阅读说明：本技术 一种非晶制带冷却铜辊用高硬度铜镍硅铬合金及其制备方法 (High-hardness copper-nickel-silicon-chromium alloy for amorphous strip cooling copper roller and preparation method thereof ) 是由 甘章华 刘意 吴传栋 王佳敏 吴浩 于 2021-09-10 设计创作，主要内容包括：本发明提供了一种非晶制带冷却铜辊用高硬度铜镍硅铬合金及其制备方法,涉及铜合金材料技术领域。本发明提供的非晶制带冷却铜辊用高硬度铜镍硅铬合金,以质量百分比计,包括以下化学成分：Cu 98.8～99.4％,Ni 0.4～0.8％,Si 0.1～0.2％,Cr 0.1～0.2％；所述非晶制带冷却铜辊用高硬度铜镍硅铬合金的制备方法包括：将固溶处理后的合金依次进行调幅时效处理和深冷处理,得到所述非晶制带冷却铜辊用高硬度铜镍硅铬合金；所述调幅时效处理包括依次进行调幅分解和时效处理。本发明提供的非晶制带冷却铜辊用高硬度铜镍硅铬合金的硬度达到HB≥180,同时导电率≥76IACS％。(The invention provides a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller and a preparation method thereof, and relates to the technical field of copper alloy materials. The invention provides a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller, which comprises the following chemical components in percentage by mass: 98.8-99.4% of Cu, 0.4-0.8% of Ni, 0.1-0.2% of Si and 0.1-0.2% of Cr; the preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller comprises the following steps: carrying out amplitude modulation aging treatment and deep cooling treatment on the alloy subjected to the solution treatment in sequence to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out. The hardness of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller provided by the invention reaches HB (British hardness) more than or equal to 180, and the electric conductivity is more than or equal to 76 IACS.)

1. A high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller comprises the following chemical components in percentage by mass: 98.8-99.4% of Cu, 0.4-0.8% of Ni, 0.1-0.2% of Si and 0.1-0.2% of Cr;

the preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller comprises the following steps:

carrying out amplitude modulation aging treatment and deep cooling treatment on the alloy subjected to the solution treatment in sequence to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out.

2. The high-hardness copper-nickel-silicon-chromium alloy for amorphous strip-cooling copper rollers as claimed in claim 1, wherein the hardness of the high-hardness copper-nickel-silicon-chromium alloy for amorphous strip-cooling copper rollers is not less than 180HB, and the conductivity is not less than 76 IACS%.

3. The high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller as claimed in claim 1, wherein the temperature of spinodal decomposition is 320-360 ℃, and the time of spinodal decomposition is 30-50 min; the temperature of the aging treatment is 450-460 ℃, and the heat preservation time of the aging treatment is 90-180 min.

4. The high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-cooling copper roller as claimed in claim 1 or 3, wherein the rate of temperature rise from room temperature to the decomposition temperature of spinodal decomposition is 10 to 12 ℃/min; and the temperature rising rate from the temperature of amplitude modulation decomposition to the temperature of aging treatment is 10-12 ℃/min.

5. The method for preparing the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller as claimed in any one of claims 1 to 4, comprising the following steps:

carrying out amplitude modulation aging treatment and deep cooling treatment on the alloy subjected to the solution treatment in sequence to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out.

6. The method of manufacturing according to claim 5, wherein the method of manufacturing the solution-treated alloy includes: the alloy raw material is sequentially subjected to casting, hot forging, cold forging and solution treatment to obtain the alloy after solution treatment.

7. The method according to claim 5 or 6, wherein the temperature of the solution treatment is 900 to 950 ℃, the holding time of the solution treatment is 90 to 150min, and the atmosphere of the solution treatment is an argon atmosphere or a nitrogen atmosphere.

8. The method of claim 6, further comprising, after the solution treatment: and (3) placing the obtained solid solution alloy into ice water for cooling.

9. The preparation method according to claim 5 or 6, wherein the temperature of the cryogenic treatment is less than or equal to-196 ℃, and the time of the cryogenic treatment is 2-5 hours.

10. The preparation method according to claim 6, wherein the temperature of the hot forging is 900-1000 ℃, the time of the hot forging is 30-60 min, the total forging ratio of the hot forging is not less than 5, and the heating protective atmosphere of the hot forging is argon atmosphere or nitrogen atmosphere.

Technical Field

The invention relates to the technical field of copper alloy materials, in particular to a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller and a preparation method thereof.

Background

The main industrial production process of the existing amorphous thin belt is single-roller melt spinning, and the principle of the single-roller melt spinning is that metal liquid flows onto a cooling copper roller through a nozzle, the cooling copper roller rotates at a high speed, high-pressure cooling water is introduced into the cooling copper roller, and the metal liquid is spun out while the cooling copper roller rotates at a high speed to form the amorphous thin belt with the thickness of 18-35 microns. This single roll melt spinning process can achieve cooling rates of up to 100 kilo-hertz per second.

