CN108004425A - A kind of preparation method of Cu-Cr-Zr-Mg alloys - Google Patents

A kind of preparation method of Cu-Cr-Zr-Mg alloys Download PDF

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CN108004425A
CN108004425A CN201711181549.5A CN201711181549A CN108004425A CN 108004425 A CN108004425 A CN 108004425A CN 201711181549 A CN201711181549 A CN 201711181549A CN 108004425 A CN108004425 A CN 108004425A
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alloys
preparation
alloy
blocks
temperature
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杨晓红
陈昱
邹军涛
肖鹏
梁淑华
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Xian University of Technology
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Xian University of Technology
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

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Abstract

The invention discloses a kind of preparation method of Cu Cr Zr Mg alloys, is specially:Cu blocks, Cu Zr intermediate alloys, Cr and Mg are placed in crucible, in vaccum sensitive stove, under argon gas protection, carry out melting, cooling, obtains Cu Cr Zr Mg alloys;Then Cu Cr Zr Mg alloys be dissolved, aging strengthening model, that is, obtain Cu Cr Zr Mg alloy finished products.The present invention obtains the tiny copper alloy of even tissue, crystal grain by introducing trace element Mg into Cu Cr Zr alloys.The high temperature resistant phase CrCu of disperse is generated after solid solution, aging strengthening model2(ZrMg), with Cr phase cooperative reinforcing Copper substrates, Cu Cr Zr alloy properties are further improved, obtain the good copper alloy of high strength & high electric-conduction, heat endurance.

