CN109355525A - Multiple dimensioned polynary high-strength highly-conductive chrome zirconium copper alloy material of one kind and preparation method thereof - Google Patents
Multiple dimensioned polynary high-strength highly-conductive chrome zirconium copper alloy material of one kind and preparation method thereof Download PDFInfo
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- CN109355525A CN109355525A CN201811309681.4A CN201811309681A CN109355525A CN 109355525 A CN109355525 A CN 109355525A CN 201811309681 A CN201811309681 A CN 201811309681A CN 109355525 A CN109355525 A CN 109355525A
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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
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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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 discloses multiple dimensioned polynary high-strength highly-conductive chrome zirconium copper alloy materials of one kind for belonging to non-ferrous metals processing field and preparation method thereof.The weight percent group of the alloy material become Cr 0.05~0.75%, Zr 0.05~0.2%, remaining be Cu, by ingredient, feed intake, melting and casting, homogenizing annealing processing, hot extrusion, solution treatment, cold drawing, ageing treatment, secondary cold drawing, obtained from online annealing processing.500 DEG C~600 DEG C of 300~700MPa of tensile strength, 150~600MPa of yield strength, elongation 10~30%, 70~95%IACS of conductivity, softening temperature, the alternating bending frequency 1 × 10 of the alloy material5~1 × 108It is secondary, fully meet the demand of the key areas such as accurate cable, electric railway contact wire, resistance welding electrode.
Description
Technical field
The invention belongs to non-ferrous metals processing field, in particular to a kind of multiple dimensioned polynary high-strength highly-conductive chrome zirconium copper alloy
Material and preparation method thereof.
Background technique
It is Cu-Cr-Zr system alloy intensity with higher and good electrical and thermal conductivity and good solderability, anti-oxidant
The excellent comprehensive performances such as property, wearability have been widely used in the lead frame of large scale integrated circuit, Large Electric locomotive
In the fields such as conticaster crystallizer liner and resistance welding electrode in aerial condutor, heat exchange environment, become electronic circuit industry
Structure function material in high-strength highly-conductive electrical domain.
The reinforcing means of high strength and high conductivity Cu-Cr-Zr series copper alloy mainly have solution strengthening, ageing strengthening, refined crystalline strengthening
With working hardening etc..In Cu-Cr-Zr system alloy, the element to be dissolved strengthened copper alloy in the form of atom mainly have Sn, Ag, Ce,
Ni, Al, Zn etc..Wherein Ag and Sn is alloying element selected in this patent, and addition Ag main function is the expansion for hindering Cr atom
The process of dissipating, effectively inhibits precipitation and its agglomeration of Cr phase, delays the overaging of Cu-Cr-Zr alloy, to improve conjunction
The high-temperature stability of gold, increases the intensity of alloy；The effect for adding Sn is that Sn is easy the segregation on crystal boundary and dislocation line, not only
The Precipitation for inhibiting Cr in ag(e)ing process after hot rolling, keeps Cr precipitate tiny, goes back pinning dislocation, hinder the movement of dislocation,
Recovery and recrystallization is postponed.The present invention in Cu-Cr alloy mainly by adding various microelements and improving at processing heat
Reason system, developing one kind has multiple dimensioned polynary high-strength highly-conductive Cu-Cr-Zr system alloy material, meets different field and closes to copper
The use demand of golden material.
Summary of the invention
The purpose of the present invention is to provide a kind of multiple dimensioned polynary high-strength highly-conductive chrome zirconium copper alloy material and its preparation sides
Method, which is characterized in that the weight percent group of the alloy material become Cr 0.05~0.75%, Zr 0.05~0.2%, its
Remaining is Cu；
Having partial size on the horizontal and vertical section of the alloy material is the bean cotyledon shape of the face-centred cubic structure of 2nm~10nm
Cr phase, it is 1 × 10 that density, which is precipitated,21~5 × 1022m-3；
Having partial size on the horizontal and vertical section of the alloy material is More's item of the body-centered cubic structure of 5nm~10nm
Line shape Cr phase, it is 5 × 10 that density, which is precipitated,22~2 × 1023m-3；
Having partial size on the horizontal and vertical section of the alloy material is the structure disk of the face-centered cubic knot of 50nm~100nm
Shape Cu5Zr phase, it is 1 × 10 that density, which is precipitated,17~5 × 1018m-3；
Having partial size on the horizontal and vertical section of the alloy material is the face-centred cubic structure of 20nm~50nm
CuCrZr phase, it is 1 × 10 that density, which is precipitated,17~5 × 1017m-3；
Alloy<100>texture accounts for 15~25% in the alloy material, and alloy<110>texture accounts for 15~25%, and alloy<
111>texture accounts for 25~45%, alloy<112>texture 13~30%.
