CN114032414A - Modified copper-chromium alloy and preparation method and application thereof - Google Patents
Modified copper-chromium alloy and preparation method and application thereof Download PDFInfo
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- CN114032414A CN114032414A CN202111363659.XA CN202111363659A CN114032414A CN 114032414 A CN114032414 A CN 114032414A CN 202111363659 A CN202111363659 A CN 202111363659A CN 114032414 A CN114032414 A CN 114032414A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Abstract
The invention relates to a modified copper-chromium alloy and a preparation method and application thereof, wherein the modified copper-chromium alloy comprises the following raw materials in percentage by mass: 0.6 to 1.0 percent of chromium, 0.03 to 0.1 percent of rare earth metal and the balance of copper and impurities; the rare earth metals comprise light rare earth metals and heavy rare earth metals, the light rare earth metals comprise two types of lanthanum and cerium, and the heavy rare earth metals comprise three types of gadolinium, yttrium and erbium. The copper-chromium alloy material contains specific types of light rare earth metals and specific types of heavy rare earth metals, copper and chromium are added according to specific proportions, the light rare earth metals and the heavy rare earth metals, the copper and the chromium are in synergistic action, the mass percentage of the rare earth metals in the modified copper-chromium alloy is controlled, and the tensile strength of the copper-chromium alloy is effectively improved on the basis of keeping good conductivity.
Description
Technical Field
The invention relates to the technical field of copper alloy preparation, in particular to a modified copper-chromium alloy and a preparation method and application thereof.
Background
The copper-chromium alloy is a common precipitation strengthening copper alloy, has the characteristics of high strength and excellent conductivity, can be used for preparing products such as lead frames, crystallizers, vacuum valves, guide hoods, high-voltage switch elastic sheets, contact wires and the like, and is widely applied to the fields of electronic components, nuclear industry, aerospace, rail transit and the like. However, with the development of industry, the conventional copper-chromium alloy cannot satisfy the requirements of tensile strength and electric conductivity at the same time, so that the development of a copper-chromium alloy with high tensile strength and excellent electric conductivity is required.
Disclosure of Invention
Based on the modified copper-chromium alloy, the invention provides the modified copper-chromium alloy, and the preparation method and the application thereof.
The technical scheme of the invention for solving the technical problems is as follows.
The modified copper-chromium alloy comprises the following preparation raw materials in percentage by mass:
0.6 to 1.0 percent of chromium, 0.03 to 0.1 percent of rare earth metal and the balance of copper and impurities; the rare earth metals comprise light rare earth metals and heavy rare earth metals, the light rare earth metals comprise two types of lanthanum and cerium, and the heavy rare earth metals comprise three types of gadolinium, yttrium and erbium.
In some embodiments, the mass ratio of the lanthanum to the cerium in the modified copper-chromium alloy is 1 (0.2-5).
In some embodiments, the mass ratio of the lanthanum to the cerium in the modified copper-chromium alloy is 1 (0.5-2).
In some embodiments, the mass ratio of the gadolinium to the yttrium to the erbium in the modified copper-chromium alloy is 1 (0.5-5) to (0.2-5).
In some embodiments, the mass ratio of the gadolinium to the yttrium to the erbium in the modified copper-chromium alloy is 1 (1-2) to (0.5-2).
In some embodiments, the mass ratio of the light rare earth metal to the heavy rare earth metal in the modified copper-chromium alloy is 1 (1-9).
In some embodiments, the mass ratio of the light rare earth metal to the heavy rare earth metal in the modified copper-chromium alloy is 1 (1-3).
In some of these embodiments, the impurities comprise Sn, Pb, Bi, O, H, S, P, Ni, Si, Fe, or Al atoms in the modified copper-chromium alloy; calculated by mass percent, Ni is less than or equal to 0.05 percent, Fe is less than or equal to 0.03 percent, Al is less than or equal to 0.05 percent, S is less than or equal to 0.005 percent, and other impurities are less than or equal to 0.2 percent.
The invention provides a preparation method of a modified copper-chromium alloy, which comprises the following steps:
mixing the preparation raw materials of the modified copper-chromium alloy, and then carrying out fusion casting to obtain an alloy ingot;
and sequentially carrying out hot working treatment and aging treatment on the alloy ingot.
