CN106399749A - High strength and high elasticity copper, nickel and silicon system alloy material and preparation method thereof - Google Patents

High strength and high elasticity copper, nickel and silicon system alloy material and preparation method thereof Download PDF

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CN106399749A
CN106399749A CN201610874673.9A CN201610874673A CN106399749A CN 106399749 A CN106399749 A CN 106399749A CN 201610874673 A CN201610874673 A CN 201610874673A CN 106399749 A CN106399749 A CN 106399749A
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alloy
temperature
nickel
alloy material
high strength
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CN106399749B (en
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刘峰
黄国杰
马吉苗
彭丽军
米绪军
邵烨
解浩峰
廖骏骏
李艳锋
冯雪
尹向前
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China Youyan Technology Group Co ltd
NINGBO XINGYE SHENGTAI GROUP CO Ltd
NINGBO XINGYE XINTAI NEW ELECTRONIC MATERIAL CO Ltd
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Ningbo Xingye Xintai New Electronic Material Co Ltd
NINGBO XINGYE SHENGTAI GROUP CO Ltd
Beijing General Research Institute for Non Ferrous Metals
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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
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • 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
    • 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

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Abstract

The invention discloses a high strength and high elasticity copper, nickel and silicon system alloy material and a preparation method thereof. The material comprises, by weight percentage, 0.5%-3.0% of Ni, 0.3%-3.0% of Co, 0.25%-1.5% of Si, 0.01%-0.05% of Mg, 0.002%-0.005% of B, 0.02%-0.05% of mixed rare earth (Sc:Y:La=1:3:5) and the balance Cu, wherein the mass ratio of nickel to cobalt is 0.5-6.0, the material further at least comprises one or two of four elements of Cr, Ti, Ag and Zr and the total content of the alloy elements is 0.02%-0.5%; and by means of smelting and casting, hot rolling, face milling, rough rolling, intermediate annealing, intermediate rolling, high-temperature fast solution treatment, finish rolling and ageing treatment, the material is prepared and obtained. The high strength and high elasticity copper, nickel and silicon system alloy material totally meets the using requirements of high-density lead frame terminals and high-end electronic component precision connecting and inserting terminals of a super large scale integrated circuit for a copper alloy material.

Description

A kind of high strength and high flexibility cupro-nickel Si system alloy material and preparation method thereof
Technical field
The present invention relates to a kind of high strength and high flexibility cupro-nickel Si system alloy material and preparation method thereof, belong to non-ferrous metals processing neck Domain.
Background technology
The high strength and high flexibility acid bronze alloy performance such as rely on its high intensity, excellent elasticity, endurance, elastic hysteresis little, extensively Be used in the industries such as medical treatment, aviation and navigation navigation instrument, machine-building, instrument and instrument manufacturing.On domestic market Copper-Nickel-Aluminium Alloy mainly based on the materials such as tin-phosphor bronze and beryllium-bronze, answer with anti-by the elastic performance due to Sn-P-Cu alloy Power relaxation property is poor, is mostly applied in the use environment relatively low to elastic performance requirement.
Beraloy is a kind of alloy of Precipitation strengthening, have after fixation rates high intensity, hardness, Elastic limit, and good stability, have anti-corrosion, wear-resisting, endurance, low temperature resistant, nonmagnetic, electrical and thermal conductivity is good, impact when The series of advantages such as spark will not be produced, be described as " king of coloured elastomeric material ", can be widely applied to electronic apparatus, communication instrument The multiple fields such as device, Aero-Space, petrochemical industry, metallurgical mine, vehicle appliance, machine-building, it has also become the development of the national economy In indispensable essential industry material.Beryllium-bronze can be divided into high beryllium copper (Be according to beryllium content height：1.6-2.2%) and low Beryllium copper (Be：0.15-0.7%) alloy two class, wherein high beallon belongs to high strength type elastic alloy, and low beryllium content copper alloy belongs to Conductivity type elastic alloy.In late 1990s, developing rapidly with automobile industry, the consumption of electronic component obtains quickly Increase, the performance requirement also more and more higher to beraloy, especially the control system position in automobile engine nacelle part, Its operating temperature is higher, and shakes severity it is desirable to beraloy has higher high temperature resistant and stress relaxation resistance power, This makes high intensity beryllium-bronze cannot meet the requirement of automobile high-current relay and high temperature connector.2003, Brush Wellman company pass through adjust low-beryllium bronze alloy in Ni, Be constituent content ratio and production technology, have developed one kind have high-strength (tensile strength is more than 1000MPa, and conductance is more than for degree, high conductivity and high resistance to stress relaxed type beraloy -390 alloy 40%IACS, the stress relaxation-resistant of 150 DEG C of insulation 1000h is more than 85%), breach C17200 alloy and there is the low conductance of high intensity Rate and C17510 alloy have the low intensive performance bottleneck of high conductivity, are successfully applied in automobile high-current relay and connector Field.
