CN115369281A - High-strength high-conductivity chromium-zirconium-copper alloy and preparation method thereof - Google Patents
High-strength high-conductivity chromium-zirconium-copper alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of chromium-zirconium-copper alloy preparation and processing, in particular to a high-strength high-conductivity chromium-zirconium-copper alloy and a preparation method thereof, wherein the preparation method comprises the following steps: preparing materials, smelting, casting and post processing; the prepared raw materials are charged into a furnace and heated to be completely melted, the melted raw materials are physically stirred by an electromagnetic stirring device, and after an alloy ingot is cast by an alloy melt, the alloy ingot is post-processed to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product; according to the invention, high-melting-point metal elements are combined by smelting and casting, a strengthening phase formed among Cu, cr, zr, nb, si, ti, ag and Fe is effectively utilized, the strength of the chromium-zirconium-copper alloy is fully improved, and the conductivity of the alloy is not greatly influenced; the strength and the electric conductivity of the alloy cast ingot can be further enhanced through later-stage processing, and the alloy cast ingot can be effectively processed into a chromium-zirconium-copper alloy product with high strength and high electric conductivity.
Description
Technical Field
The invention relates to the technical field of preparation and processing of chromium-zirconium-copper alloy, in particular to high-strength and high-conductivity chromium-zirconium-copper alloy and a preparation method thereof.
Background
The chromium-zirconium-copper alloy is a comprehensive alloy with both strength and conductivity, which is widely applied, mainly used in the industrial fields of consumer electronics, electric locomotives, heat exchange, welding and the like, and some special military and aerospace fields are gradually popularized and used, and is mainly characterized by higher conductivity, lower strength, poor high-temperature performance, and poorer stress relaxation and elasticity.
The chromium-zirconium-copper material can easily obtain the performance of more than 400MPa of strength and more than 75 percent of electric conductivity IACS through normal processing technology, and if the deformation is increased and the proper heat treatment technology is matched, the performance of more than 500MPa of strength and more than 80 percent of electric conductivity IACS, such as chromium-zirconium-copper bars and plates and strips, can be obtained. However, the high strength is obtained by large deformation, the high conductivity depends on overaging treatment, and the intrinsic ultimate strength of the material is not essentially optimized. In some special application fields, the chromium-zirconium-copper material needs to ensure high conductivity, and simultaneously, the strength and other comprehensive properties are further improved to adapt to more complex use requirements, so that the comprehensive properties of the material are improved, and the research is mostly microalloying.
At present, the microalloying development and research of chromium-zirconium-copper materials in China have a plurality of achievements, and according to the prior art, the performance of the alloy is mainly influenced by the contents of main elements Cr and Zr, the microalloying is insufficient, and the obtained alloy has larger difference of comprehensive properties. The copper alloy prepared by the prior art has insufficient comprehensive performance, and is difficult to prepare the copper chromium zirconium series alloy material with high strength and high conductivity.
Disclosure of Invention
The invention provides a high-strength high-conductivity chromium-zirconium-copper alloy and a preparation method thereof, aiming at the defects in the prior art.
The technical scheme of the invention is as follows: a high-strength high-conductivity chromium-zirconium-copper alloy and a preparation method thereof comprise the following steps:
s1, preparing materials
According to the mass percentage content: 0.6-1.0% of Cr element, 0.05-0.12% of Zr element, 0.02-0.06% of Si element, 0.02-0.06% of Fe element, 0.05-0.15% of Nb element, 0.05-0.15% of Ti element, 0.05-0.15% of Ag element, the balance of Cu element;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 45-50 min at 1250-1300 ℃; adding Cr element raw material, introducing inert gas through the bottom of the smelting furnace to degas for 30-60 min; then heating to 1300-1350 ℃, and adding the copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 25-45 min to obtain a molten raw material; physically stirring the melted raw materials by using an electromagnetic stirring device for 5-10 min, then preserving heat, standing for 6-10 min, cooling to 1150-1250 ℃ after the furnace front detection is qualified, vacuumizing for 10-20 min, degassing, electromagnetically stirring for 5-20 min again, and adding rare earth to obtain an alloy melt;
s3, casting
Casting the alloy melt obtained in the step S2 into a round ingot or a flat ingot through a crystallizer at 1200-1250 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
And (4) performing post-processing on the alloy ingot obtained in the step (S3) to obtain the high-strength high-conductivity chromium-zirconium-copper alloy.
Further, in step S1, the Cr element is added in the form of high-purity Cr blocks or Cr powder billets, the Zr element is added in the form of a CuZr alloy, the Si element is added in the form of a copper-silicon master alloy, the Fe element is added in the form of a copper-iron master alloy, the Nb element is added in the form of a chromium-niobium master alloy, the Ti element is added in the form of a copper-titanium master alloy, the Ag element is added in the form of Ag blocks, and the Cu element is added in the form of an alloy, electrolytic Cu blocks; the addition of a certain amount of Si element can form a compound with Cr3Si as a main component, the softening temperature and the high-temperature stability of the alloy are improved, the addition of a certain amount of Fe element can refine crystal grains, the coarsening of the alloy element is inhibited, the matrix is strengthened by cooperating with other alloy elements, the addition of a certain amount of Nb element can improve the high-temperature performance of the alloy, the crystal grains are refined, the addition of a certain amount of Ti element can form a compound with Cu4Ti as a main component or a dispersed simple substance state, the elasticity and the strength of the alloy are improved, the stress relaxation performance of the material is improved, the addition of a certain amount of Ag element can improve the electric conduction performance and the heat conduction performance of the material, and the recrystallization temperature and the creep strength of the material are obviously improved.
Further, the preparation process of the Cr powder blank comprises the following steps: filling high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to be pressed for 6-10 min under the condition of 200-300 Mpa to obtain a Cr powder blank; the raw material adopts Cr powder blank which is helpful for rapid and uniform distribution of Cr element in the melt, enhances the smelting efficiency, shortens the smelting time and reduces the impurity pollution.
