Copper alloy and preparation method and application thereof

Abstract

The invention relates to a copper alloy and a preparation method and application thereof. The copper alloy comprises the following components in percentage by mass: 0.2 wt%-1.5 wt% of Cr, 0.05 wt%-0.5 wt% of Zr, 0.01 wt%-0.15 wt% of Mn, 0.01 wt%-0.2 wt% of Li, 0.01 wt%-0.15 wt% of Bi, 0.01 wt%-0.1 wt% of Ca, 0.02 wt%-0.2 wt% of B and the balance of Cu and impurities, and the content of each element also meets the condition that (f + 1.5 e + 3d) / 2-(a + b + 0.5 c + g) 2 / 10 is less than or equal to 0.20. The copper alloy not only has high heat-conducting property, but also has high strength and high temperature resistance, can meet the multi-dimensional comprehensive requirements of the integrated circuit packaging field on comprehensive use performance, cost and the like, and has a wide industrial application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of alloys, and in particular to a copper alloy and a preparation method and application thereof. Background Art

[0002] Among pure metals, copper has the second highest thermal conductivity, which is 398W / (m·K) at room temperature, second only to silver's 428W / (m·K). Based on its excellent electrical and thermal conductivity, pure copper is widely used in integrated circuits, power cables, radiators and other fields. However, pure copper cannot be used in harsh working environments due to its low strength, low hardness, and easy deformation and oxidation when used in high-temperature environments. For example, the preheating plate in the integrated circuit packaging and testing equipment requires good thermal conductivity and must not deform during long-term service in an environment of -55℃ to 175℃, so as to avoid deviations in accuracy and subsequent damage to the chip. Obviously, pure copper cannot meet the use requirements and its high-temperature strength needs to be improved.

[0003] By using the alloying principle, adding alloying elements to pure copper can improve the strength of copper alloys, that is, solid solution strengthening. However, the solid solution formed by the added elements and copper causes lattice distortion of the copper matrix, resulting in a decrease in thermal conductivity. The more elements are added, the greater the damage to thermal conductivity. At present, there are many types and grades of commercial copper alloys. Commonly used ones include brass, nickel silver, and bronze. Compared with pure copper, although they have improved mechanical properties, corrosion resistance, and processing performance, the addition of a large amount of alloying elements, such as zinc, nickel, tin, silicon, aluminum, iron and other elements, leads to too low copper content and a significant decrease in thermal conductivity. Other high-strength and high-conductivity copper alloys are prone to deformation in high-temperature environments due to insufficient thermal strength, and cannot be used in scenarios with high dimensional accuracy requirements such as integrated circuit packaging and testing equipment.

[0004] Therefore, there is an urgent need to develop a copper alloy material that can withstand high temperatures, has high thermal conductivity and high strength, and at the same time is relatively low in cost and easy to industrialize and apply. Summary of the invention

[0005] Based on this, it is necessary to provide a copper alloy and its preparation method and application to address the above-mentioned problems; the copper alloy not only has high thermal conductivity, but also has high strength and high temperature resistance, and can meet the comprehensive requirements of the integrated circuit packaging field for comprehensive performance, cost and other dimensions, and has broad prospects for industrial application.

[0006] A copper alloy comprises the following components: Cr is a%=0.2wt%-1.5wt%, Zr is b%=0.05wt%-0.5wt%, Mn is c%=0.01wt%-0.15wt%, Li is d%=0.01wt%-0.2wt%, Bi is e%=0.01wt%-0.15wt%, Ca is f%=0.01wt%-0.1wt%, B is g%=0.02wt%-0.2wt%, and the balance is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0007] In one embodiment, the copper alloy comprises the following components: Cr is a%=0.3wt%-1.2wt%, Zr is b%=0.05wt%-0.3wt%, Mn is c%=0.03wt%-0.15wt%, Li is d%=0.03wt%-0.18wt%, Bi is e%=0.03wt%-0.12wt%, Ca is f%=0.01wt%-0.07wt%, B is g%=0.04wt%-0.15wt%, and the balance is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0008] In one embodiment, the copper alloy comprises the following components: Cr is a%=0.5wt%-1.0wt%, Zr is b%=0.1wt%-0.3wt%, Mn is c%=0.05wt%-0.12wt%, Li is d%=0.05wt%-0.15wt%, Bi is e%=0.05wt%-0.10wt%, Ca is f%=0.01wt%-0.05wt%, B is g%=0.06wt%-0.12wt%, and the balance is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0009] In one embodiment, the impurities include less than 0.02 wt % Cd, less than 0.03 wt % Fe, and less than 0.05 wt % Pb.

