CN116287848A - Low-beryllium multicomponent copper alloy for crystallizer and preparation method thereof - Google Patents

Low-beryllium multicomponent copper alloy for crystallizer and preparation method thereof Download PDF

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CN116287848A
CN116287848A CN202310237918.7A CN202310237918A CN116287848A CN 116287848 A CN116287848 A CN 116287848A CN 202310237918 A CN202310237918 A CN 202310237918A CN 116287848 A CN116287848 A CN 116287848A
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copper alloy
low
sintering
beryllium
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舒永春
王培�
乔石
郝振华
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Zhengzhou University
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • 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
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Abstract

The invention provides a low-beryllium multi-component copper alloy for a crystallizer and a preparation method thereof, wherein the copper alloy comprises the following elements in percentage by mass: 0.5 to 1.5 weight percent of Be, 0.8 to 1.5 weight percent of Ni, 0.3 to 0.6 weight percent of Cr, 0.1 to 0.25 weight percent of Zr0.05 to 0.5 weight percent of Ag, 0.01 to 0.1 weight percent of rare earth and the balance of Cu. The invention adopts the gas atomization powder preparation-powder metallurgy method to prepare the copper alloy, has lower beryllium content, reduces toxicity and cost, has uniform and fine grain size, and has the characteristics of high hardness, good thermal conductivity and excellent heat resistance; the hardness of the copper alloy is 346-421HV, and the tensile strength is 1050-1305MPa; conductivity is 44.9-50.9% IACS; the average grain size is about 9-15 μm.

Description

Low-beryllium multicomponent copper alloy for crystallizer and preparation method thereof
Technical Field
The invention relates to the technical field of nonferrous metal material processing, in particular to a low-beryllium multicomponent copper alloy for a crystallizer and a preparation method thereof.
Background
The beryllium copper alloy is copper alloy taking beryllium as a main alloy element, is also called beryllium bronze, is a typical aging strengthening alloy, has high strength and hardness after solution strengthening treatment, has good corrosion resistance, wear resistance, heat conducting property and the like, and is used for the fields of aerospace, electrical appliances, instrument chemical industry, dies, crystallizers and the like.
The amorphous alloy melt-spun machine requires the crystallizer to have higher heat conduction, strength, hardness and other performances, and also has good thermal fatigue resistance and good corrosion resistance. Beryllium bronze for a crystallizer can provide higher cooling speed for alloy melt, so that amorphous structure is obtained. However, beryllium bronze crystallizers suffer from the following problems: 1) The toxicity and the cost are high, cu-2.6Be-0.5Co-0.3Si and Cu-2.0Be-0.5Co-0.3Si are common crystallizer beryllium bronze, the hardness is high, the wear resistance is good, but Be is relatively expensive, toxic and cancerogenic, and the physical health of people is damaged; 2) The heat conductivity and the hardness are difficult to balance, the strength of the high-strength and high-conductivity copper alloy is improved mainly by precipitation strengthening of the second phase, and the strengthening alloy needs to keep higher electric conductivity. Therefore, there is a need to develop beryllium copper alloys that have low beryllium content without reducing hardness.
The addition of alloying elements to copper requires three factors to be considered: 1) The added element can form solid solution with copper; 2) The added element has less influence on the conductivity of the copper matrix; 3) Precipitation of alloying elements may form a strengthening phase. At present, the alloying elements added into copper generally comprise nickel, cobalt, zirconium, titanium, rare earth and other elements, for example, the addition of nickel and cobalt can refine grains in the alloy material and improve the uniformity of internal tissues; the addition of zirconium can improve the softening temperature of the beryllium copper alloy and refine the recrystallized grains; the strength of the beryllium copper alloy can be effectively enhanced by the titanium; the rare earth elements can refine grains, so that the grains are uniform, and the strength and corrosion resistance of the beryllium copper alloy can be effectively improved. Although the above elements are added, the low beryllium copper alloy still has a problem of low strength.
In addition, beryllium copper alloys are usually cast-rolled, and this way of forming easily results in uncontrollable grain sizes and not uniform distribution, and thus in a way that the added elements do not perform well. Therefore, improvements in the method of producing beryllium copper are also a major issue to be addressed.