Further, the step S4 specifically includes: carrying out hot rolling treatment on the alloy ingot casting in the step S3 to obtain a hot rolled plate; then carrying out high-temperature rapid solution treatment on the hot rolled plate, milling the surface of the hot rolled plate, and then carrying out rough rolling to obtain an alloy plate; then, carrying out intermediate annealing treatment on the alloy plate, and then carrying out intermediate rolling on the alloy plate to obtain an alloy strip; then, carrying out aging treatment and finish rolling on the alloy strip, and finally carrying out surface treatment on the alloy strip to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product; the obtained high-strength high-conductivity chromium-zirconium-copper alloy can meet the requirements of both strength and conductivity by cold rolling and surface treatment of the plate.
Further, the hot rolling treatment and the rapid solution treatment comprise the following specific steps: putting the alloy ingot casting obtained in the step S3 into a stepping furnace, preserving heat for 4-6 h at 850-1000 ℃, and then carrying out hot rolling to obtain a hot rolled plate with the thickness of 14-20 mm; then carrying out on-line spraying water-cooling solid solution treatment on the hot rolled plate; wherein the finishing temperature is controlled between 750 and 850 ℃; the hot rolling treatment can obviously improve the processing technique performance of the alloy cast ingot, the coarse grains are crushed, the micro cracks are healed, the casting defects are reduced, the as-cast structure is converted into a deformed structure, the work hardening is eliminated, the continuous cold processing is facilitated, the alloy elements and the strengthening phases thereof in the alloy can be dispersed and distributed in the matrix through the rapid solution treatment, and the local aggregation or segregation is prevented.
The specific steps of face milling and rough rolling are as follows: guiding the hot rolled plate into a surface milling machine for double-sided milling, wherein the single-sided milling amount is 0.3-1 mm; then, roughly rolling the alloy plate, and cold-rolling the alloy plate with the processing rate of 85-100% to obtain the alloy plate with the thickness of 1.5-1.9 mm; the alloy plate can be preliminarily processed into a plate with a certain thickness through face milling treatment and cold rolling treatment, surface defects of the alloy material are removed, and preparation is made for subsequent cold rolling.
Further, the intermediate annealing treatment specifically comprises the following steps: carrying out on-line intermediate annealing treatment on the alloy plate, keeping the temperature for 3.5-4.5 h at the annealing temperature of 300-500 ℃, and introducing inert gas for protection; the middle rolling comprises the following specific steps: carrying out medium rolling on the alloy plate after annealing treatment, and carrying out cold rolling with the processing rate of 60-90% to obtain an alloy strip with the thickness of 0.1-0.7 mm; the intermediate annealing can eliminate the deformation strengthening effect of the alloy plate, soften the alloy plate material, recover the plastic deformation capability of the alloy plate material, recover the lattice distortion, eliminate the internal stress, recrystallize the structure, homogenize the grain size of the alloy material and improve the anisotropy; the alloy plate which is preliminarily processed into a certain thickness is further cold-rolled into an alloy strip, so that the mechanical property and the technological property of the alloy strip can be further improved.
Further, the finish rolling treatment comprises the following specific steps: keeping the temperature for 3 to 4 hours at the annealing temperature of between 400 and 500 ℃, and introducing inert gas for protection and cooling; performing finish rolling on the alloy strip, wherein the finish rolling processing rate is 20-60%; the surface treatment comprises the following specific steps: carrying out shaping and low-temperature annealing stabilization treatment on the cold-rolled alloy strip, and finally carrying out pickling, alkali washing degreasing and passivation treatment to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product; the cold rolling can further strengthen the strength of the alloy strip, and the alloy strip can be subjected to surface treatment to form a high-strength high-conductivity chromium-zirconium-copper alloy product meeting the requirements through surface treatment.
Further, the step S4 specifically includes: adding the alloy ingot casting obtained in the step S3 into a resistance furnace or a gas furnace, preserving heat for 1-3 h at 900-980 ℃, and then carrying out hot forging or hot extrusion treatment; introducing inert atmosphere for protection, keeping the temperature for 0.5 to 3 hours at the temperature of 950 to 1000 ℃, and rapidly quenching to obtain an alloy plate; then, carrying out cold deformation treatment on the alloy plate to obtain a plate blank; carrying out aging treatment on the plate blank; performing secondary cold deformation treatment on the time-effect treated plate blank to obtain a plate; finally, machining the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy; the structure of the alloy cast ingot can be improved through hot forging or hot extrusion treatment, the alloy strength can be enhanced through cold deformation treatment, and the plate can be effectively processed into a high-strength high-conductivity chromium-zirconium-copper alloy product meeting the requirements through machining treatment.
Further, the cold deformation treatment and the aging treatment specifically comprise the following steps: cold deformation treatment is carried out on the alloy plate, the cold deformation amount is 20-80%, cold forging or cold pressing or cold rolling is adopted as a deformation mode, and a plate blank meeting the requirement is forged; introducing inert atmosphere for protection, preserving heat for 1-5 h at the temperature of 300-500 ℃, and cooling along with the furnace; the cold deformation treatment can play a certain role in processing and hardening the alloy plate and enhance the mechanical property of the alloy plate.
Further, the secondary cold deformation and machining treatment comprises the following specific steps: performing secondary cold forging deformation on the plate blank subjected to the aging treatment, wherein the deformation amount of the cold forging is 10-20%, and preparing a plate; then milling the surface of the plate to prepare the high-strength high-conductivity chromium-zirconium-copper alloy; the secondary cold forging deformation can further enhance the strength and hardness of the alloy plate, and the milled surface can effectively remove surface defects and improve the surface quality.
