CN105018782B - A kind of copper alloy of the silicon containing cobalt - Google Patents
A kind of copper alloy of the silicon containing cobalt Download PDFInfo
- Publication number
- CN105018782B CN105018782B CN201510439092.8A CN201510439092A CN105018782B CN 105018782 B CN105018782 B CN 105018782B CN 201510439092 A CN201510439092 A CN 201510439092A CN 105018782 B CN105018782 B CN 105018782B
- Authority
- CN
- China
- Prior art keywords
- copper alloy
- copper
- phase
- precipitated phase
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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 present invention relates to a kind of copper alloy of silicon containing cobalt, it is characterised in that including following weight composition：Wherein copper, two kinds of element sums of zinc are more than 95wt%, and inevitable impurity content is less than 0.2%.Preferably, the copper alloy contains the matrix phase and Co of copper zinc αsolidsolutionxSiyPrecipitated phase；The CoxSiyPrecipitated phase Dispersed precipitate is in described matrix phase；Area percentage >=95% of described matrix phase, the CoxSiyThe area ratio of precipitated phase is 0.01% 5%.
Description
Technical field
Alloy field of the present invention, refers specifically to a kind of copper alloy of silicon containing cobalt.
Background technology
Brass is widely used in each row each due to its good electric conductivity, corrosion resistance, good cold and hot working performance
Industry, is the indispensable metal material of current generation, and copper resource is limited, and with continuous exploitation, Resources Reserve constantly subtracts
It is few.It is widely used in medical treatment, aviation using tin-phosphor bronze as the high intensity of representative, high resiliency, endurance, Albrac, leads to
The connector of the industry such as letter, automobile, electric, terminal, relay, spring, on switching component.But it belongs to bronze series
Alloy, copper content is high, and containing high level, more expensive metal Sn in tin-phosphor bronze, the prices of raw materials cause the product valency
Lattice remain high.As market competition is increasingly fierce, enterprise enters the small profits epoch, and active demand reduces each side into carrying originally
High-profit level, for the enterprise of above-mentioned industry, it would be highly desirable to which a kind of inexpensive elastomeric material for meeting use requirement reduces cost.
Brass is, using copper, zinc as main body copper alloy, can to constitute complex brass by adding other alloying elements, meet
Different demands.It has good processing performance, mechanical performance and corrosion resisting property to brass alloys, is most widely used in non-ferrous metal
One of general alloy material.The rich reserves of zinc, the prices of raw materials are far below copper, therefore the brass cost of raw material is generally less than green grass or young crops
Copper.Improve some performances of brass by corresponding scheme, the demand for alloing it to meet more application fields is substituted using blue or green
Copper could meet material, from Resources Reserve, enterprise profit, all be a big trend.
Occur in that a few money Complex Elastic brass materials are used to substitute tin-phosphor bronze on Vehicles Collected from Market, but in practical application
During there are many problems.Although having reached that the use of elasticity of substitution material will in the indexs such as tensile strength, yield strength
Ask, but material base attribute causes high temperature durability energy, creep-resistant property to be worse than phosphor bronze, and service life and poor reliability are in phosphorus
Bronze, use environment is restricted.In addition, with the lightweight of device used in above-mentioned industry in recent years, minimizing, to phosphor bronze
Alternative materials, or even phosphor bronze is in itself, it is proposed that higher requirement and challenge.For example, for flexible member, wanting small-sized
Change and keep meeting the chucking power or screen resilience of use requirement, unique mode is exactly to improve the modulus of elasticity of material, and this refers to
Mark is determined by the base attribute of material, and phosphor bronze modulus of elasticity is in 110GPa or so, and brass class alternative materials are due to solid
The increase of molten reinforcing ratio, makes modulus of elasticity further reduce, in 105GPa or so, it is impossible to meet elastomeric material application field small
Type, light-weighted demand.Next, in order to seek miniaturization, thin-walled property, it is desirable to constitute this component material with higher
The balance of intensity and intensity and elongation percentage.It is well known that intensity is conflict with plasticity, material processes hard by cold deformation
Change can cause elongation percentage to decline to improve intensity, and making the plastic working ability of material reduces, using being restricted.In addition, one
A little high currents and the application field for requiring maximum operation (service) temperature, such as power connector requirement have higher conductance, and current phosphorus is blue or green
Copper conductance objectively needs the alternative materials of more high conductivity to occur in 16%IACS or so, and current alternative materials are such as
One-ton brass, for the consideration of cost and mechanical property, makes more alloying elements be solid-solubilized in matrix phase, this makes materials conductive rate
Lifting by great limitation, can only achieve 20%IACS or so.
Such as current a brass replacement tin-phosphor bronze material, national standard HSn70-1, American Standard C44300, its composition are Cu：
70%-73%, Sn：0.9%-1.2%, surplus is Zn, by processing hardening mechanical property can be made to reach above-mentioned industry material
Use requirement, but its 1000h stress relaxation-resistants rate under 100 DEG C of 50% yield strength primary stress be only less than 80%, it is difficult
To meet persistence requirements.
What and for example Publication No. CN103088229A Chinese patent application was announced a is dropped by reducing Sn contents
The tin-phosphor bronze alternative materials of low cost.Its main component is Sn：0.01%-2.5%, P：0.01-0.3%, Fe：0.01-
0.5, Ni：0.01-0.5%, Mn：0.01-0.1%, surplus is Cu；Its conductance is only 10%-16%IACS, application field by
To limitation.In addition, the cost range of decrease is less, Cu contents bring up to more than 97% while reduction Sn contents, and the integrated cost range of decrease is only
For 5%-10%.
The content of the invention
The technical problems to be solved by the invention, which are to provide one kind, can significantly reduce cost of alloy and with more low stress pine
Relaxation rate, the copper alloy containing cobalt, silicon more resistant to creep, more high-yield-ratio, more high elastic modulus and more preferable conductance.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：The copper alloy of the silicon containing cobalt, it is characterised in that
Including following weight composition：
Wherein copper, two kinds of element sums of zinc are more than 95wt%, and inevitable impurity content is less than 0.2%.
Preferably, the copper alloy contains the matrix phase and Co of copper zinc αsolidsolutionxSiyPrecipitated phase；The CoxSiyPrecipitated phase
Dispersed precipitate is in described matrix phase；Area percentage >=95% of described matrix phase, the CoxSiyThe area ratio of precipitated phase is
0.01%-5%.
It is preferred that the CoxSiyQuantity accounting >=90% of the particle diameter between 10-200nm in precipitated phase, particle diameter 200nm with
On≤10%.
The atomic ratio Cu/Zn of the copper and zinc can be 2.3-15.8, the mass fraction of the copper and zinc meets 0.65≤
([Cu]/3+1)/([Zn]+5)≤3.5。
Yield strength/tensile strength >=85% of above-mentioned copper alloy；100 DEG C, 1000H, 50% yield strength primary stress
Under the conditions of stress relaxation rate≤15%.
Further, the copper alloy can also be containing 0.01-3.5wt% Sn elements, 0.01%-4.0wt% Al and
At least one of 0.01%-3wt% Ni.
Further, the copper alloy in above-mentioned each scheme can also the P containing 0.01%-0.35wt%.
The copper alloy also contains ComPnPrecipitated phase, the ComPnThe area ratio of precipitated phase is 0.01%-5%.
In above-mentioned each scheme, the copper alloy can also include the A that total content is 0.0001%-2%, and the A is selected from
0.01wt%-1.5wt% Mn, 0.01wt%-1.5wt% Fe, 0.001wt%-0.3wt% Cr, 0.001wt%-
0.2wt% Zr, 0.001wt%-0.5wt% Mg, 0.001wt%-0.8wt% Ti, 0.0005wt%-0.3wt% B
At least one of with 0.0001wt%-0.1wt% Re.
