when the particle size is too large, the sintering properties of the powder are poor.
Preferably, the specific operation steps of the sintering treatment in the step (2) include: firstly, pressing alloy powder under the pressure of 30-300MPa to obtain a powder compact; then sintering the powder compact at the temperature of 900-1100 ℃ and under the pressure of 0-10MPa in a reducing atmosphere for 0.5-2 h. Or sintering the alloy powder by adopting electric spark activated sintering in a reducing atmosphere or an inert atmosphere, wherein the sintering temperature is 800-950 ℃, and the pressure maintaining time is 10-45 min. The pressing pressure and sintering temperature in the sintering process need to be controlled within a proper range, the density of the powder blank is low due to too low pressing pressure, the product is easy to deform after sintering, the internal stress of the pressed blank is increased due to too high pressing pressure, and the sintering defects such as warping, cracking and the like are easy to occur; when the sintering temperature is too low, the powder blank is difficult to fully densify, so that the sintered blank contains defects such as air holes and the like, and is easy to break in the subsequent wire drawing process; however, if the sintering temperature is too high, the sintered body is easily deformed and the cost is high.
Preferably, the reducing atmosphere refers to a hydrogen gas, decomposed ammonia (a hydrogen-nitrogen mixed gas into which ammonia is decomposed), and/or a carbon monoxide atmosphere. By adopting the reducing atmosphere for sintering, oxygen on the surface of the powder particles can be reduced in the process of temperature rise, the oxygen content of the product is reduced, and the processing performance and the conductivity of the final product are facilitated.
Preferably, the cold-working deformation treatment in the step (3) is carried out at room temperature (15-30 ℃), and the deformation of the material in the process is 0-80%, and more preferably 40-80%. After cold rolling/room temperature drawing/cold forging deformation processing, a large amount of dislocation is introduced, and sufficient power is provided for subsequent uniform nucleation and precipitation of Cr phase, so that the mechanical property of the plate is improved.
Preferably, the temperature of the aging treatment in the step (4) is 200-600 ℃, and the time is 0.5-2 h. After aging treatment, supersaturated solid solution element Cr in the alloy matrix can be separated out from the matrix, the dislocation density is reduced, the conductivity of the alloy is improved, and the strength of the alloy is improved due to the dispersion distribution of Cr.
The copper-chromium-magnesium alloy subjected to cold rolling deformation and aging treatment is suitable for the application fields of various sockets, switches, vehicle-mounted parts and the like.
Example 1:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 0.25 wt.%, the Mg content is 0.10 wt.%, the conductivity is 90% IACS, the tensile strength is 550MPa, the elongation is 25%, the stress relaxation rate is 69% under the condition of × 1000h at 120 ℃, and the high-temperature hardness is 120HV after the alloy is kept at 500 ℃ for 30 min.
The preparation method of the high-conductivity high-strength Cu-Cr-Mg alloy comprises the following steps:
(1) according to the alloy composition, the mass percentage of Cr/(Cu + Cr + Mg) is 0.25 percent, namely, the chromium content in the needed copper-chromium-magnesium alloy is 0.25 percent by weight, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; (2) pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; (3) cold rolling the sintered blank to obtain a Cu-Cr-Mg plate, wherein the deformation strain of the sintered blank is 0; (4) the Cu-Cr-Mg plate is subjected to aging treatment at 480 ℃ for 0.5h to obtain the high-conductivity high-strength Cu-Cr-Mg alloy.
Example 2:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 0.50 wt.%, the Mg content is 0.10 wt.%, the electric conductivity is 87% IACS, the tensile strength is 625MPa, the elongation is 23%, the stress relaxation rate under the condition of 120 ℃ and × 1000 hours is 70%, and the high-temperature hardness after the heat preservation in the environment at 500 ℃ for 30min is 125 HV.
The preparation method of the high-conductivity high-strength Cu-Cr-Mg alloy comprises the following steps:
(1) according to the alloy composition, the mass percentage of Cr/(Cu + Cr + Mg) is 0.50 percent, namely, the chromium content in the needed copper-chromium-magnesium alloy is 0.50 percent by weight, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; (2) pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; (3) cold rolling the sintered blank to obtain a Cu-Cr-Mg plate, wherein the deformation strain of the sintered blank is 0; (4) the Cu-Cr-Mg plate is subjected to aging treatment at 480 ℃ for 0.5h to obtain the high-conductivity high-strength Cu-Cr-Mg alloy.