Disclosure of Invention
The invention provides a low-beryllium multicomponent copper alloy for a crystallizer and a preparation method thereof, and the prepared copper alloy has lower beryllium content and reduced toxicity and cost; the high strength of the beryllium copper alloy and the high thermal conductivity of the chromium copper alloy are achieved; the grain size is uniform and fine; has the characteristics of high hardness, good thermal conductivity and excellent heat resistance, the hardness is 346-421HV, and the tensile strength is 1050-1305MPa; conductivity is 44.9-50.9% IACS; the average grain size is about 9-15 μm.
The technical scheme of the invention is realized as follows: the low-beryllium multicomponent copper alloy for the crystallizer comprises the following elements in percentage by mass: 0.5 to 1.5 weight percent of Be, 0.8 to 1.5 weight percent of Ni, 0.3 to 1.0 weight percent of Cr, 0.1 to 0.25 weight percent of Zr0.05 to 0.5 weight percent of Ag, 0.01 to 0.1 weight percent of rare earth and the balance of Cu.
The set range of Be content reduces the cost while guaranteeing the alloy strength. The increase of Cr is beneficial to improving the alloy strength but can lead to the reduction of the alloy conductivity, and if the Cr content is higher than 1.0 weight percent, the alloy conductivity is lower; the Cr content is lower than 0.3 weight percent, and the alloy strength is lower. The aging strengthening of Zr is not obvious, so that the influence of the independent addition on the alloy strength is not great, the Zr and the Cr are added in a matched manner, the aging strengthening effect of Cr element is promoted, and the ratio of the Cr element to the Zr element is 3:1-5:1. The addition of Ag can regulate and control the conductivity of the alloy without reducing the strength of the alloy, and the addition of rare earth elements refines grains and improves the crystallization temperature of the alloy.
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
(1) Weighing a low-beryllium copper alloy raw material, and performing gas atomization to prepare powder after smelting to obtain metal powder;
(2) Sintering and densifying the metal powder to obtain a low-beryllium copper alloy blank;
(3) Forging, solid solution and aging treatment are carried out on the low-beryllium copper alloy blank, and the low-beryllium copper alloy is obtained.
Further, in the step (1), the method for preparing powder by gas atomization comprises the following steps: heating the raw materials to a molten state after smelting, discharging the raw materials into an air atomizer, discharging the raw materials at 1300-1700 ℃, enabling the air atomization pressure to be 10-50 MPa, enabling an air source to be argon or nitrogen, and enabling air atomization to obtain metal powder.
Further, in the step (1), the smelting method comprises the following steps: weighing low beryllium copper alloy raw materials, loading the raw materials into a smelting furnace, raising the temperature of the smelting furnace to 1200-1500 ℃ until the alloy is completely melted, preserving heat for 5-10 min, regulating the power of the smelting furnace for 3-5 times, uniformly melting the raw materials, and standing for 5-10 min. The power of the smelting furnace is regulated and controlled for 3-5 times, the regulated and controlled power is larger for a while and smaller for a while, for example, the smelting power is increased by 15-25%, the smelting power is kept for a period of time, then the smelting power is regulated and returned, the smelting power is repeated for 3-5 times, the power difference is generated, the fluctuation stirring effect is realized, and the homogenization is promoted.
Further, in the step (2), the sintering method is die pressing blank-sintering, spark plasma sintering or hot isostatic pressing sintering.
Further, the specific method of the die pressing blank-sintering is as follows: transferring the metal powder into a mould or a cold isostatic pressing mould sleeve, and mould pressing under 300-500 MPa to prepare a cold blank; and (3) putting the cold blank into a sintering furnace, and sintering in vacuum or hydrogen atmosphere to obtain a low-beryllium copper alloy blank, wherein the sintering temperature is 750-1000 ℃, and the heat preservation time is 5-300 min.
Further, the specific method of Spark Plasma Sintering (SPS) is as follows: transferring the metal powder into a graphite mold, heating to 750-980 ℃ under vacuum and 5-80MPa pressure, and preserving heat for 3-60 min.
Further, hot isostatic pressing sintering: transferring the metal powder into a closed metal die sleeve for pressurizing such as heat, heating to 800-950 ℃ under the pressure of 10-70MPa, and keeping the temperature for 15-120 min.