The effect of copper and zinc and proportioning：Zn is solid-solubilized in Cu, is formed single-phase αsolidsolution, is played a part of solution strengthening, structure
Into the matrix of alloy structure.Zn contents can be formed less than 38% to be needed to meet certain relation between αsolidsolution, but copper zinc,
When copper zinc atom is than ＜ 2.3, during copper zinc mass ratio ([Cu]/3+1)/([Zn]+5) ＜ 0.68, because the zinc that copper is entered in solid solution is excessive,
Cause that matrix conductive rate and modulus of elasticity are relatively low, high temperature durability drastically declines, it is impossible to meet in use to electric current transmission, signal
The requirement such as transmission, unit interval temperature increase amount, chucking power, durability.When copper zinc atom is than Cu/Zn ＞ 15.8, mass ratio
Distortion of lattice caused by solid solution is few during ([Cu]/3+1)/([Zn]+5) ＞ 2.88, causes cobalt and silicon compound to be solid-solution in lattice and is formed
Solid solution stablizing effect it is bad, it is necessary to higher temperature, which is quickly cooled down, could form the saturated solid solution of cobalt and silicon compound,
And to aoxidize dezincification at high temperature very serious for brass, it is impossible to meet production requirement.Ratio and scope of the invention by controlling copper zinc,
Cobalt and silicon compound is set still to also have higher solid solubility at 600 DEG C, saturation can be formed by now directly carrying out online water cooling solid solution
Solid solution, meets the condition of further Precipitation, and it is interval to extend technique, in solid solution process without by secondary solution treatment or
Very fast cooling, needing after hot rolling as described in CN104232987A is rapidly cooled down with liquid nitrogen, greatly reduces resource
Consumption and production cost.It is preferred that copper zinc atom than Cu/Zn be 2.4-15, mass ratio 0.69≤([Cu]/3+1)/([Zn]+5)≤
2.76 from mass fraction preferred Cu mass fraction in 81%-92%.
The effect of cobalt and silicon and proportioning：Individually during addition Co elements, it is solid-solution in matrix, passes through the effect of solution strengthening
Improve the intensity of material.Si zinc equivalent coefficient is 10, adds zinc of the Si equivalent to 10 units of addition of a unit, reduces
Alpha phase zone, expands β phase regions, and the raising strength of materials is formed by solution strengthening and the harder β phases of promotion.But both individually add
The conductance and modulus of elasticity of material can be reduced, it is impossible to play a part of improving elastic properties of materials durability.Co and Si are added simultaneously,
Cobalt silicon intermetallic compound can be formed, by solid solution aging technique, compound is separated out, and Dispersed precipitate is on matrix, by itself
The Co and Si for wanting solid solution to enter matrix phase reduction conductance are excluded outside matrix, improve the conductance of material.Dispersed precipitate exists
Tiny precipitated phase in matrix phase, sliding and the dislocation of lattice can be hindered when occurring the plastic deformation less than recrystallization temperature
Movement, form more dislocations and dislocation pile up, that is, form Cottrell air mass, it is higher when material is obtained than independent solid solution
Intensity and Qu Qiang intensity and tensile strength ratio.Dispersed precipitate precipitated phase tiny on matrix, due to its resistance to distortion of lattice
Hinder and to the pinning effect of dislocation, make material bigger stress of needs when occurring elastic deformation, that is, improve the elasticity of material
Modulus.Same principle, improves the difficulty being plastically deformed during temperature in elastic properties of materials deformation range and relatively high, i.e.,
Improve the stress relaxation-resistant ability of material.Co elements deteriorate more than the hot-working character of 3wt% materials, less than 0.01wt%,
Can not the enough precipitated phase improvement material properties of quantity of formation.Si elements can produce hot-short, and serious reduction more than 0.5% material
Conductance, can not form enough precipitated phases less than 0.01wt% improves material property.
The feature of the microstructure of the copper alloy has：Copper zinc solid solution constitute α phases be matrix phase, its area accounting >=
95%, the Co that cobalt and silicon are formedxSiyIntermetallic compound Dispersed precipitate is on matrix, its area proportion 0.01%-5%.
Due to cobalt silicon intermetallic compound particle diameter in Nano grade, it is necessary to shoot micro-organization chart by surface sweeping Electronic Speculum or transmission electron microscope
Piece, then calculate the ratio shared by its area.CoxSiyThe type of intermetallic compound is supporting by ESEM or transmission electron microscope
EDS energy spectrum analysis confirms that its type is described by x/y values, and x/y is between 0.2-3；When x/y values are more than 3 or less than 0.2, its
Precipitated phase is limited to the improvement result of material property, and compound its x/y preferably is between 0.5-2.Precipitated phase area ratio is small
It is not enough to material properties improvement in 0.01%, separate out phase area accounting and be more than 5%, start to deteriorate properties, and
Precipitated phase has the trend of agglomeration, and its effect for improving metallicity is weakened.It is preferred that Phase Proportion is separated out in 0.05%-4%,
α Phase Proportion >=96%, more preferably separates out Phase Proportion in 0.1%-3.5%, α Phase Proportion >=96.5%.
Co in the copper alloy tissuexSiyAccounting of the precipitated phase particle diameter between 10-200nm is more than 90%, and remaining is particle diameter
In more than 200nm.Particle diameter is smaller, the obstruction to slip and position when metal is less than the plastic deformation below recrystallization temperature
Wrong pinning effect is stronger, the more dislocations of formation and dislocation pile up, material is obtained higher intensity and yield tensile ratio.Similarly,
In elastic deformation, make the stress of the generation elastic deformation of material bigger, material is obtained higher modulus of elasticity and more preferable height
Warm durability.Meanwhile, precipitated phase particle diameter is smaller, and the obstruction to electric transmission is smaller, material is obtained higher conductance.It is preferred that
Precipitated phase particle diameter accounting between 10nm-200nm is more than 92%, and more preferably precipitated phase particle diameter accounting between 10nm-200nm is big
In 95%.
Elastomeric material in application most pay close attention to 2 points be elasticity and elasticity persistence.The surrender of elastic main and material
When modulus of elasticity is related for intensity/tensile strength.The yield strength of material is necessarily less than tensile strength, applies stress and exceedes surrender
Intensity is to produce plastic deformation, and tensile strength is higher, and the amount of plastic deformation that material can be born before fracture failure is bigger, and surrender is strong
Degree is higher, and the maximum flexibility deformation that can be born is bigger, and modulus of elasticity is bigger, under same elastic displacement, can obtain
Screen resilience is bigger.Therefore to same material, want to make material have more preferable elasticity, it is necessary to obtain surrender as high as possible strong
Degree/tensile strength and modulus of elasticity.
Copper alloy provided by the present invention containing cobalt, silicon, due to tiny CoxSiyIntermetallic compound precipitated phase disperse
It is distributed in copper zinc-base body phase, matrix is enhanced first, improve the tensile strength and yield strength of material, secondly, in material
Plastic history in can hinder the sliding of lattice and the extension of dislocation, produce more dislocations and dislocation pile up, these
Dislocation and dislocation pile up, make material obtain higher yield strength, that is, obtain higher yield strength/tensile strength ratio.This
Outside, Dispersed precipitate Co tiny on matrixxSiyIntermetallic compound precipitated phase, due to its obstruction and contraposition to distortion of lattice
Wrong pinning effect, makes material bigger stress of needs when occurring elastic deformation, so as to improve the modulus of elasticity of material.This
Copper alloy of the invention containing cobalt, silicon, its yield strength/tensile strength compares ＞ than ＞ 85%, preferably yield strength/tensile strength
88%, more preferably yield strength/tensile strength is than ＞ 92%.
Elastic persistence be exactly material when by lasting applied stress, (80 DEG C of ＞), energy when especially temperature is higher
Enough abilities for keeping accommodating power enough, describe its elastic persistence in materialogy using stress relaxation rate.This is described
Characteristic needs clear and definite three conditions, initially applies stress value, and percentage description, test temperature, the test of conventional yield strength are held
The continuous time.The stress relaxation ability of material is substantially just less than the integration of the compacted property deformation of yield strength, specific in above three
Under the conditions of test, the reduced rate of yield strength is stress relaxation rate, and stress relaxation rate is lower, illustrates the elastic persistence of material
Better.