The chilled copper rolls play a critical role in the performance of the amorphous ribbon. Firstly, in order to realize rapid solidification, the copper roller is required to have high thermal conductivity, and heat can be rapidly transferred from the surface of the copper roller to high-pressure water in the copper roller and is taken away by water. Therefore, it is generally required to prepare the cooling copper roller from a copper alloy having a high copper content. Secondly, the hardness of the cooling copper roll will affect the lamination factor of the amorphous ribbon. Improving the surface finish of the amorphous ribbon will increase the lamination factor, and in order to improve the finish of the amorphous ribbon, the surface of the copper roll is required to have low surface roughness. At present, when an amorphous thin strip is prepared, in order to obtain the amorphous thin strip with high surface smoothness, a 600-mesh sand paper impeller is generally adopted to polish a copper roller while the amorphous thin strip is spun, if the hardness of the copper roller is not enough, the sand paper impeller is very easy to form deep scratches on the surface of the copper roller, so that the surface roughness of the copper roller is improved, and finally the surface smoothness of the prepared amorphous thin strip is reduced, and the lamination coefficient is reduced. Therefore, the copper roll for an amorphous ribbon is generally required to have higher hardness as well as better thermal conductivity.

Generally, the thermal conductivity of copper alloys is proportional to the electrical conductivity, and since thermal conductivity measurements are relatively cumbersome and electrical conductivity measurements are relatively simple, the industry typically measures the thermal conductivity of copper alloys by measuring electrical conductivity. The standard of the domestic industrial performance indexes of the amorphous strip cooling copper roller at present is as follows: the hardness HB is more than or equal to 120, and the electric conductivity is more than or equal to 76 IACS%.

Pure copper has excellent electric and thermal conductivity, but is soft and has hardness of only about HV40, so that the pure copper cannot be used for preparing amorphous strip cooling rollers.

At present, chromium zirconium copper is mainly used for preparing cooling copper rollers in amorphous industry at home and abroad. Chinese patent ZL201010575117.4 discloses a manufacturing method of a chromium-zirconium-copper cooling roller, the hardness of the cooling roller reaches HB (HB) which is more than or equal to 130, and the electric conductivity (IACS) is more than or equal to 80 percent.

With the rapid development of the amorphous industry, higher requirements are put on the surface smoothness of an amorphous thin strip, and the lamination coefficient is required to be improved from 0.75 to more than 0.84, which requires a cooling copper roller to have higher smoothness. The hardness of the chromium zirconium copper is usually HB 130-140, the hardness value is low, and when a sand paper impeller is used for grinding, scratches are easily left on the surface of a cooling copper roller, so that the surface smoothness is reduced. If the hardness can be improved from about HB130 to about HB180, the surface smoothness of the copper roller can be obviously improved when the sand paper impeller is used for grinding. The addition of alloy elements such as phosphorus and tin to chromium zirconium copper may increase the hardness of chromium zirconium copper to be more than HB180, but the conductivity will drop sharply at this time, and the requirement of the conductivity being more than or equal to 76 IACS% cannot be met.

The copper nickel silicon alloy is a typical high-strength high-conductivity copper alloy. The main strengthening phase in the copper-nickel-silicon alloy is delta-Ni₂Si phase, the silicon element being formed of delta-Ni₂The essential elements of the Si phase, the adverse effect being that the presence of silicon will reduce the electrical and thermal conductivity. When silicon exists as a solid solution element in the copper matrix, the conductivity is lowered. Therefore, it is desirable that the silicon is entirely formed into δ -Ni₂Si precipitates out of phase without being dissolved in the copper matrix. The document 'CuNiSi- (Cr, Zr) alloy deformation aging behavior and performance research' reports that Cu-2% Ni-0.5% Si and Cu-2% Ni-0.5% Si-0.3% Cr alloy, after the traditional solid solution and aging process, the CuNiSi hardness is HV225 and the electric conductivity is 41.3 IACS%; the CuNiSiCr alloy has the hardness of HV225 and the conductivity of 43.3IACS percent. After two-stage aging of 50% low-temperature rolling, 50% low-temperature rolling and 375 ℃ aging for 1h, the CuNiSi hardness is HV189, and the electric conductivity is 61.5 IACS%; the hardness of the CuNiSiCr alloy is HV209, and the conductivity is 54.7 IACS%. Chinese patent ZL201610872819.6 disclosureA copper-nickel-silicon alloy material for lead frame and its preparation method are disclosed, the material comprises the following components: 0.8-1.8% of Ni, 0.15-0.35% of Si, 0.01-0.05% of P, 0.10-0.15% of Mg, 0.05-0.1% of Fe, 0.2-0.4% of Cr, 0.07-0.15% of Zn, and at least one or two of V, Mn and Ti, wherein the total content of the elements is 0.02-0.5%, and the balance is copper; the best combination of the 7 examples of this patent is example 6, hardness is HV180, conductivity 65 IACS%, when the corresponding components are: 1.8% of Ni, 0.18% of Si, 0.04% of P, 0.13% of Mg, 0.05% of Fe, 0.4% of Cr, 0.15% of Zn and 0.5% of Ti.