Beryllium-bronze is due to this hypertoxic element containing beryllium, the health of serious harm people in process of production.Each cubic metre As long as in the air has the dust of one milligram of beryllium, will make one to catch acute pneumonia berylliosis of lung disease, the compound of beryllium is in the group of animal Knit with blood plasma in formed solubility colloid substance, make histoorgan occur various pathologies, in lung and bone, beryllium is also possible to draw Send out cancer.Additionally, when beryllium-bronze uses under higher than 200 DEG C of environment, its intensity, elasticity drastically decline, and stress relaxation rate is up to More than 40%, lead to relay in working order under arc extinguishing ability, the change of spring load characteristic, elastic performance drastically reduces, very To operational failure.Further, since the complex manufacturing of beraloy, structure property is sensitive to heat treatment, in technological operation Difference easily cause that grain size is uneven, hardening constituent separate out uneven, lead to alloy under arms during easily occur The service life that crackle reduces material is short.Cu-Ti, Cu-Ni-Al, Cu- that the former Soviet Union, the U.S., Japan and China develop in succession The new no beryllium elastic copper alloy such as Ni-Sn, " Ka Milong ", " card thick forest ", MHII15-20 and spedex alloy.These alloys all have There is at a relatively high intensity (>=1000MPa), and remain in that higher intensity and stable elastic performance at 150 DEG C, but The conductance ratio of these alloys is relatively low, no more than 15%IACS, less than high beraloy.
In the recent period, Japanese JX day ore metal Co., Ltd. passes through to adjust working process parameter and the microstructure form of alloy (CN 101646791, CN 101646792, CN103052728, CN103361512 etc.), develops a series of different conditions High strength and high flexibility Cu-Ni-Co-Si system conductivity type copper alloy, its performance, close to even more than low beryllium alloy performance, meets varying environment Under use requirement.Therefore, develop environmentally friendly high-performance elastic copper high-strength, high-elastic, conductive, that high resistance to stress is lax to close Gold is very meaningful for abundant China high property copper alloy system.
Content of the invention
The main object of the present invention is the deficiency making up existing copper alloy property, develops a kind of high strength and high flexibility cupro-nickel silicon systems Alloy material and preparation method thereof.
A kind of high strength and high flexibility cupro-nickel Si system alloy material, the percentage by weight of this material consists of：Ni 0.5～3.0%, Co 0.3～3.0%, Si 0.25～1.5%, Mg 0.01～0.05%, B 0.002～0.005%, mischmetal (Sc：Y： La, the weight ratio preferably 1 between three elements:3:5) 0.02～0.05%, wherein Ni are 0.5～6.0 with the mass ratio of Co, Remaining be Cu, in addition also at least include in alloy tetra- kinds of elements of Cr, Ti, Ag, Zr one or two, alloying element total content is 0.02～0.5%, preferably 0.05～0.3%, the average grain size of described Cu alloy material is 2 μm～10 μm, and crystal grain chi Very little standard deviation meet σ be less than 1.0 μm, can be observed on the horizontal and vertical section of Cu alloy material particle diameter be 2nm～ The Ni of 10nm2Si and Co2Si precipitated phase (merges and is referred to as (Ni, Co)2Si precipitated phase) individual number density be 5 × 1013～5 × 1014 Individual/mm3, wherein particle diameter is 2nm～5nm (Ni, Co)2Si precipitated phase number density and particle diameter are 5nm～10nm (Ni, Co)2Si analyses The ratio going out phase number density is 1～3.
Added alloys producing：
Nickel, cobalt：Nickel, cobalt element main and element silicon formation Ni in ag(e)ing process2Si and Co2Si precipitated phase, with nickel, The difference of cobalt element content, the quantity of two kinds of precipitated phases changes, but because nickel, cobalt element physical characteristic are more similar, Ni2Si and Co2Si precipitated phase has homogeny in characteristic aspect such as form, sizes.Therefore, two class precipitated phases are referred to as (Ni, Co)2Si precipitated phase.
Magnesium：Magnesium elements act primarily as refinement Ni in ag(e)ing process2Si and Co2Si precipitated phase, promotes the disperse analysis of precipitated phase Go out, effectively improve stress relaxation-resistant and the yield strength of alloy.
Boron：From copper-boron binary phase diagraml, in 1013 DEG C of eutectic temperature, maxima solubility in copper for the boron is 0.05wt%, the decline with temperature is rapidly decreased to zero, but boron and copper do not form compound, mainly assemble in crystal boundary, reduce The plastic deformation ability of alloy.Additionally, adding micro boron element in the alloy, because boron element radius differs larger with copper, Easily cause strict distortion of lattice, significantly improve the elastic performance of alloy.
Mischmetal：Add the effect of rare earth in copper alloy：(1) rare earth can oxygen effectively and in alloy, sulphur, lead and The elements such as bismuth combine, and generate high melting compound, play the effect of the impurity such as deoxidation, desulfurization；(2) can be with copper or other alloys Element forms high melting compound, with high melting compound or originally as forming core core, the tissue of refining alloy.When in alloy When adding single rare earth element, because rare earth element has the chemical property of ripple alive, can rapid and copper and other elements generation Reaction, during melting and casting, particularly with for semicontinuous big ingot casting it is easy to uneven the showing of structure property occurs As.Fusing point due to rare-earth elements of lanthanum, scandium and yttrium three is respectively 799 DEG C, 1541 DEG C and 1522 DEG C, by the alloy Three kinds of rare earth elements of compound interpolation, are easily combined with impurity element first with lanthanum element, the impurity elements such as alloy oxygen, sulphur are entered Row removal of impurities is processed；And then using the higher feature of scandium and yttrium fusing point, lasting, stable change is carried out to the tissue of alloy Matter effect is it is ensured that the uniformity of alloy grain size.