Copper alloy provided by the present invention containing cobalt, silicon, due to tiny CoxSiyIntermetallic compound precipitated phase disperse
Be distributed on matrix, be continuously in material under elastic deformation state, hinder and slow down crystal boundary and the compacted property of lattice deformation and
Dislocation, the spreading of dislocation pile up, incorgruous dislocation, which merge, to disappear, so as to reduce the stress relaxation rate of material, improves material
Elastic persistence.Alloy is at 100 DEG C, 1000H, carries out endurance life test under the conditions of 50% yield strength primary stress, its stress
Stress relaxation rate≤10% in stress relaxation rate≤12% in relaxation rate≤15%, preferred scheme, more preferably scheme.
The effect of tin and proportioning：The copper alloy can also further contain Sn elements, and its mass percent is 0.01%-
3.5%.Sn can further stablize the solid solution condition of cobalt silicon intermetallic compound, suppress the quick analysis of the precipitated phase in high temperature
Go out, so as to reduce the ratio of more than 200nm precipitated phases.In addition, Sn by solution strengthening effect, can also improve the intensity of material
And hardness.Tin can also suppress dezincification, improve material corrosion resistance.Tin can also improve material hot-dip and plating performance and
Brazing property.Sn can not be functioned as described above less than 0.01%, and Sn is higher than 3.5%, can produce Sn segregation, make material composition not
Uniformly, cause performance uneven, while cracking risk when increasing hot-working.It is preferred that Sn constituent contents are 0.05wt%-
3.0wt%, more preferably Sn constituent contents are 0.1wt%-2.5wt%.
The effect of al and ni and proportioning：The copper alloy can also further contain at least one of Al, Ni element, wherein Al's
Mass percent is 0.01%-4.0%, and Ni mass percent is 0.01wt%-3wt%.Ni and Al can improve material
Heat resistance and hot-workability, while playing a part of solution strengthening, improve material corrosion resistance.In addition, Ni and Al can be in timeliness
During suppress cobalt silicon intermetallic compound and grow up, put forward particle diameter cobalt silicon intermetallic compound ratio between 10nm-150nm
It is high.In addition, Ni can further strengthen matrix, improve conductance, improve modulus of elasticity, improve with Si formation nisiloy precipitated phases
The elastic persistence and chucking power of material.Ni, Al content, which are less than 0.01%, to be functioned as described above, and Ni is more than more than 3%, Al
4% can seriously reduce conductance, reduce modulus of elasticity.It is preferred that Ni mass percent is：0.01%-2.5%, Al quality hundred
It is 0.05-3.5% to divide ratio, and more preferably Ni mass percent is：0.02%-2.0%, Al mass percent are 0.1%-
3.0%.
The proportioning of phosphorus and effect：The copper alloy can further contain P element, and its mass percent is 0.01%-0.35%.
P can also form the intermetallic compound Co that can be separated out with ComPn.Now its Microstructure characteristics is：Copper zinc α phases constitute base
Body, CoxSiyPrecipitated phase and ComPnPrecipitated phase coexists, and Dispersed precipitate is in matrix phase, wherein area percentage >=90% of α phases,
CoxSiyPrecipitated phase occupied area ratio is 0.01%-5%, ComPnPrecipitated phase occupied area ratio is 0.01%-5%.Cobalt phosphorus metal
Between compound be distributed on matrix, can effectively slow down cobalt silicon intermetallic compound growth rate in ag(e)ing process, make it
Grain is more tiny, improves the uniformity that cobalt silicon intermetallic compound disperses on matrix, and strengthening it improves material mechanical performance, leads
The effect of electrical property, high temperature durability performance.P element can produce hot-short, the oxidation of aggravation matrix higher than 0.35% material, seriously
The conductance of material is reduced, can not form enough precipitated phases less than 0.01wt% improves material property.It is preferred that P content exists
0.01%-0.30%, more preferably P content is in 0.01%-0.25%.
The copper alloy can be further containing at least one of elements A, and A is selected from：Mn：0.01wt%-1.5wt%, Fe：
0.01wt%-1.5wt%；Cr：0.001wt%-0.3wt%, Zr：0.001wt%-0.2wt%, Mg：0.001wt%-
0.5wt%, Ti：0.001wt%-0.8wt%, B：0.0005wt%-0.3wt% and RE：0.0005wt%-0.1wt%.
The proportioning and effect of manganese and iron：Mn and Fe can be effectively improved CoxSiyThe distribution of precipitated phase, makes its distribution more equal
Even, decentralization is more preferable, so as to strengthen the effect of precipitated phase.Mn can also the deoxidation in fusion process, improve metal purity, also
The hot-working character of material can be improved, Mn and Fe have solution strengthening effect, the basic mechanical performance of material can be improved, dropped
The modulus of elasticity of low material.Mn, Fe content, which are less than 0.01%, to be functioned as described above, and Mn is more than 1.5%, Fe and is more than 1.5%,
Conductance can be seriously reduced, modulus of elasticity is reduced, it is impossible to meet the use demand of this kind of material, while Fe contents are more than 1.5%
The decay resistance of material can seriously be reduced.It is preferred that Mn content is in 0.05%-1.3%, Fe content in 0.02%-1.2%,
More preferably Mn content is in 0.08%-1.0%, and Fe content is in 0.05%-1.0%.
Chromium, the proportioning of zirconium and titanium and effect：Copper alloy in such scheme can form few in hot-working and solid solution process
The cobalt and silicon compound for measuring strip is separated out, and the compound phase of this kind of strip can deteriorate the performance of metal.Cr, Zr, Ti addition can
Suppress the formation of this pattern compound.In addition, Cr and Zr can improve material softening temperature and elevated temperature strength, material is lifted
High-temperature stability, reduce its stress relaxation rate.Cr and Zr are added simultaneously, can form Cr2Zr compounds, improvement result is better than
When both individually add, while can also improve the anti-caking and welding performance of material.Ti can also improve the corrosion-resistant of material
Performance.Cr contents are less than 0.001wt% less than 0.001%, Zr contents less than 0.001%, Ti contents, it is impossible to play corresponding make
With Ti contents larger can reduce the conductance of material more than 0.8%, while Ti contains higher than 0.8%, Cr contents higher than 0.3%, Zr
Amount can be such that the production cost and the cost of raw material of material significantly raises higher than 0.2%.It is preferred that Cr：0.005wt%-0.25wt%,
Zr：0.005wt%-0.15wt%, Ti：0.005wt%-0.6wt%.More preferably：Cr：0.008wt%-0.20wt%, Zr：
0.008wt%-0.10wt%, Ti：0.008wt%-0.5wt%.
Boron, the proportioning of magnesium and rare earth and effect：Wherein B, Mg, Re can suppress crystal boundary reaction, and reduction is distributed on crystal boundary
CoxSiyThe quantity of precipitated phase, the hardness after reduction copper alloy solution treatment, road cold-forming property after improvement.B can also be improved
The anti-dezincification ability of brass, improves corrosion resistance.B, Mg can also improve the stress relaxation resistance of material, improve the cold and hot of material
Processing characteristics.Re can improve the purity of metal in melting with removal of impurities, deoxygenation, and the fusing point of rare earth is high, can make in melting
For the core of crystallization, the column crystal content in ingot casting is reduced, increases the content of equiax crystal, improves the hot-working character of material.It is dilute
Soil does not have above-mentioned effect less than 0.0002wt%.Content of rare earth can form high-temperature oxide and be mingled with more than 0.1wt%, deteriorate
Metallicity.It is preferred that B：0.001wt%-0.2wt%, Mg：0.005wt%-0.3wt%, RE：0.0008wt%-0.08wt%；
More preferably B：0.002wt%-0.15wt%, Mg：0.01wt%-0.2wt%, RE：0.001wt%-0.05wt%.
The processing of above-mentioned copper alloy, can be processed into Strip, bar, wire rod according to different application demands.