[0010] A method for preparing the copper alloy as described above comprises the following steps:

[0011] S1, weighing Cu ingot, Cu-Cr master alloy, Cu-Zr master alloy, Cu-Mn master alloy, Cu-Li master alloy, Cu-Bi master alloy, Cu-Ca master alloy, and Cu-B master alloy according to element ratio;

[0012] S2, performing a first smelting of the Cu ingot, the Cu-Cr master alloy and the Cu-Zr master alloy to obtain a first alloy melt, and then adding the Cu-Mn master alloy, the Cu-Li master alloy, the Cu-Bi master alloy, the Cu-Ca master alloy and the Cu-B master alloy to perform a second smelting to obtain a second alloy melt;

[0013] S3, after adding a modifier to the second alloy melt, performing a third smelting to obtain a third alloy melt, casting the third alloy melt to obtain an alloy ingot, and subjecting the alloy ingot to a solution treatment and an aging treatment to obtain the copper alloy.

[0014] In one embodiment, step S1 satisfies at least one of the following conditions:

[0015] (1) The purity of the Cu ingot is ≥99.90%;

[0016] (2) The content of Cr in the Cu-Cr master alloy is 5wt%-15wt%;

[0017] (3) The content of Zr element in the Cu-Zr master alloy is 40wt%-50wt%;

[0018] (4) The content of Mn element in the Cu-Mn master alloy is 25wt%-35wt%;

[0019] (5) The content of Li element in the Cu-Li master alloy is 2wt%-10wt%;

[0020] (6) The content of Bi element in the Cu-Bi master alloy is 25wt%-35wt%;

[0021] (7) The content of Ca element in the Cu-Ca master alloy is 15wt%-25wt%;

[0022] (8) The content of B element in the Cu-B master alloy is 2wt%-10wt%.

[0023] In one embodiment, step S2 satisfies at least one of the following conditions:

[0024] (1) The first smelting further includes adding a refining agent, wherein the amount of the refining agent is 0.2%-0.5% of the total mass of the raw materials in the preparation method;

[0025] (2) The temperature of the first smelting is 1150° C.-1200° C.;

[0026] (3) The temperature of the second smelting is 1100°C-1150°C.

[0027] In one embodiment, step S3 satisfies at least one of the following conditions:

[0028] (1) The modifier is selected from at least one of a titanium-boron modifier and an aluminum-titanium-boron modifier;

[0029] (2) The amount of the modifier used is 0.01%-0.03% of the total mass of the raw materials in the preparation method;

[0030] (3) The third smelting includes: first heating to 1150° C.-1180° C., spraying fire, stirring and keeping warm for 2 min-3 min, then keeping warm at 1100° C.-1150° C. for 10 min-20 min, and finally heating to 1150° C.-1200° C. to obtain a third alloy melt;

[0031] (4) The solution treatment comprises: keeping the temperature at 920° C. to 960° C. for 1.5 h to 2 h, and then quenching after the temperature is maintained at 920° C. to 960° C.;

[0032] (5) The aging treatment includes: keeping the temperature at 440°C-480°C for 3h-4h.

[0033] An alloy device, wherein the material of the alloy device is selected from the copper alloy mentioned above.

[0034] An integrated circuit packaging and testing device comprises the alloy device as described above.

[0035] The copper alloy described in the present invention has trace amounts of specific elements and satisfies specific element content relationships, which is not only beneficial for grain refinement, deoxidation and dehydrogenation, thereby improving strength and electrical and thermal conductivity, but also beneficial for improving thermal strength. At the same time, Ca, Li and Bi are reacted to generate a dispersed high-melting point compound phase to improve hot hardness, so that the copper alloy has both good thermal conductivity and heat resistance, as well as excellent room temperature strength and high temperature strength, thereby making the thermal conductivity of the copper alloy described in the present invention as high as 320W / (m·K) or more, the room temperature yield strength as high as 530MPa or more, the room temperature tensile strength as high as 640MPa or more, the yield strength at a high temperature of 200°C as high as 480MPa or more, and the tensile strength at a high temperature of 200°C as high as 600MPa or more.

[0036] In addition, the copper alloy described in the present invention does not contain precious elements such as Ag and rare earths, and the raw material and production costs are relatively low. It can meet the comprehensive requirements of parts for integrated circuit packaging and testing equipment in terms of thermal conductivity, high temperature resistance, cost, market acceptance, etc., and has broad prospects for industrial application. DETAILED DESCRIPTION

[0037] For ease of understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific implementation methods or embodiments, and are not intended to limit the present invention. The optional scope of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of related listed items, and the combinations include any two related listed items, any more related listed items, or all related listed items.