Compared with the prior art, the invention has the beneficial effects that: the invention can prepare the high-strength high-conductivity chromium-zirconium-copper alloy component content close to the optimal production through the raw material proportion; the high-melting-point metal elements are combined by smelting and casting, a strengthening phase formed among Cu, cr, zr, nb, si, ti, ag and Fe is effectively utilized, the strength of the chromium-zirconium-copper alloy can be fully improved, and the conductivity of the alloy is not greatly influenced; in the smelting process, the effects of degassing, purifying tiny impurities, stirring melt and the like can be simultaneously realized by bottom blowing of inert gas, the molten raw materials are electromagnetically stirred, vacuum degassing is applied, and the density, the components and the temperature of the chromium-zirconium-copper alloy are effectively improved and homogenized; electromagnetic stirring is applied during the casting process, so that a casting blank with uniform components, fine grains and pure matrix can be obtained, the strength and the conductivity of the alloy casting ingot can be further enhanced through later-stage processing, the elasticity and the stress relaxation of the alloy are improved, and the alloy casting ingot can be effectively processed into a chromium-zirconium-copper alloy product with high strength and high conductivity.
Drawings
FIG. 1 is a flow chart of the operation of the present invention.
Detailed Description
Example 1
The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof shown in figure 1 comprise the following steps:
s1, preparing materials
According to the mass percentage content: 0.6% of Cr element, 0.05% of Zr element, 0.02% of Si element, 0.02% of Fe element, 0.05% of Nb element, 0.05% of Ti element, 0.05% of Ag element, and the balance of Cu element;
cr element is added in the form of high-purity Cr blocks, zr element is added in the form of CuZr40 alloy, si element is added in the form of CuSi20 master alloy, fe element is added in the form of CuFe50 master alloy, nb element is added in the form of Cu60Nb40 master alloy, ti element is added in the form of CuTi50 master alloy, ag element is added in the form of Ag blocks, and Cu element is added in the form of alloy and electrolytic Cu blocks;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting at 1250 ℃ for 45min; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 30min; then heating to 1300 ℃, and adding a copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 25min to obtain a molten raw material; physically stirring the molten raw materials by using an electromagnetic stirring device for 5min, then preserving heat and standing for 6min, cooling to 1150 ℃ after the detection in front of the furnace is qualified, vacuumizing for 10min, degassing, electromagnetically stirring for 5min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 0.6 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 2 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.02 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a flat ingot through a crystallizer at 1200 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
Carrying out conventional post-processing on the alloy ingot obtained in the step S3 to obtain a high-strength high-conductivity chromium-zirconium-copper alloy; the method comprises the following specific steps: putting the alloy ingot obtained in the step S3 into a heating furnace, and preserving heat for 0.8h at the temperature of 830 ℃; then carrying out hot forging treatment, and preserving heat for 0.6h at 860 ℃; cold rolling after high-temperature solution treatment, wherein the rolling deformation is 80%; and finally, milling the surface of the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy.
Example 2
The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof shown in figure 1 comprise the following steps:
s1, preparing materials
According to the mass percentage content: 0.8% of Cr element, 0.09% of Zr element, 0.04% of Si element, 0.04% of Fe element, 0.1% of Nb element, 0.1% of Ti element, 0.1% of Ag element, and the balance of Cu element;
cr element is added in the form of high-purity Cr blocks, zr element is added in the form of CuZr40 alloy, si element is added in the form of CuSi20 master alloy, fe element is added in the form of CuFe50 master alloy, nb element is added in the form of Cu60Nb40 master alloy, ti element is added in the form of CuTi50 master alloy, ag element is added in the form of Ag blocks, and Cu element is added in the form of alloy and electrolytic Cu blocks;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 47min at 1275 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 45min; then heating to 1325 ℃, and adding the copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 35min to obtain a molten raw material; physically stirring the molten raw materials by using an electromagnetic stirring device for 7min, then preserving heat, standing for 8min, cooling to 1200 ℃ after the detection in front of the furnace is qualified, vacuumizing for 15min, degassing, electromagnetically stirring for 12min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 2 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 3 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.06 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a slab ingot through a crystallizer at the temperature of 1220 ℃; in the casting process, electromagnetic stirring action is simultaneously exerted on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
Carrying out conventional post-processing on the alloy ingot obtained in the step S3 to obtain a high-strength high-conductivity chromium-zirconium-copper alloy; the method comprises the following specific steps: putting the alloy ingot obtained in the step S3 into a heating furnace, and preserving heat for 1.8h at 880 ℃; then, carrying out hot forging treatment, and preserving heat for 1.5h at 900 ℃; cold rolling is carried out after high-temperature solution treatment, and the rolling deformation is 84%; and finally, milling the surface of the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy.
Example 3
As shown in fig. 1, a high strength and high conductivity chromium zirconium copper alloy and a preparation method thereof comprises:
s1, preparing materials
According to the mass percentage content: 1.0% cr element, 0.05% zr element, 0.02% si element, 0.06% fe element, 0.15% nb element, 0.15% ti element, 0.15% ag element, balance Cu element;
the Cr element is added in the form of high-purity Cr blocks, the Zr element is added in the form of CuZr40 alloy, the Si element is added in the form of CuSi20 intermediate alloy, the Fe element is added in the form of CuFe50 intermediate alloy, the Nb element is added in the form of Cu60Nb40 intermediate alloy, the Ti element is added in the form of CuTi50 intermediate alloy, the Ag element is added in the form of Ag blocks, and the Cu element is added in the form of alloy and electrolytic Cu blocks;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 50min at 1300 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 60min; then heating to 1350 ℃, and adding the copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 45min to obtain a molten raw material; physically stirring the molten raw materials for 10min by using an electromagnetic stirring device, then preserving heat and standing for 10min, cooling to 1250 ℃ after the detection in front of the furnace is qualified, vacuumizing for 20min, degassing, electromagnetically stirring for 20min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 3 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 4 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.1 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a flat ingot through a crystallizer at 1250 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
Carrying out conventional post-processing on the alloy ingot obtained in the step S3 to obtain a high-strength high-conductivity chromium-zirconium-copper alloy; the method comprises the following specific steps: putting the alloy ingot obtained in the step S3 into a heating furnace, and preserving heat for 2.5 hours at the temperature of 900 ℃; then carrying out hot forging treatment, and preserving heat for 2h at 950 ℃; cold rolling after high-temperature solution treatment, wherein the rolling deformation is 89%; and finally, milling the surface of the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy.