One or both of tetra- kinds of elements of Ti, Ag, Mg, Sn are included at least in the alloy, wherein Ti, Ag, Mg and Sn
Content be 0.05~0.2%, alloying element total content be 0.1~0.4%.
Alloying element total content is preferably 0.15~0.3% in the alloy.
The tensile strength of the alloy material is 300~700MPa, yield strength is 150~600MPa, elongation 10
~30%, conductivity is 70~95%IACS, softening temperature is 500~600 DEG C, alternating bending frequency is 1 × 105~1 × 108
It is secondary.
The preparation method of the multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material, which is characterized in that including with
Lower step: a. carries out ingredient according to mass percent, feeds intake, melting and casting；B. homogenizing annealing is handled；C. hot extrusion；d.
Solution treatment；E. cold drawing；F. ageing treatment；G. cold drawing；H. online annealing is handled.
Wherein melting described in step a and casting use vacuum medium frequency induction furnace, and smelting temperature is 1230~1280 DEG C, casting
Temperature is 1150~1200 DEG C.
Wherein melting and casting technique described in step a are as follows: cathode copper are added before melting in vaccum sensitive stove, in copper chromium
Between alloy, copper zirconium intermediate alloy add one of pure titanium, fine silver, pure tin and pure magnesium or two after the above material melts
Kind, temperature is risen to 1230~1280 DEG C, after melt is completely melt, uniform stirring, casting temperature is controlled 1150~1200
DEG C, it casts after keeping the temperature 20min.
Wherein homogenizing annealing described in step b processing be to heat alloy cast ingot in stepping batch-type furnace, temperature be 900~
950 DEG C, soaking time is 6~12h.
Wherein the extruding finishing temperature of hot extrusion described in step c is 800~850 DEG C, extrusion ratio 15~30.
Wherein solid solution temperature described in step d is 900~1000 DEG C, and soaking time is 2~6h, and the type of cooling is water
It is cold.
Wherein the working modulus of cold drawing described in step e is 60~80%.
Wherein aging temperature described in step f is 400~500 DEG C, 6~10h of soaking time, and the type of cooling is air-cooled.
Wherein the working modulus of cold drawing described in step g is 30~50%.
Wherein the temperature of the processing of online annealing described in step h is 450~550 DEG C, 10~20cm/s of annealing speed, cooling side
Formula be it is air-cooled, protective gas is pure hydrogen.
The invention has the benefit that
The present invention carries out copper alloy by thermodynamic software, higher temperature solid solution and corresponding timeliness associated processing technology
The regulation of ingredient design and optimization and microstructure obtains a kind of high-strength high conductivity of multiple dimensioned polynary precipitated phase Dispersed precipitate
Chrome zirconium copper alloy material, 300~700MPa of tensile strength of alloy material, 150~600MPa of yield strength, elongation 10~
30%, 70~95%IACS of conductivity, 500 DEG C~600 DEG C of softening temperature, alternating bending frequency 1 × 105~1 × 108It is secondary, completely
Meets the needs of key areas such as accurate cable, electric railway contact wire, resistance welding electrode.
Detailed description of the invention
Fig. 1 is that the TEM of Cu-Cr-Zr-Ag alloy schemes；
Fig. 2 and Fig. 3 is that the HRTEM of Cu-Cr-Zr-Ag alloy schemes.
Specific embodiment
The present invention provides a kind of multiple dimensioned polynary high-strength highly-conductive chrome zirconium copper alloy materials and preparation method thereof, tie below
Closing embodiment, the present invention is described further.