[0039] The applicant has found through long-term research that in addition to solid solution strengthening, crystal defects such as precipitation phase, grain boundary, dislocation, etc. formed by strengthening methods such as dispersion precipitation strengthening, fine grain strengthening and work hardening can reduce the electrical conductivity and thermal conductivity by affecting the resistance increment. Specifically, the resistance increments of vacancies and solid solution atoms with an atomic fraction of 1% are 1.6μΩ·cm and 2.5μΩ·cm, respectively, and 1cm 2 / cm 3 The grain boundary and 1cm / cm 3 The resistance increment of the dislocations is 31.2×10 -7 μΩ·cm and 1.0×10 -7 μΩ·cm, from which it can be seen that the order of magnitude of the resistance increment of grain boundaries and dislocations is only 1 / 10 of that of vacancies and solid solution atoms. 7 Moreover, during full aging, the precipitation phase has little effect on the conductivity of the copper alloy. When the tensile strength of the copper alloy increases by 1 MPa, only 0.03-0.08% IACS conductivity is lost.

[0040] Based on this, the present invention provides a copper alloy, comprising the following components: Cr is a%=0.2wt%-1.5wt%, Zr is b%=0.05wt%-0.5wt%, Mn is c%=0.01wt%-0.15wt%, Li is d%=0.01wt%-0.2wt%, Bi is e%=0.01wt%-0.15wt%, Ca is f%=0.01wt%-0.1wt%, B is g%=0.02wt%-0.2wt%, and the balance is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0041] Among them, Cr and Zr form precipitation phases in Cu, which have a dispersed precipitation strengthening effect on copper alloys; Cr, Zr, Mn, and B have the effect of refining grains, which is beneficial to improving strength and plasticity; the melting points of Cr, Zr, and Mn are all higher than Cu, which is beneficial to increasing the recrystallization temperature of copper alloys, thereby improving heat resistance, and Zr can also improve creep resistance, which is beneficial to improving high-temperature performance; Li, B, and Mn have the effect of deoxidation and dehydrogenation, which can effectively prevent oxygen inclusion and hydrogen absorption in copper liquid due to high temperature during smelting, and Mn can also remove iron impurities in the raw materials of copper ingots, reduce the damage of impurities and inclusions to thermal conductivity and mechanical properties, and thereby improve service life; Bi has a low solubility in Cu and exists almost in the form of particles in copper alloys, which can not only improve cutting performance, but also react with Cu2O to form a hard phase, which is beneficial to further deoxidation; Ca and Li can react with Bi to form a dispersed high-melting point compound phase, which is beneficial to improving heat resistance and high-temperature strength.

[0042] The copper alloy described in the present invention has trace amounts of specific elements and satisfies specific element content relationships, so that the copper alloy has both good thermal conductivity and heat resistance, as well as excellent room temperature strength and high temperature strength, thereby making the thermal conductivity of the copper alloy described in the present invention as high as 320W / (m·K) or more, the room temperature yield strength as high as 530MPa or more, the room temperature tensile strength as high as 640MPa or more, the yield strength under high temperature conditions of 200°C as high as 480MPa or more, and the tensile strength under high temperature conditions of 200°C as high as 600MPa or more.

[0043] In addition, the copper alloy described in the present invention does not contain precious elements such as Ag and rare earths, and the raw material and production costs are relatively low. It can meet the comprehensive requirements of alloy products in various technical fields for thermal conductivity, high temperature resistance, cost, market acceptance and other multiple dimensions, and has broad prospects for industrial application.

[0044] It is understandable that |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20 means (f+1.5e+3d) / 2 and (a+b+0.5c+g) 2 The absolute value of the / 10 difference is less than or equal to 0.20.

[0045] In one embodiment, Cr is a% = 0.2wt%-1.5wt%, including but not limited to any point value among 0.2wt%, 0.25wt%, 0.3wt%, 0.5wt%, 0.67wt%, 0.93wt%, 1.0wt%, 1.15wt%, 1.2wt%, 1.25wt%, 1.4wt%, 1.5wt% or any range value between two thereof.

[0046] In one embodiment, Zr is b% = 0.05wt%-0.5wt%, including but not limited to any point value among 0.05wt%, 0.1wt%, 0.12wt%, 0.25wt%, 0.3wt%, 0.36wt%, 0.43wt%, 0.48wt%, 0.5wt% or any range value between two thereof.