The existing copper-nickel-silicon alloy is difficult to simultaneously meet the requirements that the HB of an amorphous strip cooling copper roller is more than or equal to 180 and the electric conductivity is more than or equal to 76IACS percent.

Disclosure of Invention

The invention aims to provide a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller and a preparation method thereof, and the hardness of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller reaches HB (HB) not less than 180, and the electric conductivity is not less than 76IACS, so that the high-hardness copper-nickel-silicon-chromium alloy has excellent hardness and thermal conductivity.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller, which comprises the following chemical components in percentage by mass: 98.8-99.4% of Cu, 0.4-0.8% of Ni, 0.1-0.2% of Si and 0.1-0.2% of Cr;

the preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller comprises the following steps:

carrying out amplitude modulation aging treatment and deep cooling treatment on the alloy subjected to the solution treatment in sequence to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out.

Preferably, the hardness of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller is not less than 180HB, and the electric conductivity is not less than 76 IACS%.

Preferably, the temperature of the amplitude modulation decomposition is 320-360 ℃, and the time of the amplitude modulation decomposition is 30-50 min; the temperature of the aging treatment is 450-460 ℃, and the heat preservation time of the aging treatment is 90-180 min.

Preferably, the heating rate of the temperature from room temperature to the temperature of the amplitude modulation decomposition is 10-12 ℃/min; and the temperature rising rate from the temperature of amplitude modulation decomposition to the temperature of aging treatment is 10-12 ℃/min.

The invention provides a preparation method of a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller, which comprises the following steps:

carrying out amplitude modulation aging treatment and deep cooling treatment on the alloy subjected to the solution treatment in sequence to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out.

Preferably, the preparation method of the alloy after solution treatment comprises the following steps: the alloy raw material is sequentially subjected to casting, hot forging, cold forging and solution treatment to obtain the alloy after solution treatment.

Preferably, the temperature of the solution treatment is 900-950 ℃, the heat preservation time of the solution treatment is 90-150 min, and the atmosphere of the solution treatment is argon atmosphere or nitrogen atmosphere.

Preferably, the solution treatment further comprises: and (3) placing the obtained solid solution alloy into ice water for cooling.

Preferably, the temperature of the subzero treatment is less than or equal to-196 ℃, and the time of the subzero treatment is 2-5 h.

Preferably, the temperature of the hot forging is 900-1000 ℃, the time of the hot forging is 30-60 min, the total forging ratio of the hot forging is not less than 5, and the heating protective atmosphere of the hot forging is argon atmosphere or nitrogen atmosphere.

The invention provides a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller, which comprises the following chemical components in percentage by mass: 98.8-99.4% of Cu, 0.4-0.8% of Ni, 0.1-0.2% of Si and 0.1-0.2% of Cr; the preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller comprises the following steps: subjecting the alloy after solution treatment to amplitude modulation in sequencePerforming aging treatment and subzero treatment to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out. The invention adopts amplitude modulation aging treatment to replace aging treatment, locally improves the concentration of silicon through amplitude modulation decomposition, and is beneficial to delta-Ni during subsequent aging treatment₂The precipitation of the Si precipitated phase solves the problem that a supersaturated solid solution cannot be obtained when the silicon content is too low, so that the aging effect can be still realized when the silicon content is low, and the hardness and the heat conductivity of the alloy are improved. The hardness of the high-hardness copper-nickel-silicon-chromium alloy provided by the invention is improved by 38% compared with that of the existing chromium-zirconium-copper alloy for the amorphous belt cooling copper roller, and the electric conductivity is equivalent. The smelting and heat treatment process of the high-hardness copper-nickel-silicon-chromium alloy is relatively simple, stable in performance and suitable for industrial large-scale production.

Drawings

FIG. 1 is a microstructure of the high hardness Cu-Ni-Si-Cr alloy for the amorphous strip-making cooling copper roll prepared in example 1 after etching.