Example 4
The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof shown in figure 1 comprise the following steps:
s1, preparing materials
According to the mass percentage content: 0.6% of Cr element, 0.05% of Zr element, 0.02% of Si element, 0.02% of Fe element, 0.05% of Nb element, 0.05% of Ti element, 0.05% of Ag element, and the balance of Cu element;
the Cr element is added in the form of a Cr powder blank, the Zr element is added in the form of CuZr40 alloy, the Si element is added in the form of CuSi20 master alloy, the Fe element is added in the form of CuFe50 master alloy, the Nb element is added in the form of Cu60Nb40 master alloy, the Ti element is added in the form of CuTi50 master alloy, the Ag element is added in the form of Ag lumps, and the Cu element is added in the form of alloy and electrolytic Cu lumps;
the preparation process of the Cr powder blank comprises the following steps: filling high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to be pressed for 6min under the condition of 200Mpa to obtain a Cr powder blank;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 45min at 1250 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 30min; then heating to 1300 ℃, and adding a copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 25min to obtain a molten raw material; physically stirring the molten raw materials by using an electromagnetic stirring device for 5min, then preserving heat, standing for 6min, cooling to 1150 ℃ after the furnace front detection is qualified, vacuumizing for 10min, degassing, electromagnetically stirring for 5min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 0.6 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 2 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.02 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a flat ingot through a crystallizer at 1200 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
Carrying out hot rolling treatment on the alloy ingot obtained in the step S3 to obtain a hot rolled plate; then carrying out high-temperature rapid solution treatment on the hot rolled plate, milling the surface of the hot rolled plate, and then carrying out rough rolling to obtain an alloy plate; then, carrying out intermediate annealing treatment on the alloy plate, and then carrying out intermediate rolling on the alloy plate to obtain an alloy strip; then, carrying out aging treatment and finish rolling on the alloy strip, and finally carrying out surface treatment on the alloy strip to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product;
the hot rolling treatment and the rapid solution treatment comprise the following specific steps: putting the alloy ingot casting in the step S3 into a stepping furnace, preserving heat for 4 hours at 850 ℃, and then carrying out hot rolling to obtain a hot rolled plate with the thickness of 14 mm; then carrying out on-line spraying water-cooling solid solution treatment on the hot rolled plate; wherein the finishing temperature is controlled at 750 ℃;
the specific steps of face milling and rough rolling are as follows: guiding the hot rolled plate into a milling machine for double-sided milling, wherein the milling amount of a single side is 0.3mm; then, carrying out rough rolling on the alloy plate, and carrying out cold rolling with the machining rate of 85% to obtain the alloy plate with the thickness of 1.5 mm;
the intermediate annealing treatment comprises the following specific steps: carrying out on-line intermediate annealing treatment on the alloy plate, keeping the temperature for 3.5 hours at the annealing temperature of 300 ℃, and introducing nitrogen and hydrogen for protection;
the concrete steps of the medium rolling are as follows: carrying out medium rolling on the alloy plate after annealing treatment, and carrying out cold rolling with the processing rate of 60% to obtain an alloy strip with the thickness of 0.1 mm;
the aging treatment comprises the following specific steps: keeping the temperature for 3 hours at the annealing temperature of 400 ℃, and introducing helium gas for protection and cooling; performing finish rolling on the alloy strip, wherein the finish rolling processing rate is 20%;
the surface treatment comprises the following specific steps: and (3) carrying out shaping and low-temperature annealing stabilization treatment on the cold-rolled alloy strip, and finally carrying out pickling, alkali washing degreasing and passivation treatment to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
Example 5
The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof shown in figure 1 comprise the following steps:
s1, preparing materials
According to the mass percentage content: 0.8% of Cr element, 0.09% of Zr element, 0.04% of Si element, 0.04% of Fe element, 0.1% of Nb element, 0.1% of Ti element, 0.1% of Ag element, and the balance of Cu element;
the Cr element is added in a form of a Cr powder blank, the Zr element is added in a form of CuZr40 alloy, the Si element is added in a form of CuSi20 intermediate alloy, the Fe element is added in a form of CuFe50 intermediate alloy, the Nb element is added in a form of Cu60Nb40 intermediate alloy, the Ti element is added in a form of CuTi50 intermediate alloy, the Ag element is added in a form of Ag blocks, and the Cu element is added in a form of alloy and electrolytic Cu blocks;
the preparation process of the Cr powder blank comprises the following steps: filling high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to be pressed for 8min under the condition of 250Mpa to obtain a Cr powder blank;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 47min at 1275 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 45min; then heating to 1325 ℃, and adding a copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 35min to obtain a molten raw material; physically stirring the molten raw materials by using an electromagnetic stirring device for 7min, then preserving heat, standing for 8min, cooling to 1200 ℃ after the detection in front of the furnace is qualified, vacuumizing for 15min, degassing, electromagnetically stirring for 12min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 2 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 3 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.06 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a flat ingot through a crystallizer at the temperature of 1220 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into a chute in the casting process;
s4, post-processing
Carrying out hot rolling treatment on the alloy ingot obtained in the step S3 to obtain a hot rolled plate; then carrying out high-temperature rapid solution treatment on the hot rolled plate, milling the surface of the hot rolled plate, and then carrying out rough rolling to obtain an alloy plate; then, carrying out intermediate annealing treatment on the alloy plate, and then carrying out intermediate rolling on the alloy plate to obtain an alloy strip; then carrying out aging treatment and finish rolling on the alloy strip, and finally carrying out surface treatment on the alloy strip to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product;