Embodiment 1:
Alloy uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and pure in the present embodiment
Silver, alloying component see the table below the embodiment 1 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and fine silver in vaccum sensitive stove, to
After upper material melts, temperature is risen to 1230 DEG C, after melt is completely melt, the temperature control of uniform stirring, casting exists
It 1150 DEG C, casts after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 900 DEG C, is protected
The warm time is 12h, and ingot casting is then carried out hot extrusion, and at 800 DEG C, extrusion ratio 15 then carries out water cooling for temperature control after extruding.
C. solution treatment: carrying out solution treatment for above-mentioned alloy after extruding, and solid solution temperature is 900 DEG C, when heat preservation
Between be 6h, the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 60%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 400 DEG C,
Soaking time is 10h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 30%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 450 DEG C,
Annealing speed 20cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
It see the table below the embodiment 1 in 2 and table 3 by above step treated its microstructure of alloy and performance.
Embodiment 2:
Alloy uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, fine silver in the present embodiment
With pure titanium, alloying component see the table below the embodiment 2 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, fine silver and pure titanium in vaccum sensitive stove,
After the above material melts, temperature is risen to 1280 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1200 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 950 DEG C, is protected
The warm time is 6h, and ingot casting is then carried out hot extrusion, and at 850 DEG C, extrusion ratio 30 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 1000 DEG C, heat preservation
Time is 2h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 80%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 500 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 50%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 550 DEG C,
Annealing speed 10cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step see the table below the embodiment 2 in 2 and table 3.
Embodiment 3:
Alloy uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure magnesium in the present embodiment
With pure titanium, alloying component is shown in Table 1 embodiment 3.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure magnesium and pure titanium in vaccum sensitive stove,
After the above material melts, temperature is risen to 1260 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1170 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 920 DEG C, is protected
The warm time is 8h, and ingot casting is then carried out hot extrusion, and at 820 DEG C, extrusion ratio 25 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 950 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 70%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 475 DEG C,
Soaking time is 4h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 40%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 500 DEG C,
Annealing speed 15cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step see the table below the embodiment 3 in 2 and table 3.
Embodiment 4:
Alloy uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure magnesium in the present embodiment
And pure tin, the ingredient of alloy are shown in Table the embodiment 4 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure magnesium and pure tin in vaccum sensitive stove,
After the above material melts, temperature is risen to 1250 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1200 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 910 DEG C, is protected
The warm time is 10h, and ingot casting is then carried out hot extrusion, and at 850 DEG C, extrusion ratio 20 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 900 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 60%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 500 DEG C,
Soaking time is 8h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 40%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 500 DEG C,
Annealing speed 20cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 4 in 2 and table 3.
Embodiment 5:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure
Magnesium and pure tin, alloying component are shown in Table the embodiment 5 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure magnesium and pure tin in vaccum sensitive stove,
After the above material melts, temperature is risen to 1230 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1200 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 920 DEG C, is protected
The warm time is 8h, and ingot casting is then carried out hot extrusion, and at 825 DEG C, extrusion ratio 20 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 950 DEG C, heat preservation
Time is 6h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 65%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 450 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 30%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 525 DEG C,
Annealing speed 15cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 5 in 2 and table 3.
Embodiment 6:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure
Silver and pure tin, the ingredient of alloy are shown in Table the embodiment 6 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure magnesium and pure tin in vaccum sensitive stove,
After the above material melts, temperature is risen to 1250 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1175 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 900 DEG C, is protected
The warm time is 8h, and ingot casting is then carried out hot extrusion, and at 825 DEG C, extrusion ratio 30 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 950 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 60%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 500 DEG C,
Soaking time is 10h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 40%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 500 DEG C,
Annealing speed 10cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 6 in 2 and table 3.
Embodiment 7:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and pure
Tin, the ingredient of alloy are shown in Table the embodiment 7 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and pure tin in vaccum sensitive stove, to
After upper material melts, temperature is risen to 1250 DEG C, after melt is completely melt, the temperature control of uniform stirring, casting exists
It 1150 DEG C, casts after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 950 DEG C, is protected
The warm time is 8h, and ingot casting is then carried out hot extrusion, and at 800 DEG C, extrusion ratio 30 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 950 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 80%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 500 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 50%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 475 DEG C,
Annealing speed 10cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 7 in 2 and table 3.