Detailed Description

The invention provides a high-hardness copper-nickel-silicon-chromium alloy for an amorphous strip cooling copper roller, which comprises the following chemical components in percentage by mass: 98.8-99.4% of Cu, 0.4-0.8% of Ni, 0.1-0.2% of Si and 0.1-0.2% of Cr;

the preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller comprises the following steps:

carrying out amplitude modulation aging treatment and deep cooling treatment on the alloy subjected to the solution treatment in sequence to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out.

The high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller preferably comprises the following chemical components in percentage by mass: 99.05-99.3% of Cu, 0.4-0.6% of Ni, 0.1-0.15% of Si and 0.15-0.2% of Cr.

The preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller provided by the invention comprises the following steps:

and sequentially carrying out amplitude modulation aging treatment and cryogenic treatment on the alloy subjected to the solution treatment to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller.

In the present invention, the method for preparing the alloy after the solution treatment preferably includes: the alloy raw material is sequentially subjected to casting, hot forging, cold forging and solution treatment to obtain the alloy after solution treatment.

In the present invention, the alloy raw materials preferably include electrolytic copper, electrolytic nickel, metallic silicon, and metallic chromium; the purity of the electrolytic copper is preferably >99.99 wt%; the purity of the electrolytic nickel is preferably >99.9 wt%; the purity of the metallic silicon is preferably >99.3 wt%; the purity of the metallic chromium is preferably >99.2 wt%. The invention has no special requirements on the specific proportion of the alloy raw materials, and is suitable for obtaining the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller, which meets the chemical component requirements.

In the present invention, the casting preferably includes melting and casting performed in this order; the smelting temperature is preferably 1100-1300 ℃, and more preferably 1200 ℃; the smelting time is preferably 0.5-1 h, and more preferably 1 h. In the present invention, the melting is preferably performed in a medium frequency induction furnace. In the present invention, the order of adding the alloy raw materials at the time of melting is preferably: electrolytic copper, electrolytic nickel, metallic silicon and metallic chromium.

In the present invention, the casting is preferably performed in a graphite mold; the casting temperature is preferably 1200 ℃.

In the invention, the hot forging temperature is preferably 900-1000 ℃, and more preferably 950 ℃; the time for hot forging is preferably 30-60 min, and more preferably 30 min; the total forging ratio of the hot forging is preferably not less than 5, more preferably 6; the heating protective atmosphere for the hot forging is preferably an argon atmosphere or a nitrogen atmosphere. The invention limits the technological parameters of hot forging in the range, can effectively reduce the deformation resistance and improve the plasticity of the alloy.

In the present invention, the forging ratio in the cold forging is preferably not less than 5, more preferably 6. The present invention can obtain a higher hardness of the alloy by limiting the forging ratio of cold forging to the above range.

In the invention, the temperature of the solution treatment is preferably 900-950 ℃, and more preferably 920-950 ℃; the heat preservation time of the solution treatment is preferably 90-150 min, and more preferably 100-130 min. The atmosphere of the solution treatment is argon atmosphere or nitrogen atmosphere. In the present invention, during the solution treatment, a supersaturated solid solution is formed in preparation for the subsequent am aging treatment to achieve high hardness.

In the present invention, it is preferable that the solution treatment further comprises: and (4) placing the obtained solid solution alloy in ice water for cooling to obtain the alloy after the solid solution treatment. The invention can prevent solid solution decomposition and harmful phase precipitation by cooling in ice water.

In the invention, the amplitude modulation aging treatment comprises the steps of amplitude modulation decomposition and aging treatment in sequence. In the invention, the temperature of amplitude modulation decomposition is preferably 320-360 ℃, and more preferably 340 ℃; the time for amplitude modulation decomposition is preferably 30-50 min; the temperature of the aging treatment is preferably 450-460 ℃; the heat preservation time of the aging treatment is preferably 90-180 min, and more preferably 120-150 min. The invention adopts amplitude modulation aging treatment to replace aging treatment, locally improves the concentration of silicon through amplitude modulation decomposition, and is beneficial to delta-Ni during subsequent aging treatment₂The precipitation of the Si precipitated phase solves the problem that a supersaturated solid solution cannot be obtained when the silicon content is too low, so that the aging effect can be still realized when the silicon content is low, and the hardness and the heat conductivity of the alloy are improved.

In the invention, the heating rate of heating from room temperature to the temperature of amplitude modulation decomposition is preferably 10-12 ℃/min; the temperature rise rate from the temperature of amplitude modulation decomposition to the temperature of aging treatment is preferably 10-12 ℃/min. The invention limits the temperature rise rate to reduce the thermal stress and prevent the alloy from cracking.

In the present invention, the temperature of the cryogenic treatment is preferably not more than-196 ℃, more preferably-196 ℃, and the cryogenic treatment is preferably carried out in liquid nitrogen; the time of the cryogenic treatment is preferably 2-5 hours, and more preferably 3-4 hours. In the invention, the cryogenic treatment can reduce the solubility of solute atoms in a matrix so as to improve the conductivity; promote the precipitation of solute atoms in the form of a second phase to increase hardness.