Description

A kind of preparation method of Cu-Cr-Zr-Mg alloys
Technical field
The invention belongs to copper alloy preparing technical field, is related to a kind of preparation method of Cu-Cr-Zr-Mg alloys.
Background technology
CuCrZr alloys belong to typical ageing strengthening type alloy, have good electrical and thermal conductivity performance and higher-strength Copper alloy, is widely used in circuit lead frame material, electric railway contact line, contact material, continuous cast mold etc. Field.With the fast development of modern electric power industry, the requirement of higher is proposed to the performance of CuCrZr alloys.It is and traditional CuCrZr alloys cannot meet requirement, it is necessary to the copper alloy of mining inetesity higher.Compound augmentation is to prepare at present The main method of copper alloy with high strength and high conductivity, it is desirable to by add the 4th constituent element, under conditions of conductivity is not significantly reduced, Further improve the intensity and heat endurance of CuCrZr alloys.
The addition of Mg can generate a kind of intermetallic compound CrCu with Zr2(ZrMg), multiphase precipitation is played after solid solution aging Strengthen the effect of Copper substrate, so as to lift the hardness and heat endurance of alloy in the case of conductivity loss less.
The content of the invention
The object of the present invention is to provide a kind of preparation method of Cu-Cr-Zr-Mg alloys, to ensure copper alloy conductivity On the basis of obtain with high intensity, the copper alloy of heat endurance.
The technical solution adopted in the present invention is a kind of preparation method of Cu-Cr-Zr-Mg alloys, specifically according to the following steps Implement:
Step 1, Cu-Zr intermediate alloys are prepared;
Step 2, Cu-Cr-Zr-Mg alloys are prepared:
Cu blocks, Cu-Zr intermediate alloys, Cr and Mg are placed sequentially in crucible from the bottom to top, in vaccum sensitive stove It is interior, under argon gas protection, melting is carried out, cooling, obtains Cu-Cr-Zr-Mg alloys;
Step 3, Cu-Cr-Zr-Mg alloys are heat-treated:
The Cu-Cr-Zr-Mg alloys obtained to step 2 are dissolved, aging strengthening model, that is, obtain Cu-Cr-Zr-Mg alloys Finished product.
The features of the present invention also resides in,
The mass percentage of Zr is 20~80% in Cu-Zr intermediate alloys.
Step 1 is specially:The Cu blocks for polishing clean, Zr blocks are sequentially placed into vacuum arc melting furnace from the bottom to top, taken out Vacuum is to 1 × 10-3More than Pa, melting is carried out under argon gas protection, controls electric current to melt repeatedly in 250~350A in fusion process Refining 3~5 times, every time 1.5~2min.
In step 2 fusion process, alloy is heated to 1050~1150 DEG C first, keeps the temperature 3~5min;1350 are warming up to again ~1500 DEG C, keep the temperature 18~30min.
In step 2 fusion process, vacuum degree control is 1 × 10-3More than Pa.
Solid solution temperature is 850~1000 DEG C in step 3, and soaking time is 0.5~2h, then water quenching.
Aging temperature is 400~560 DEG C, and soaking time is 3~5h.
In obtained Cu-Cr-Zr-Mg alloys, according to mass percent:Cr contents are that 0.5%~1.2%, Zr contents are 0.1~0.8%, Mg content are 0.03~0.5%, surplus Cu.
The invention has the advantages that the present invention obtains tissue by introducing trace element Mg into Cu-Cr-Zr alloys Uniformly, the tiny copper alloy of crystal grain.The high temperature resistant phase CrCu of disperse is generated after solid solution, aging strengthening model2(ZrMg), with Cr Phase cooperative reinforcing Copper substrate, further improves Cu-Cr-Zr alloy properties, and it is good to obtain high strength & high electric-conduction, heat endurance Copper alloy.
Brief description of the drawings
Fig. 1 is the process flow chart of preparation method of the present invention;
Fig. 2 is the as cast condition SEM photograph of Cu-Cr-Zr alloys;
Fig. 3 is the as cast condition SEM photograph of Cu-Cr-Zr-Mg alloys prepared by the present invention;
Fig. 4 is the performance comparison figure for the Cu-Cr-Zr-Mg alloy aging states that Cu-Cr-Zr alloys are prepared with the present invention.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The present invention provides a kind of preparation method of Cu-Cr-Zr-Mg alloys, its flow is as shown in Figure 1, specifically by following Step is implemented:
Step 1, the preparation of Cu-Zr intermediate alloys
The Cu blocks for polishing clean, Zr blocks are sequentially placed into vacuum arc melting furnace from the bottom to top, first it is evacuated down to 1 × 10-3More than Pa, then leads to argon gas as gas is protected, electric current should be controlled in 250~350A, melt back 3~5 in fusion process Secondary, 1.5~2min, obtains Cu- (20~80) %Zr intermediate alloys every time.
Step 2, the preparation of Cu-Cr-Zr-Mg alloys
Cu blocks, Cu-Zr intermediate alloys, Cr and Mg are placed sequentially in appropriate crucible from the bottom to top, by vacuum Induction furnace is evacuated down to 1 × 10-3More than Pa, is filled with a small amount of argon gas, starts melting.Alloy is heated to 1050~1150 first DEG C, keep the temperature 3~5min;1350~1500 DEG C are warming up to again, keep the temperature 18~30min;Last furnace cooling.
Step 3, the heat treatment of Cu-Cr-Zr-Mg alloys
The Cu-Cr-Zr-Mg alloys obtained in step 2 are put into heat-treatment furnace be dissolved, aging strengthening model.Solid solution Treatment temperature is 850~1000 DEG C, and soaking time is 0.5~2h, water quenching;Aging temp is 400~560 DEG C, soaking time 3 ~5h.It is machined, obtain Cu-Cr-Zr-Mg alloy products.
Cr contents are that 0.5%~1.2%, Zr contents are 0.1~0.8%, Mg contents in obtained Cu-Cr-Zr-Mg alloys For 0.03~0.5%, surplus Cu.Mg elements are introduced into Cu-Cr-Zr alloys by the present invention, can significantly improve CuCrZr conjunctions The performance of gold.The addition of alloying element Mg produces superposition effect with Zr, plays the role of precipitation strength, generates and changes between a kind of metal Compound CrCu2(ZrMg), multiphase precipitation strength Copper substrate is played the role of after solid solution aging, so that little in conductivity loss In the case of lifted alloy hardness and heat endurance.