Chromium, zirconium, silver and titanium：The interpolation of above four kinds of elements main with (Ni, Co)2Si phase acts synergistically, and improves and closes The combination property of gold.Silver element adds in fine copper alloy and acts primarily as solid solution effect, but adds in Cu-Ni-Co-Si system alloy Plus, (Ni, Co) can be promoted2While Si phase separates out, growing up of precipitated phase can be suppressed again, be obviously improved the strengthening of silver element Effect.Chromium, zirconium and titanium elements one side can promote (Ni, Co)2While Si phase separates out, growing up of precipitated phase can be suppressed again, On the other hand, three kinds of elements can separate out the precipitated phase of simple substance or form hardening constituent with copper, but analysed by nickel, cobalt and three kinds of elements of silicon The impact going out and spreading, the Precipitating Feature of three kinds of precipitated phases also there occurs significant change, can be obviously improved the comprehensive of alloy Energy.
Alloy grain and the control of precipitate size：Open in CN103361512 alloy, the crystallite dimension increasing alloy can Effectively to improve the stress relaxation resistance of alloy.But high strength and high flexibility copper alloy service condition is often below 200 DEG C, Under this environment, mainly in transgranular generation, crystal boundary becomes the barrier hindering dislocation motion for the motion of dislocation, and crystal boundary is more, and dislocation is got over Difficult motion.In addition, the size of precipitated phase and uniformity also can effectively hinder the motion of dislocation, precipitate size is less, and effect is got over Substantially.Therefore, pass through in this patent using high temperature quick solid solution treatment technology, in the premise ensureing the solid solution completely of alloying element energy Down it is ensured that alloy has rational crystallite dimension.In addition, the regulation and control by follow-up system of ageing treatment, it is possible to obtain preferably Precipitate size and the spread.
It is a further object of the present invention to provide the preparation method of above-mentioned high strength and high flexibility cupro-nickel Si system alloy material.
A kind of preparation method of high strength and high flexibility cupro-nickel Si system alloy material, comprises the following steps：A. according to mass percent Carry out dispensing, feed intake, melting and casting, b. hot rolling, c. milling face, d. roughing, e. intermediate annealing process, roll in f., g. high temperature is fast Fast solution treatment, h. finish rolling, i. Ageing Treatment.
In step a, founding is carried out using antivacuum intermediate frequency furnace, the temperature of described melting is 1250～1300 DEG C, The temperature control of described casting is at 1180～1230 DEG C.
Before melting, add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot or add copper chromium intermediate alloy, pure titanium, One of fine silver and copper zirconium intermediate alloy or two kinds, temperature are risen to 1250～1300 DEG C, after melt is completely melt, uniformly Stirring, casting temperature controls at 1180～1230 DEG C, casts after insulation 20min.
In step b, above-mentioned alloy cast ingot is heated in stepping batch-type furnace, temperature is 920～950 DEG C, during insulation Between be 2～6h, then carry out hot rolling again, finishing temperature control, at 800～850 DEG C, subsequently carries out water-cooled.
In step d, the sheet alloy behind milling face is carried out roughing, cold processing ratio is 80～90%.
In step e, cold rolling rear sheet material to be placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature is 600～ 700 DEG C, temperature retention time is 6～10h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
In step f, roll during the sheet alloy after annealing is carried out, cold processing ratio is 70～80%.
In step g, will be cold rolling after sheet alloy carry out high temperature quick solid solution treatment, solid solution temperature be 950 DEG C～ 1050 DEG C, annealing speed 8～12m/min, 50～70 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
In step h, the alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 10～50%.
In step i, cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 350～550 DEG C, temperature retention time is 1～6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Advantages of the present invention：The present invention passes through thermodynamic software, high temperature quick solid solution treatment and the supporting place of corresponding timeliness Reason technology carries out the regulation and control of composition design and optimization and microstructure to copper alloy, and a kind of fine microstructures of acquisition are uniform, precipitated phase The high strength and high flexibility cupro-nickel Si system alloy material of Dispersed precipitate, its chemical composition is：Ni 0.5～3.0%, Co 0.3～3.0%, Si 0.25～1.5%, Mg 0.01～0.05%, B 0.002～0.005%, mischmetal (Sc：Y：La=1:3:5)0.02 ～0.05%, wherein nickel and the mass ratio of cobalt are 0.5～6.0, and remaining is Cu, wherein also at least includes tetra- kinds of Cr, Ti, Ag, Zr Element one or two, alloying element total content be 0.02～0.5%, preferably 0.05～0.3%.Described Cu alloy material flat All crystallite dimension is 2 μm～10 μm, and the standard deviation of crystallite dimension meets σ and is less than 1.0 μm, Cu alloy material laterally and The Ni that particle diameter is 2nm～10nm be can be observed on longitudinal cross-section2Si and Co2Si precipitated phase (merges and is referred to as (Ni, Co)2Si separates out Phase) individual number density be 5 × 1013～5 × 1014Individual/mm3, wherein particle diameter is 2nm～5nm (Ni, Co)2Si precipitated phase number is close Degree and particle diameter are 5nm～10nm (Ni, Co)2The ratio of Si precipitated phase number density is 1～3.By melting and casting, hot rolling, Milling face, roughing, intermediate annealing, in roll, high temperature quick solid solution treatment, finish rolling and Ageing Treatment prepare this material.The present invention High strength and high flexibility cupro-nickel Si system alloy material tensile strength sigmab800～950MPa, yield strength σ0.2750～850MPa, moulds Property elongation percentage δ 4～10%, conductance 40～50%IACS, elastic modulus E 125～135GPa, the resistance to stress of 100h under room temperature Relaxation rate 95～99%, fully meets great scale integrated circuit high-density lead frame terminal and high-end electronic components and parts are accurate The use requirement to Cu alloy material for the plug terminal.