The hardness of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller is preferably not less than 180HB, and more preferably 181-205 HB; the conductivity is preferably 76IACS or more, more preferably 77-79 IACS.

The invention also provides a preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller, which comprises the following steps:

carrying out amplitude modulation aging treatment and deep cooling treatment on the alloy subjected to the solution treatment in sequence to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller; the amplitude modulation aging treatment comprises amplitude modulation decomposition and aging treatment which are sequentially carried out.

In the invention, the preparation method of the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip cooling copper roller is consistent with that described in the foregoing, and details are not repeated here.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

S1, preparing high-hardness copper-nickel-silicon-chromium alloy with the total mass of 1 kg according to the mass fractions of 98.8 percent of Cu, 0.8 percent of Ni, 0.2 percent of Si and 0.2 percent of Cr. The raw materials are electrolytic copper (purity >99.99 wt%), electrolytic nickel (purity >99.9 wt%), metallic silicon (purity >99.3 wt%) and metallic chromium (purity >99.2 wt%).

S2, adopting a medium-frequency induction furnace to smelt, wherein the smelting crucible is a high-purity corundum crucible, the smelting temperature is 1200 ℃, the smelting time is 1 hour, and the raw materials are electrolytic copper, electrolytic nickel, metallic silicon and metallic chromium in sequence.

And S3, casting the alloy in the S2 into a graphite mold after slag removal, wherein the mold is cylindrical and has the size of phi 50 multiplied by 100 mm. And after cooling, pouring the cast ingot out of the graphite mold to obtain the copper-nickel-silicon-chromium alloy cast ingot with the size of phi 50 multiplied by 60 mm.

S4, placing the copper-nickel-silicon-chromium alloy cast ingot in a box type resistance furnace with argon protection, heating to 950 ℃, preserving heat for 30 minutes, forging by adopting impact forging, upsetting to 20mm in height, drawing to 60mm in height, upsetting to 20mm in height, and performing total forging ratio of 6.

And S5, cold forging by adopting impact forging, drawing to 60mm in height, upsetting to 20mm in height, drawing to 60mm in height, and obtaining the cylindrical alloy ingot with the size of phi 49 multiplied by 60mm, wherein the total forging ratio is 6.

S6, placing the cylindrical alloy ingot with the diameter of 49 multiplied by 60mm in the S5 into a box-type resistance furnace with argon protection, heating to 900 ℃, preserving the heat for 150 minutes, taking out, rapidly quenching into ice water, and ensuring that the final cooling temperature is 0 ℃.

S7, drying the alloy in the S6, and then placing the dried alloy in a box-type resistance furnace for amplitude-modulated aging treatment, wherein the heating rate is 10 ℃/min, the temperature is increased to 360 ℃, and the temperature is kept for 30 min; then the temperature is increased to 450 ℃ and the temperature is preserved for 150 min.

And S8, taking the alloy in the S7 out, air-cooling to room temperature, placing the alloy in liquid nitrogen, and carrying out cryogenic treatment at-196 ℃ for 5 hours to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous belt-making cooling copper roller.

Example 2

S1, preparing high-hardness copper-nickel-silicon-chromium alloy with the total mass of 1 kg according to the mass fractions of 99.05 percent of Cu, 0.6 percent of Ni, 0.15 percent of Si and 0.2 percent of Cr. The raw materials are electrolytic copper (purity >99.99 wt%), electrolytic nickel (purity >99.9 wt%), metallic silicon (purity >99.3 wt%) and metallic chromium (purity >99.2 wt%).

S2, adopting a medium-frequency induction furnace to smelt, wherein the smelting crucible is a high-purity corundum crucible, the smelting temperature is 1200 ℃, the smelting time is 1 hour, and the raw materials are electrolytic copper, electrolytic nickel, metallic silicon and metallic chromium in sequence.

And S3, casting the alloy in the S2 into a graphite mold after slag removal, wherein the mold is cylindrical and has the size of phi 50 multiplied by 100 mm. And after cooling, pouring the cast ingot out of the graphite mold to obtain the copper-nickel-silicon-chromium alloy cast ingot with the size of phi 50 multiplied by 60 mm.

S4, placing the copper-nickel-silicon-chromium alloy cast ingot in a box type resistance furnace with argon protection, heating to 950 ℃, preserving heat for 30 minutes, forging by adopting impact forging, upsetting to 20mm in height, drawing to 60mm in height, upsetting to 20mm in height, and performing total forging ratio of 6.