Example 3:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 1.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 84% IACS, the tensile strength is 700MPa, the elongation is 21%, the stress relaxation rate is 71% under the condition of 120 ℃ and × 1000h, and the high-temperature hardness is 130HV after the alloy is kept at 500 ℃ for 30 min.
The preparation method of the high-conductivity high-strength Cu-Cr-Mg alloy comprises the following steps:
(1) according to the alloy composition, the mass percentage of Cr/(Cu + Cr + Mg) is 1.00 percent, namely, the chromium content in the needed copper-chromium-magnesium alloy is 1.00 percent by weight, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; (2) pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; (3) cold rolling the sintered blank to obtain a Cu-Cr-Mg plate, wherein the deformation strain of the sintered blank is 0; (4) the Cu-Cr-Mg plate is subjected to aging treatment at 480 ℃ for 0.5h to obtain the high-conductivity high-strength Cu-Cr-Mg alloy.
Example 4:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 2.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 81% IACS, the tensile strength is 760MPa, the elongation is 21%, the stress relaxation rate is 73% under the condition of 120 ℃ and × 1000h, and the high-temperature hardness is 135HV after the alloy is kept at 500 ℃ for 30 min.
The preparation method of the high-conductivity high-strength Cu-Cr-Mg alloy comprises the following steps:
(1) according to the alloy composition, the mass percentage of Cr/(Cu + Cr + Mg) is 2.00 percent, namely, the chromium content in the needed copper-chromium-magnesium alloy is 2.00 percent by weight, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; (2) pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; (3) cold rolling the sintered blank to obtain a Cu-Cr-Mg plate, wherein the deformation strain of the sintered blank is 0; (4) the Cu-Cr-Mg plate is subjected to aging treatment at 480 ℃ for 0.5h to obtain the high-conductivity high-strength Cu-Cr-Mg alloy.
Example 5:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 4.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 78% IACS, the tensile strength is 810MPa, the elongation is 18%, the stress relaxation rate is 75% under the condition of 120 ℃ and × 1000h, and the high-temperature hardness is 140HV after the alloy is kept in a 500 ℃ environment for 30 min.
The preparation method of the high-conductivity high-strength Cu-Cr-Mg alloy comprises the following steps:
(1) according to the alloy composition, the mass percentage of Cr/(Cu + Cr + Mg) is 4.00 percent, namely, the chromium content in the needed copper-chromium-magnesium alloy is 4.00 percent by weight, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; (2) pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; (3) cold rolling the sintered blank to obtain a Cu-Cr-Mg plate, wherein the deformation strain of the sintered blank is 0; (4) the Cu-Cr-Mg plate is subjected to aging treatment at 480 ℃ for 0.5h to obtain the high-conductivity high-strength Cu-Cr-Mg alloy.
Example 6:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 8.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 75% IACS, the tensile strength is 850MPa, the elongation is 16%, the stress relaxation rate is 77% under the condition of 120 ℃ and × 1000h, and the high-temperature hardness is 143HV after the alloy is kept at 500 ℃ for 30 min.
The preparation method of the high-conductivity high-strength Cu-Cr-Mg alloy comprises the following steps:
(1) according to the alloy composition, the mass percentage of Cr/(Cu + Cr + Mg) is 8.00 percent, namely, the chromium content in the needed copper-chromium-magnesium alloy is 8.00 percent by weight, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; (2) pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; (3) cold rolling the sintered blank to obtain a Cu-Cr-Mg plate, wherein the deformation strain of the sintered blank is 0; (4) the Cu-Cr-Mg plate is subjected to aging treatment at 480 ℃ for 0.5h to obtain the high-conductivity high-strength Cu-Cr-Mg alloy.
Example 7:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 0.25 wt.%, the Mg content is 0.10 wt.%, the electric conductivity is 87% IACS, the tensile strength is 625MPa, the elongation is 17%, the stress relaxation rate is 74% under the condition of × 1000h at 120 ℃, and the high-temperature hardness is 146HV after the alloy is kept in a 500 ℃ environment for 30 min.
The manufacturing method of example 7 is the same as example 1 except that the cold rolling deformation amount in step (3) is 40%.
Example 8:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 0.50 wt.%, the Mg content is 0.10 wt.%, the conductivity is 84% IACS, the tensile strength is 700MPa, the elongation is 15%, the stress relaxation rate is 75% under the condition of × 1000h at 120 ℃, and the high-temperature hardness is 154HV after 30min of heat preservation in an environment at 500 ℃.