Below by specific embodiment, the present invention will be further described, but is not meant to the scope of the present invention Restriction.
Specific embodiment
The high strength and high flexibility cupro-nickel Si system alloy material of the present invention, it contains chemical composition Ni0.5 of following percetage by weight ～3.0%, Co 0.3～3.0%, Si 0.25～1.5%, Mg 0.01～0.05%, B 0.002～0.005%, mixing is dilute Native (Sc：Y：La=1:3:5) 0.02～0.05%, wherein Ni are 0.5～6.0 with the mass ratio of Co, and remaining is Cu, wherein also extremely Include less tetra- kinds of elements of Cr, Ti, Ag, Zr one or two, alloying element total content be 0.02～0.5%, preferably 0.05～ 0.3%.The average grain size of described Cu alloy material is 2 μm～10 μm, and the standard deviation of crystallite dimension meets σ and is less than 1.0 μm, the Ni that particle diameter is 2nm～10nm be can be observed on the horizontal and vertical section of Cu alloy material2Si and Co2Si separates out Phase (merges and is referred to as (Ni, Co)2Si precipitated phase) individual number density be 5 × 1013～5 × 1014Individual/mm3, wherein particle diameter be 2nm～ 5nm(Ni、Co)2Si precipitated phase number density and particle diameter are 5nm～10nm (Ni, Co)2The ratio of Si precipitated phase number density is 1 ～3.
The preparation of above-mentioned high strength and high flexibility cupro-nickel Si system alloy material and processing method, including following technological process：A. according to Mass percent carry out dispensing, feed intake, melting and casting, b. hot rolling, c. milling face, d. roughing, e. intermediate annealing process, in f. Roll, g. high temperature quick solid solution treatment, h. finish rolling, i. Ageing Treatment.Wherein, specific feeding sequence is：Before melting, in non-real Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in empty induction furnace, after above material all melts, continue to add Cu- mischmetal In intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot or interpolation copper chromium intermediate alloy, pure titanium, fine silver and copper zirconium intermediate alloy One or two, temperature is risen to 1250～1300 DEG C, after melt is completely melt, uniform stirring, and the temperature control of casting exists 1180～1230 DEG C, cast after insulation 20min；Hot-rolled temperature is 920～950 DEG C, and temperature retention time is 2～6h, finishing temperature control System is at 800～850 DEG C；The working modulus of roughing is 80～90%；Annealing temperature is 600 DEG C～700 DEG C, and temperature retention time is 6 ～10h, the type of cooling is the mixed gas of hydrogen and nitrogen.In the working modulus rolled be 70～80%；High temperature quick solid solution treatment, Solid solution temperature is 950 DEG C～1050 DEG C, annealing speed 8～12m/min, 50～70 DEG C/s of cooling velocity, and the type of cooling is Nitrogen and the mixed gas of hydrogen；The working modulus of finish rolling is 10～50%；Aging temp is 350～550 DEG C, and temperature retention time is 1 ～6h, the type of cooling is the mixed gas of hydrogen and nitrogen.
Embodiment 1
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy and Cu-3%B intermediate alloy.The composition of alloy is shown in Table 1 embodiment 1.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot, temperature is risen to 1250 DEG C, treats melt After being completely melt, uniform stirring, the temperature control of casting, at 1180 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 920 DEG C, temperature retention time For 6h, then carry out hot rolling again, finishing temperature control, at 800 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 80%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 700 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 80%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1050 DEG C, annealing speed 8m/min, 70 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 10%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 350 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 1 in 2.
Embodiment 2
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy and Cu-3%B intermediate alloy.The composition of alloy is shown in Table 1 embodiment 2.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot, temperature is risen to 1275 DEG C, treats melt After being completely melt, uniform stirring, the temperature control of casting, at 1220 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 935 DEG C, temperature retention time For 4h, then carry out hot rolling again, finishing temperature control, at 825 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 85%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 650 DEG C, temperature retention time is 8h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 10m/min, 60 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 30%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 450 DEG C, Temperature retention time is 4h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 2 in 2.
Embodiment 3
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy and Cu-3%B intermediate alloy.The composition of alloy is shown in Table 1 embodiment 3.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot, temperature is risen to 1300 DEG C, treats melt After being completely melt, uniform stirring, the temperature control of casting, at 1230 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 2h, then carry out hot rolling again, finishing temperature control, at 850 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 90%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 600 DEG C, temperature retention time is 10h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 70%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 950 DEG C, annealing speed 12m/min, 50 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 50%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 550 DEG C, Temperature retention time is 1h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 3 in 2.