Further, in the step (3), the forging method is as follows: and (3) carrying out annular forging and ring rolling on the sintered blank at the temperature of 750-850 ℃ to obtain an annular workpiece, wherein the forging deformation rate is greater than 50%.
Further, in the step (3), the method of solid solution and aging treatment is as follows: heating the forged workpiece to 760-950 ℃, preserving heat for 30min-3h, quenching, aging the quenched workpiece at 350-500 ℃, preserving heat for 2-6 h, and cooling to room temperature to obtain the low-beryllium copper alloy.
Further, in the step (2), firstly, metal powder is put into a ball ink tank, the diameter of a grinding ball is selected to be 12-20mm, the ball powder ratio is 5-10:1, ball milling and mixing are carried out for 1-4 hours under the condition of 20-45 r/min of rotating speed, and then sintering densification treatment is carried out.
The invention has the beneficial effects that:
the low beryllium copper alloy can simultaneously exert the solid solution failure strengthening of Be-Ni and Cr-Zr, and has the high strength of the beryllium copper alloy and the high thermal conductivity of the chromium copper alloy; the Ni element delays the decomposition of solid solution, inhibits the grain boundary reaction and improves the precipitation hardening effect of the alloy; zr/rare earth prevents the growth of copper alloy grains in the heating process, improves the crystallization temperature and improves the stress relaxation resistance.
Compared with the casting-rolling forming process, the low beryllium copper alloy obtained by adopting the gas atomization powder preparation-powder metallurgy method has uniform and smaller grain size, and simultaneously improves the problem of rare earth/Ni/Co enrichment. The casting-rolling formed beryllium copper alloy is easy to form a second phase with high Ni/Co content in an alloy matrix, so that the enrichment problem of Ni/Co elements is caused, the grain size of the low-beryllium copper alloy prepared by a powder metallurgy method is small and uniform, the second phase containing Ni/Co elements is refined, meanwhile, the separation of gamma phases (Cu-Be and Cr) at a grain boundary is facilitated, and the reinforcing effect is fully exerted.
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In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a microstructure gold phase diagram of a low beryllium copper multicomponent alloy of the invention wherein: FIG. 1-a is a golden phase diagram of comparative example 2; FIG. 1-b is a golden phase diagram of example 4; FIG. 1-c is a golden phase diagram of example 1; FIG. 1-d is the golden phase diagram of example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
The low-beryllium copper alloy raw material is from electrolytic copper, beryllium copper master alloy or pure beryllium, pure nickel or nickel copper alloy, chromium copper alloy (Cu-5.0 Cr), pure cobalt particles or cobalt copper alloy, pure zirconium particles or zirconium copper alloy, pure silver particles or silver copper alloy, single element rare earth or mixed rare earth, and the raw materials comprise the following elements in percentage by mass: 0.5 to 1.5 weight percent of Be, 0.8 to 1.5 weight percent of Ni, 0.3 to 1.0 weight percent of Cr, 0.1 to 0.25 weight percent of Zr, 0.05 to 0.5 weight percent of Ag, 0.01 to 0.1 weight percent of rare earth and the balance of Cu.
Example 1
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
1) Weighing electrolytic copper, beryllium copper master alloy (Cu-2.0 Be), nickel copper alloy, silver copper alloy and mixed rare earth, and forming the following low-beryllium copper alloy components in percentage by mass: 0.9wt% of Be, 1.0wt% of Ni, 0.5wt% of Cr, 0.15wt% of Zr, 0.5wt% of Ag, 0.035wt% of mixed rare earth (lanthanum and cerium) and the balance of Cu;
2) Smelting by adopting a vacuum induction furnace, raising the temperature to 1250 ℃ until the raw materials are completely melted, preserving the heat for 5min, regulating the power of the smelting furnace for 5 times (for example, raising the smelting power from 8KW to 10KW, maintaining for 3 min, then regulating back to 8KW, repeating for 5 times) so that the raw materials are uniformly melted, and standing for 10min;
3) And (3) atomizing and pulverizing: heating to make copper alloy be molten, discharging to enter an air atomizer, discharging at 1500 ℃, enabling air atomization pressure to be 30MPa, enabling an air atomization air source to be argon or nitrogen, and enabling air atomization to obtain metal powder;
4) Molding and pressing a blank: ball milling (200 min, rotating speed 30 r/min) is carried out on the proportioned metal powder, and then the metal powder is transferred into a mould for mould pressing (400 MPa) to prepare a cold blank;
5) Sintering: putting the cold blank into a sintering furnace, taking hydrogen as protective gas, keeping the sintering temperature at 930 ℃ for 25min, and sintering to obtain a low-beryllium copper alloy blank;
6) Forging: performing annular forging and ring rolling on the sintered blank at 750-850 ℃, wherein the forging deformation rate is 50%;
7) Solid solution and aging treatment: and heating the forged annular workpiece to 900 ℃, preserving heat for 60min, and then quenching. Aging the quenched workpiece: and (3) maintaining the temperature at 450 ℃ for 200min, and cooling to room temperature to obtain the low-beryllium copper alloy annular workpiece.