[0047] In one embodiment, Mn is c% = 0.01wt%-0.15wt%, including but not limited to any point value among 0.01wt%, 0.02wt%, 0.03wt%, 0.05wt%, 0.06wt%, 0.10wt%, 0.12wt%, 0.14wt%, 0.15wt% or any range value between two thereof.

[0048] In one embodiment, Li is d% = 0.01wt%-0.2wt%, including but not limited to any point value among 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.11wt%, 0.14wt%, 0.15wt%, 0.18wt%, 0.2wt% or any range value between two thereof.

[0049] In one embodiment, Bi is e% = 0.01wt%-0.15wt%, including but not limited to any point value among 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.09wt%, 0.10wt%, 0.12wt%, 0.14wt%, 0.15wt% or any range value between two thereof.

[0050] In one embodiment, Ca is f% = 0.01wt%-0.1wt%, including but not limited to any point value among 0.01wt%, 0.02wt%, 0.03wt%, 0.05wt%, 0.07wt%, 0.09wt%, 0.1wt% or any range value between two thereof.

[0051] In one embodiment, B is g% = 0.02wt%-0.2wt%, including but not limited to any point value among 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.10wt%, 0.12wt%, 0.15wt%, 0.17wt%, 0.18wt%, 0.2wt% or any range value between two thereof.

[0052] Preferably, the copper alloy comprises the following components: a%=0.3wt%-1.2wt% of Cr, b%=0.05wt%-0.3wt% of Zr, c%=0.03wt%-0.15wt% of Mn, d%=0.03wt%-0.18wt% of Li, e%=0.03wt%-0.12wt% of Bi, f%=0.01wt%-0.07wt% of Ca, g%=0.04wt%-0.15wt% of B, and the remainder is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0053] Further preferably, the copper alloy comprises the following components: a%=0.5wt%-1.0wt% of Cr, b%=0.1wt%-0.3wt% of Zr, c%=0.05wt%-0.12wt% of Mn, d%=0.05wt%-0.15wt% of Li, e%=0.05wt%-0.10wt% of Bi, f%=0.01wt%-0.05wt% of Ca, g%=0.06wt%-0.12wt% of B, and the remainder is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0054] In one embodiment, the copper alloy comprises the following components: 1.25wt% Cr, 0.43wt% Zr, 0.02wt% Mn, 0.02wt% Li, 0.14wt% Bi, 0.09wt% Ca, 0.17wt% B, the balance being Cu and unavoidable impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0055] In one embodiment, the copper alloy comprises the following components: 0.67wt% Cr, 0.25wt% Zr, 0.12wt% Mn, 0.14wt% Li, 0.04wt% Bi, 0.05wt% Ca, 0.05wt% B, the balance being Cu and unavoidable impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0056] In one embodiment, the copper alloy comprises the following components: 0.93wt% Cr, 0.12wt% Zr, 0.10wt% Mn, 0.11wt% Li, 0.09wt% Bi, 0.03wt% Ca, 0.10wt% B, the balance being Cu and unavoidable impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0057] In one embodiment, the copper alloy comprises the following components: 0.25wt% Cr, 0.10wt% Zr, 0.06wt% Mn, 0.05wt% Li, 0.03wt% Bi, 0.02wt% Ca, 0.02wt% B, the balance being Cu and unavoidable impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0058] In one embodiment, the copper alloy comprises the following components: 1.40wt% Cr, 0.48wt% Zr, 0.14wt% Mn, 0.18wt% Li, 0.12wt% Bi, 0.09wt% Ca, 0.18wt% B, the balance being Cu and unavoidable impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0059] In one embodiment, the copper alloy comprises the following components: 1.15wt% Cr, 0.36wt% Zr, 0.05wt% Mn, 0.04wt% Li, 0.02wt% Bi, 0.03wt% Ca, 0.03wt% B, the balance being Cu and unavoidable impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0060] In one embodiment, impurities in the copper alloy include less than 0.02 wt % Cd, less than 0.03 wt % Fe, and less than 0.05 wt % Pb.

[0061] The present invention provides a method for preparing the copper alloy as described above, comprising the following steps:

[0062] S1, weighing Cu ingot, Cu-Cr master alloy, Cu-Zr master alloy, Cu-Mn master alloy, Cu-Li master alloy, Cu-Bi master alloy, Cu-Ca master alloy, and Cu-B master alloy according to element ratio;

[0063] S2, performing a first smelting of the Cu ingot, the Cu-Cr master alloy and the Cu-Zr master alloy to obtain a first alloy melt, and then adding the Cu-Mn master alloy, the Cu-Li master alloy, the Cu-Bi master alloy, the Cu-Ca master alloy and the Cu-B master alloy to perform a second smelting to obtain a second alloy melt;

[0064] S3, after adding a modifier to the second alloy melt, performing a third smelting to obtain a third alloy melt, casting the third alloy melt to obtain an alloy ingot, and subjecting the alloy ingot to a solution treatment and an aging treatment to obtain the copper alloy.