Embodiment 4
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy and Cu-3%B intermediate alloy.The composition of alloy is shown in Table 1 embodiment 4.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot, temperature is risen to 1260 DEG C, treats melt After being completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 920 DEG C, temperature retention time For 4h, then carry out hot rolling again, finishing temperature control, at 800 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 85%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 600 DEG C, temperature retention time is 8h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 12m/min, 60 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 20%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 400 DEG C, Temperature retention time is 4h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 4 in 2.
Embodiment 5
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy and Cu-3%B intermediate alloy.The composition of alloy is shown in Table 1 embodiment 5.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot, temperature is risen to 1280 DEG C, treats melt After being completely melt, uniform stirring, the temperature control of casting, at 1210 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 2h, then carry out hot rolling again, finishing temperature control, at 820 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 85%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 650 DEG C, temperature retention time is 8h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1050 DEG C, annealing speed 12m/min, 50 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 30%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 400 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 5 in 2.
Embodiment 6
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy and Cu-3%B intermediate alloy.The composition of alloy is shown in Table 1 embodiment 6.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy and magnesium ingot, temperature is risen to 1250 DEG C, treats melt After being completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 920 DEG C, temperature retention time For 4h, then carry out hot rolling again, finishing temperature control, at 800 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 85%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 600 DEG C, temperature retention time is 8h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 12m/min, 50 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 30%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 400 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 6 in 2.
Embodiment 7
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy and fine silver.The composition of alloy is shown in Table 1 embodiment 7.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot and fine silver, temperature is risen to 1270 DEG C, treats After melt is completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 4h, then carry out hot rolling again, finishing temperature control, at 820 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 80%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 600 DEG C, temperature retention time is 10h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 12m/min, 70 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 40%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 450 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 7 in 2.
Embodiment 8
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy, fine silver and copper zirconium intermediate alloy.The composition of alloy is shown in Table 1 embodiment 8.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot, fine silver and copper zirconium intermediate alloy, by temperature Rise to 1300 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting, at 1220 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 940 DEG C, temperature retention time For 4h, then carry out hot rolling again, finishing temperature control, at 850 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 90%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 650 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 70%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 10m/min, 60 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 50%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 450 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 8 in 2.
Embodiment 9
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy and copper chromium intermediate alloy.The composition of alloy is shown in Table 1 embodiment 9.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot and copper chromium intermediate alloy, temperature is risen to 1250 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting, at 1220 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 4h, then carry out hot rolling again, finishing temperature control, at 850 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 80%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 700 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 10m/min, 60 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 30%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 450 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 9 in 2.
Embodiment 10
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy, copper chromium intermediate alloy and pure titanium.The composition of alloy is shown in Table 1 embodiment 10.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot, copper chromium intermediate alloy and pure titanium, by temperature Rise to 1270 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 6h, then carry out hot rolling again, finishing temperature control, at 820 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 80%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 600 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 950 DEG C, annealing speed 10m/min, 50 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 10%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 450 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 10 in 2.
Embodiment 11
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy, copper chromium and copper zirconium intermediate alloy.The composition of alloy is shown in Table 1 embodiment 11.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot, copper chromium and copper zirconium intermediate alloy, by temperature Rise to 1300 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 6h, then carry out hot rolling again, finishing temperature control, at 850 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 90%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 600 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 10m/min, 70 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 30%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 450 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 11 in 2.
Embodiment 12
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy and pure titanium.The composition of alloy is shown in Table 1 embodiment 12.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot and pure titanium, temperature is risen to 1300 DEG C, treats After melt is completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 6h, then carry out hot rolling again, finishing temperature control, at 830 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 80%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 630 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 950 DEG C, annealing speed 10m/min, 70 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 40%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 400 DEG C, Temperature retention time is 2h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 12 in 2.
Embodiment 13
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy and copper zirconium intermediate alloy.The composition of alloy is shown in Table 1 embodiment 13.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot and copper zirconium intermediate alloy, temperature is risen to 1250 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting, at 1180 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 920 DEG C, temperature retention time For 6h, then carry out hot rolling again, finishing temperature control, at 800 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 85%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 630 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 950 DEG C, annealing speed 10m/min, 70 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 50%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 500 DEG C, Temperature retention time is 3h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 13 in 2.
Embodiment 14
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy, copper chromium intermediate alloy and pure titanium.The composition of alloy is shown in Table 1 embodiment 14.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot, copper chromium intermediate alloy and pure titanium, by temperature Rise to 1270 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 6h, then carry out hot rolling again, finishing temperature control, at 820 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 80%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 650 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 75%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 1000 DEG C, annealing speed 10m/min, 60 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 50%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 500 DEG C, Temperature retention time is 4h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 14 in 2.
Embodiment 15
The alloy of the present invention adopts following raw material melting：Cathode copper, pure cobalt, electrolytic nickel, pure silicon, magnesium ingot, Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy, fine silver and pure titanium.The composition of alloy is shown in Table 1 embodiment 15.
1. melting：Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in non-vacuum induction furnace, treat that above material all melts Afterwards, continue to add Cu- mischmetal intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot, fine silver and pure titanium, temperature is risen to 1250 DEG C, after melt is completely melt, uniform stirring, the temperature control of casting, at 1200 DEG C, is cast after insulation 20min.