The performances of the low beryllium copper alloy annular workpiece obtained in the embodiment are as follows: the strength is improved, the hardness reaches 346HV, and the tensile strength is 1050MPa; conductivity 50.9% iacs; the average grain size was about 10. Mu.m (see FIG. 1-c).
Example 2
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
1) Weighing electrolytic copper, beryllium copper master alloy (Cu-2.0 Be), pure nickel, chromium copper alloy (Cu-5.0 Cr), pure zirconium particles, pure silver particles and mixed rare earth, and forming the following low-beryllium copper alloy components in percentage by mass: 0.9wt% of Be, 1.0wt% of Ni, 0.75wt% of Cr, 0.15wt% of Zr, 0.5wt% of Ag, 0.05wt% of mixed rare earth (lanthanum and cerium) and the balance of Cu;
2) Smelting by adopting a vacuum induction furnace, raising the temperature to 1250 ℃ until the raw materials are completely melted, preserving the heat for 5min, regulating the power of the smelting furnace for 5 times, uniformly melting the raw materials, and standing for 10min;
3) And (3) atomizing and pulverizing: heating to make copper alloy be molten, discharging to enter an air atomizer, discharging at 1500 ℃, enabling air atomization pressure to be 30MPa, enabling an air atomization air source to be argon or nitrogen, and enabling air atomization to obtain metal powder;
4) Molding and pressing a blank: ball milling (200 min, rotating speed 30 r/min) is carried out on the proportioned metal powder, and then the metal powder is transferred into a mould for mould pressing (400 MPa) to prepare a cold blank;
5) Sintering: putting the cold blank into a sintering furnace, taking hydrogen as protective gas, keeping the sintering temperature at 930 ℃ for 25min, and sintering to obtain a low-beryllium copper alloy blank;
6) Forging: performing annular forging and ring rolling on the sintered blank at 750-850 ℃, wherein the forging deformation rate is 60%;
7) Solid solution aging treatment: and heating the forged annular workpiece to 900 ℃, preserving heat for 60min, and then quenching. Aging the quenched workpiece: and (3) maintaining the temperature at 450 ℃ for 200min, and cooling to room temperature to obtain the low-beryllium copper alloy annular workpiece.
Compared with the embodiment 1, the embodiment improves the Cr and rare earth contents, and the obtained low-beryllium copper alloy annular workpiece has the following properties: the strength is further improved, the hardness is 375HV, and the tensile strength is 1208MPa; a small decrease in conductivity of 47.8% iacs occurred; the average grain size does not vary much, about 10 μm (see FIG. 1-d).