The invention provides application of the modified copper-chromium alloy in preparing a copper-chromium alloy product.
The invention provides a copper-chromium alloy product, which is made of the modified copper-chromium alloy.
Compared with the prior art, the modified copper-chromium alloy has the following beneficial effects:
through analysis, the raw materials for traditionally preparing the copper-chromium alloy generally contain impurities Sn, Pb, Bi, O, S, P, Ni, Fe or Al and the like, wherein low-melting-point metal impurities of Sn, Pb, Bi, Al and the like are easy to form intermetallic compounds with lower melting points with matrix copper, so that the high-temperature mechanical property of the copper-chromium alloy is reduced; o, S, H, P, the phenomenon of pinhole defect and hot brittleness of the copper-chromium alloy can be caused by non-metal impurities, and the conductivity and the high-temperature stability of the copper-chromium alloy are reduced; and Fe and Ni are easy to be dissolved in the matrix copper in a solid mode, so that the conductivity of the product is reduced.
The modified copper-chromium alloy is prepared from raw materials including chromium, rare earth metals, copper and impurities in specific percentage, wherein the rare earth metals include light rare earth metals and heavy rare earth metals, the light rare earth metals include two types of lanthanum and cerium, and the heavy rare earth metals include three types of gadolinium, yttrium and erbium; the light rare earth metal and the heavy rare earth metal of specific species are added with copper and chromium according to specific proportion, the light rare earth metal can react with impurity atoms such as O, H, S, P in the preparation raw material to form corresponding compounds, and the corresponding compounds are removed from the melt in the form of slag phase, thereby effectively playing the role of purifying the melt; furthermore, the heavy rare earth metal can form a high-melting-point compound with low-melting-point metal impurities such as Sn, Pb, Bi, Al and the like in the preparation raw materials, so that the thermal stability of the copper-chromium alloy can be effectively improved; form stable chemical substances with impurity elements such as Ni, Fe and the like, and reduce the influence of the stable chemical substances on the conductivity of the copper-chromium alloy; the light rare earth metal and the heavy rare earth metal have synergistic effect with copper and chromium, and the mass percentage of the rare earth metal in the modified copper-chromium alloy is controlled, so that the tensile strength of the copper-chromium alloy is effectively improved on the basis of keeping better conductive performance.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. It is to be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The invention provides a modified copper-chromium alloy, which comprises the following raw materials in percentage by mass:
0.6 to 1.0 percent of chromium, 0.03 to 0.1 percent of rare earth metal and the balance of copper and impurities; the rare earth metals comprise light rare earth metals and heavy rare earth metals, the light rare earth metals comprise two types of lanthanum and cerium, and the heavy rare earth metals comprise three types of gadolinium, yttrium and erbium.
The modified copper-chromium alloy is prepared from raw materials including chromium, rare earth metals, copper and impurities in specific percentage, wherein the rare earth metals include light rare earth metals and heavy rare earth metals, the light rare earth metals include two types of lanthanum and cerium, and the heavy rare earth metals include three types of gadolinium, yttrium and erbium; the light rare earth metal and the heavy rare earth metal of specific species are added with copper and chromium according to specific proportion, the light rare earth metal can react with impurity atoms such as O, H, S, P in the preparation raw material to form corresponding compounds, and the corresponding compounds are removed from the melt in the form of slag phase, thereby effectively playing the role of purifying the melt; furthermore, the heavy rare earth metal can form a high-melting-point compound with low-melting-point metal impurities such as Sn, Pb, Bi, Al and the like in the preparation raw materials, so that the thermal stability of the copper-chromium alloy can be effectively improved; form stable chemical substances with impurity elements such as Ni, Fe and the like, and reduce the influence of the stable chemical substances on the conductivity of the copper-chromium alloy; the light rare earth metal and the heavy rare earth metal have synergistic effect with copper and chromium, and the mass percentage of the rare earth metal in the modified copper-chromium alloy is controlled, so that the tensile strength of the copper-chromium alloy is effectively improved on the basis of keeping better conductive performance.
In some examples, the modified copper-chromium alloy is prepared from the following raw materials in percentage by mass:
0.8 to 1.0 percent of chromium, 0.06 to 0.1 percent of rare earth metal and the balance of copper and impurities;
in some examples, the modified copper-chromium alloy is prepared from the following raw materials in percentage by mass:
0.8 percent of chromium, 0.1 percent of rare earth metal and the balance of copper and impurities.
In some examples, the mass ratio of lanthanum to cerium in the modified copper-chromium alloy is 1 (0.2-5). It is understood that the mass ratio of lanthanum to cerium may be 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.8, 1:1, 1:0.2, 1:1.2, 1:4.5, 1:2, 1:3, 1:4, 1:5, etc.
In some specific examples, the mass ratio of lanthanum to cerium in the modified copper-chromium alloy is 1 (0.5-2).
In some preferred examples, the modified copper-chromium alloy has a lanthanum to cerium mass ratio of 1: 0.5.
In some examples, the mass ratio of gadolinium to yttrium to erbium in the modified copper-chromium alloy is 1 (0.5-5) to (0.2-5).
In some specific examples, the mass ratio of gadolinium to yttrium to erbium in the modified copper-chromium alloy is 1 (1-2) to (0.5-2).
In some preferred examples, the modified copper-chromium alloy comprises gadolinium, yttrium and erbium in a mass ratio of 1:1: 0.5.
In some examples, the modified copper-chromium alloy has a mass ratio of light rare earth metal to heavy rare earth metal of 1 (1-9). It is understood that the mass ratio of the light rare earth metal to the heavy rare earth metal may be 1:1, 1:1.1, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:2.8, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1: 9.
In some specific examples, the modified copper-chromium alloy has a mass ratio of light rare earth metal to heavy rare earth metal of 1 (1-5); optionally, the mass ratio of the light rare earth metal to the heavy rare earth metal is 1 (1-3).
In some preferred examples, the modified copper-chromium alloy has a weight ratio of light rare earth metal to heavy rare earth metal of 1: 3.
On the basis of specific components, the modified copper-chromium alloy further controls the mass ratio of lanthanum to cerium, the mass ratio of gadolinium to yttrium to erbium, and the mass ratio of light rare earth metal to heavy rare earth metal, and is favorable for further improving the tensile strength of the copper-chromium alloy.
In some of these examples, the control requirements for impurities in the raw materials of the preparation of the modified copper-chromium alloy are: less than or equal to 0.05 percent of Ni, less than or equal to 0.03 percent of Fe, less than or equal to 0.05 percent of Al, less than or equal to 0.005 percent of S and less than or equal to 0.2 percent of other impurities. The embodiment of the invention provides a preparation method of a modified copper-chromium alloy, which comprises the steps of S10-S60.
Step S10: and mixing the preparation raw materials of the modified copper-chromium alloy, and then casting to obtain an alloy ingot.
In some of these examples, in step S10, the chromium is added in the form of an alloy of chromium and copper, i.e., a copper-chromium master alloy.
In some examples, the rare earth metal is added as an alloy with copper in step S10. It can be understood that lanthanum, cerium, gadolinium, yttrium and erbium can be respectively smelted with copper to obtain copper lanthanum, copper cerium, copper gadolinium, copper yttrium and copper erbium intermediate alloy, and lanthanum, cerium, gadolinium, yttrium and erbium can be mixed first and then smelted with copper to obtain copper rare earth intermediate alloy.
In some specific examples, in step S10, the copper and lanthanum and cerium are mixed and melted, and the copper and gadolinium, yttrium and erbium are mixed and melted, so as to obtain the copper-rare earth intermediate alloy respectively.
In some examples, in step S10, the fusion casting step includes:
and smelting the mixture of the raw materials, and then casting to obtain an alloy ingot.
In some examples, in step S10, the melting temperature is 1400 ℃ to 1450 ℃, and the time is 5min to 15 min; optionally, the smelting temperature is 1410-1430 ℃ and the time is 10-15 min.
In some specific examples, in step S10, the temperature of smelting is 1420 ℃ and the time is 10 min.
In some examples, in step S10, the copper and the chromium are mixed and melted, and then the rare earth metal is added for melting. It is understood that in some specific examples, in step S10, the copper and copper-chromium master alloy is melted at the melting temperature, and then the rare earth master alloy is added for melting.
In some preferred examples, in step S10, the Cu-Cr master alloy is first incubated at 1420 deg.C for 5min, and then the RE master alloy is added and incubated for 5 min.