[0065] In step S1, it can be understood that the raw materials are weighed according to the element ratio in the required copper alloy product, and the copper alloy product satisfies: Cr is a%=0.2wt%-1.5wt%, Zr is b%=0.05wt%-0.5wt%, Mn is c%=0.01wt%-0.15wt%, Li is d%=0.01wt%-0.2wt%, Bi is e%=0.01wt%-0.15wt%, Ca is f%=0.01wt%-0.1wt%, B is g%=0.02wt%-0.2wt%, and the balance is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20.

[0066] In one embodiment, the purity of the Cu ingot is ≥99.90%.

[0067] In one embodiment, the content of Cr element in the Cu-Cr master alloy is 5wt%-15wt%, including but not limited to any point value among 5wt%, 8wt%, 10wt%, 12wt%, 15wt% or any range value between two thereof.

[0068] In one embodiment, the content of Zr element in the Cu-Zr master alloy is 40wt%-50wt%, including but not limited to any point value among 40wt%, 42wt%, 45wt%, 48wt%, 50wt% or any range value between two thereof.

[0069] In one embodiment, the content of Mn element in the Cu-Mn master alloy is 25wt%-35wt%, including but not limited to any point value among 25wt%, 27wt%, 30wt%, 34wt%, 35wt% or any range value therebetween.

[0070] In one embodiment, the content of Li element in the Cu-Li master alloy is 2wt%-10wt%, including but not limited to any point value among 2wt%, 5wt%, 7wt%, 8wt%, 10wt% or any range value between two thereof.

[0071] In one embodiment, the content of Bi element in the Cu-Bi master alloy is 25wt%-35wt%, including but not limited to any point value among 25wt%, 26wt%, 28wt%, 30wt%, 35wt% or any range value between two thereof.

[0072] In one embodiment, the content of Ca element in the Cu-Ca master alloy is 15wt%-25wt%, including but not limited to any point value among 15wt%, 18wt%, 20wt%, 24wt%, 25wt% or any range value between two thereof.

[0073] In one embodiment, the content of B element in the Cu-B master alloy is 2wt%-10wt%, including but not limited to any point value among 2wt%, 5wt%, 7wt%, 8wt%, 10wt% or any range value between two thereof.

[0074] In step S2, the first smelting further includes adding a refining agent, the amount of which is 0.2%-0.5% of the total mass of the raw materials in the preparation method. By adding the refining agent to assist smelting, the generation of scum can be effectively suppressed. It can be understood that the present invention does not limit the specific type of the refining agent, and existing substances or commercial products can be used.

[0075] In one embodiment, the temperature of the first smelting is 1150°C-1200°C, including but not limited to any point value among 1150°C, 1160°C, 1170°C, 1180°C, 1190°C, 1200°C or any range value between two thereof.

[0076] Specifically, the Cu ingot, the Cu-Cr master alloy and the Cu-Zr master alloy are placed at the bottom of a smelting device, a refining agent is added and covered with charcoal, the temperature is raised to 1150-1200° C. until all the materials are melted, and the surface scum is filtered off to obtain a first alloy melt.

[0077] In one embodiment, the temperature of the second smelting is 1100°C-1150°C, including but not limited to any point value among 1100°C, 1110°C, 1120°C, 1130°C, 1140°C, 1150°C or any range value between two thereof.

[0078] Preferably, the temperature of the first smelting is 1150°C-1200°C, and the temperature of the second smelting is 1100°C-1150°C, so that the highest temperature during the smelting process of the preparation method of the present invention does not exceed 1200°C.

[0079] In step S3, the preparation method of the present invention homogenizes the composition and structure, eliminates the internal stress, and improves the strength through solution treatment and aging treatment, so that the prepared copper alloy has excellent comprehensive performance.

[0080] Preferably, the modifier is selected from at least one of a titanium-boron modifier and an aluminum-titanium-boron modifier.

[0081] Further preferably, the amount of the modifier is 0.01%-0.03% of the total mass of the raw materials in the preparation method, including but not limited to any point value among 0.01%, 0.02%, 0.03% or any range value between the two.