Example 3
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
1) Weighing electrolytic copper, beryllium copper master alloy (Cu-2.0 Be), cobalt particles, chromium copper alloy (Cu-5.0 Cr), pure zirconium particles, pure silver particles and mixed rare earth, and forming the following low-beryllium copper alloy components in percentage by mass: 0.9wt% of Be, 1.0wt% of Co, 0.5wt% of Cr, 0.15wt% of Zr, 0.5wt% of Ag, 0.05wt% of mixed rare earth (lanthanum and cerium) and the balance of Cu;
2) Smelting by adopting a vacuum induction furnace, raising the temperature to 1250 ℃ until the raw materials are completely melted, preserving the heat for 5min, regulating the power of the smelting furnace for 5 times, uniformly melting the raw materials, and standing for 10min;
3) And (3) atomizing and pulverizing: heating to make copper alloy be molten, discharging to enter an air atomizer, discharging at 1500 ℃, enabling air atomization pressure to be 30MPa, enabling an air atomization air source to be argon or nitrogen, and enabling air atomization to obtain metal powder;
4) And (3) hot isostatic pressing sintering: ball milling (200 min, rotating speed 30 r/min) is carried out on the proportioned metal powder, then the metal powder is transferred into a hot isostatic pressing die sleeve, the sintering temperature is 850 ℃, the pressing pressure is 50MPa, the temperature is kept for 30min, and the low-beryllium copper alloy blank is obtained through sintering;
5) Forging: performing annular forging and ring rolling on the sintered blank at 750-850 ℃, wherein the forging deformation rate is 60%;
6) Solid solution aging treatment: and heating the forged annular workpiece to 900 ℃, preserving heat for 60min, and then quenching. Aging the quenched workpiece: and (3) maintaining the temperature at 450 ℃ for 200min, and cooling to room temperature to obtain the low-beryllium copper alloy annular workpiece.
Relative to example 2, the obtained low beryllium copper alloy annular workpiece has the following properties: the compactness of the hot isostatic pressing process product is further improved, the hardness is 405HV, and the tensile strength is 1305MPa; a small increase in conductivity of 48.3% iacs occurred; the average grain size does not vary much, about 10-15 μm.
Example 4
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
1) Weighing electrolytic copper, beryllium copper master alloy (Cu-2.0 Be), cobalt particles, chromium copper alloy (Cu-5.0 Cr), pure zirconium particles, pure silver particles and mixed rare earth, and forming the following low-beryllium copper alloy components in percentage by mass: 0.9wt% of Be, 1.0wt% of Co, 0.5wt% of Cr, 0.15wt% of Zr, 0.5wt% of Ag, 0.05wt% of mixed rare earth (lanthanum and cerium) and the balance of Cu;
2) Smelting by adopting a vacuum induction furnace, raising the temperature to 1250 ℃ until the raw materials are completely melted, preserving the heat for 5min, regulating the power of the smelting furnace for 5 times, uniformly melting the raw materials, and standing for 10min;
3) And (3) atomizing and pulverizing: heating to make copper alloy be molten, discharging to enter an air atomizer, discharging at 1500 ℃, enabling air atomization pressure to be 30MPa, enabling an air atomization air source to be argon or nitrogen, and enabling air atomization to obtain metal powder;
4) SPS hot press molding: ball milling (200 min, rotating speed 30 r/min) is carried out on the proportioned metal powder, then the metal powder is transferred into an SPS graphite mould, the temperature is quickly raised to 800 ℃, the pressing pressure is 50MPa, the temperature is kept for 5min, and the low-beryllium copper alloy blank is obtained through sintering;
6) Forging: performing annular forging and ring rolling on the sintered blank at 750-850 ℃, wherein the forging deformation rate is 60%;
7) Solid solution aging treatment: and heating the forged annular workpiece to 900 ℃, preserving heat for 60min, and then quenching. Aging the quenched workpiece: and (3) maintaining the temperature at 450 ℃ for 200min, and cooling to room temperature to obtain the low-beryllium copper alloy annular workpiece.
Compared with the embodiment 3, the SPS sample has the characteristics of good compactness and fine grains, and the obtained low-beryllium copper alloy annular workpiece has the following properties: the hardness is improved greatly, the hardness is 421HV, and the tensile strength is 1293MPa; the method comprises the steps of carrying out a first treatment on the surface of the The conductivity was reduced slightly to 44.9% iacs; the average grain size was reduced to about 9 μm. (see FIG. 1-b)
Comparative example 1
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
1) Weighing electrolytic copper, beryllium copper master alloy, nickel copper alloy, silver copper alloy and mixed rare earth, and forming the following low-beryllium copper alloy components in percentage by mass: be0.9wt%, ni 1.0wt%, ag 0.5wt%, mixed rare earth (lanthanum and cerium) 0.035wt% and Cu the rest;
2) Smelting by adopting a vacuum induction furnace, raising the temperature to 1250 ℃ until the alloy is completely melted, preserving the heat for 5min, regulating the power of the smelting furnace for 5 times, uniformly melting the raw materials, standing for 10min, and casting by using a die to obtain a billet.