The manufacturing method of example 8 is the same as example 2 except that the cold rolling deformation amount in step (3) is 40%.
Example 9:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 1.00 wt.%, the Mg content is 0.10 wt.%, the electric conductivity is 81% IACS, the tensile strength is 775MPa, the elongation is 14%, the stress relaxation rate under the condition of 120 ℃ × 1000h is 76%, and the high-temperature hardness after 30min heat preservation in the environment of 500 ℃ is 160 HV.
The manufacturing method of example 9 is the same as example 3 except that the cold rolling deformation amount in step (3) is 40%.
Example 10:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 2.00 wt.%, the Mg content is 0.10 wt.%, the electric conductivity is 78% IACS, the tensile strength is 850MPa, the elongation is 12%, the stress relaxation rate is 78% under the condition of 120 ℃ and × 1000h, and the high-temperature hardness is 165HV after the alloy is kept at 500 ℃ for 30 min.
The manufacturing method of example 10 is the same as example 4 except that the cold rolling deformation amount in step (3) is 40%.
Example 11:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 4.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 75% IACS, the tensile strength is 910MPa, the elongation is 10%, the stress relaxation rate under the condition of 120 ℃ and × 1000h is 80%, and the high-temperature hardness after the heat preservation in the environment of 500 ℃ for 30min is 169 HV.
The manufacturing method of example 11 is the same as example 5 except that the cold rolling deformation amount in step (3) is 40%.
Example 12:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 8.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 73% IACS, the tensile strength is 960MPa, the elongation is 9%, the stress relaxation rate under the condition of 120 ℃ and × 1000 hours is 82%, and the high-temperature hardness after 30min heat preservation in a 500 ℃ environment is 173 HV.
The manufacturing method of example 12 is the same as example 6 except that the cold rolling deformation amount in step (3) is 40%.
Example 13:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 0.25 wt.%, the Mg content is 0.10 wt.%, the conductivity is 83% IACS, the tensile strength is 675MPa, the elongation is 12%, the stress relaxation rate under the condition of 120 ℃ and × 1000h is 80%, and the high-temperature hardness after the heat preservation in the environment of 500 ℃ for 30min is 165 HV.
The manufacturing method of example 13 is the same as example 1 except that the cold rolling deformation amount in step (3) is 80%.
Example 14:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 0.50 wt.%, the Mg content is 0.10 wt.%, the electric conductivity is 80% IACS, the tensile strength is 750MPa, the elongation is 10%, the stress relaxation rate is 81% under the condition of 120 ℃ × 1000h, and the high-temperature hardness is 170HV after the alloy is kept for 30min in a 500 ℃ environment.
The manufacturing method of example 14 is the same as example 2 except that the cold rolling deformation amount in step (3) is 80%.
Example 15:
the high-conductivity high-strength copper-chromium-magnesium alloy disclosed by the invention has the advantages that the Cr content is 1.00 wt.%, the Mg content is 0.10 wt.%, the electric conductivity is 78% IACS, the tensile strength is 825MPa, the elongation is 9%, the stress relaxation rate is 83% under the condition of × 1000h at 120 ℃, and the high-temperature hardness is 176HV after the alloy is kept for 30min in an environment at 500 ℃.
The manufacturing method of example 15 is the same as example 3 except that the cold rolling deformation amount in step (3) is 80%.
Example 16:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 2.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 76% IACS, the tensile strength is 900MPa, the elongation is 8%, the stress relaxation rate is 85% under the condition of 120 ℃ and × 1000h, and the high-temperature hardness is 180HV after the alloy is kept at 500 ℃ for 30 min.
The manufacturing method of example 16 is the same as example 4 except that the cold rolling deformation amount in step (3) is 80%.
Example 17:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 4.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 74% IACS, the tensile strength is 970MPa, the elongation is 7%, the stress relaxation rate is 88% under the condition of × 1000h at 120 ℃, and the high-temperature hardness is 186HV after the alloy is kept for 30min in an environment at 500 ℃.
The manufacturing method of example 17 is the same as example 5 except that the cold rolling deformation amount in step (3) is 80%.