Embodiment 1
The Cu blocks for polishing clean, Zr are sequentially placed into vacuum arc melting furnace from the bottom to top, first it is evacuated down to 1 × 10-3More than, then lead to argon gas as protection gas, electric current should be controlled in fusion process in 250A, melt back 5 times, each 2min, Obtain Cu-20%Zr intermediate alloys.The alloy that target component is Cu-1.0Cr-0.15Zr-0.06Mg is prepared, is weighed calculating Cu-20%Zr intermediate alloys, Cr, Mg and Cu blocks be placed in graphite crucible, be evacuated down to 1 × 10-3More than Pa, is filled with A small amount of Ar gas, starts melting.Alloy is heated to 1100 DEG C first, keeps the temperature 3min, then is warming up to 1350 DEG C, keeps the temperature 25min, with Furnace cooling is but.Cu-Cr-Zr-Mg alloys are put into heat-treatment furnace be dissolved, aging strengthening model.Solid solution temperature is 860 DEG C, keep the temperature 1h, water quenching;Aging temp is 400 DEG C, machined when insulation 4 is small, obtains Cu-Cr-Zr-Mg alloy products.
Embodiment 2
The Cu blocks for polishing clean, Zr are sequentially placed into vacuum arc melting furnace from the bottom to top, first it is evacuated down to 1 × 10-3More than, then lead to argon gas as protection gas, electric current should be controlled in fusion process in 300A, melt back 4 times, every time 1.5min, obtains Cu-40%Zr intermediate alloys.The alloy that target component is Cu-0.8Cr-0.20Zr-0.08Mg is prepared, will be counted Calculate load weighted Cu-40%Zr intermediate alloys, Cr, Mg and Cu blocks be placed in graphite crucible, be evacuated down to 1 × 10-3Pa More than, a small amount of Ar gas is filled with, starts melting.Alloy is heated to 1130 DEG C first, keeps the temperature 3min, then is warming up to 1380 DEG C, is protected Warm 26min, furnace cooling.Cu-Cr-Zr-Mg alloys are put into heat-treatment furnace be dissolved, aging strengthening model.Solution treatment Temperature is 900 DEG C, keeps the temperature 2h, water quenching;Aging temp is 450 DEG C, machined when insulation 3 is small, obtains Cu-Cr-Zr-Mg Alloy product.
Embodiment 3
The Cu blocks for polishing clean, Zr are sequentially placed into vacuum arc melting furnace from the bottom to top, first it is evacuated down to 1 × 10-3More than, then lead to argon gas as protection gas, electric current should be controlled in fusion process in 350A, melt back 3 times, each 2min, Obtain Cu-50%Zr intermediate alloys.The alloy that target component is Cu-0.9Cr-0.25Zr-0.12Mg is prepared, is weighed calculating Cu-50%Zr intermediate alloys, Cr, Mg and Cu blocks be placed in graphite crucible, be evacuated down to 1 × 10-3More than Pa, is filled with A small amount of Ar gas, starts melting.Alloy is heated to 1080 DEG C first, keeps the temperature 4min, then is warming up to 1450 DEG C, keeps the temperature 30min, with Furnace cooling is but.Cu-Cr-Zr-Mg alloys are put into heat-treatment furnace be dissolved, aging strengthening model.Solid solution temperature is 980 DEG C, keep the temperature 1.5h, water quenching;Aging temp is 560 DEG C, machined when insulation 3.5 is small, obtains Cu-Cr-Zr-Mg alloy systems Product.
Embodiment 4
The Cu blocks for polishing clean, Zr are sequentially placed into vacuum arc melting furnace from the bottom to top, first it is evacuated down to 1 × 10-3More than, then lead to argon gas as protection gas, should control electric current 270A again in fusion process, melt back 4 times, each 2min, Obtain Cu-80%Zr intermediate alloys.The alloy that target component is Cu-1.2Cr-0.18Zr-0.03Mg is prepared, is weighed calculating Cu-80%Zr intermediate alloys, Cr, Mg and Cu blocks be placed in graphite crucible, be evacuated down to 1 × 10-3More than Pa, is filled with A small amount of Ar gas, starts melting.Alloy is heated to 1050 DEG C first, keeps the temperature 5min, then is warming up to 1400 DEG C, keeps the temperature 20min, with Furnace cooling is but.Cu-Cr-Zr-Mg alloys are put into heat-treatment furnace be dissolved, aging strengthening model.Solid solution temperature is 850 DEG C, keep the temperature 2h, water quenching;Aging temp is 500 DEG C, machined when insulation 4.5 is small, obtains Cu-Cr-Zr-Mg alloy systems Product.
Embodiment 5
The Cu blocks for polishing clean, Zr are sequentially placed into vacuum arc melting furnace from the bottom to top, first it is evacuated down to 1 × 10-3More than, then lead to argon gas as protection gas, electric current should be controlled in fusion process in 320A, melt back 3 times, every time 1.5min, obtains Cu-60%Zr intermediate alloys.The alloy that target component is Cu-0.8Cr-0.3Zr-0.18Mg is prepared, will be calculated Load weighted Cu-60%Zr intermediate alloys, Cr, Mg and Cu blocks are placed in corundum crucible, are evacuated down to 1 × 10-3Pa with On, a small amount of Ar gas is filled with, starts melting.Alloy is heated to 1150 DEG C first, keeps the temperature 5min, then is warming up to 1500 DEG C, is kept the temperature 18min, furnace cooling.Cu-Cr-Zr-Mg alloys are put into heat-treatment furnace be dissolved, aging strengthening model.Solution treatment temperature Spend for 1000 DEG C, keep the temperature 1h, water quenching;Aging temp is 480 DEG C, machined when insulation 3 is small, obtains Cu-Cr-Zr-Mg conjunctions Golden product.
Fig. 2 and 3 is respectively the as cast condition SEM photograph for the Cu-Cr-Zr-Mg alloys that Cu-Cr-Zr alloys are prepared with the present invention.According to Wei Fu Zr areas in brilliant white region in piece, the as cast condition stereoscan photograph of contrast Cu-Cr-Zr alloys can be seen that, add alloying element After Mg, point bar-shaped distribution of the Cu-Cr-Zr-Mg alloys Fu Zr areas by lamellar distribution shifts for interruption, significantly refines Alloy structure, alleviates the segregation of alloying element, and alloy structure is more uniform.
Fig. 4 is Cu-Cr-Zr alloys and the performance comparison figure of the Cu-Cr-Zr-Mg alloy aging states of the invention prepared.Can be with Find out, the addition of alloying element Mg influences the conductivity of alloy hardness that is little, but significantly lifting alloy, is closed to improving copper The intensity and high temperature softening resistance of gold have certain realistic meaning.

Claims (8)

1. a kind of preparation method of Cu-Cr-Zr-Mg alloys, it is characterised in that specifically implement according to the following steps:
Step 1, Cu-Zr intermediate alloys are prepared;
Step 2, Cu-Cr-Zr-Mg alloys are prepared:
Cu blocks, Cu-Zr intermediate alloys, Cr and Mg are placed sequentially in crucible from the bottom to top, in vaccum sensitive stove, argon Under gas shielded, melting is carried out, cooling, obtains Cu-Cr-Zr-Mg alloys;
Step 3, Cu-Cr-Zr-Mg alloys are heat-treated:
The Cu-Cr-Zr-Mg alloys obtained to step 2 are dissolved, aging strengthening model, that is, obtain Cu-Cr-Zr-Mg alloys into Product.
2. the preparation method of a kind of Cu-Cr-Zr-Mg alloys according to claim 1, it is characterised in that in the Cu-Zr Between in alloy the mass percentage of Zr be 20~80%.
A kind of 3. preparation method of Cu-Cr-Zr-Mg alloys according to claim 1 or 2, it is characterised in that the step 1 is specially:The Cu blocks for polishing clean, Zr blocks are sequentially placed into vacuum arc melting furnace from the bottom to top, are evacuated down to 1 × 10- 3More than Pa, melting is carried out under argon gas protection, and electric current is controlled in fusion process in 250~350A, melt back 3~5 times, often Secondary 1.5~2min.
4. the preparation method of a kind of Cu-Cr-Zr-Mg alloys according to claim 1, it is characterised in that the step 2 is molten During refining, alloy is heated to 1050~1150 DEG C first, keeps the temperature 3~5min;1350~1500 DEG C are warming up to again, insulation 18 ~30min.
5. the preparation method of a kind of Cu-Cr-Zr-Mg alloys according to claim 1, it is characterised in that the step 2 is molten During refining, vacuum degree control is 1 × 10-3More than Pa.
6. the preparation method of a kind of Cu-Cr-Zr-Mg alloys according to claim 1, it is characterised in that in the step 3 Solid solution temperature is 850~1000 DEG C, and soaking time is 0.5~2h, then water quenching.
7. the preparation method of a kind of Cu-Cr-Zr-Mg alloys according to claim 1, it is characterised in that at the timeliness It is 400~560 DEG C to manage temperature, and soaking time is 3~5h.
A kind of 8. preparation method of Cu-Cr-Zr-Mg alloys according to claim 1, it is characterised in that obtained Cu- In Cr-Zr-Mg alloys, according to mass percent:Cr contents are that 0.5%~1.2%, Zr contents are 0.1~0.8%, Mg contents For 0.03~0.5%, surplus Cu.
CN201711181549.5A 2017-11-23 2017-11-23 A kind of preparation method of Cu-Cr-Zr-Mg alloys Pending CN108004425A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109266883A (en) * 2018-09-17 2019-01-25 西安理工大学 A kind of preparation method of Cu-Cr-Zr-Mg alloy bar material
CN109913691A (en) * 2019-04-22 2019-06-21 南通科誉德摩尔新材料有限公司 A kind of manufacture craft of high-strength compound chromium-zirconium-copper material
CN111593225A (en) * 2020-06-15 2020-08-28 西安斯瑞先进铜合金科技有限公司 Preparation method for improving strength of chromium-zirconium-copper bar
CN111992726A (en) * 2020-07-24 2020-11-27 江苏威拉里新材料科技有限公司 Smelting process of vacuum gas atomization CuCrZr powder for additive manufacturing
CN114309910A (en) * 2021-12-31 2022-04-12 浙江工业大学 Electron beam welding process and postweld heat treatment method for copper-chromium-zirconium alloy
CN115283774A (en) * 2022-07-29 2022-11-04 中国电子科技集团公司第五十五研究所 Treatment process of Cu-Cr-Zr alloy lead for packaging shell