3) Solid solution aging treatment: heating the blank to 900 ℃, and carrying out quenching treatment after heat preservation for 60 min; aging the quenched workpiece: and (3) maintaining the temperature at 450 ℃ for 200min, and cooling to room temperature to obtain the low-beryllium copper alloy annular workpiece.
The measured properties of the low beryllium copper alloy annular workpiece are as follows: hardness 210HV, tensile strength 526MPa, conductivity 50.5% IACS; the average grain size is 20-50 μm, and the grain size is uneven; the second phase is of a larger size and is enriched in nickel phase.
Comparative example 2
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
1) Weighing electrolytic copper, beryllium copper master alloy, nickel copper alloy, silver copper alloy and mixed rare earth, and forming the following low-beryllium copper alloy components in percentage by mass: 0.9wt% of Be, 1.0wt% of Ni, 0.5wt% of Cr, 0.15wt% of Zr, 0.5wt% of Ag, 0.035wt% of mixed rare earth (lanthanum and cerium) and the balance of Cu;
2) Smelting by adopting a vacuum induction furnace, raising the temperature to 1250 ℃ until the alloy is completely melted, preserving heat for 5min, regulating the power of the smelting furnace for 5 times, uniformly melting raw materials, standing for 10min, and casting by a die to obtain a billet;
3) Solid solution aging treatment: heating the blank to 900 ℃, and carrying out quenching treatment after heat preservation for 60 min; aging the quenched workpiece: the aging temperature is 450 ℃, the temperature is kept for 200min, and the ring-shaped workpiece of the low beryllium copper alloy is obtained after cooling to room temperature;
the low beryllium copper alloy annular workpiece has the following properties: hardness 280HV, tensile strength 765MPa, conductivity 53.1% IACS; the average grain size is 20-50 μm, and the grain size is uneven; the second phase is of a larger size and there is a nickel phase enrichment (see fig. 1-a).
Comparative example 3
The preparation method of the low-beryllium multi-component copper alloy for the crystallizer comprises the following steps:
1) Weighing electrolytic copper, beryllium copper master alloy (Cu-2.0 Be), nickel copper alloy, silver copper alloy and mixed rare earth, and forming the following low-beryllium copper alloy components in percentage by mass: be0.9wt%, ni 1.0wt%, ag 0.5wt%, mixed rare earth (lanthanum and cerium) 0.035wt% and Cu the rest;
2) Smelting by adopting a vacuum induction furnace, raising the temperature to 1250 ℃ until the raw materials are completely melted, preserving the heat for 5min, regulating the power of the smelting furnace for 5 times, uniformly melting the raw materials, and standing for 10min;
3) And (3) atomizing and pulverizing: heating to make copper alloy be molten, discharging to enter an air atomizer, discharging at 1500 ℃, enabling air atomization pressure to be 30MPa, enabling an air atomization air source to be argon or nitrogen, and enabling air atomization to obtain metal powder;
4) Molding and pressing a blank: ball milling (200 min, rotating speed 30 r/min) is carried out on the proportioned metal powder, and then the metal powder is transferred into a mould for mould pressing (400 MPa) to prepare a cold blank;
5) Sintering: putting the cold blank into a sintering furnace, taking hydrogen as protective gas, keeping the sintering temperature at 930 ℃ for 25min, and sintering to obtain a low-beryllium copper alloy blank;
6) Solid solution aging treatment: heating the blank to 900 ℃, preserving heat for 60min, and then quenching. Aging the quenched workpiece: the aging temperature is 450 ℃, the temperature is kept for 200min, and the low beryllium copper alloy is obtained after cooling to the room temperature.
The embodiment adopts a powder metallurgy process, and the obtained low-beryllium copper alloy has the following properties: hardness is 295HV, tensile strength is 824MPa, and conductivity is 51.7% IACS; the grain size is uniform and obviously refined, and the average size is 10 mu m, because the powder metallurgy technology effectively regulates the grain size of the copper alloy; the second phase is reduced in size and distributed more uniformly.