Embodiment 8:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and pure
Magnesium, the ingredient of alloy are shown in Table the embodiment 8 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and pure magnesium in vaccum sensitive stove, to
After upper material melts, temperature is risen to 1280 DEG C, after melt is completely melt, the temperature control of uniform stirring, casting exists
It 1170 DEG C, casts after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 930 DEG C, is protected
The warm time is 10h, and ingot casting is then carried out hot extrusion, and at 800 DEG C, extrusion ratio 20 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 950 DEG C, heat preservation
Time is 2h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 70%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 500 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 50%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 475 DEG C,
Annealing speed 10cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 8 in 2 and table 3.
Embodiment 9:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and pure
Titanium, the ingredient of alloy are shown in Table the embodiment 9 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy and pure titanium in vaccum sensitive stove, to
After upper material melts, temperature is risen to 1240 DEG C, after melt is completely melt, the temperature control of uniform stirring, casting exists
It 1200 DEG C, casts after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 900 DEG C, is protected
The warm time is 10h, and ingot casting is then carried out hot extrusion, and at 820 DEG C, extrusion ratio 20 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 1000 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 70%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 500 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 50%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 500 DEG C,
Annealing speed 10cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 9 in 2 and table 3.
Embodiment 10:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure
Titanium and pure tin, the ingredient of alloy are shown in Table the embodiment 10 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure titanium and pure tin in vaccum sensitive stove,
After the above material melts, temperature is risen to 1250 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1200 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 900 DEG C, is protected
The warm time is 10h, and ingot casting is then carried out hot extrusion, and at 850 DEG C, extrusion ratio 30 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 1000 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 80%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 500 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 30%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 500 DEG C,
Annealing speed 20cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 10 in 2 and table 3.
Embodiment 11:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure
Silver and pure tin, the ingredient of alloy are shown in Table the embodiment 11 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, fine silver and pure tin in vaccum sensitive stove,
After the above material melts, temperature is risen to 1230 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1170 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 930 DEG C, is protected
The warm time is 10h, and ingot casting is then carried out hot extrusion, and at 800 DEG C, extrusion ratio 30 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 900 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 60%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 400 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 30%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 450 DEG C,
Annealing speed 20cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 11 in 2 and table 3.
Embodiment 12:
Alloy in the present embodiment uses following raw material melting: cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, pure
Silver-colored and pure magnesium, the ingredient of alloy are shown in Table the embodiment 12 in 1.
A. melting: being added cathode copper, copper chromium intermediate alloy, copper zirconium intermediate alloy, fine silver and pure magnesium in vaccum sensitive stove,
After the above material melts, temperature is risen to 1250 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting
At 1170 DEG C, cast after keeping the temperature 20min.
B. homogenization and hot extrusion: above-mentioned alloy cast ingot is heated in stepping batch-type furnace, and temperature is 900 DEG C, is protected
The warm time is 10h, and ingot casting is then carried out hot extrusion, and at 850 DEG C, extrusion ratio 20 then carries out water cooling for temperature control after extruding.
C. solution treatment: will carry out solution treatment in above-mentioned copper bar after extruding, solid solution temperature is 1000 DEG C, heat preservation
Time is 4h, and the type of cooling is water cooling.
D. the bar after solution treatment cold drawing: is subjected to cold drawing, working modulus 70%.
E. ageing treatment: placing bell-type annealing furnace for wire rod after cold drawing and carry out ageing treatment, and aging temp is 400 DEG C,
Soaking time is 6h, and the type of cooling is air-cooled.
F. the alloy after ageing treatment cold drawing: is subjected to cold drawing, working modulus 50%.
G. online annealing is handled: the alloy wire wire rod after drawing is subjected to online annealing processing, annealing temperature is 450 DEG C,
Annealing speed 10cm/s, the type of cooling is cooling for room temperature, and protective gas is pure hydrogen gas.
Its microstructure of alloy and performance handled by above step is shown in Table the embodiment 12 in 2 and table 3.
The alloying component formula (wt%) of 1 embodiment 1-12 of table
The alloy microstructure of 2 embodiment 1-12 of table
The alloy property table of 3 embodiment 1-12 of table
Remarks: the alternating bending frequency of alloy material uses GBT 4909.5-2009 bare wire test method.