2. hot rolling：Above-mentioned alloy cast ingot is placed in stepping batch-type furnace and is heated, temperature is 950 DEG C, temperature retention time For 6h, then carry out hot rolling again, finishing temperature control, at 820 DEG C, subsequently carries out water-cooled.
3. roughing：Sheet alloy behind milling face is carried out roughing, cold processing ratio is 80%.
4. intermediate annealing process：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out intermediate annealing process, annealing temperature For 650 DEG C, temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
5. roll in：Roll during sheet alloy after annealing is carried out, cold processing ratio is 80%.
6. high temperature quick solid solution treatment：Sheet alloy after will be cold rolling carries out high temperature quick solid solution treatment, solution treatment temperature Spend for 950 DEG C, annealing speed 10m/min, 60 DEG C/s of cooling velocity, the type of cooling is the mixed gas of nitrogen and hydrogen.
7. finish rolling：Alloy strip steel rolled stock after solution treatment is carried out finish rolling, cold processing ratio is 50%.
8. Ageing Treatment：Cold rolling rear sheet material is placed bell-type annealing furnace and carries out Ageing Treatment, aging temp is 350 DEG C, Temperature retention time is 6h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
Through above melting and casting, hot rolling, milling face, roughing, intermediate annealing process, in roll, high temperature quick solid solution treatment, After the working processes such as finish rolling, Ageing Treatment, its performance is shown in Table the embodiment 15 in 2.
The alloying component formula (wt%) of table 1 embodiment 1-15
The alloy property table of table 2 embodiment 1-15
Remarks：(1) N (2nm～10nm)：Particle diameter is the individual number density of (Ni, Co) 2Si precipitated phase of 2nm～10nm；
(2)λ：Particle diameter is the individual number density of 2nm～5nm precipitated phase is the individual number density of 5nm～10nm precipitated phase with particle diameter Ratio.
The present invention relates to a kind of high strength and high flexibility cupro-nickel Si system alloy material and preparation method thereof.The percentage by weight of this material Consist of：Ni 0.5～3.0%, Co 0.3～3.0%, Si 0.25～1.5%, Mg 0.01～0.05%, B 0.002～ 0.005%, mischmetal (Sc：Y：La=1:3:5) 0.02～0.05%, wherein nickel and the mass ratio of cobalt are 0.5～6.0, its Remaining for Cu, wherein also at least include tetra- kinds of elements of Cr, Ti, Ag, Zr one or two, alloying element total content is 0.02～ 0.5%, preferably 0.05～0.3%.The average grain size of described Cu alloy material is 2 μm～10 μm, and the mark of crystallite dimension Quasi- deviation meets σ and is less than 1 μm, and it is 2nm～10nm's that particle diameter can be observed on the horizontal and vertical section of Cu alloy material (Ni、Co)2The individual number density of Si precipitated phase is 5 × 1013～5 × 1014Individual/mm3, wherein particle diameter is 2nm～5nm (Ni, Co)2Si Precipitated phase number density and particle diameter are 5nm～10nm (Ni, Co)2The ratio of Si precipitated phase number density is 1～3.The present invention's The tensile strength sigma of high strength and high flexibility cupro-nickel Si system alloy materialb800～950MPa, yield strength σ0.2750～850MPa, plasticity Elongation percentage δ 4～10%, electrical conductivity 40～50%IACS, elastic modulus E 125～135GPa, the resistance to stress pine of 100h under room temperature Relaxation rate 95～99%, fully meets great scale integrated circuit high-density lead frame terminal and high-end electronic components and parts precision connects The use requirement to Cu alloy material for the insertion terminal.

Claims (10)

1. a kind of high strength and high flexibility cupro-nickel Si system alloy material it is characterised in that：The percentage by weight of this alloy material consists of：Ni 0.5～3.0%, Co 0.3～3.0%, Si 0.25～1.5%, Mg 0.01～0.05%, B 0.002～0.005%, mixing Rare earth (Sc：Y：La=1:3:5) 0.02～0.05%, wherein Ni are 0.5～6.0 with the mass ratio of Co, and remaining is Cu；Described conjunction The average grain size of golden material is 2 μm～10 μm, and the standard deviation of crystallite dimension meets σ and is less than 1.0 μm, in alloy material Horizontal and vertical section on can be observed particle diameter be 2nm～10nm Ni2Si and Co2Si precipitated phase (merges and is referred to as (Ni, Co)2Si precipitated phase) individual number density be 5 × 1013～5 × 1014Individual/mm3, wherein particle diameter is (Ni, the Co) of 2nm～5nm2Si separates out Phase number density and particle diameter are (Ni, the Co) of 5nm～10nm2The ratio of Si precipitated phase number density is 1～3.
2. high strength and high flexibility cupro-nickel Si system alloy material according to claim 1 it is characterised in that：This alloy material is also at least Including one of tetra- kinds of elements of Cr, Ti, Ag, Zr or two kinds, and contained above-mentioned element is the 0.02～0.5% of total content.
3. a kind of preparation method of high strength and high flexibility cupro-nickel Si system alloy material it is characterised in that：Comprise the following steps：a：According to matter Amount percentage carry out dispensing, feed intake, melting and casting；b：Hot rolling；c：Milling face；d：Roughing；e：Intermediate annealing process；f：In roll； g：High temperature quick solid solution treatment；h：Finish rolling；i：Ageing Treatment.
4. high strength and high flexibility cupro-nickel Si system alloy material according to claim 3 preparation method it is characterised in that：Using non- Vacuum medium frequency induction furnace carries out founding, and the temperature of described melting is 1250～1300 DEG C, and the temperature of described casting is 1180～ 1230℃.
5. high strength and high flexibility cupro-nickel Si system alloy material according to claim 3 preparation method it is characterised in that：In non-real Add cathode copper, electrolytic nickel, pure cobalt, pure silicon in empty induction furnace, after above material all melts, continue to add Cu- mischmetal Intermediate alloy, Cu-3%B intermediate alloy, magnesium ingot and at least add one of copper chromium, copper chromium intermediate alloy, fine silver and pure titanium Or two kinds, temperature is risen to 1250～1300 DEG C, after melt is completely melt, casts after uniform stirring.
6. high strength and high flexibility cupro-nickel Si system alloy material according to claim 3 preparation method it is characterised in that：Described The temperature of hot rolling is 920～950 DEG C, and temperature retention time is 2～6h, and the finishing temperature after hot rolling is 800～850 DEG C.
7. high strength and high flexibility cupro-nickel Si system alloy material according to claim 3 preparation method it is characterised in that：Described Intermediate annealing process temperature is 600～700 DEG C, and temperature retention time is 6～10h, and the type of cooling is the mixed gas of hydrogen and nitrogen.
8. high strength and high flexibility cupro-nickel Si system alloy material according to claim 3 preparation method it is characterised in that：Described Roughing working modulus be 80～90%, described in roll working modulus be 70～80%.
9. high strength and high flexibility cupro-nickel Si system alloy material according to claim 3 preparation method it is characterised in that：Described Quickly continuous solid solution temperature is 950～1050 DEG C to high temperature, annealing speed 8～12m/min, 50～70 DEG C/s of cooling velocity, The type of cooling is the mixed gas of nitrogen and hydrogen.
10. high strength and high flexibility corson alloy material according to claim 3 preparation method it is characterised in that：Described Aging temperature is 350～550 DEG C, and temperature retention time is 1～6h.
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CN106987738A (en) * 2017-03-31 2017-07-28 江西理工大学 A kind of Cu Ni Si Co Ti RE copper alloys and preparation method thereof
CN107541588A (en) * 2017-09-18 2018-01-05 宁波兴业盛泰集团有限公司 The online vertical solution treatment equipment and its processing method of a kind of high strength and high flexibility Cu, Ni and Co Si system alloy
CN107988512A (en) * 2017-11-30 2018-05-04 中铝洛阳铜加工有限公司 A kind of high strength and high flexibility cupro-nickel silicon cobalt system lead frame processing technology
CN108315579A (en) * 2018-03-06 2018-07-24 北京科技大学 Texture rare earth CuNiSiCr alloy materials and preparation process and application
CN108393369A (en) * 2018-03-05 2018-08-14 清远楚江铜业有限公司 A kind of terminal copper plate/strip processing technology
CN109355529A (en) * 2018-12-08 2019-02-19 雷纳德流体智能科技江苏股份有限公司 One Albatra metal
CN111074092A (en) * 2019-12-26 2020-04-28 浙江杭机新型合金材料有限公司 High-strength high-conductivity copper-nickel-silicon alloy material and preparation method thereof
CN111621668A (en) * 2020-05-21 2020-09-04 宁波金田铜业(集团)股份有限公司 Nickel-silicon copper alloy strip and preparation method thereof
CN112111671A (en) * 2020-09-17 2020-12-22 宁波兴业盛泰集团有限公司 Environment-friendly conductive elastic copper alloy, preparation method thereof and application thereof in connector
CN112322917A (en) * 2020-10-16 2021-02-05 山西春雷铜材有限责任公司 Preparation method of Cu-Cr-Si-Ti copper alloy plate strip
CN113061777A (en) * 2021-03-25 2021-07-02 上海五星铜业股份有限公司 Brass alloy and preparation method thereof
CN113234959A (en) * 2021-05-18 2021-08-10 中国科学院宁波材料技术与工程研究所 Multi-element composite microalloyed high-strength high-conductivity copper alloy material and preparation method thereof
CN113699401A (en) * 2021-08-31 2021-11-26 山西春雷铜材有限责任公司 Preparation method of high-strength high-bending copper-nickel-silicon alloy strip
CN113981264A (en) * 2021-12-28 2022-01-28 宁波兴业盛泰集团有限公司 Copper alloy material and preparation method and application thereof
CN114453418A (en) * 2022-01-05 2022-05-10 广东中发摩丹科技有限公司 Short-process preparation method of high-strength high-conductivity Cu-Ni-Co-Si-Li alloy high-precision band
CN115094258A (en) * 2022-07-13 2022-09-23 浙江惟精新材料股份有限公司 High-strength high-plasticity high-bending Cu-Ni-Si-Co alloy and preparation method and application thereof
CN115233032A (en) * 2022-08-01 2022-10-25 河南云锦空天特导新材料有限公司 Copper alloy wire and preparation method and application thereof
CN115896538A (en) * 2022-10-27 2023-04-04 中色奥博特铜铝业有限公司 High-performance copper-nickel-silicon-chromium alloy plate and processing method and application thereof
CN116555625A (en) * 2023-05-08 2023-08-08 大连理工大学 Multi-scale multiphase coherent precipitation strengthening Cu-Ni-Al-Co-Cr-Ti high-temperature-resistant copper alloy and preparation method thereof

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CN103173649A (en) * 2011-12-21 2013-06-26 北京有色金属研究总院 Anti-stress relaxation beryllium free copper alloy with high strength and high elasticity as well as preparation and processing methods thereof
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CN106987738B (en) * 2017-03-31 2018-11-09 江西理工大学 A kind of Cu-Ni-Si-Co-Ti-RE copper alloys and preparation method thereof
CN106987738A (en) * 2017-03-31 2017-07-28 江西理工大学 A kind of Cu Ni Si Co Ti RE copper alloys and preparation method thereof
CN107541588A (en) * 2017-09-18 2018-01-05 宁波兴业盛泰集团有限公司 The online vertical solution treatment equipment and its processing method of a kind of high strength and high flexibility Cu, Ni and Co Si system alloy
CN107988512A (en) * 2017-11-30 2018-05-04 中铝洛阳铜加工有限公司 A kind of high strength and high flexibility cupro-nickel silicon cobalt system lead frame processing technology
CN108393369B (en) * 2018-03-05 2020-05-19 清远楚江铜业有限公司 Processing technology of copper plate strip for terminal
CN108393369A (en) * 2018-03-05 2018-08-14 清远楚江铜业有限公司 A kind of terminal copper plate/strip processing technology
CN108315579A (en) * 2018-03-06 2018-07-24 北京科技大学 Texture rare earth CuNiSiCr alloy materials and preparation process and application
CN109355529A (en) * 2018-12-08 2019-02-19 雷纳德流体智能科技江苏股份有限公司 One Albatra metal
CN111074092A (en) * 2019-12-26 2020-04-28 浙江杭机新型合金材料有限公司 High-strength high-conductivity copper-nickel-silicon alloy material and preparation method thereof
CN111074092B (en) * 2019-12-26 2021-08-17 浙江杭机新型合金材料有限公司 High-strength high-conductivity copper-nickel-silicon alloy material and preparation method thereof
CN111621668A (en) * 2020-05-21 2020-09-04 宁波金田铜业(集团)股份有限公司 Nickel-silicon copper alloy strip and preparation method thereof
CN112111671A (en) * 2020-09-17 2020-12-22 宁波兴业盛泰集团有限公司 Environment-friendly conductive elastic copper alloy, preparation method thereof and application thereof in connector
CN112322917A (en) * 2020-10-16 2021-02-05 山西春雷铜材有限责任公司 Preparation method of Cu-Cr-Si-Ti copper alloy plate strip
CN113061777A (en) * 2021-03-25 2021-07-02 上海五星铜业股份有限公司 Brass alloy and preparation method thereof
CN113061777B (en) * 2021-03-25 2022-01-28 上海五星铜业股份有限公司 Brass alloy and preparation method thereof
CN113234959A (en) * 2021-05-18 2021-08-10 中国科学院宁波材料技术与工程研究所 Multi-element composite microalloyed high-strength high-conductivity copper alloy material and preparation method thereof
CN113699401A (en) * 2021-08-31 2021-11-26 山西春雷铜材有限责任公司 Preparation method of high-strength high-bending copper-nickel-silicon alloy strip
CN113981264A (en) * 2021-12-28 2022-01-28 宁波兴业盛泰集团有限公司 Copper alloy material and preparation method and application thereof
CN113981264B (en) * 2021-12-28 2022-03-29 宁波兴业盛泰集团有限公司 Copper alloy material and preparation method and application thereof
CN114453418A (en) * 2022-01-05 2022-05-10 广东中发摩丹科技有限公司 Short-process preparation method of high-strength high-conductivity Cu-Ni-Co-Si-Li alloy high-precision band
CN115094258A (en) * 2022-07-13 2022-09-23 浙江惟精新材料股份有限公司 High-strength high-plasticity high-bending Cu-Ni-Si-Co alloy and preparation method and application thereof
CN115094258B (en) * 2022-07-13 2023-02-17 浙江惟精新材料股份有限公司 High-strength high-plasticity high-bending Cu-Ni-Si-Co alloy and preparation method and application thereof
CN115233032A (en) * 2022-08-01 2022-10-25 河南云锦空天特导新材料有限公司 Copper alloy wire and preparation method and application thereof
CN115896538A (en) * 2022-10-27 2023-04-04 中色奥博特铜铝业有限公司 High-performance copper-nickel-silicon-chromium alloy plate and processing method and application thereof
CN115896538B (en) * 2022-10-27 2024-04-26 中色正锐(山东)铜业有限公司 High-performance copper-nickel-silicon-chromium alloy plate and processing method and application thereof
CN116555625A (en) * 2023-05-08 2023-08-08 大连理工大学 Multi-scale multiphase coherent precipitation strengthening Cu-Ni-Al-Co-Cr-Ti high-temperature-resistant copper alloy and preparation method thereof
CN116555625B (en) * 2023-05-08 2024-07-19 大连理工大学 Multi-scale multiphase coherent precipitation strengthening Cu-Ni-Al-Co-Cr-Ti high-temperature-resistant copper alloy and preparation method thereof

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