the hot rolling treatment and the rapid solution treatment comprise the following specific steps: placing the alloy ingot in the step S3 into a stepping furnace, preserving heat for 5 hours at the temperature of 920 ℃, and then carrying out hot rolling to obtain a hot rolled plate with the thickness of 17 mm; then carrying out on-line spraying water-cooling solid solution treatment on the hot rolled plate; wherein the finishing temperature is controlled at 800 ℃;
the specific steps of face milling and rough rolling are as follows: guiding the hot rolled plate into a milling machine for double-sided milling, wherein the milling amount of a single side is 0.6mm; then, carrying out rough rolling on the alloy plate, and carrying out cold rolling with the machining rate of 90% to obtain the alloy plate with the thickness of 1.7 mm;
the intermediate annealing treatment comprises the following specific steps: carrying out on-line intermediate annealing treatment on the alloy plate, preserving heat for 4 hours at the annealing temperature of 400 ℃, and introducing nitrogen and hydrogen for protection;
the concrete steps of the medium rolling are as follows: carrying out medium rolling on the alloy plate subjected to annealing treatment, and carrying out cold rolling with the machining rate of 80% to obtain an alloy strip with the thickness of 0.4 mm;
the aging treatment comprises the following specific steps: keeping the temperature for 3.5h at the annealing temperature of 450 ℃, and introducing helium gas for protection and cooling; performing finish rolling on the alloy strip, wherein the finish rolling processing rate is 40%;
the surface treatment comprises the following specific steps: and (3) carrying out shaping and low-temperature annealing stabilization treatment on the cold-rolled alloy strip, and finally carrying out pickling, alkali washing degreasing and passivation treatment to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
Example 6
As shown in fig. 1, a high strength and high conductivity chromium zirconium copper alloy and a preparation method thereof comprises:
s1, preparing materials
According to the mass percentage content: 1.0% cr element, 0.12% zr element, 0.06% si element, 0.06% fe element 0.15% nb element, 0.15% ti element, 0.15% ag element, balance Cu element;
the Cr element is added in the form of a Cr powder blank, the Zr element is added in the form of CuZr40 alloy, the Si element is added in the form of CuSi20 master alloy, the Fe element is added in the form of CuFe50 master alloy, the Nb element is added in the form of Cu60Nb40 master alloy, the Ti element is added in the form of CuTi50 master alloy, the Ag element is added in the form of Ag lumps, and the Cu element is added in the form of alloy and electrolytic Cu lumps;
the preparation process of the Cr powder blank comprises the following steps: filling high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to be pressed for 10min under the condition of 300Mpa to obtain a Cr powder blank;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 50min at 1300 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 60min; then heating to 1350 ℃, and adding the copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 45min to obtain a molten raw material; physically stirring the molten raw materials for 10min by using an electromagnetic stirring device, then preserving heat and standing for 10min, cooling to 1250 ℃ after the detection in front of the furnace is qualified, vacuumizing for 20min, degassing, electromagnetically stirring for 20min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 3 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 4 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.1 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a flat ingot through a crystallizer at 1250 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into a chute in the casting process;
s4, post-processing
Carrying out hot rolling treatment on the alloy ingot obtained in the step S3 to obtain a hot rolled plate; then carrying out high-temperature rapid solid solution treatment on the hot rolled plate, milling the surface of the hot rolled plate, and carrying out rough rolling to obtain an alloy plate; then, carrying out intermediate annealing treatment on the alloy plate, and then carrying out intermediate rolling on the alloy plate to obtain an alloy strip; then, carrying out aging treatment and finish rolling on the alloy strip, and finally carrying out surface treatment on the alloy strip to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product;
the hot rolling treatment and the rapid solution treatment comprise the following specific steps: placing the alloy cast ingot obtained in the step S3 into a stepping furnace, preserving heat for 6 hours at the temperature of 1000 ℃, and then carrying out hot rolling to obtain a hot rolled plate with the thickness of 20 mm; then carrying out on-line spraying water-cooling solution treatment on the hot rolled plate; wherein the finishing temperature is controlled at 850 ℃;
the specific steps of face milling and rough rolling are as follows: guiding the hot rolled plate into a milling machine for double-sided milling, wherein the milling amount of a single side is 1mm; then, carrying out rough rolling on the alloy plate, and carrying out cold rolling with the machining rate of 99% to obtain the alloy plate with the thickness of 1.9 mm;
the intermediate annealing treatment comprises the following specific steps: carrying out on-line intermediate annealing treatment on the alloy plate, preserving heat for 4.5h at the annealing temperature of 500 ℃, and introducing nitrogen and hydrogen for protection;
the concrete steps of the medium rolling are as follows: carrying out medium rolling on the alloy plate after annealing treatment, and carrying out cold rolling with the machining rate of 90% to obtain an alloy strip with the thickness of 0.7 mm;
the aging treatment comprises the following specific steps: keeping the temperature for 4 hours at the annealing temperature of 500 ℃, and introducing helium gas for protection and cooling; performing finish rolling on the alloy strip, wherein the finish rolling processing rate is 60%;
the surface treatment comprises the following specific steps: and (3) carrying out shaping and low-temperature annealing stabilization treatment on the cold-rolled alloy strip, and finally carrying out pickling, alkali washing degreasing and passivation treatment to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
Example 7
As shown in fig. 1, a high strength and high conductivity chromium zirconium copper alloy and a preparation method thereof comprises:
s1, preparing materials
According to the mass percentage content: 0.6% of Cr element, 0.05% of Zr element, 0.02% of Si element, 0.02% of Fe element, 0.05% of Nb element, 0.05% of Ti element, 0.05% of Ag element, the balance of Cu element;
the Cr element is added in a form of a Cr powder blank, the Zr element is added in a form of CuZr40 alloy, the Si element is added in a form of CuSi20 intermediate alloy, the Fe element is added in a form of CuFe50 intermediate alloy, the Nb element is added in a form of Cu60Nb40 intermediate alloy, the Ti element is added in a form of CuTi50 intermediate alloy, the Ag element is added in a form of Ag blocks, and the Cu element is added in a form of alloy and electrolytic Cu blocks;