It is processed into plate, the preparation method of band comprises the steps successively：
Method 1：Dispensing → melting → vertical D.C.casting ingot casting → heating rolling → solution treatment → milling face → once cold rolling
→ one-level aging strengthening model → cleaning → secondary cold-rolling → secondary time effect heat treatment → cleaning → into preceding cold rolling → finished product destressing
Aging strengthening model → cleaning → slitting → packaging；
Wherein, the smelting temperature is 1080 DEG C -1280 DEG C, and vertical D.C.casting temperature is 1060 DEG C -1260 DEG C, starts to add
Hot rolling start rolling temperature is 700 DEG C -900 DEG C, and finishing temperature is not less than 600 DEG C, and hot rolling rate is 60%-95%.Described
Solution treatment is to carry out on-line cooling after the completion of hot rolling, and cooling medium is air or water, cooling velocity is 10 DEG C/min-150 DEG C/
S。
Or, method 2：Dispensing → melting → horizontal casting → solution treatment → milling face → once cold rolling → one-level timeliness heat
Processing → cleaning → secondary cold-rolling → secondary time effect heat treatment → cleaning → into preceding cold rolling → finished product destressing aging strengthening model →
Cleaning → slitting → packaging；
Described horizontal casting smelting temperature is 1080 DEG C -1280 DEG C, and horizontal casting temperature is 1050 DEG C -1250 DEG C, institute
The solution treatment stated is on-line cooling after casting, and cooling medium is air or water, and cooling velocity is 10 DEG C/min-150 DEG C/S.
Method 1 with band production method described in method 2 once, it is secondary and into preceding cold processing ratio be 5%-
95%, one-level aging strengthening model temperature is 350 DEG C -650 DEG C, and soaking time is 10min-10h, firing rate is 2-50 DEG C/
Min, cooling velocity is 5-50 DEG C/min, and described secondary time effect heat treatment temperature is 300 DEG C -600 DEG C, and soaking time is
10min-10h, firing rate is 2-50 DEG C/min, and cooling velocity is 5-50 DEG C/min, at described finished product destressing timeliness heat
It is 100 DEG C -300 DEG C to manage temperature, and soaking time is 10min-10h, and firing rate is 2-50 DEG C/min, and cooling velocity is 5-50
℃/min.It is described cold rolling different according to product specification and performance from aging strengthening model group technology number of times, it can increase or decrease,
But at least ensure more than twice.Aging strengthening model described in above-mentioned band production method can be online mode, and temperature is 200
DEG C -750 DEG C, speed is 20m/min-250m/min.
Method 3：Dispensing → melting → vertical semi-continuous casting or horizontal continuous-casting → heating extruding → solution treatment →
Drawing → one-level aging strengthening model → redraing → secondary time effect heat treatment → into preceding drawing → finished product destressing timeliness
Heat treatment → alignment → scale → packaging；
Wherein, the smelting temperature is 1080 DEG C -1280 DEG C, and vertical D.C.casting temperature is 1060 DEG C -1260 DEG C, and level connects
It is 1050 DEG C -1250 DEG C to cast temperature, and extrusion temperature is 650 DEG C -900 DEG C, and described solution treatment is online cold after the completion of extruding
But, cooling medium is air or water, and cooling velocity is 10 DEG C/min-150 DEG C/S.Described drawing, redraing, a Cheng Qian
Drawing working modulus is 3%-80%.Described one-level aging strengthening model temperature is 350 DEG C -650 DEG C, and soaking time is 10min-
10h, firing rate is 2-50 DEG C/min, and cooling velocity is 5-50 DEG C/min.Described secondary time effect heat treatment temperature is 300
DEG C -600 DEG C, soaking time is 10min-10h, and firing rate is 2-50 DEG C/min, and cooling velocity is 5-50 DEG C/min.Described
Finished product destressing aging strengthening model temperature is 100 DEG C -300 DEG C, and soaking time is 10min-10h, firing rate is 2-50 DEG C/
Min, cooling velocity is 5-50 DEG C/min.The cold drawing is with aging strengthening model group technology number of times according to product specification and performance
Difference, can be increased or decreased, but at least be ensured more than twice.
Method:4：Dispensing → melting → vertical semi-continuous casting/horizontal continuous-casting → heating extruding → solution treatment →
Drawing → one-level the aging strengthening model → secondary of once falling falls drawing → secondary time effect heat treatment → continuous drawing aging strengthening model → packaging.
Wherein, the smelting temperature is 1080 DEG C -1280 DEG C, and vertical D.C.casting temperature is 1060 DEG C -1260 DEG C, and level connects
It is 1050 DEG C -1250 DEG C to cast temperature, and extrusion temperature is 650 DEG C -900 DEG C, and described solution treatment is cold to be carried out after the completion of extruding
But, cooling medium is air or water, and cooling velocity is 10 DEG C/min-150 DEG C/S.
Method 5：Dispensing → melting → horizontal continuous-casting/Continuous Up casting → solution treatment → once falls drawing → one-level
Aging strengthening model → secondary drawing → secondary time effect heat treatment → continuous drawing aging strengthening model → packaging.
Wherein, the smelting temperature is 1080 DEG C -1280 DEG C, and horizontal casting temperature is 1050 DEG C -1250 DEG C, above draws continuous
Casting temperature is 1060 DEG C -1260 DEG C, described solution treatment to be cooled down after the completion of casting, cooling medium for air or
Water, cooling velocity is 10 DEG C/min-150 DEG C/S.
In wire production method described in method 4 and method 5, described once fall to draw with secondary drawing working modulus is 5%-
60%, the plane skin technique that can increase a time 1%-3% removes surface defect.The one-level aging strengthening model temperature is 350
DEG C -650 DEG C, soaking time is 10min-10h, and firing rate is 2-50 DEG C/min, and cooling velocity is 5-50 DEG C/min, described
Secondary time effect heat treatment temperature is 300 DEG C -600 DEG C, and soaking time is 10min-10h, and firing rate is 2-50 DEG C/min, cooling
Speed is 5-50 DEG C/min, and described continuous drawing aging strengthening model is according to different passageway base specifications, respectively successively using large-scale
Continuous drawing aging strengthening model machine, medium-sized continuous drawing aging strengthening model machine, small-sized continuous drawing aging strengthening model machine, finished product life
Produce with small-sized continuous drawing aging strengthening model machine.
In above-mentioned 1-5 preparation method, its two-stage time effect Technology for Heating Processing plays a key effect to finished material performance.Institute
It is 350 DEG C -650 DEG C to state one-level aging temp, and the secondary time effect temperature is 300 DEG C -600 DEG C.After a cold working, pass through
One-level aging strengthening model controls the precipitation ratio and granularity of precipitated phase.After secondary cold working, it is heat-treated and is controlled by secondary time effect
The distributional pattern of precipitated phase processed.And the more abundant, granularity of precipitated phase precipitation is smaller, distribution is more uniform, and the properties of material are better.
Aging strengthening model is carried out beyond said temperature scope, it is impossible to produced a desired effect.
In summary, copper alloy provided by the present invention has the bullet of higher yield strength/tensile strength values and Geng Gao
Property modulus, so as to there is preferably elastic and higher resilience chucking power；And stress relaxation rate is low, stress relaxation resistance is good,
Elastic persistence is good；Also there is higher conductance simultaneously, conduction is good during use, chucking power is big, heating is few, material into
Shape is good, and service life is long.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the finished product of embodiment 74, and multiple is 29000 times；White wire inframe is mutually in figure
CoxSiyPrecipitated phase.
Fig. 2 is the transmission electron microscope picture of the finished product of embodiment 82, and multiple is 43000 times；White wire inframe is mutually in figure
CoxSiyPrecipitated phase.
Fig. 3 is the transmission electron microscope picture of the finished product of embodiment 80, and multiple is 71000 times；White wire inframe is mutually in figure
CoxSiyPrecipitated phase.
Fig. 4 is the transmission electron microscope picture of the finished product of embodiment 81, and multiple is 43000 times；White wire inframe is mutually in figure
CoxSiyPrecipitated phase.