From example 1 and comparative examples 1 to 3, it is known that example 1 simultaneously adds Cr and Zr elements and adopts an aerosolization-sintering-forging process, and the strength of the resulting low beryllium copper alloy annular workpiece is improved because: example 1 combines Cr element age strengthening with fine grain strengthening of an aerosolization-sintering powder metallurgy process; the forging treatment has the strengthening effect of work hardening on the alloy, and meanwhile, the forging treatment refines the second phase of the alloy, and twin crystal and dislocation defects are introduced, so that the twin crystal and dislocation defects can Be used as nucleation cores for solid solution aging, and the solid solution aging strengthening effect of Be element and Cr element is improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The low-beryllium multicomponent copper alloy for the crystallizer is characterized by comprising the following elements in percentage by mass: 0.5 to 1.5 weight percent of Be, 0.8 to 1.5 weight percent of Ni, 0.3 to 1.0 weight percent of Cr, 0.1 to 0.25 weight percent of Zr, 0.05 to 0.5 weight percent of Ag, 0.01 to 0.1 weight percent of rare earth and the balance of Cu.
2. The method for preparing the low beryllium multicomponent copper alloy for use in a mold as recited in claim 1, comprising the steps of:
(1) Weighing a low-beryllium copper alloy raw material, and performing gas atomization to prepare powder after smelting to obtain metal powder;
(2) Sintering and densifying the metal powder to obtain a low-beryllium copper alloy blank;
(3) Forging, solid solution and aging treatment are carried out on the low-beryllium copper alloy blank, and the low-beryllium copper alloy is obtained.
3. The method of claim 2, wherein in step (1), the method of pulverizing by aerosolization comprises: heating the raw materials to a molten state after smelting, discharging the raw materials into an air atomizer, discharging the raw materials at 1300-1700 ℃, enabling the air atomization pressure to be 10-50 MPa, enabling an air source to be argon or nitrogen, and enabling air atomization to obtain metal powder.
4. The method of claim 2, wherein in step (1), the smelting method comprises: the low beryllium copper alloy raw material is put into a smelting furnace, the temperature of the smelting furnace is increased to 1200-1500 ℃ until the alloy is completely melted, the temperature is kept for 5-10 min, the power of the smelting furnace is regulated and controlled for 3-5 times, the raw material is melted uniformly, and the standing is carried out for 5-10 min.
5. The method of claim 2, wherein in step (2), the sintering is a green compact-sintering, spark plasma sintering or hot isostatic pressing sintering.
6. The preparation method according to claim 5, wherein the specific method of the compression molding blank-sintering is as follows: transferring the metal powder into a mould or a cold isostatic pressing mould sleeve, and mould pressing under 300-500 MPa to prepare a cold blank; and (3) putting the cold blank into a sintering furnace, and sintering in vacuum or hydrogen atmosphere to obtain a low-beryllium copper alloy blank, wherein the sintering temperature is 750-1000 ℃, and the heat preservation time is 5-300 min.
7. The preparation method according to claim 5, wherein the specific method of spark plasma sintering is as follows: transferring the metal powder into a graphite mold, heating to 750-980 ℃ under vacuum and 5-80MPa pressure, and preserving heat for 3-60 min.
8. The preparation method according to claim 5, wherein the specific method of hot isostatic pressing sintering is as follows: transferring the metal powder into a closed metal die sleeve for pressurizing such as heat, heating to 800-950 ℃ under the pressure of 10-70MPa, and keeping the temperature for 15-120 min.
9. The method of claim 2, wherein in step (3), the forging method comprises: performing annular forging and ring rolling on the sintered blank at 750-850 ℃ to obtain an annular workpiece, wherein the forging deformation rate is greater than 50%; the solid solution and aging treatment method comprises the following steps: heating the forged workpiece to 760-950 ℃, preserving heat for 30min-3h, quenching, aging the quenched workpiece at 350-500 ℃, preserving heat for 2-6 h, and cooling to room temperature to obtain the low-beryllium copper alloy.
10. The method according to claim 2, 5, 6, 7 or 8, wherein in the step (2), metal powder is firstly put into a ball ink tank, the diameter of grinding balls is selected to be 12-20mm, the ball powder ratio is 5-10:1, ball milling and mixing are carried out for 1-4 hours under the condition of 20-45 r/min of rotating speed, and then sintering densification treatment is carried out.
CN202310237918.7A 2023-03-13 2023-03-13 Low-beryllium multicomponent copper alloy for crystallizer and preparation method thereof Pending CN116287848A (en)

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