the preparation process of the Cr powder blank comprises the following steps: filling high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to be pressed for 6min under the condition of 200Mpa to obtain a Cr powder blank;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 45min at 1250 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 30min; then heating to 1300 ℃, and adding a copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 25min to obtain a molten raw material; physically stirring the molten raw materials by using an electromagnetic stirring device for 5min, then preserving heat, standing for 6min, cooling to 1150 ℃ after the furnace front detection is qualified, vacuumizing for 10min, degassing, electromagnetically stirring for 5min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 0.6 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 2 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.02 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a round ingot through a crystallizer at 1200 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
Adding the alloy ingot obtained in the step S3 into a resistance furnace or a gas furnace, preserving heat for 1h at 900 ℃, and then carrying out hot forging or hot extrusion treatment; introducing helium gas for protection, keeping the temperature at 950 ℃ for 0.5h, and rapidly quenching to obtain an alloy plate; then, carrying out cold deformation treatment on the alloy plate to obtain a plate blank; carrying out aging treatment on the plate blank; performing secondary cold deformation treatment on the time-effect treated plate blank to obtain a plate; finally, machining the plate to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product;
the cold deformation treatment and the aging treatment comprise the following specific steps: cold deformation treatment is carried out on the alloy plate, the cold deformation amount is 20%, the deformation mode adopts cold forging or cold pressing or cold rolling, and a plate blank meeting the requirement is forged; introducing helium gas for protection, keeping the temperature for 1h at 300 ℃, and cooling along with the furnace;
the secondary cold deformation and machining treatment comprises the following specific steps: performing secondary cold forging deformation on the plate blank subjected to the aging treatment, wherein the deformation amount of the cold forging is 10%, and preparing a plate; and then milling the surface of the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
Example 8
The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof shown in figure 1 comprise the following steps:
s1, preparing materials
According to the mass percentage content: 0.8% of Cr element, 0.09% of Zr element, 0.04% of Si element, 0.04% of Fe element, 0.1% of Nb element, 0.1% of Ti element, 0.1% of Ag element, the balance of Cu element;
the Cr element is added in the form of a Cr powder blank, the Zr element is added in the form of CuZr40 alloy, the Si element is added in the form of CuSi20 master alloy, the Fe element is added in the form of CuFe50 master alloy, the Nb element is added in the form of Cu60Nb40 master alloy, the Ti element is added in the form of CuTi50 master alloy, the Ag element is added in the form of Ag lumps, and the Cu element is added in the form of alloy and electrolytic Cu lumps;
the preparation process of the Cr powder blank comprises the following steps: filling high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to perform compaction for 8min under the condition of 250Mpa to obtain a Cr powder blank;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 47min at 1275 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 45min; then heating to 1325 ℃, and adding a copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 35min to obtain a molten raw material; physically stirring the molten raw materials by using an electromagnetic stirring device for 7min, then preserving heat, standing for 8min, cooling to 1200 ℃ after the detection in front of the furnace is qualified, vacuumizing for 15min, degassing, electromagnetically stirring for 12min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 2 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 3 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.06 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a round ingot through a crystallizer at the temperature of 1220 ℃; in the casting process, electromagnetic stirring action is simultaneously exerted on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
Adding the alloy ingot obtained in the step S3 into a resistance furnace or a gas furnace, preserving heat for 2 hours at 940 ℃, and then carrying out hot forging or hot extrusion treatment; introducing helium gas for protection, preserving heat for 2 hours at the temperature of 975 ℃, and rapidly quenching to obtain an alloy plate; then, carrying out cold deformation treatment on the alloy plate to obtain a plate blank; carrying out aging treatment on the plate blank; performing secondary cold deformation treatment on the time-effect treated plate blank to obtain a plate; finally, machining the plate to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product;
the cold deformation treatment and the aging treatment comprise the following specific steps: cold deformation treatment is carried out on the alloy plate, the cold deformation amount is 50%, the deformation mode adopts cold forging or cold pressing or cold rolling, and a plate blank meeting the requirement is forged; introducing helium gas for protection, keeping the temperature for 3 hours at 400 ℃, and cooling along with the furnace;
the secondary cold deformation and machining treatment comprises the following specific steps: performing secondary cold forging deformation on the plate blank subjected to the aging treatment, wherein the deformation amount of the cold forging is 15%, and preparing a plate; and then milling the surface of the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
Example 9
The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof shown in figure 1 comprise the following steps:
s1, preparing materials
According to the mass percentage content: 1.0% of Cr element, 0.12% of Zr element, 0.06% of Si element, 0.06% of Fe element, 0.15% of Nb element, 0.15% of Ti element, 0.15% of Ag element, and the balance of Cu element;
the Cr element is added in the form of a Cr powder blank, the Zr element is added in the form of CuZr40 alloy, the Si element is added in the form of CuSi20 master alloy, the Fe element is added in the form of CuFe50 master alloy, the Nb element is added in the form of Cu60Nb40 master alloy, the Ti element is added in the form of CuTi50 master alloy, the Ag element is added in the form of Ag lumps, and the Cu element is added in the form of alloy and electrolytic Cu lumps;
the preparation process of the Cr powder blank comprises the following steps: filling high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to be pressed for 10min under the condition of 300Mpa to obtain a Cr powder blank;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 50min at 1300 ℃; adding Cr element raw material, introducing argon through the bottom of the smelting furnace, and degassing for 60min; then heating to 1350 ℃, and adding the copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 45min to obtain a molten raw material; physically stirring the molten raw materials for 10min by using an electromagnetic stirring device, then preserving heat and standing for 10min, cooling to 1250 ℃ after the detection in front of the furnace is qualified, vacuumizing for 20min, degassing, electromagnetically stirring for 20min again, and adding rare earth to obtain an alloy melt; wherein, the covering agent adopts cullet accounting for 3 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, the fluxing agent adopts calcium oxide accounting for 4 percent of the total amount of the mixture of the Cu element raw material and the Fe element raw material, and the addition amount of the copper-magnesium intermediate alloy is 0.1 percent of the total amount of the mixture of the Cu element raw material, the Fe element raw material and the Cr element raw material;