Fig. 5 is the scanning electron microscopic picture of the finished product of embodiment 52, and multiple is 10000 times；White phase is turned white to light color in figure
Small area block is CoxSiyPrecipitated phase.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Scheme 1
This programme includes comparative example 1,2 and embodiment 3 to embodiment 12
This programme is tested for composition, illustrates Cu and Zn content and with the influence for comparing copper alloy performance.According to design
Composition carries out dispensing, and raw material include cathode copper, 0# zinc, metallic cobalt, copper silicon intermediate alloy.Taken on the blank after the completion of extruding
Sample, tests composition after its stove, and tester is inductively coupled plasma spectrometer (ICP).Each group dispensing is respectively in 10Kg intermediate frequencies
Founding ingot casting in stove, is lathed the extruding ingot castings of Φ 50, is squeezed into the blanks of Φ 15, the online water cooling of extruded stock.Extruded stock is entered successively
The following processing of row：Working modulus cold drawing → 450 DEG C timeliness the heat of 60% working modulus cold drawing → 550 DEG C aging strengthening model 5h → 30%
Handle the finished product heat treatment 3h → cleaning of working modulus cold drawing → 280 DEG C of 4h → 20%.Finished product is processed into the standard pull tension samples of Φ 7,
Tensile test is carried out to sample on 10 tons of hydraulic drawbench, its tensile strength, yield strength, elongation percentage, modulus of elasticity is tested.Into
Product are cut into 80cm length and measure its conductance with electric bridge tester.Each item data is as shown in table 1 and continued 1.
Table 1
Continued 1
Above-mentioned table 1 and continued 1 are primarily to Cu, Zn relationship between quality and atomic ratio are to each phase of material in explanation matrix
Close the influence of performance.Case 1 and contrast case 2 are such as contrasted, its copper zinc atom ratio and relationship between quality exceed right, its
Middle embodiment 1 enters matrix due to excessive Zn solid solutions, causes matrix conductive rate and modulus of elasticity relatively low, and mechanical property, which is improved, to be had
Limit, it is impossible to meet use requirement.Embodiment 2 enters matrix due to very few Zn solid solutions, and caused distortion of lattice is few, causes cobalt silication
The stablizing effect that compound is solid-solution in the solid solution of lattice formation is bad, it is difficult to super saturated solid solution is formed under the conditions of on-line solution
Body, so that the condition of cobalt silicon phase disperse educt can not be met, causes materials conductive rate relatively low, and modulus of elasticity and mechanical property are improved
It is limited, it is impossible to which that satisfaction is used.And Cu, Zn relationship between quality and atomic ratio within the scope of the claims, pass through in embodiment 3-12
Contrast, material properties are significantly improved, and conductance, mechanical property effectively increase, hence it is evident that higher than contrast case.
Scheme 2
This programme is tested for composition, including embodiment 13-23, and as shown in table 2, wherein embodiment 13 and embodiment 14 is
Contrast case, not in the composition range of patent requirements, for illustrate alloying element or its ratio exceed claimed range harm and
As a result.Illustrate Co and Si content and with the influence for comparing copper alloy performance, carry out dispensing according to design composition, raw material include
Cathode copper, 0# zinc, metallic cobalt, copper silicon intermediate alloy.Sampled on the blank after the completion of extruding, test composition after its stove, tested
Instrument is inductively coupled plasma spectrometer (ICP).The each group dispensing founding ingot casting in 10Kg intermediate frequency furnaces respectively, is lathed Φ 50
Ingot casting is extruded, the blanks of Φ 15, the online water cooling of extruded stock is squeezed into.Extruded stock is processed as follows successively：60% working modulus is cold
Working modulus cold drawing → 450 DEG C aging strengthening model the 4h of drawing → 550 DEG C aging strengthening model 5h → 30% → 20% working modulus is cold drawn
Pull out → 280 DEG C of finished product heat treatment 3h → cleanings.Finished product is processed into the standard pull tension samples of Φ 7, to sample on 10 tons of hydraulic drawbench
Tensile test is carried out, its tensile strength, yield strength is tested, prolongs
Stretch rate, modulus of elasticity.Finished product is cut into 80cm length and measures its conductance with electric bridge tester.Each item data is as shown in table 2.
Table 2
Above-mentioned table 2 is mainly used in illustrating each basic performance of the change to material of two kinds of alloying element different contents of Co, Si
Influence, from embodiment 15-22 with contrast case 13, contrast case 14 described in data can be seen that Co of the present invention
Content need to be between 0.01%-3%, and described element silicon need to be between 0.01-0.5%.Any one element is not in the scope
Interior, the combination property of material can not all meet demand.
Scheme 3
This programme is used to illustrate influence of the Phase Proportion in copper alloy microstructure to material property, including embodiment 23-
32, as shown in table 3, wherein embodiment 23 and embodiment 24 are contrast case, and Phase Proportion is not in the range of patent requirements, for saying
The harm of the bright undesirable scope of copper alloy microstructure and result.Dispensing is carried out according to design composition, raw material include electricity
Solve copper, 0# zinc, metallic cobalt, copper silicon intermediate alloy.Sampled on the blank after the completion of extruding, test composition after its stove, tester
Device is inductively coupled plasma spectrometer (ICP).The each group dispensing founding ingot casting in 10Kg intermediate frequency furnaces respectively, is lathed Φ 50 and squeezes
Die casting ingot, is squeezed into the blanks of Φ 15, the online water cooling of extruded stock.Extruded stock is processed as follows successively：60% working modulus is cold drawn
Pull out the working modulus cold drawing of the working modulus cold drawing → 450 DEG C aging strengthening model 4h of → 550 DEG C of aging strengthening model 5h → 30% → 20%
→ 280 DEG C of finished products are heat-treated 3h → cleaning.Finished product is processed into the standard pull tension samples of Φ 7, and sample is entered on 10 tons of hydraulic drawbench
Row tensile test, tests its tensile strength, yield strength, elongation percentage, modulus of elasticity.Finished product is cut into 80cm length electric bridge testers
Measure its conductance.Each item data is as shown in table 3 and continued 3.
Table 3
Continued 3
Because precipitated phase diameter is in nanoscale, therefore its Phase Proportion is evaluated on SEM or TEM pictures, first measures it
Precipitated phase diameter, is judging its ratio.A kind of copper alloy of silicon containing cobalt of the present invention, it separates out phase area in 0.01%-
5%, precipitated phase area ratio is less than 0.01%, not enough to material properties improvement, separates out phase area accounting and is more than
5%, start to deteriorate properties, and precipitated phase has the trend of agglomeration, its effect for improving metallicity is weakened.From upper
Table 3 is stated it can be seen that this conclusion.
Scheme 4
This programme is used to illustrate the Co in copper alloy microstructurexSiyInfluence of the precipitate size to material property, including
Embodiment 33-38, wherein embodiment 33 and embodiment 34 are contrast case, and cobalt and silicon compound size accounting is not in patent requirements model
In enclosing, harm and result for illustrating the undesirable scope of copper alloy microstructure.Dispensing is carried out according to design composition, it is former
Material includes cathode copper, 0# zinc, metallic cobalt, copper silicon intermediate alloy.On the blank after the completion of extruding sample, test after its stove into
Point, tester is inductively coupled plasma spectrometer (ICP).Each group dispensing founding ingot casting, car in 10Kg intermediate frequency furnaces respectively
The extruding ingot castings of Φ 50 are whittled into, the blanks of Φ 15, the online water cooling of extruded stock is squeezed into.Extruded stock is processed as follows successively：60%
It is cold that the working modulus cold drawing of working modulus cold drawing → one-level aging strengthening model → 30% → secondary time effect is heat-treated → 20% working modulus
Drawing → 280 DEG C finished product heat treatment 3h → cleaning.Finished product is processed into the standard pull tension samples of Φ 7, to sample on 10 tons of hydraulic drawbench
Product carry out tensile test, test its tensile strength, yield strength, elongation percentage, modulus of elasticity.Finished product is cut into 80cm length and surveyed with electric bridge
Examination instrument measures its conductance.By adjusting two-stage time effect Technology for Heating Processing in above-mentioned technique, change CoxSiyThe granularity of precipitated phase.