[0082] In one embodiment, the third smelting includes: first heating to 1150°C-1180°C, spraying fire, stirring and keeping warm for 2min-3min, then keeping warm at 1100°C-1150°C for 10min-20min to homogenize the alloy and float impurities, remove slag and impurities, and finally heating to 1150°C-1200°C to obtain a third alloy melt.

[0083] Preferably, the mold material used in the third alloy melt casting step is beryllium copper. Using a beryllium copper mold with fast heat dissipation to cast the alloy ingot is conducive to rapid cooling of the alloy ingot, which can effectively prevent component segregation, reduce waste generation, and save process costs.

[0084] In one embodiment, the solution treatment comprises: keeping the temperature at 920° C.-960° C. for 1.5 h-2 h, and quenching after the keeping temperature is completed.

[0085] Preferably, the quenching comprises immersing in water within 20 seconds and maintaining the immersion state for at least 2 minutes after boiling stops.

[0086] Preferably, during the quenching process, the water temperature is less than or equal to 55°C.

[0087] In one embodiment, the aging treatment comprises: keeping the temperature at 440° C.-480° C. for 3 h-4 h.

[0088] The present invention provides an alloy device, wherein the material of the alloy device is selected from the copper alloy mentioned above.

[0089] Specifically, the alloy device includes but is not limited to a pre-heating plate, a refrigeration plate, etc., so that the alloy device has performance advantages such as high thermal conductivity, high strength, and high temperature resistance.

[0090] The present invention also provides an integrated circuit packaging and testing equipment, including the alloy device as described above, which meets the comprehensive requirements of the alloy devices in the integrated circuit packaging and testing equipment for thermal conductivity, high temperature resistance, cost, market acceptance and other dimensions, and has broad prospects for industrial application.

[0091] The copper alloy and its preparation method and application will be further described below by the following specific examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. If no specific conditions are specified in the examples, the conventional conditions or the conditions recommended by the manufacturer are followed. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be obtained commercially.

[0092] It should be noted that the sources of materials used in the embodiments and comparative examples of the present application are as follows: Cu ingots were purchased from Ningbo Jintian Copper Industry, model T2 copper bar; Cu-Cr master alloy was purchased from Shanghai Youfeng Alloy, model CuCr10; Cu-Zr master alloy was purchased from Shanghai Youfeng Alloy, model CuZr40; Cu-Mn master alloy was purchased from Shanghai Youfeng Alloy, model CuMn30; Cu-Li master alloy was purchased from Shanghai Youfeng Alloy, model CuLi5; Cu-Bi master alloy was purchased from Shanghai Youfeng Alloy, model CuBi30; Cu-Ca master alloy was purchased from Shanghai Youfeng Alloy, model CuCa20; Cu-B master alloy was purchased from Shanghai Youfeng Alloy, model CuB5; refining agent was purchased from Xuzhou Huazhong Aluminum Industry, model HZ-WNQ; the modifier is aluminum-titanium-boron modifier purchased from Ningbo Jiangbei Dongfan Metal, model DF-1.

[0093] Example 1

[0094] According to the element composition shown in Table 1, Cu ingots, Cu-Cr master alloys, Cu-Zr master alloys, Cu-Mn master alloys, Cu-Li master alloys, Cu-Bi master alloys, Cu-Ca master alloys, and Cu-B master alloys were weighed.

[0095] The Cu ingot and the Cu-Cr master alloy and the Cu-Zr master alloy are placed at the bottom of the induction furnace, and a refining agent of 0.40wt% of the total weight of the raw materials is added and covered with charcoal, and the temperature is raised to 1180°C until all the materials are melted, and the surface scum is filtered off; the temperature is adjusted to 1120°C, and Cu-Mn master alloy, Cu-Li master alloy, Cu-Bi master alloy, Cu-Ca master alloy and Cu-B master alloy are added, and after melting, they are fully stirred to ensure that the alloy liquid has a uniform composition; a total weight of 0 .02wt% of modifier, heat to 1160℃, spray fire, stir and keep warm for 2 minutes; keep it at 1120℃ for 20 minutes to homogenize the alloy and float the impurities, and remove the slag and impurities; heat to 1180℃, take it out of the furnace, and pour it into an alloy ingot in a mold, and cool it to room temperature; put it in a muffle furnace, quickly heat it to 950℃ with the furnace, keep it warm for 2h, take it out of the furnace, and immediately immerse it in water for quenching; put it in a muffle furnace, quickly heat it to 450℃ with the furnace, keep it warm for 4h, take it out of the furnace, and air cool it to room temperature.

[0096] Embodiment 2-6

[0097] According to the element composition shown in Table 1, the copper alloys of Examples 2-6 were prepared using the same preparation method as Example 1.