s3, casting
Casting the alloy melt obtained in the step S2 into a round ingot through a crystallizer at 1250 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post-processing
Adding the alloy ingot obtained in the step S3 into a resistance furnace or a gas furnace, preserving heat for 3 hours at 980 ℃, and then carrying out hot forging or hot extrusion treatment; introducing helium gas for protection, preserving heat for 3 hours at the temperature of 1000 ℃, and rapidly quenching to obtain an alloy plate; then, carrying out cold deformation treatment on the alloy plate to obtain a plate blank; carrying out aging treatment on the plate blank; performing secondary cold deformation treatment on the time-effect treated plate blank to obtain a plate; finally, machining the plate to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product;
the cold deformation treatment and the aging treatment comprise the following specific steps: cold deformation treatment is carried out on the alloy plate, the cold deformation amount is 80%, the deformation mode adopts cold forging or cold pressing or cold rolling, and a plate blank meeting the requirement is forged; introducing helium gas for protection, preserving heat for 5h at 500 ℃, and cooling along with the furnace;
the specific steps of secondary cold deformation and machining treatment are as follows: performing secondary cold forging deformation on the plate blank subjected to the aging treatment, wherein the deformation amount of the cold forging is 20%, and preparing a plate; and then milling the surface of the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
Examples of the experiments
12 different chromium-zirconium-copper alloys are prepared by the methods of examples 1 to 9 and a conventional casting method, and chemical components of the prepared chromium-zirconium-copper alloys are detected, wherein specific detection results are shown in table 1;
wherein, the chromium-zirconium-copper alloy prepared by the conventional casting method corresponds to the comparative examples 1, 2 and 3 respectively; the formulation of comparative example 1 was 0.07% CuZr alloy, 0.5% Cr blocks, and the balance Cu blocks; the ingredients of comparative example 2 were 0.1% of CuZr alloy, 0.8% of Cr blocks, and the balance of Cu blocks; the formulation of comparative example 3 was 0.13% CuZr alloy, 1.1% Cr blocks, the balance Cu blocks;
table 1: chemical component contents of 12 different chromium-zirconium-copper alloys
And (4) conclusion: as can be seen from the data in Table 1, the chromium-zirconium-copper alloy prepared by the method of examples 1 to 9 has lower gas content in the chemical composition; from examples 7 to 9, it can be seen that the chromium zirconium copper alloy which is post-processed by the process of the present invention has a higher purity.
The performance of 12 different chromium-zirconium-copper alloys is detected, and the specific detection results are shown in table 2;
table 2: performance test meter for 12 different chromium-zirconium-copper alloys
And (4) conclusion: as can be seen from the data in table 2, the chromium-zirconium-copper alloys prepared in examples 1 to 9 have higher tensile strength and higher conductivity; from the examples 4 to 6, it can be seen that the chromium-zirconium-copper alloy processed in the later period by the process of the invention has higher tensile strength and conductivity than the chromium-zirconium-copper alloy produced by the conventional processing in the examples 1 to 3; as can be seen from the data in Table 2, example 6 prepared by the method of the present invention has the highest conductivity effect, the optimal comprehensive contrast, high strength and high conductivity, and can have certain advantages of elasticity and stress relaxation resistance.
Claims (10)
1. A high-strength high-conductivity chromium-zirconium-copper alloy and a preparation method thereof are characterized by comprising the following steps:
s1, preparing materials
According to the mass percentage content: 0.6 to 1.0% of Cr element, 0.05 to 0.12% of Zr element, 0.02 to 0.06% of Si element, 0.02 to 0.06% of Fe element, 0.05 to 0.15% of Nb element, 0.05 to 0.15% of Ti element, 0.05 to 0.15% of Ag element, and the balance of Cu element;
s2, smelting
Adding the Cu raw material, the Fe raw material, the covering agent and the fluxing agent prepared in the step S1 into an induction furnace, and smelting for 45-50 min at 1250-1300 ℃; adding Cr element raw material, introducing inert gas through the bottom of the smelting furnace to degas for 30-60 min; then heating to 1300-1350 ℃, and adding the copper-magnesium intermediate alloy for deoxidation; then adding the Si element raw material, the Nb element raw material and the Ag element raw material prepared in the step S1, and continuously heating for 25-45 min to obtain a molten raw material; physically stirring the molten raw materials for 5-10 min by using an electromagnetic stirring device, then preserving heat, standing for 6-10 min, cooling to 1150-1250 ℃ after the detection in front of the furnace is qualified, vacuumizing for 10-20 min, degassing, electromagnetically stirring for 5-20 min again, and adding rare earth to obtain an alloy melt;
s3, casting
Casting the alloy melt obtained in the step S2 into a round ingot or a flat ingot through a crystallizer at 1200-1250 ℃; in the casting process, simultaneously applying electromagnetic stirring action on a crystallizer to obtain an alloy ingot; adding a Ti element raw material and a Zr element raw material into the chute in the casting process;
s4, post processing
And (4) performing post-processing on the alloy ingot obtained in the step (S3) to obtain the high-strength high-conductivity chromium-zirconium-copper alloy.
2. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 1, wherein the Cr element is added in the form of high-purity Cr blocks or Cr powder billets in step S1, the Zr element is added in the form of CuZr alloy, the Si element is added in the form of copper-silicon master alloy, the Fe element is added in the form of copper-iron master alloy, the Nb element is added in the form of chromium-niobium master alloy, the Ti element is added in the form of copper-titanium master alloy, the Ag element is added in the form of Ag blocks, and the Cu element is added in the form of alloy or electrolytic Cu blocks.
3. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 2, wherein the preparation process of the Cr powder blank comprises the following steps: and filling the high-purity deoxidized Cr powder into a rubber sleeve, and putting the rubber sleeve into a cold isostatic press to perform compaction for 6-10 min under the condition of 200-300 Mpa to obtain a Cr powder blank.
4. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 1, wherein the step S4 specifically comprises: carrying out hot rolling treatment on the alloy ingot casting in the step S3 to obtain a hot rolled plate; then carrying out high-temperature rapid solution treatment on the hot rolled plate, milling the surface of the hot rolled plate, and then carrying out rough rolling to obtain an alloy plate; then, carrying out intermediate annealing treatment on the alloy plate, and then carrying out intermediate rolling on the alloy plate to obtain an alloy strip; and then carrying out aging treatment and finish rolling on the alloy strip, and finally carrying out surface treatment on the alloy strip to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product.
5. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 4, wherein the hot rolling treatment and the rapid solution treatment specifically comprise the following steps: putting the alloy ingot casting in the step S3 into a stepping furnace, preserving the heat for 4-6 h at the temperature of 850-1000 ℃, and then carrying out hot rolling to obtain a hot rolled plate with the thickness of 14-20 mm; then carrying out on-line spraying water-cooling solid solution treatment on the hot rolled plate; wherein the finishing temperature is controlled between 750 and 850 ℃;
the specific steps of face milling and rough rolling are as follows: guiding the hot rolled plate into a surface milling machine for double-sided milling, wherein the single-sided milling amount is 0.3-1 mm; then the alloy sheet is subjected to rough rolling, and is subjected to cold rolling with the processing rate of 85-100% to obtain the alloy sheet with the thickness of 1.5-1.9 mm.
6. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 4, wherein the intermediate annealing treatment comprises the following specific steps: carrying out on-line intermediate annealing treatment on the alloy plate, keeping the temperature for 3.5-4.5 h at the annealing temperature of 300-500 ℃, and introducing inert gas for protection;
the middle rolling comprises the following specific steps: and (3) carrying out medium rolling on the alloy plate after annealing treatment, and carrying out cold rolling with the working ratio of 60-90% to obtain an alloy strip with the thickness of 0.1-0.7 mm.
7. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 4, wherein the aging treatment comprises the following specific steps: keeping the temperature for 3 to 4 hours at the annealing temperature of between 400 and 500 ℃, and introducing inert gas for protection and cooling; performing finish rolling on the alloy strip, wherein the finish rolling processing rate is 20-60%;
the surface treatment comprises the following specific steps: and (3) carrying out shaping and low-temperature annealing stabilization treatment on the cold-rolled alloy strip, and finally carrying out pickling, alkali washing degreasing and passivation treatment to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
8. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 1, wherein the step S4 is specifically as follows: adding the alloy ingot casting in the step S3 into a resistance furnace or a gas furnace, preserving heat for 1-3 h at 900-980 ℃, and then carrying out hot forging or hot extrusion treatment; introducing inert atmosphere for protection, preserving the heat for 0.5 to 3 hours at the temperature of 950 to 1000 ℃, and rapidly quenching to obtain an alloy plate; then, carrying out cold deformation treatment on the alloy plate to obtain a plate blank; carrying out aging treatment on the plate blank; performing secondary cold deformation treatment on the time-effect treated plate blank to obtain a plate; finally, machining the plate to obtain a high-strength high-conductivity chromium-zirconium-copper alloy product;
9. the high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 8, wherein the cold deformation treatment and the aging treatment comprise the following steps: cold deformation treatment is carried out on the alloy plate, the cold deformation amount is 20-80%, cold forging or cold pressing or cold rolling is adopted as a deformation mode, and a plate blank meeting the requirement is forged; introducing inert atmosphere for protection, preserving the heat for 1-5 h at the temperature of 300-500 ℃, and cooling along with the furnace.
10. The high-strength high-conductivity chromium-zirconium-copper alloy and the preparation method thereof according to claim 8, wherein the secondary cold deformation and machining treatment comprises the following specific steps: performing secondary cold forging deformation on the plate blank subjected to the aging treatment, wherein the deformation amount of the cold forging is 10-20%, and preparing a plate; and then milling the surface of the plate to obtain the high-strength high-conductivity chromium-zirconium-copper alloy product.
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|---|---|---|---|---|
| CN105088000A (en) * | 2015-09-02 | 2015-11-25 | 河南科技大学 | High-strength and high-conductivity rare earth copper alloy for contact lines and preparation method thereof |
| CN106086507A (en) * | 2016-06-06 | 2016-11-09 | 中色科技股份有限公司 | A kind of Cu-Cr-Zr alloy for preparing screw-contact and processing technique thereof |
| CN110453106A (en) * | 2019-07-29 | 2019-11-15 | 西安斯瑞先进铜合金科技有限公司 | It is a kind of it is antivacuum under draw the production technology of continuous casting copper-iron alloy slab ingot |
| CN113699400A (en) * | 2021-08-31 | 2021-11-26 | 山西春雷铜材有限责任公司 | Preparation method of low-cost large-ingot-casting copper-chromium-zirconium alloy plate strip |
| CN114318032A (en) * | 2021-11-29 | 2022-04-12 | 陕西斯瑞新材料股份有限公司 | Preparation method of high-strength high-conductivity copper alloy Cu-Cr-Zr-Nb |
-
2022
- 2022-09-26 CN CN202211177263.0A patent/CN115369281A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088000A (en) * | 2015-09-02 | 2015-11-25 | 河南科技大学 | High-strength and high-conductivity rare earth copper alloy for contact lines and preparation method thereof |
| CN106086507A (en) * | 2016-06-06 | 2016-11-09 | 中色科技股份有限公司 | A kind of Cu-Cr-Zr alloy for preparing screw-contact and processing technique thereof |
| CN110453106A (en) * | 2019-07-29 | 2019-11-15 | 西安斯瑞先进铜合金科技有限公司 | It is a kind of it is antivacuum under draw the production technology of continuous casting copper-iron alloy slab ingot |
| CN113699400A (en) * | 2021-08-31 | 2021-11-26 | 山西春雷铜材有限责任公司 | Preparation method of low-cost large-ingot-casting copper-chromium-zirconium alloy plate strip |
| CN114318032A (en) * | 2021-11-29 | 2022-04-12 | 陕西斯瑞新材料股份有限公司 | Preparation method of high-strength high-conductivity copper alloy Cu-Cr-Zr-Nb |
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