Each item data is as shown in table 4.
Table 4
As can be seen that diameter Co between 10nm-200nm from upper table 4xSiyPrecipitated phase proportion is higher, and material is comprehensive
Close performance better.Demand is met, the Co in the size rangexSiyPrecipitated phase proportion need to be more than 90%, preferably greater than
92%, more preferably greater than 95%.
Scheme 5
This programme is used to illustrate influences of the Sn to more than 200nm compound precipitated phases in copper alloy microstructure, including reality
A 39-43 is applied, wherein embodiment 43 is contrast case, illustrate that Sn contents exceed harm and the result of right.According to
Design composition and carry out dispensing, raw material include cathode copper, 0# zinc, metallic cobalt, copper silicon intermediate alloy, metallic tin.Completed in extruding
Sampled on blank afterwards, test composition after its stove, tester is inductively coupled plasma spectrometer (ICP).Each group dispensing point
The founding ingot casting not in 10Kg intermediate frequency furnaces, is lathed the extruding ingot castings of Φ 50, is squeezed into the blanks of Φ 15, the online water cooling of extruded stock.It is right
Extruded stock is processed as follows successively：The working modulus cold drawing of 60% working modulus cold drawing → 550 DEG C aging strengthening model 5h → 30%
Working modulus cold drawing → 280 DEG C finished product heat treatment 3h → the cleaning of → 450 DEG C of aging strengthening model 4h → 20%.Finished product is processed into Φ 7
Standard pull tension sample, carries out tensile test to sample on 10 tons of hydraulic drawbench, tests its tensile strength, yield strength, extension
Rate, modulus of elasticity.Finished product is cut into 80cm length and measures its conductance with electric bridge tester.Each item data is as shown in table 5.
Table 5
As can be seen from Table 5, the addition of Sn elements effectively reduces in single visual field granularity in more than 200nm CoxSiy
The number of precipitated phase, and with the increase of Sn additions, material mechanical performance is improved significantly, and is seen by contrasting case,
Sn too high levels can cause conductance seriously to reduce, it is impossible to meet use demand.
Scheme 6
This programme is used for the influence for illustrating that Ni, Al separate out Phase Proportion to compound between 10-150nm in copper alloy tissue,
Including embodiment 44-50.Wherein embodiment 49 and embodiment 50 are contrast case, illustrate that Ni, Al content exceed claim model
The harm enclosed and result.Dispensing is carried out according to design composition, raw material include cathode copper, 0# zinc, metallic cobalt, the conjunction of copper silicon centre
Gold, metallic nickel, metallic aluminium.Sampled on the blank after the completion of extruding, test composition after its stove, tester is inductive etc.
Ion mass spectrometry (ICP).The each group dispensing founding ingot casting in 10Kg intermediate frequency furnaces respectively, is lathed the extruding ingot castings of Φ 50, is squeezed into
The blanks of Φ 15, the online water cooling of extruded stock.Extruded stock is processed as follows successively：60% working modulus cold drawing → 550 DEG C timeliness
It is heat-treated the working modulus cold drawing → 280 DEG C finished product heat of the working modulus cold drawing → 450 DEG C aging strengthening model 4h of 5h → 30% → 20%
Handle 3h → cleaning.Finished product is processed into the standard pull tension samples of Φ 7, and tensile test is carried out to sample on 10 tons of hydraulic drawbench, surveys
Try its tensile strength, yield strength, elongation percentage, modulus of elasticity.Finished product is cut into 80cm length and measures its conductance with electric bridge tester.
Each item data is as shown in table 6.
Table 6
Scheme 7
This programme is used to illustrate Mn, Fe, P to Co in copper alloy tissuexSiyThe influence of the precipitated phase spread, its spread is led to
Cross separate out distributed mutually variance evaluated, method be corresponding scanning electron microscopic picture is divided into 3 × 3 grid, statistics often
Co in individual gridxSiyThe number of precipitated phase, then calculates it and expects and variance.This programme includes embodiment 51-61.Wherein implement
Example 59, embodiment 60 and embodiment 61 are contrast case, illustrate that Mn, Fe, P content exceed harm and the knot of right
Really.Dispensing is carried out according to design composition, raw material include closing in the middle of cathode copper, 0# zinc, metallic cobalt, copper silicon intermediate alloy, copper phosphorus
Gold, manganese metal, metallic aluminium.Sampled on the blank after the completion of extruding, test composition after its stove, tester is inductive etc.
Ion mass spectrometry (ICP).The each group dispensing founding ingot casting in 10Kg intermediate frequency furnaces respectively, is lathed the extruding ingot castings of Φ 50, is squeezed into
The blanks of Φ 15, the online water cooling of extruded stock.Extruded stock is processed as follows successively：60% working modulus cold drawing → 550 DEG C timeliness
It is heat-treated the working modulus cold drawing → 280 DEG C finished product heat of the working modulus cold drawing → 450 DEG C aging strengthening model 4h of 5h → 30% → 20%
Handle 3h → cleaning.Finished product is processed into the standard pull tension samples of Φ 7, and tensile test is carried out to sample on 10 tons of hydraulic drawbench, surveys
Try its tensile strength, yield strength, elongation percentage, modulus of elasticity.Finished product is cut into 80cm length and measures its conductance with electric bridge tester.
Each item data is as shown in table 7 and continued 7.
Table 7
Continued 7
Upper table 7 and continued 7 describe the uniformity coefficient of cobalt silicon distributed mutually by variance, and variance yields is smaller, illustrate that it is distributed
More uniform, then cobalt silicon relative material substrate performance improves more, as can be seen that adding with several elements in upper table
Plus, variance yields diminishes, and material property is become better and better.But as contrasted case, if the element exceedes right, to conduction
Rate has serious weakening, it is impossible to which satisfaction is used.
Scheme 8
This programme is used for the influence for illustrating that addition Cr, Zr, Ti element is formed to strip cobalt and silicon compound, and method is observation phase
Answer the number of strip compound in scanning electron microscopic picture.This programme includes embodiment 62-68.Dispensing is carried out according to design composition,
Raw material include cathode copper, 0# zinc, metallic cobalt, copper chromium intermediate alloy, copper zirconium intermediate alloy, copper titanium intermediate alloy.Extruding
Sampled on blank after, test composition after its stove, tester is inductively coupled plasma spectrometer (ICP).Each group dispensing
The founding ingot casting in 10Kg intermediate frequency furnaces, is lathed the extruding ingot castings of Φ 50, is squeezed into the blanks of Φ 15, the online water cooling of extruded stock respectively.
Extruded stock is processed as follows successively：60% working modulus cold drawing → 550 DEG C aging strengthening model 5h → 30% working modulus is cold drawn
Pull out the finished product heat treatment 3h → cleaning of working modulus cold drawing → 280 DEG C of → 450 DEG C of aging strengthening model 4h → 20%.Finished product is processed into Φ
7 standard pull tension samples, carry out tensile test to sample on 10 tons of hydraulic drawbench, test its tensile strength, yield strength, extension
Rate, modulus of elasticity.Finished product is cut into 80cm length and measures its conductance with electric bridge tester.Each item data is as shown in table 8 and continued 8.
Table 8
Continued 8
As shown in upper table 8 and continued 8, the addition of Cr, Zr, Ti alloying element effectively reduces strip in single visual field
CoxSiyThe number of precipitated phase.The presence of this strip compound can weaken the effect that precipitated phase is lifted to material property.Therefore
The presence of this strip compound is reduced as far as possible.