Example 18:
the high-conductivity high-strength copper-chromium-magnesium alloy has the advantages that the Cr content is 8.00 wt.%, the Mg content is 0.10 wt.%, the conductivity is 72% IACS, the tensile strength is 1030MPa, the elongation is 5%, the stress relaxation rate is 90% under the condition of 120 ℃ and × 1000h for 1000h, and the high-temperature hardness is 190HV after the alloy is kept for 30min in a 500 ℃ environment.
Example 18 was prepared in the same manner as example 6 except that the cold rolling deformation amount in step (3) was 80%. FIG. 1 shows the texture of the sample of this example, and it can be seen that the Cr precipitate phase is in a nanoscale distribution (50-300 nm).
Comparative example 1:
according to the alloy composition, the mass percent of Cr/(Cu + Cr + Mg) is 0.25%, and the mass percent of Mg/(Cu + Cr + Mg) is 0.10%, namely, the mass percent of chromium in the needed copper-chromium-magnesium alloy is 0.25 wt%, and the mass percent of magnesium is 0.10 wt% to match a pure copper block, a copper-chromium intermediate alloy block and a copper-magnesium intermediate alloy block; the Cu-Cr-Mg alloy is obtained by the conventional casting and cold rolling deformation processing technology, wherein the cold rolling deformation is 80%, and then the aging treatment is carried out at the temperature of 480 ℃ for 0.5 h.
The Cu-Cr-Mg alloy is tested for electric conductivity and strength, and the result shows that the Cu-Cr-Mg alloy has the electric conductivity of 82% IACS, the tensile strength of 375MPa, the elongation of 12%, the stress relaxation rate of 65% under the condition of × 1000h at 120 ℃, and the high-temperature hardness of 141HV after being kept at 500 ℃ for 30 min.
Comparative example 2:
according to the alloy composition, the mass percent of Cr/(Cu + Cr + Mg) is 0.50%, and the mass percent of Mg/(Cu + Cr + Mg) is 0.10%, namely, the mass percent of chromium in the needed copper-chromium-magnesium alloy is 0.50 wt%, and the mass percent of magnesium is 0.10 wt% to match a pure copper block, a copper-chromium intermediate alloy block and a copper-magnesium intermediate alloy block; the Cu-Cr-Mg alloy is obtained by the conventional casting and cold rolling deformation processing technology, wherein the cold rolling deformation is 80%, and then the aging treatment is carried out at the temperature of 480 ℃ for 0.5 h.
The Cu-Cr-Mg alloy is tested for conductivity and strength, and the result shows that the Cu-Cr-Mg alloy has the conductivity of 80 percent IACS, the tensile strength of 475MPa, the elongation of 10 percent, the stress relaxation rate of 67 percent under the condition of × 1000 hours at 120 ℃ and the high-temperature hardness of 144HV after being kept for 30min at the temperature of 500 ℃.
Comparative example 3:
according to the alloy composition, the mass percent of Cr/(Cu + Cr + Mg) is 1.00 percent, and the mass percent of Mg/(Cu + Cr + Mg) is 0.10 percent, namely, the required copper-chromium-magnesium alloy comprises 1.00wt percent of chromium and 0.10wt percent of magnesium, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; the Cu-Cr-Mg alloy is obtained by the conventional casting and cold rolling deformation processing technology, wherein the cold rolling deformation is 80%, and then the aging treatment is carried out at the temperature of 480 ℃ for 0.5 h.
The Cu-Cr-Mg alloy is tested for electric conductivity and strength, and the result shows that the Cu-Cr-Mg alloy has the electric conductivity of 78% IACS, the tensile strength of 530MPa, the elongation of 9%, the stress relaxation rate of 68% under the condition of × 1000h at 120 ℃, and the high-temperature hardness of 148HV after being kept at 500 ℃ for 30 min.
Comparative example 4:
according to the alloy composition, the mass percent of Cr/(Cu + Cr + Mg) is 2.00 percent, and the mass percent of Mg/(Cu + Cr + Mg) is 0.10 percent, namely, the required copper-chromium-magnesium alloy comprises 2.00 percent by weight of chromium and 0.10 percent by weight of magnesium, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; the Cu-Cr-Mg alloy is obtained by the conventional casting and cold rolling deformation processing technology, wherein the cold rolling deformation is 80%, and then the aging treatment is carried out at the temperature of 480 ℃ for 0.5 h.