And S5, cold forging by adopting impact forging, drawing to 60mm in height, upsetting to 20mm in height, drawing to 60mm in height, and obtaining the cylindrical alloy ingot with the size of phi 49 multiplied by 60mm, wherein the total forging ratio is 6.

S6, placing the cylindrical alloy ingot with the diameter of 49 multiplied by 60mm in the S5 into a box-type resistance furnace with argon protection, heating to 920 ℃, preserving the heat for 130 minutes, taking out, rapidly quenching into ice water, and ensuring that the final cooling temperature is 0 ℃.

S7, blow-drying the alloy in the S6, and then placing the alloy in a box-type resistance furnace for amplitude-modulated aging treatment, wherein the heating rate is 10 ℃/min, the temperature is increased to 340 ℃, and the temperature is kept for 30 min; then the temperature is increased to 450 ℃ and the temperature is preserved for 150 min.

And S8, taking the alloy in the S7 out, air-cooling to room temperature, placing the alloy in liquid nitrogen, and carrying out cryogenic treatment at-196 ℃ for 5 hours to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous belt-making cooling copper roller.

Example 3

S1, preparing high-hardness copper-nickel-silicon-chromium alloy with the total mass of 1 kg according to the mass fractions of 99.3 percent of Cu, 0.4 percent of Ni, 0.1 percent of Si and 0.2 percent of Cr. The raw materials are electrolytic copper (purity >99.99 wt%), electrolytic nickel (purity >99.9 wt%), metallic silicon (purity >99.3 wt%) and metallic chromium (purity >99.2 wt%).

S2, adopting a medium-frequency induction furnace to smelt, wherein the smelting crucible is a high-purity corundum crucible, the smelting temperature is 1200 ℃, the smelting time is 1 hour, and the raw materials are electrolytic copper, electrolytic nickel, metallic silicon and metallic chromium in sequence.

And S3, casting the alloy in the S2 into a graphite mold after slag removal, wherein the mold is cylindrical and has the size of phi 50 multiplied by 100 mm. And after cooling, pouring the cast ingot out of the graphite mold to obtain the copper-nickel-silicon-chromium alloy cast ingot with the size of phi 50 multiplied by 60 mm.

S4, placing the copper-nickel-silicon-chromium alloy cast ingot in a box type resistance furnace with nitrogen protection, heating to 950 ℃, preserving heat for 30 minutes, forging by adopting impact forging, upsetting to 20mm in height, drawing to 60mm in height, upsetting to 20mm in height, and performing total forging ratio of 6.

And S5, cold forging by adopting impact forging, drawing to 60mm in height, upsetting to 20mm in height, drawing to 60mm in height, and obtaining the cylindrical alloy ingot with the size of phi 49 multiplied by 60mm, wherein the total forging ratio is 6.

S6, placing the cylindrical alloy ingot with the diameter of 49 multiplied by 60mm in the S5 into a box-type resistance furnace with nitrogen protection, heating to 950 ℃, preserving the heat for 90 minutes, taking out, rapidly quenching into ice water, and ensuring that the final cooling temperature is 0 ℃.

S7, blow-drying the alloy in the S6, and then placing the alloy in a box-type resistance furnace for amplitude-modulated aging treatment, wherein the heating rate is 10 ℃/min, the temperature is increased to 320 ℃, and the temperature is kept for 50 min; then the temperature is increased to 450 ℃ and the temperature is preserved for 150 min.

And S8, taking the alloy in the S7 out, air-cooling to room temperature, placing the alloy in liquid nitrogen, and carrying out cryogenic treatment at-196 ℃ for 5 hours to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous belt-making cooling copper roller.

Example 4

S1, preparing high-hardness copper-nickel-silicon-chromium alloy with the total mass of 1 kg according to the mass fractions of 98.9 percent of Cu, 0.8 percent of Ni, 0.2 percent of Si and 0.1 percent of Cr. The raw materials are electrolytic copper (purity >99.99 wt%), electrolytic nickel (purity >99.9 wt%), metallic silicon (purity >99.3 wt%) and metallic chromium (purity >99.2 wt%).

S2, adopting a medium-frequency induction furnace to smelt, wherein the smelting crucible is a high-purity corundum crucible, the smelting temperature is 1200 ℃, the smelting time is 1 hour, and the raw materials are electrolytic copper, electrolytic nickel, metallic silicon and metallic chromium in sequence.

And S3, casting the alloy in the S2 into a graphite mold after slag removal, wherein the mold is cylindrical and has the size of phi 50 multiplied by 100 mm. And after cooling, pouring the cast ingot out of the graphite mold to obtain the copper-nickel-silicon-chromium alloy cast ingot with the size of phi 50 multiplied by 60 mm.