Scheme 9
This programme is used to illustrate B, Mg, Re to CoxSiyThe inhibitory action that precipitated phase is separated out on crystal boundary, method is observation phase
Answer the Co being distributed in scanning electron microscopic picture on crystal boundaryxSiyThe number of precipitated phase.This programme includes embodiment 69-75, according to setting
Count composition and carry out dispensing, raw material include cathode copper, 0# zinc, metallic cobalt, copper boron intermediate alloy, and copper magnesium intermediate alloy is mixed dilute
Soil.Sampled on the blank after the completion of extruding, test composition after its stove, tester is inductively coupled plasma spectrometer
(ICP).The each group dispensing founding ingot casting in 10Kg intermediate frequency furnaces respectively, is lathed the extruding ingot castings of Φ 50, is squeezed into the blanks of Φ 15, squeezes
The online water cooling of pressed compact.Extruded stock is processed as follows successively：60% working modulus cold drawing → 550 DEG C aging strengthening model 5h →
Working modulus cold drawing → 280 DEG C of 30% working modulus cold drawing → 450 DEG C aging strengthening model 4h → 20% finished product heat treatment 3h → clear
Wash.Finished product is processed into the standard pull tension samples of Φ 7, carries out tensile test to sample on 10 tons of hydraulic drawbench, tests its tension strong
Degree, yield strength, elongation percentage, modulus of elasticity.Finished product is cut into 80cm length and measures its conductance with electric bridge tester.Each item data is such as
Shown in table 9.
Table 9
As shown in upper table 9, B, Mg, Re addition effectively reduce the Co being distributed on crystal boundaryxSiyThe number of precipitated phase,
This compound being distributed on crystal boundary has not significant impact to material macro property, but is easily become in punch process engineering
Formation of crack, produces burr, and influence is used.Therefore to avoid as far as possible.
Scheme 10
This programme is used for the processing method for illustrating different shape material, including embodiment 69-85, wherein embodiment 69-70
According to preparation method 4 and the output wire rod of method 5, trimmed size is Φ 0.5mm embodiments 71-72 according to the output rod of preparation method 3
Material, trimmed size is Φ 15mm, and embodiment 73-75 is according to the output band of preparation method 2, and trimmed size is 0.3mm, wherein implementing
Example 73 is American Standard C51900, as a comparison case.Embodiment 76-85 is according to the output band of preparation method 1, trimmed size
0.3mm.Wherein embodiment 76 is American Standard C42500, and embodiment 77 is American Standard C26000, and embodiment 78 is American Standard C44300, as
Contrast case.As shown in table 10 and continued 10.
Table 10
Continued 10
Such as upper table 10 and continued 10 are copper alloy mass production processes output finished product of the present invention, and test items
Performance.By can be seen that copper alloy of the present invention with contrast case contrast, due to CoxSiyThe generation of precipitated phase, it is every
Performance has obtained the lifting of significant effective.
Scheme 11
This programme is used for the elastic persistence for contrasting a kind of copper alloy of silicon containing cobalt, and compares the stress relaxation rate of material.
Choose the band that embodiment 73-85 is prepared, the stress relaxation resistance of test material.Test is according to ASTM E328-2002
(2008) standard is carried out, and the primary stress of the 50% sample yield strength, measurement note are loaded to the cantilever beam that respective samples are constituted
Record its drafts.Then 1000h is incubated at 100 DEG C respectively, measures its springback capacity.According to test data, the stress of material is calculated
Relaxation rate, calculation formula is：Stress relaxation rate=(drafts-springback capacity)/drafts × 100%, as a result as shown in table 11.
Table 11
As can be seen from Table 11, there is CoxSiyThe embodiment 74 and embodiment 75 of precipitated phase, embodiment 79 to embodiment 85,
Its stress relaxation rate is obviously improved compared to embodiment 77 and 78, greatly improves it poor as the elastic persistence of brass
The characteristics of.And existing common elastic material C 51900 i.e. embodiment 73 is contrasted, C42500 is embodiment 76, there is CoxSiyPrecipitated phase
Embodiment its stress relaxation rate at or below current material.This explanation is in existing CoxSiyRelative resilient persistence is separated out to change
On the basis of kind, P, B, Mg, Cr, Zr are further improved to elastic properties of materials persistence.
Claims (10)
1. the copper alloy of a kind of silicon containing cobalt, it is characterised in that including following weight composition：
Wherein copper, two kinds of element sums of zinc are more than 95wt%, and inevitable impurity content is less than 0.2%；
The atomic ratio Cu/Zn of the copper and zinc is 2.3-15.8, and the mass fraction of the copper and zinc meets 0.65≤([Cu]/3+
1)/([Zn]+5)≤3.5；
The copper alloy contains the matrix phase and Co of copper zinc αsolidsolutionxSiyPrecipitated phase；The CoxSiyPrecipitated phase Dispersed precipitate is in institute
State in matrix phase；Area percentage >=95% of described matrix phase, the CoxSiyThe area ratio of precipitated phase is 0.01%-5%.
2. copper alloy according to claim 1, it is characterised in that the CoxSiyParticle diameter is between 10-200nm in precipitated phase
Quantity accounting >=90%, particle diameter more than 200nm≤10%.
3. copper alloy according to claim 2, it is characterised in that yield strength/tensile strength >=85% of the copper alloy；
100 DEG C, 1000H, stress relaxation rate≤15% under the conditions of 50% yield strength primary stress.
4. the copper alloy according to claims 1 to 3 any claim, it is characterised in that the copper alloy also contains 0.01-
At least one of 3.5wt% Sn elements, 0.01%-4.0wt% Al and 0.01%-3wt% Ni.
5. the copper alloy according to claims 1 to 3 any claim, it is characterised in that the copper alloy also contains
0.01%-0.35wt% P.
6. copper alloy according to claim 5, it is characterised in that the copper alloy also contains ComPnPrecipitated phase, the ComPnAnalysis
The area ratio for going out phase is 0.01%-5%.
7. copper alloy according to claim 4, it is characterised in that the copper alloy also P containing 0.01%-0.35wt%.
8. copper alloy according to claim 7, it is characterised in that the copper alloy also contains ComPnPrecipitated phase, the ComPnAnalysis
The area ratio for going out phase is 0.01%-5%.
9. copper alloy according to claim 4, it is characterised in that it is 0.0001%-2% that the copper alloy, which also includes total content,
A, the A be selected from 0.01wt%-1.5wt% Mn, 0.01wt%-1.5wt% Fe, 0.001wt%-0.3wt% Cr,
0.001wt%-0.2wt% Zr, 0.001wt%-0.5wt% Mg, 0.001wt%-0.8wt% Ti, 0.0005wt%-
At least one of 0.3wt% B and 0.0001wt%-0.1wt% Re.