In some examples, the alloy ingot obtained in step S10 has a diameter of 100mm to 300 mm.
Step S20: and (4) carrying out hot working treatment on the alloy ingot obtained in the step (S10) to obtain an alloy bar.
In some examples, in step S20, the hot working process is: preserving the heat of the alloy ingot obtained in the step S10 at 850-980 ℃ for 30-120 min, and then carrying out hot extrusion to obtain an alloy bar; optionally, the alloy ingot is kept at 900-980 ℃ for 50-80 min.
In some specific examples, in step S20, the hot working process is: and (3) preserving the heat of the alloy cast ingot at 950 ℃ for 60min, and then carrying out hot extrusion.
In some examples, the hot extrusion temperature is 850 ℃ to 980 ℃ in step S20; optionally, the temperature of the hot extrusion is 850 ℃ to 950 ℃.
In some specific examples, the temperature of the hot extrusion is 950 ℃ in step S20.
Step S30: and carrying out solution treatment on the alloy bar subjected to the hot working treatment.
In some examples, in step S30, the solution treatment is: preserving the heat of the alloy bar after the hot processing treatment at 920-1040 ℃ for 60-240 min, and cooling; optionally, the alloy bar subjected to the hot working treatment is kept at 950-1000 ℃ for 90-180 min.
In some specific examples, in step S30, the solution treatment is: and (3) preserving the heat of the alloy bar subjected to the hot processing treatment for 120min at 980 ℃, and cooling.
In some examples, in step S30, the cooling manner is fan cooling or water cooling.
It is understood that step S30 may be omitted.
Step S40: and (4) performing cold working treatment on the alloy bar subjected to the solution treatment in the step S30.
It is understood that when step S30 is not performed, the alloy bar after hot working is cooled and then cold worked.
In some examples, in step S40, the cold working process is: and drawing the alloy bar subjected to the solution treatment.
It is understood that step S40 may be omitted.
Step S50: and (4) carrying out aging treatment on the alloy bar.
In some examples, in step S50, the temperature of the aging treatment is 430 ℃ to 500 ℃, and the aging time is 0.5h to 4 h; optionally, the temperature of the aging treatment is 440-470 ℃, and the aging time is 1-3 h.
In some specific examples, in step S50, the temperature of the aging treatment is 450 ℃, and the aging time is 2 h.
The aging treatment is carried out under specific conditions, which is beneficial to the dispersion and precipitation of chromium and balances the strength and the conductivity of the copper-chromium alloy.
The copper-chromium alloy is prepared from the specific components under the specific process, namely parameters, so that the tensile strength of the copper-chromium alloy is further improved on the basis of keeping better conductive performance. The preparation method of the modified copper-chromium alloy has the advantages of simple process and high production efficiency, and can realize batch production.
An embodiment of the invention provides application of the modified copper-chromium alloy in preparation of a copper-chromium alloy product.
Another embodiment of the present invention provides a copper-chromium alloy product, wherein the material of the product comprises the modified copper-chromium alloy.
The modified copper-chromium alloy is used for copper-chromium alloy products, and can endow the copper-chromium alloy products with higher conductivity and tensile strength.
In some embodiments, the copper-chromium alloy article includes, but is not limited to, a lead frame, a mold, a vacuum valve, a dome, a high voltage switch dome, and a contact wire.
In some embodiments, the material of the copper-chromium alloy product may be the modified copper-chromium alloy, that is, the modified copper-chromium alloy product is directly prepared from the modified copper-chromium alloy. In other embodiments, the copper-chromium alloy article may comprise other materials in addition to the modified copper-chromium alloy described above.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The modified copper-chromium alloy and the preparation method and application thereof according to the present invention are exemplified below, and it is understood that the modified copper-chromium alloy and the preparation method and application thereof according to the present invention are not limited to the following examples.
Example 1
S1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (the mass ratio of lanthanum to cerium is 1: 1) and a component B (the mass ratio of gadolinium to yttrium to erbium is 1:1: 1) in a mass ratio of component A to component B to 1:1, mixing to obtain mixed rare earth metal, and smelting to obtain a copper rare earth intermediate alloy with the rare earth metal content of 9-11%; copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
S2: casting
Charging the copper and copper-chromium intermediate alloy into a furnace, heating to 1420 ℃, preserving heat for 5min, adding the copper-rare earth intermediate alloy, preserving heat for 5min, and casting into a circular cast ingot with the diameter of 150 mm.