S4, placing the copper-nickel-silicon-chromium alloy cast ingot in a box type resistance furnace with nitrogen protection, heating to 950 ℃, preserving heat for 30 minutes, forging by adopting impact forging, upsetting to 20mm in height, drawing to 60mm in height, upsetting to 20mm in height, and performing total forging ratio of 6.

And S5, cold forging by adopting impact forging, drawing to 60mm in height, upsetting to 20mm in height, drawing to 60mm in height, and obtaining the cylindrical alloy ingot with the size of phi 49 multiplied by 60mm, wherein the total forging ratio is 6.

S6, placing the cylindrical alloy ingot with the diameter of 49 multiplied by 60mm in the S5 into a box-type resistance furnace with nitrogen protection, heating to 900 ℃, preserving heat for 150 minutes, taking out, rapidly quenching into ice water, and ensuring that the final cooling temperature is 0 ℃.

S7, drying the alloy in the S6, and then placing the dried alloy in a box-type resistance furnace for amplitude-modulated aging treatment, wherein the heating rate is 10 ℃/min, the temperature is increased to 360 ℃, and the temperature is kept for 30 min; then the temperature is increased to 450 ℃ and the temperature is kept for 90 min.

And S8, taking the alloy in the S7 out, air-cooling to room temperature, placing the alloy in liquid nitrogen, and carrying out cryogenic treatment at-196 ℃ for 5 hours to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous belt-making cooling copper roller.

Example 5

S1, preparing high-hardness copper-nickel-silicon-chromium alloy with the total mass of 1 kg according to the mass fractions of 99.4 percent of Cu, 0.4 percent of Ni, 0.1 percent of Si and 0.1 percent of Cr. The raw materials are electrolytic copper (purity >99.99 wt%), electrolytic nickel (purity >99.9 wt%), metallic silicon (purity >99.3 wt%) and metallic chromium (purity >99.2 wt%).

S2, adopting a medium-frequency induction furnace to smelt, wherein the smelting crucible is a high-purity corundum crucible, the smelting temperature is 1200 ℃, the smelting time is 1 hour, and the raw materials are electrolytic copper, electrolytic nickel, metallic silicon and metallic chromium in sequence.

And S3, casting the alloy in the S2 into a graphite mold after slag removal, wherein the mold is cylindrical and has the size of phi 50 multiplied by 100 mm. And after cooling, pouring the cast ingot out of the graphite mold to obtain the copper-nickel-silicon-chromium alloy cast ingot with the size of phi 50 multiplied by 60 mm.

S4, placing the copper-nickel-silicon-chromium alloy cast ingot in a box type resistance furnace with nitrogen protection, heating to 950 ℃, preserving heat for 30 minutes, forging by adopting impact forging, upsetting to 20mm in height, drawing to 60mm in height, upsetting to 20mm in height, and performing total forging ratio of 6.

And S5, cold forging by adopting impact forging, drawing to 60mm in height, upsetting to 20mm in height, drawing to 60mm in height, and obtaining the cylindrical alloy ingot with the size of phi 49 multiplied by 60mm, wherein the total forging ratio is 6.

S6, placing the cylindrical alloy ingot with the diameter of 49 multiplied by 60mm in the S5 into a box-type resistance furnace with nitrogen protection, heating to 950 ℃, preserving the heat for 90 minutes, taking out, rapidly quenching into ice water, and ensuring that the final cooling temperature is 0 ℃.

S7, blow-drying the alloy in the S6, and then placing the alloy in a box-type resistance furnace for amplitude-modulated aging treatment, wherein the heating rate is 10 ℃/min, the temperature is increased to 320 ℃, and the temperature is kept for 50 min; then the temperature is increased to 450 ℃ and the temperature is preserved for 120 min.

And S8, taking the alloy in the S7 out, air-cooling to room temperature, placing the alloy in liquid nitrogen, and carrying out cryogenic treatment at-196 ℃ for 5 hours to obtain the high-hardness copper-nickel-silicon-chromium alloy for the amorphous belt-making cooling copper roller.

Comparative example 1

The preparation method of Cu-0.8% Cr-0.2% Zr comprises the following steps:

s1, preparing the copper-chromium-zirconium alloy according to the mass fractions of Cu 99%, Cr 0.8% and Zr 0.2%, wherein the total mass is 1 kg. The raw materials are electrolytic copper (purity >99.99 wt%), metallic chromium (purity >99.2 wt%) and metallic zirconium (purity >99.9 wt%).

S2, smelting by adopting a medium-frequency induction furnace, wherein the smelting crucible is a high-purity corundum crucible, the smelting temperature is 1200 ℃, the smelting time is 1 hour, and the raw materials are electrolytic copper, metal chromium and metal zirconium in sequence.