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103540788A (en) * 2013-10-14 2014-01-29 北京科技大学 Cr nano-structure crystal grain copper preparation method
CN104195360A (en) * 2014-08-26 2014-12-10 华南理工大学 Mg or Mg alloy grain refinement method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103540788A (en) * 2013-10-14 2014-01-29 北京科技大学 Cr nano-structure crystal grain copper preparation method
CN104195360A (en) * 2014-08-26 2014-12-10 华南理工大学 Mg or Mg alloy grain refinement method

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109266883A (en) * 2018-09-17 2019-01-25 西安理工大学 A kind of preparation method of Cu-Cr-Zr-Mg alloy bar material
CN109913691A (en) * 2019-04-22 2019-06-21 南通科誉德摩尔新材料有限公司 A kind of manufacture craft of high-strength compound chromium-zirconium-copper material
CN111593225A (en) * 2020-06-15 2020-08-28 西安斯瑞先进铜合金科技有限公司 Preparation method for improving strength of chromium-zirconium-copper bar
CN111992726A (en) * 2020-07-24 2020-11-27 江苏威拉里新材料科技有限公司 Smelting process of vacuum gas atomization CuCrZr powder for additive manufacturing
CN114309910A (en) * 2021-12-31 2022-04-12 浙江工业大学 Electron beam welding process and postweld heat treatment method for copper-chromium-zirconium alloy
CN115283774A (en) * 2022-07-29 2022-11-04 中国电子科技集团公司第五十五研究所 Treatment process of Cu-Cr-Zr alloy lead for packaging shell
CN115283774B (en) * 2022-07-29 2023-11-24 中国电子科技集团公司第五十五研究所 Treatment process of Cu-Cr-Zr alloy lead wire for packaging shell

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