[0098] Example 7

[0099] The difference between Example 7 and Example 1 is that the Cu ingot and the Cu-Cr master alloy and the Cu-Zr master alloy are placed at the bottom of the induction furnace, a refining agent of 0.30wt% of the total mass of the raw materials is added and covered with charcoal, the temperature is raised to 1160°C until all the materials are melted, and the surface scum is filtered off; the temperature is adjusted to 1110°C, and the Cu-Mn master alloy, the Cu-Li master alloy, the Cu-Bi master alloy, the Cu-Ca master alloy, and the Cu-B master alloy are added, and after melting, they are fully stirred to ensure that the alloy liquid has a uniform composition; and the addition The total mass of the raw materials is 0.03wt% of the modifier, the temperature is raised to 1180℃, flame sprayed, stirred and kept warm for 3 minutes; it is kept at 1100℃ for 15 minutes to homogenize the alloy and float the impurities, and the slag and impurities are removed; the temperature is raised to 1200℃, taken out of the furnace, and cast into an alloy ingot in a mold, and cooled to room temperature; it is placed in a muffle furnace, and the temperature is rapidly raised to 920℃ with the furnace, and kept warm for 1.5h, taken out of the furnace, and immediately immersed in water for quenching; it is placed in a muffle furnace, and the temperature is rapidly raised to 480℃ with the furnace, and kept warm for 3h, taken out of the furnace, and air-cooled to room temperature.

[0100] Comparative Examples 1-8

[0101] According to the element composition shown in Table 1, the copper alloys of Comparative Examples 1-8 were prepared by the same preparation method as Example 1.

[0102] Table 1

[0103]

[0104]

[0105] The copper alloys obtained in Examples 1-7 and Comparative Examples 1-8 were subjected to performance tests, and the test results are shown in Table 1, wherein: the test method for thermal conductivity is in accordance with GB / T3651-2008 "Method for measuring high temperature thermal conductivity of metals"; the test method for room temperature yield strength and room temperature tensile strength is in accordance with GB / T228.1-2021 "Metallic material tensile test Part 1: Room temperature test method"; the test method for 200°C yield strength and 200°C tensile strength is in accordance with GB / T228.2-2015 "Metallic material tensile test Part 2: High temperature test method".

[0106] Table 2

[0107]

[0108] It can be seen from the data in Table 2 that the copper alloys prepared by the component formulas and preparation methods of Examples 1-7 of the present application have a thermal conductivity of ≥320 W / (m·K), and have excellent thermal conductivity; room temperature yield strength ≥530 MPa, room temperature tensile strength ≥640 MPa, 200°C yield strength ≥480 MPa, and 200°C tensile strength ≥600 MPa. They have very high strength at room temperature and high temperature environments, strong resistance to thermal deformation, and can be used at high temperatures. Therefore, all performance properties meet the use requirements of integrated circuit packaging and testing equipment.

[0109] Comparative Example 1 is pure copper, containing only a small amount of impurities, and no alloying elements are added. Although it has a high thermal conductivity, its room temperature and high temperature strength are low and it is easy to deform; Comparative Example 2 adds excessive alloying elements. Although it has a high strength, the thermal conductivity is too low because the Cu content is only 95.12%, which is not conducive to heat dissipation; Comparative Example 3 only adds Cr and Zr, and the strengthening effect is limited, and lacks the effect of deoxidation, dehydrogenation and impurity removal of other elements. There are too many inclusions and defects, so the thermal conductivity and mechanical properties are not ideal; Comparative Example 4 does not add Ca and B i, it is impossible to form a high melting point compound, so the thermal strength and hot hardness are poor; Comparative Example 5 does not add Mn, Li and B, and the effects of deoxidation, dehydrogenation and grain refinement are poor, so the thermal conductivity and mechanical properties need to be improved; Comparative Example 6 only adds a trace amount of Mn, Li, B, Ca and Bi, and the Cu content is 99.38%, which is similar to Comparative Example 1. Although the thermal conductivity is very good, the strength and heat resistance are poor; The content of each added element in Comparative Examples 7 and 8 does not conform to the relationship |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.20, so the overall performance deviation.

[0110] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0111] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A copper alloy, characterized in that: In terms of mass percentage, the following components are included: a% = 0.2wt% -1.5wt% of Cr, b% = 0.05wt% -0.5wt% of Zr, c% = 0.01wt% -0.15wt% of Mn, d% = 0.01wt% -0.2wt% of Li, e% = 0.01wt% -0.15wt% of Bi, f% = 0.01wt% -0.1wt% of Ca, g% = 0.02wt% -0.2wt% of B, and the remainder is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.