S3: hot working treatment
And (3) keeping the temperature of the round cast ingot obtained in the step (S2) at 950 ℃ for 60min, and extruding the round cast ingot into an alloy cast rod with the diameter of 30 mm.
S4: solution treatment
And (3) preserving the heat of the round cast ingot subjected to the hot processing treatment of S3 for 120min at 980 ℃, and quickly putting into water for cooling.
S5: cold working treatment
And drawing the alloy cast rod with the diameter of 30mm into an alloy rod with the diameter of 20mm in multiple passes.
S6: aging treatment
And (3) preserving the heat of the alloy bar subjected to the cold working treatment of S5 for 120min at 450 ℃.
Example 2
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (the mass ratio of lanthanum to cerium is 1: 2) and a component B (the mass ratio of gadolinium to yttrium to erbium is 1: 2: 2) in a mass ratio of component A to component B to be 1:2 mixing to obtain mixed rare earth metal, and smelting to obtain a copper rare earth intermediate alloy with the rare earth metal content of 9-11%; as well as copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
Example 3
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (the mass ratio of lanthanum to cerium is 2: 1) and a component B (the mass ratio of gadolinium to yttrium to erbium is 2: 2: 1) in a mass ratio of component A to component B of 1:3 mixing to obtain mixed rare earth metal, and smelting to obtain a copper rare earth intermediate alloy with the rare earth metal content of 9-11%; as well as copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
Example 4
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (the mass ratio of lanthanum to cerium is 1: 5) and a component B (the mass ratio of gadolinium to yttrium to erbium is 1: 0.5: 0.2) according to the mass ratio of the component A to the component B of 1:9 mixing to obtain mixed rare earth metal, and smelting to obtain copper rare earth intermediate alloy with the rare earth metal content of 9-11%; as well as copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
Example 5
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (the mass ratio of lanthanum to cerium is 1: 0.2) and a component B (the mass ratio of gadolinium to yttrium to erbium is 1: 5: 5) in a mass ratio of component A to component B of 1:9 mixing to obtain mixed rare earth metal, and smelting to obtain copper rare earth intermediate alloy with the rare earth metal content of 9-11%; as well as copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
Example 6
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (the mass ratio of lanthanum to cerium is 1: 1) and a component B (the mass ratio of gadolinium to yttrium to erbium is 1:1: 1) in a mass ratio of component A to component B to 1:1, mixing to obtain mixed rare earth metal, and smelting to obtain a copper rare earth intermediate alloy with the rare earth metal content of 9-11%; copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.9 percent of chromium, 0.08 percent of copper rare earth intermediate alloy, and the balance of copper and impurities.
Example 7
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (the mass ratio of lanthanum to cerium is 1: 1) and a component B (the mass ratio of gadolinium to yttrium to erbium is 1:1: 1) in a mass ratio of component A to component B to 1:1, mixing to obtain mixed rare earth metal, and smelting to obtain a copper rare earth intermediate alloy with the rare earth metal content of 9-11%; copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 1.0 percent of chromium, 0.06 percent of copper rare earth intermediate alloy, and the balance of copper and impurities.
Comparative example 1
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; smelting the component A (the mass ratio of lanthanum to cerium is 1: 1) to obtain a copper-rare earth intermediate alloy with the rare earth metal content of 9-11%; as well as copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
Comparative example 2
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; smelting the component B (the mass ratio of gadolinium to yttrium to erbium is 1:1: 1) to obtain a copper-rare earth intermediate alloy with the rare earth metal content of 9-11%; as well as copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
Comparative example 3
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; as well as copper and impurities.
Preparing materials: respectively taking the mass percentages of copper and copper-chromium intermediate alloy as follows: 0.8% of chromium and the balance of copper and impurities.
Comparative example 4
The method is basically the same as example 1, and is different from the method in the following specific points:
s1: preparing raw materials and ingredients
Preparing raw materials: smelting copper and chromium to obtain a copper-chromium intermediate alloy containing 5-10% of chromium; mixing a component A (lanthanum and cerium in a mass ratio of 1: 1) and a component B (yttrium and erbium in a mass ratio of 1: 1) in a mass ratio of component A to component B of 1:1, mixing to obtain mixed rare earth metal, and smelting to obtain a copper rare earth intermediate alloy with the rare earth metal content of 9-11%; copper and impurities.
Preparing materials: respectively taking the mass percentages of copper, copper-chromium intermediate alloy and copper-rare earth intermediate alloy as follows: 0.8% of chromium, 0.1% of copper rare earth intermediate alloy, and the balance of copper and impurities.
The mass ratios or mass percentages between the components of the examples and comparative examples are shown in table 1.
TABLE 1
The main components of the copper-chromium alloys obtained in the examples and comparative examples are shown in Table 2.
TABLE 2
The mechanical property and the conductivity of the improved copper-chromium alloy obtained in each embodiment and each proportion are tested, wherein the mechanical property comprises the tensile strength at room temperature and high temperature; the measurement standards for conductivity and tensile strength are as follows:
conductivity: GB/T351-2019;
room temperature tensile strength: 297 GB-T228.1-2010;
high-temperature tensile strength: GB/T4338-2006;
the test results are shown in table 3.
TABLE 3
As can be seen from Table 3, the tensile strength at room temperature and the tensile strength at high temperature in examples 1 to 7 were higher than those of the comparative examples, and the electrical conductivity was maintained at 80AICS or more; namely, the copper-chromium alloy prepared in each embodiment has good comprehensive performance of tensile strength and conductivity at room temperature and high temperature; the tensile strength of the copper-chromium alloy prepared in the embodiment 3 is greatly improved at room temperature and high temperature, the conductivity is kept at 83.42%, and the comprehensive performance is excellent. Comparative example 1 does not add heavy rare earth metals, and has poor high-temperature mechanical properties; comparative example 2 the conductivity dropped below 80AICS without the addition of light rare earth metals; comparative example 3 does not add any rare earth metal, and the mechanical property and the conductivity are poor; comparative example 4, no specific rare earth metal was used in combination, and the improvement of the high temperature tensile strength was limited.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the patent of the invention is subject to the content of the appended claims, and the description can be used for explaining the content of the claims.
Claims (10)
1. The modified copper-chromium alloy is characterized by comprising the following preparation raw materials in percentage by mass:
0.6 to 1.0 percent of chromium, 0.03 to 0.1 percent of rare earth metal and the balance of copper and impurities; the rare earth metals comprise light rare earth metals and heavy rare earth metals, the light rare earth metals comprise two types of lanthanum and cerium, and the heavy rare earth metals comprise three types of gadolinium, yttrium and erbium.
2. The modified Cu-Cr alloy according to claim 1, wherein the mass ratio of La to Ce is 1 (0.2-5).
3. The modified Cu-Cr alloy according to claim 2, wherein the mass ratio of La to Ce is 1 (0.5-2).
4. The modified Cu-Cr alloy of claim 1, wherein the mass ratio of Gd, Y and Er is 1 (0.5-5) to (0.2-5).
5. The modified Cu-Cr alloy of claim 4, wherein the mass ratio of Gd, Y and Er is 1 (1-2) to (0.5-2).
6. The modified Cu-Cr alloy according to any one of claims 1 to 5, wherein the mass ratio of the light rare earth metal to the heavy rare earth metal is 1 (1) to 9).
7. The modified copper chromium alloy of any one of claims 1 to 5, wherein the impurities comprise atoms of Sn, Pb, Bi, O, H, S, P, Ni, Fe or Al; calculated by mass percent, Ni is less than or equal to 0.05 percent, Fe is less than or equal to 0.03 percent, Al is less than or equal to 0.05 percent, S is less than or equal to 0.005 percent, and other impurities are less than or equal to 0.2 percent.
8. The preparation method of the modified copper-chromium alloy is characterized by comprising the following steps of:
mixing the preparation raw materials of the modified copper-chromium alloy of any one of claims 1 to 7, and then carrying out fusion casting to obtain an alloy ingot;
and sequentially carrying out hot working treatment and aging treatment on the alloy ingot.
9. Use of a modified copper chromium alloy as claimed in any one of claims 1 to 7 in the manufacture of a copper chromium alloy article.
10. A copper-chromium alloy product, characterized in that the material comprises the modified copper-chromium alloy as claimed in any one of claims 1 to 7.
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