The Cu-Cr-Mg alloy is tested for electric conductivity and strength, and the result shows that the Cu-Cr-Mg alloy has the electric conductivity of 76 percent IACS, the tensile strength of 600MPa, the elongation of 8 percent, the stress relaxation rate of 70 percent under the condition of × 1000 hours at 120 ℃ and the high-temperature hardness of 152HV after being kept for 30 minutes at 500 ℃.
Comparative example 5:
according to the alloy composition, the mass percent of Cr/(Cu + Cr + Mg) is 4.00 percent, and the mass percent of Mg/(Cu + Cr + Mg) is 0.10 percent, namely, the required copper-chromium-magnesium alloy comprises 4.00wt percent of chromium and 0.10wt percent of magnesium, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; the Cu-Cr-Mg alloy is obtained by the conventional casting and cold rolling deformation processing technology, wherein the cold rolling deformation is 80%, and then the aging treatment is carried out at the temperature of 480 ℃ for 0.5 h.
The Cu-Cr-Mg alloy is tested for conductivity and strength, and the result shows that the Cu-Cr-Mg alloy has the conductivity of 73 percent IACS, the tensile strength of 650MPa, the elongation of 7 percent, the stress relaxation rate of 75 percent under the condition of × 1000h at 120 ℃, and the high-temperature hardness of 156HV after being kept for 30min at 500 ℃.
Comparative example 6:
according to the alloy composition, the mass percent of Cr/(Cu + Cr + Mg) is 8.00 percent, and the mass percent of Mg/(Cu + Cr + Mg) is 0.10 percent, namely, the mass percent of chromium in the needed copper-chromium-magnesium alloy is 8.00 percent, and the mass percent of magnesium is 0.10 percent, and pure copper blocks, copper-chromium intermediate alloy blocks and copper-magnesium intermediate alloy blocks are matched; the Cu-Cr-Mg alloy is obtained by the conventional casting and cold rolling deformation processing technology, wherein the cold rolling deformation is 80%, and then the aging treatment is carried out at the temperature of 480 ℃ for 0.5 h.
The Cu-Cr-Mg alloy is tested for electric conductivity and strength, and the result shows that the Cu-Cr-Mg alloy has the electric conductivity of 70 percent IACS, the tensile strength of 690MPa, the elongation of 6 percent, the stress relaxation rate of 77 percent under the condition of × 1000 hours at 120 ℃ and the high-temperature hardness of 160HV after being kept for 30 minutes at 500 ℃.
Comparative example 7:
the mass percentage of Cr/(Cu + Cr) in the alloy composition is 0.25 percent, namely, the chromium content in the needed copper-chromium alloy is 0.25 wt.% to match a pure copper block and a copper-chromium intermediate alloy block; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; carrying out cold rolling treatment on the sintered blank, wherein the cold rolling deformation is 80%, and obtaining a Cu-Cr plate; (4) the Cu-Cr alloy is obtained after the Cu-Cr plate is subjected to aging treatment at 480 ℃ for 0.5 h.
The Cu-Cr alloy is tested for conductivity and strength, and the result shows that the Cu-Cr alloy has the conductivity of 82% IACS, the tensile strength of 500MPa, the elongation of 12%, the stress relaxation rate of 55% under the condition of × 1000h at 120 ℃, and the high-temperature hardness of 120HV after being kept for 30min at 500 ℃.
Comparative example 8:
the mass percentage of Cr/(Cu + Cr) in the alloy composition is 0.50 percent, namely, the chromium content in the needed copper-chromium alloy is 0.50 wt.% to match a pure copper block and a copper-chromium intermediate alloy block; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; carrying out cold rolling treatment on the sintered blank, wherein the cold rolling deformation is 80%, and obtaining a Cu-Cr plate; (4) the Cu-Cr alloy is obtained after the Cu-Cr plate is subjected to aging treatment at 480 ℃ for 0.5 h.
The Cu-Cr alloy is tested for conductivity and strength, and the result shows that the Cu-Cr alloy has the conductivity of 80% IACS, the tensile strength of 540MPa, the elongation of 11%, the stress relaxation rate of 57% under the condition of × 1000h at 120 ℃, and the high-temperature hardness of 124HV after being kept at 500 ℃ for 30 min.
Comparative example 9:
1.00 percent of Cr/(Cu + Cr) in the alloy composition, namely 1.00 percent of chromium content in the needed copper-chromium alloy is matched with a pure copper block and a copper-chromium intermediate alloy block; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; carrying out cold rolling treatment on the sintered blank, wherein the cold rolling deformation is 80%, and obtaining a Cu-Cr plate; (4) the Cu-Cr alloy is obtained after the Cu-Cr plate is subjected to aging treatment at 480 ℃ for 0.5 h.
The Cu-Cr alloy is tested for conductivity and strength, and the result shows that the Cu-Cr alloy has the conductivity of 79 percent IACS, the tensile strength of 579MPa, the elongation of 9 percent, the stress relaxation rate of 60 percent under the condition of × 1000 hours at 120 ℃ and the high-temperature hardness of 127HV after being kept for 30min at 500 ℃.
Comparative example 10:
according to the alloy composition, the mass percentage of Cr/(Cu + Cr) is 2.00 percent, namely, the chromium content in the needed copper-chromium alloy is 2.00 percent by weight, and a pure copper block and a copper-chromium intermediate alloy block are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; carrying out cold rolling treatment on the sintered blank, wherein the cold rolling deformation is 80%, and obtaining a Cu-Cr plate; (4) the Cu-Cr alloy is obtained after the Cu-Cr plate is subjected to aging treatment at 480 ℃ for 0.5 h.
The Cu-Cr alloy is tested for conductivity and strength, and the result shows that the Cu-Cr alloy has the conductivity of 78% IACS, the tensile strength of 630MPa, the elongation of 7%, the stress relaxation rate of 62% under the condition of × 1000h at 120 ℃, and the high-temperature hardness of 133HV after being kept at 500 ℃ for 30 min.
Comparative example 11:
4.00 percent of Cr/(Cu + Cr) in the alloy composition, namely 4.00 percent of chromium content in the needed copper-chromium alloy is matched with a pure copper block and a copper-chromium intermediate alloy block; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; carrying out cold rolling treatment on the sintered blank, wherein the cold rolling deformation is 80%, and obtaining a Cu-Cr plate; (4) the Cu-Cr alloy is obtained after the Cu-Cr plate is subjected to aging treatment at 480 ℃ for 0.5 h.
The Cu-Cr alloy is tested for electric conductivity and strength, and the result shows that the Cu-Cr alloy has the electric conductivity of 77 percent IACS, the tensile strength of 670MPa, the elongation of 6 percent, the stress relaxation rate of 65 percent under the condition of × 1000 hours at 120 ℃ and 1000 hours, and the high-temperature hardness of 137HV after being kept for 30 minutes at 500 ℃.
Comparative example 12:
according to the alloy composition, the mass percentage of Cr/(Cu + Cr) is 8.00 percent, namely, the chromium content in the needed copper-chromium alloy is 8.00 percent by weight, and pure copper blocks and copper-chromium intermediate alloy blocks are matched; preparing alloy powder by adopting a gas atomization method in a nitrogen atmosphere, wherein the pressure in the gas atomization process is 0.5-0.7MPa, and the melting temperature is 1200 ℃; pressing the alloy powder under the pressure of 200MPa to obtain a powder compact; sintering the powder pressed compact for 1 hour at 1050 ℃ in a hydrogen atmosphere to obtain a sintered compact; carrying out cold rolling treatment on the sintered blank, wherein the cold rolling deformation is 80%, and obtaining a Cu-Cr plate; (4) the Cu-Cr alloy is obtained after the Cu-Cr plate is subjected to aging treatment at 480 ℃ for 0.5 h.
The Cu-Cr alloy is tested for conductivity and strength, and the result shows that the Cu-Cr alloy has the conductivity of 76 percent IACS, the tensile strength of 710MPa, the elongation of 6 percent, the stress relaxation rate of 67 percent under the condition of × 1000 hours at 120 ℃ and 1000 hours, and the high-temperature hardness of 143HV after being kept at 500 ℃ for 30 min.
The results of conducting performance tests and strength tests on the alloys prepared in the above examples 1 to 18 and comparative examples 1 to 12 of the present invention are detailed in table 1, wherein the conducting performance is obtained by using a resistivity test sample of 60mm × 3mm × 2mm prepared by a wire cutting machine, the resistivity is measured by using a double-arm bridge, and the relative conductivity of the sample is obtained by conversion according to the international annealed copper standard, the strength test and the elongation test adopt the national standard GB/T228-.
From the above examples, it can be seen that the distribution of the Cr phase is more uniform after cold rolling deformation, which can effectively avoid the generation of alloy cracks and improve the alloy strength. With the increase of the Cr content, the Cr phase content of the alloy which has the main enhancement effect is increased, so that the tensile strength of the alloy is obviously increased. After aging treatment, Cr solid-dissolved in the copper matrix can be separated out, so that the alloy Cu matrix can be purified, the conductivity can be improved, the volume of a separated phase can be increased, the strength of the alloy can be improved, and the strength and the conductivity of the alloy can be synchronously improved. The existence of Mg can improve the nucleation rate of a Cr phase, thereby realizing the distribution of dispersed fine Cr phases in the Cu-Cr-Mg alloy and improving the strength of the alloy, and can improve the recrystallization temperature of the alloy and improve the high temperature resistance of the alloy, so that the alloy can still maintain higher strength in a high-temperature environment.
TABLE 1 results of conductivity tests and Strength tests of examples 1-18 and comparative examples 1-12
From the above table, it can be seen that, compared with the traditional casting-cold rolling deformation process and the powder manufacturing-cold rolling deformation process without magnesium, on the premise of maintaining the conductivity to be basically unchanged, the tensile strength of the Cu-Cr-Mg alloy is obviously improved, the lifting amount is up to 50%, and the temperature resistance is also obviously improved.
The foregoing is considered as illustrative of the preferred embodiments of the invention and is not to be construed as limiting the invention in any way. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.
Claims (10)
1. The high-conductivity high-strength copper-chromium-magnesium alloy is characterized in that the content of Cr in the alloy is 0.05-10 wt.%, the content of Mg in the alloy is 0.10-0.50 wt.%, and the balance is Cu and inevitable impurities.
2. The copper-chromium-magnesium alloy with high electric conductivity and high strength as claimed in claim 1, wherein the alloy has an electric conductivity of 70-90% IACS and a tensile strength of 550-1030 MPa.
3. The high-conductivity high-strength copper-chromium-magnesium alloy according to claim 1, wherein the Cr content is 6.0-8.0 wt.% and the Mg content is 0.10-0.20 wt.%.
4. A preparation method of the high-conductivity high-strength copper-chromium-magnesium alloy as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
(1) preparing alloy raw materials into alloy powder by adopting an atomization method according to the content of each alloy element;
(2) sintering the alloy powder to obtain a sintered blank;
(3) carrying out cold working deformation treatment on the sintered blank to obtain a deformed Cu-Cr-Mg material;
(4) and carrying out aging treatment on the variable-form Cu-Cr-Mg material to obtain the high-conductivity high-strength copper-chromium-magnesium alloy.
5. The method for preparing the high-conductivity high-strength copper-chromium-magnesium alloy according to claim 4, wherein the atomization method in the step (1) is a gas atomization method or a water atomization method.
6. The method for preparing the high-conductivity high-strength copper-chromium-magnesium alloy as claimed in claim 5, wherein the gas atomization method adopts nitrogen or argon atomization, and the gas flow is 0.02-0.24m3Gas/sThe bulk pressure is 0.5-0.9MPa, and the temperature of atomized melt is 1050-; the water atomization method has the water flow of 110-.
7. The preparation method of the high-conductivity high-strength copper-chromium-magnesium alloy according to any one of claims 4 to 5, wherein the grain size of the alloy powder obtained in the step (1) is 10-100 μm.
8. The method for preparing the high-conductivity high-strength copper-chromium-magnesium alloy according to claim 4, wherein the sintering treatment in the step (2) comprises: firstly, pressing alloy powder under the pressure of 30-300MPa to obtain a powder compact; then sintering the powder pressed compact under the conditions of 900-1100 ℃ and 0-10MPa for 0.5-2h in a reducing atmosphere, or sintering the alloy powder by adopting an electric spark activation sintering method in a reducing atmosphere or an inert atmosphere at the sintering temperature of 800-950 ℃ and the pressure maintaining time of 10-45 min; the reducing atmosphere refers to more than one atmosphere of hydrogen, decomposed ammonia or carbon monoxide.
9. The method for preparing the high-conductivity high-strength copper-chromium-magnesium alloy according to claim 4 or 8, wherein the cold working deformation treatment comprises cold rolling, drawing or cold forging, and is performed at room temperature, and the deformation amount of the material in the process is 0-80%.
10. The method for preparing the high-conductivity high-strength copper-chromium-magnesium alloy as claimed in claim 4 or 8, wherein the temperature of the aging treatment in the step (4) is 200-600 ℃, and the time is 0.5-2 h.
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