20.

2. The copper alloy according to claim 1, characterized in that The copper alloy comprises the following components: a%=0.3wt%-1.2wt% of Cr, b%=0.05wt%-0.3wt% of Zr, c%=0.03wt%-0.15wt% of Mn, d%=0.03wt%-0.18wt% of Li, e%=0.03wt%-0.12wt% of Bi, f%=0.01wt%-0.07wt% of Ca, g%=0.04wt%-0.15wt% of B, and the remainder is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.

20.

3. The copper alloy according to claim 2, characterized in that The copper alloy comprises the following components: a%=0.5wt%-1.0wt% of Cr, b%=0.1wt%-0.3wt% of Zr, c%=0.05wt%-0.12wt% of Mn, d%=0.05wt%-0.15wt% of Li, e%=0.05wt%-0.10wt% of Bi, f%=0.01wt%-0.05wt% of Ca, g%=0.06wt%-0.12wt% of B, and the remainder is Cu and impurities, and the content of each element also satisfies: |(f+1.5e+3d) / 2-(a+b+0.5c+g) 2 / 10|≤0.

20.

4. The copper alloy according to claim 1, characterized in that The impurities include less than 0.02 wt % of Cd, less than 0.03 wt % of Fe, and less than 0.05 wt % of Pb.

5. A method for preparing a copper alloy according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1, weighing Cu ingot, Cu-Cr master alloy, Cu-Zr master alloy, Cu-Mn master alloy, Cu-Li master alloy, Cu-Bi master alloy, Cu-Ca master alloy, and Cu-B master alloy according to element ratio; S2, performing a first smelting of the Cu ingot, the Cu-Cr master alloy and the Cu-Zr master alloy to obtain a first alloy melt, and then adding the Cu-Mn master alloy, the Cu-Li master alloy, the Cu-Bi master alloy, the Cu-Ca master alloy and the Cu-B master alloy to perform a second smelting to obtain a second alloy melt; S3, after adding a modifier to the second alloy melt, performing a third smelting to obtain a third alloy melt, casting the third alloy melt to obtain an alloy ingot, and subjecting the alloy ingot to a solution treatment and an aging treatment to obtain the copper alloy.

6. The method for preparing the copper alloy according to claim 5, characterized in that: Step S1 satisfies at least one of the following conditions: (1) The purity of the Cu ingot is ≥99.90%; (2) The content of Cr in the Cu-Cr master alloy is 5wt%-15wt%; (3) The content of Zr element in the Cu-Zr master alloy is 40wt%-50wt%; (4) The content of Mn element in the Cu-Mn master alloy is 25wt%-35wt%; (5) The content of Li element in the Cu-Li master alloy is 2wt%-10wt%; (6) The content of Bi element in the Cu-Bi master alloy is 25wt%-35wt%; (7) The content of Ca element in the Cu-Ca master alloy is 15wt%-25wt%; (8) The content of B element in the Cu-B master alloy is 2wt%-10wt%.

7. The method for preparing the copper alloy according to claim 5, characterized in that: Step S2 satisfies at least one of the following conditions: (1) The first smelting further includes adding a refining agent, wherein the amount of the refining agent is 0.2%-0.5% of the total mass of the raw materials in the preparation method; (2) The temperature of the first smelting is 1150° C.-1200° C.; (3) The temperature of the second smelting is 1100°C-1150°C.

8. The method for preparing the copper alloy according to claim 5, characterized in that: Step S3 satisfies at least one of the following conditions: (1) The modifier is selected from at least one of a titanium-boron modifier and an aluminum-titanium-boron modifier; (2) The amount of the modifier used is 0.01%-0.03% of the total mass of the raw materials in the preparation method; (3) The third smelting includes: first heating to 1150° C.-1180° C., spraying fire, stirring and keeping warm for 2 min-3 min, then keeping warm at 1100° C.-1150° C. for 10 min-20 min, and finally heating to 1150° C.-1200° C. to obtain a third alloy melt; (4) The solution treatment comprises: keeping the temperature at 920° C. to 960° C. for 1.5 h to 2 h, and then quenching after the temperature is maintained at 920° C. to 960° C.; (5) The aging treatment includes: keeping the temperature at 440°C-480°C for 3h-4h.

9. An alloy device, characterized in that: The material of the alloy device is selected from the copper alloy as described in any one of claims 1-4.

10. An integrated circuit packaging and testing device, characterized in that: A device comprising the alloy as claimed in claim 9.

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