Claims (14)
1. a kind of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material, which is characterized in that the weight of the alloy material
Percentage group become Cr 0.05~0.75%, Zr 0.05~0.2%, remaining be Cu；
Having partial size on the horizontal and vertical section of the alloy material is the bean cotyledon shape Cr of the face-centred cubic structure of 2nm~10nm
Phase, it is 1 × 10 that density, which is precipitated,21~5 × 1022m-3；
Having partial size on the horizontal and vertical section of the alloy material is the Moire fringe shape of the body-centered cubic structure of 5nm~10nm
Cr phase, it is 5 × 10 that density, which is precipitated,22~2 × 1023m-3；
There is the structure that partial size is the face-centered cubic knot of 50nm~100nm discoid on the horizontal and vertical section of the alloy material
Cu5Zr phase, it is 1 × 10 that density, which is precipitated,17~5 × 1018m-3；
Having partial size on the horizontal and vertical section of the alloy material is the CuCrZr phase of the face-centred cubic structure of 20nm~50nm,
It is 1 × 10 that density, which is precipitated, in it17~5 × 1017m-3；
Alloy<100>texture accounts for 15~25% in the alloy material, and alloy<110>texture accounts for 15~25%, and alloy<111>is knitted
Structure accounts for 25~45%, alloy<112>texture 13~30%.
2. the multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material of one kind according to claim 1, which is characterized in that
One or both of tetra- kinds of elements of Ti, Ag, Mg, Sn are included at least in the alloy, wherein the content of Ti, Ag, Mg and Sn are equal
It is 0.05~0.2%, alloying element total content is 0.1~0.4%.
3. the multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material of one kind according to claim 1, which is characterized in that
Alloying element total content is preferably 0.15~0.3% in the alloy.
4. the multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material of one kind according to claim 1, which is characterized in that
The tensile strength of the alloy material is 300~700MPa, yield strength is 150~600MPa, elongation is 10~30%, leads
Electric rate is 70~95%IACS, softening temperature is 500~600 DEG C, alternating bending frequency is 1 × 105~1 × 108It is secondary.
5. a kind of preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material described in claim 1, special
Sign is, comprising the following steps: a. carries out ingredient according to mass percent, feeds intake, melting and casting；B. at homogenizing annealing
Reason；C. hot extrusion；D. solution treatment；E. cold drawing；F. ageing treatment；G. cold drawing；H. online annealing is handled.
6. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: melting described in step a and casting use vacuum medium frequency induction furnace, and smelting temperature is 1230~1280 DEG C, casting temperature
It is 1150~1200 DEG C.
7. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: melting described in step a and casting technique are as follows: cathode copper is added before melting in vaccum sensitive stove, closes among copper chromium
Gold, copper zirconium intermediate alloy add one or both of pure titanium, fine silver, pure tin and pure magnesium after the above material melts, will
Temperature rises to 1230~1280 DEG C, and after melt is completely melt, uniform stirring, casting temperature is controlled at 1150~1200 DEG C, protects
It casts after warm 20min.
8. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: the processing of homogenizing annealing described in step b is to heat alloy cast ingot in stepping batch-type furnace, and temperature is 900~950
DEG C, soaking time is 6~12h.
9. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: the extruding finishing temperature of hot extrusion described in step c is 800~850 DEG C, extrusion ratio 15~30.
10. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: solid solution temperature described in step d is 900~1000 DEG C, and soaking time is 2~6h, and the type of cooling is water cooling.
11. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: the working modulus of cold drawing described in step e is 60~80%.
12. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: aging temperature described in step f is 400~500 DEG C, 6~10h of soaking time, and the type of cooling is air-cooled.
13. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: the working modulus of cold drawing described in step g is 30~50%.
14. the preparation method of multiple dimensioned polynary high strength and high conductivity chrome zirconium copper alloy material according to claim 5, special
Sign is: the temperature of the processing of online annealing described in step h is 450~550 DEG C, 10~20cm/s of annealing speed, and the type of cooling is
Air-cooled, protective gas is pure hydrogen.
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