And S3, casting the alloy in the S2 into a graphite mold after slag removal, wherein the mold is cylindrical and has the size of phi 50 multiplied by 100 mm. And after cooling, pouring the cast ingot out of the graphite mold to obtain the copper-chromium-zirconium alloy cast ingot with the size of phi 50 multiplied by 60 mm.

S4, placing the copper chromium zirconium alloy cast ingot in a box type resistance furnace with argon protection, heating to 1000 ℃, preserving heat for 30 minutes, forging by adopting impact forging, upsetting to 20mm in height, drawing to 60mm in height, upsetting to 20mm in height, and then forging to 6 in total forging ratio.

And S5, cold forging by adopting impact forging, drawing to 60mm in height, upsetting to 20mm in height, drawing to 60mm in height, and obtaining the cylindrical alloy ingot with the size of phi 50 x 60mm, wherein the total forging ratio is 6.

S6, placing the cylindrical alloy ingot with the diameter of 50 x 60mm in the S5 into a box type resistance furnace with argon protection, heating to 980 ℃, preserving the heat for 60 minutes, taking out and quickly quenching into water.

And S7, blow-drying the alloy in the S6, placing the alloy in a box type resistance furnace for aging treatment, heating to 450 ℃ at a heating rate of 10 ℃/min, preserving heat for 240min, and then air-cooling to room temperature.

Comparative example 2

The preparation method of Cu-2.4% Ni-0.6% Si comprises the following steps: smelting and casting, hot rolling, solid solution at 900 ℃ for l.5h, water quenching, aging at 450 ℃ for 8h, and air cooling.

S1, preparing Cu-Ni-Si alloy with the total mass of 1 kg according to the mass fractions of Cu 97.0%, Ni 2.4% and Si 0.6%. The raw materials are electrolytic copper (purity >99.99 wt%), metallic nickel (purity >99.9 wt%) and metallic silicon (purity >99.3 wt%).

And S2, smelting by adopting a medium-frequency induction furnace, wherein the smelting crucible is a high-purity corundum crucible, the smelting temperature is 1200 ℃, the smelting time is 1 hour, and the raw materials are electrolytic copper, metallic nickel and metallic silicon in sequence.

And S3, casting the alloy in the S2 into a graphite mold after slag removal, wherein the mold is cylindrical and has the size of phi 50 multiplied by 100 mm. And after cooling, pouring the cast ingot out of the graphite mold to obtain the copper-nickel-silicon alloy cast ingot with the size of phi 50 multiplied by 60 mm.

S4, placing the copper chromium zirconium alloy cast ingot in a box type resistance furnace with argon protection, heating to 1000 ℃, preserving heat for 30 minutes, forging by adopting impact forging, upsetting to 20mm in height, drawing to 60mm in height, upsetting to 20mm in height, and then forging to 6 in total forging ratio.

And S5, cold forging by adopting impact forging, drawing to 60mm in height, upsetting to 20mm in height, drawing to 60mm in height, and obtaining the cylindrical alloy ingot with the size of phi 50 x 60mm, wherein the total forging ratio is 6.

S6, placing the cylindrical alloy ingot with the diameter of 50 x 60mm in the S5 into a box type resistance furnace with argon protection, heating to 900 ℃, preserving the heat for 90 minutes, taking out and quickly quenching into water.

And S7, blow-drying the alloy in the S6, placing the alloy in a box type resistance furnace for aging treatment, heating to 450 ℃ at a heating rate of 10 ℃/min, preserving heat for 480min, and then air-cooling to room temperature.

Test example

FIG. 1 shows the microstructure of the high hardness CuNiSiCr alloy for amorphous strip-making cooling copper roll prepared in example 1 after etching. The high-hardness copper-nickel-silicon-chromium alloy prepared in the embodiment 1 is prepared into a metallographic sample, and is subjected to immersion corrosion after being polished, wherein the corrosive agent is an aqueous solution containing 3g of ferric chloride, 95mL of ethanol and 2mL of hydrochloric acid, and the corrosion time is 40-60 s.

As can be seen from FIG. 1, the microstructure of the high-hardness Cu-Ni-Si-Cr alloy prepared by the invention is uniform, a large number of white bright spots are distributed on the matrix, and the microstructure is free of pores and inclusions, and is favorable for obtaining high hardness and high conductivity.

The copper alloys prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to performance tests, and the results are shown in table 1:

TABLE 1 Properties of copper alloys prepared in examples 1 to 5 and comparative examples 1 to 2

As can be seen from Table 1, the high-hardness copper-nickel-silicon-chromium alloy for the amorphous strip-making cooling copper roller prepared by the invention has the hardness of HB (British hardness) more than or equal to 180, the electric conductivity more than or equal to 76IACS (International Annealed copper Standard), and the high-hardness copper-nickel-silicon-chromium alloy has excellent hardness and thermal conductivity.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.