10. copper alloy according to claim 5, it is characterised in that it is 0.0001%-2% that the copper alloy, which also includes total content,
A, the A be selected from 0.01wt%-1.5wt% Mn, 0.01wt%-1.5wt% Fe, 0.001wt%-0.3wt% Cr,
0.001wt%-0.2wt% Zr, 0.001wt%-0.5wt% Mg, 0.001wt%-0.8wt% Ti, 0.0005wt%-
At least one of 0.3wt% B and 0.0001wt%-0.1wt% Re.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510439092.8A CN105018782B (en) | 2015-07-23 | 2015-07-23 | A kind of copper alloy of the silicon containing cobalt |
| EP16826980.1A EP3363922B1 (en) | 2015-07-23 | 2016-06-08 | Cobalt silicide-containing copper alloy |
| US15/558,477 US20180066339A1 (en) | 2015-07-23 | 2016-06-08 | Cobalt Silicide-Containing Copper Alloy |
| PCT/CN2016/000301 WO2017012283A2 (en) | 2015-07-23 | 2016-06-08 | Cobalt silicide-containing copper alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510439092.8A CN105018782B (en) | 2015-07-23 | 2015-07-23 | A kind of copper alloy of the silicon containing cobalt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105018782A CN105018782A (en) | 2015-11-04 |
| CN105018782B true CN105018782B (en) | 2017-09-26 |
Family
ID=54409079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510439092.8A Active CN105018782B (en) | 2015-07-23 | 2015-07-23 | A kind of copper alloy of the silicon containing cobalt |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20180066339A1 (en) |
| EP (1) | EP3363922B1 (en) |
| CN (1) | CN105018782B (en) |
| WO (1) | WO2017012283A2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018782B (en) * | 2015-07-23 | 2017-09-26 | 宁波博威合金板带有限公司 | A kind of copper alloy of the silicon containing cobalt |
| CN105400987A (en) * | 2015-11-10 | 2016-03-16 | 太仓捷公精密金属材料有限公司 | Copper alloy material |
| CN105385890A (en) * | 2015-11-27 | 2016-03-09 | 宁波博威合金材料股份有限公司 | Nickel and silicon contained bronze alloy and application thereof |
| CN108285988B (en) * | 2018-01-31 | 2019-10-18 | 宁波博威合金材料股份有限公司 | Precipitation strength type copper alloy and its application |
| CN108384986B (en) * | 2018-05-07 | 2020-02-21 | 宁波博威合金材料股份有限公司 | Copper alloy material and application thereof |
| CN108796296B (en) * | 2018-06-12 | 2019-08-06 | 宁波博威合金材料股份有限公司 | One Albatra metal and its application |
| CN109321780A (en) * | 2018-11-20 | 2019-02-12 | 薛中有 | A kind of brass alloys of high elastic modulus and preparation method thereof |
| CN109536756A (en) * | 2018-12-28 | 2019-03-29 | 武汉泛洲中越合金有限公司 | High-strength abrasion-proof Pb-free copper-alloy material, preparation method and piston shoes |
| CN110724851A (en) * | 2019-12-07 | 2020-01-24 | 和县卜集振兴标准件厂 | Heat-resistant corrosion-resistant alloy for switch socket and preparation method thereof |
| CN113322400A (en) * | 2020-02-28 | 2021-08-31 | 株式会社神户制钢所 | Aluminum alloy forged material and method for producing same |
| CN111363948B (en) * | 2020-04-24 | 2021-11-09 | 浙江大学 | Efficient short-process preparation method of high-strength high-conductivity copper alloy |
| CN111663063B (en) * | 2020-06-23 | 2022-04-01 | 宁波金田铜业(集团)股份有限公司 | Lead brass bar suitable for high-speed automatic processing and preparation method thereof |
| CN112048689A (en) * | 2020-09-16 | 2020-12-08 | 扬州大学 | Heat treatment method of welding nozzle |
| CN113293323B (en) * | 2021-05-27 | 2022-04-15 | 宁波金田铜业(集团)股份有限公司 | Silicon bronze bar and preparation method thereof |
| CN115838881A (en) * | 2022-12-06 | 2023-03-24 | 武汉泛洲中越合金有限公司 | Cold-deformation copper alloy and preparation method of high-precision tube bar thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1516748A (en) * | 2002-09-09 | 2004-07-28 | 三宝伸铜工业株式会社 | High-strength copper alloy |
| CN102112639A (en) * | 2008-07-31 | 2011-06-29 | 古河电气工业株式会社 | Copper alloy material for electrical and electronic components, and manufacturing method therefof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19548124C2 (en) * | 1995-12-21 | 2002-08-29 | Euroflamm Gmbh | Friction body and method for producing such |
| JP2002349573A (en) * | 2001-05-29 | 2002-12-04 | Mitsubishi Materials Corp | Sleeve and thrust plate for dynamic pressure bearing made of copper alloy having excellent abrasion- resistant property |
| JP5040140B2 (en) * | 2006-03-31 | 2012-10-03 | Ｄｏｗａメタルテック株式会社 | Cu-Ni-Si-Zn-based copper alloy |
| JP5247010B2 (en) * | 2006-06-30 | 2013-07-24 | Ｊｘ日鉱日石金属株式会社 | Cu-Zn alloy with high strength and excellent bending workability |
| CN101709405A (en) * | 2009-11-03 | 2010-05-19 | 苏州撼力铜合金材料有限公司 | High-intensity wear-resistant complex brass for automotive synchronizing rings |
| JP4672804B1 (en) * | 2010-05-31 | 2011-04-20 | Ｊｘ日鉱日石金属株式会社 | Cu-Co-Si based copper alloy for electronic materials and method for producing the same |
| KR101260912B1 (en) * | 2011-02-01 | 2013-05-06 | 주식회사 풍산 | Copper alloy for sea water and method of producing same |
| CN105018782B (en) * | 2015-07-23 | 2017-09-26 | 宁波博威合金板带有限公司 | A kind of copper alloy of the silicon containing cobalt |
-
2015
- 2015-07-23 CN CN201510439092.8A patent/CN105018782B/en active Active
-
2016
- 2016-06-08 WO PCT/CN2016/000301 patent/WO2017012283A2/en active Application Filing
- 2016-06-08 EP EP16826980.1A patent/EP3363922B1/en active Active
- 2016-06-08 US US15/558,477 patent/US20180066339A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1516748A (en) * | 2002-09-09 | 2004-07-28 | 三宝伸铜工业株式会社 | High-strength copper alloy |
| CN102112639A (en) * | 2008-07-31 | 2011-06-29 | 古河电气工业株式会社 | Copper alloy material for electrical and electronic components, and manufacturing method therefof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3363922A4 (en) | 2019-08-21 |
| US20180066339A1 (en) | 2018-03-08 |
| EP3363922B1 (en) | 2023-04-19 |
| CN105018782A (en) | 2015-11-04 |
| WO2017012283A2 (en) | 2017-01-26 |
| WO2017012283A3 (en) | 2017-03-23 |
| EP3363922A2 (en) | 2018-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105018782B (en) | A kind of copper alloy of the silicon containing cobalt | |
| CN101541987B (en) | Cu-ni-si-co-base copper alloy for electronic material and process for producing the copper alloy | |
| CN105002394B (en) | A kind of precipitation strength type brass alloys and preparation method | |
| JP5050226B2 (en) | Manufacturing method of copper alloy material | |
| CN101646791B (en) | Cu-ni-si-co-based copper alloy for electronic material, and method for production thereof | |
| EP2957646B1 (en) | High-strength cu-ni-co-si base copper alloy sheet, process for producing same, and current-carrying component | |
| KR102009755B1 (en) | Copper alloy wire material and manufacturing method thereof | |
| CN105714148B (en) | A kind of high-strength adonic of spinodal decomposition type | |
| CN102985572B (en) | Cu-Ni-Si copper alloy plate with excellent deep-draw characteristics and production method thereof | |
| JP3962751B2 (en) | Copper alloy sheet for electric and electronic parts with bending workability | |
| CN102747309A (en) | Steel for enamel and production method thereof | |
| CN110923499B (en) | Ce and B-containing titanium bronze alloy strip and preparation method thereof | |
| CN1327016C (en) | Copper base alloy with improved punchin and impacting performance and its preparing method | |
| US8951371B2 (en) | Copper alloy | |
| CN102251174A (en) | Enamel steel and preparation method of cold rolled sheet thereof | |
| CN110157945A (en) | A kind of anti-softening copper alloy and its preparation method and application | |
| CN110541119A (en) | Low-expansion iron-nickel alloy and manufacturing method thereof | |
| CN109402521A (en) | A kind of cold-heading hollow rivet steel and preparation method thereof | |
| KR102640850B1 (en) | Titanium copper alloy strip containing Nb and Al and method for producing the same | |
| JP5555154B2 (en) | Copper alloy for electrical and electronic parts and method for producing the same | |
| CN106399751A (en) | Preparing method for high-strength and high-conductivity copper alloy | |
| CN111378869B (en) | Fine-grain reinforced brass strip for connector and processing method thereof | |
| CN106435250A (en) | Machinable copper base alloy and production method thereof | |
| CN113403500A (en) | High-strength high-elasticity corrosion-resistant high-nickel-manganese-white copper alloy and preparation method and application thereof | |
| JP4032915B2 (en) | Wire for machine structure or steel bar for machine structure and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170417 Address after: 315145 Ningbo, Yinzhou Economic Development Zone, Hong Kong Road, No. 288, No. Applicant after: Ningbo Bowei alloy strip Co. Ltd. Address before: 315137 Zhejiang city of Ningbo province Yinzhou District Yunlong Town of Taiping Bridge Applicant before: Ningbo Powerway Alloy Materials Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |