CN105385890A - Nickel and silicon contained bronze alloy and application thereof - Google Patents
Nickel and silicon contained bronze alloy and application thereof Download PDFInfo
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- CN105385890A CN105385890A CN201510844139.9A CN201510844139A CN105385890A CN 105385890 A CN105385890 A CN 105385890A CN 201510844139 A CN201510844139 A CN 201510844139A CN 105385890 A CN105385890 A CN 105385890A
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Abstract
The invention relates to a nickel and silicon contained bronze alloy, and belongs to the technical field of alloy materials. The microscopic texture structure of the bronze alloy mainly comprises a base body phase and a precipitation phase dispersed on the base body phase; the base body face is a face-centered cubic solid solution, the mass ratio of the base body phase ranges from 94.5% to 99.9%, the mass ratio of the precipitation phase ranges from 0.1% to 5.5%, and the precipitation phase mainly comprises Ni2Si, Cr3Si and Cu3Zr, wherein the ratio of Ni2Si to Cr3Si is larger than or equal to 2 and smaller than or equal to 25. The bronze alloy comprises, by mass percent, 2.5%-4.5% of nickel, 0.5%-1.5% of silicon, 0.1%-0.5% of chromium, 0.05%-0.3% of zirconium and the balance copper and inevitable impurities, wherein the total content of the copper, the nickel and the silicon is larger than or equal to 99%. The nickel and silicon contained bronze alloy has the high intensity, high elasticity, good electric performance, excellent high-temperature softening property resistance and excellent stamping performance, and is particularly suitable for lead frames, connectors, welding instruments and the like in the industrial field.
Description
Technical field
The present invention relates to a kind of bell metal of nickeliferous, silicon, belong to technical field of alloy material.
Technical background
Since from the sixties in 20th century, first piece of unicircuit comes out in the world, semiconductor integrated circuit package material obtains and develops on a large scale very much.From FeNiCo (Kovar alloy) to FeNi
42the ferrous materials such as alloy all once occupied blaster fuse frame material market for a long time.Since the eighties, copper and alloy thereof are widely used in IC with its excellent electrical and thermal conductivity and make blaster fuse frame material, account for more than 80% of IC market share at present.By the end of 2009, China needed copper alloy framework copper strips 5.5 ten thousand tons year, wherein about half from external import.Along with developing rapidly of electronic information new and high technology, the kind of unicircuit is also in quick increase, and therefore researching and developing copper alloy frame material must accelerate.
Cu-Fe system is the main flow alloy of blaster fuse frame material, and using the widest is Cu-Fe-P system alloy, and this is alloy is most typical precipitation strength type.The consumption of this kind of alloy is very large, and the trade mark is maximum, has good physical strength, stress relaxation-resistant characteristic and low creep properties, is the good blaster fuse frame material of a class, accounts for more than 65% of whole blaster fuse frame material consumption.But along with band is to compactization development, while reduced thickness, the intensity improving material under the prerequisite not damaging high connductivity (heat) property must be ensured.Therefore, the requirement of blaster fuse frame material is more and more higher, and the first, the intensity of material can not reduce because of the cutting thin of thickness; The second, due to the raising of integrated level, especially large to power consumption IC, in order to the temperature keeping chip to allow, must have good heat dispersion, namely requires that the heat that semi-conductor chip is operationally produced can distribute by blaster fuse frame material in time; 3rd, the electroconductibility of material is high, and the resistance that framework produces is just little, is also beneficial to heat radiation; 4th, due to plastic packaging condition by soldering to eutectic bonding future development, plastic packaging temperature brings up to 470 DEG C by 240 DEG C, can have higher requirement to the resistance to softening at high temperature in short-term of material, for avoiding affecting laminating component performance, after requiring the plastic packaging of material, Hardness loss is not more than 20%.
The average intensity of iron bronze is at 400-450MPa, and softening temperature is 450 DEG C, does not reach the demand that blaster fuse frame material is more and more higher.And Cu-Ni-Si system is typical precipitation strength alloy, Cu-ni-si-based alloy for electronic material disclosed in Chinese patent (CN101646792A), specifically disclose Ni1.0-4.5 quality %, Si0.5-1.2 quality %, Cr0.003-0.3 quality %, wherein the weight ratio of Ni and Si is 3≤Ni/Si≤5.5, by composition and size, the individual number density of control Cr-Si compound, play the additive effect of alloying elements cr, obtain intensity, the electric conductivity good electronic material gloomy series copper alloy of section.Although this alloy has higher electroconductibility and intensity, the resistance to thermally strippable of soldering is poor, resistance to softening at high temperature can poor, processing characteristics is general.
Summary of the invention
Of the present invention for the deficiencies in the prior art, provide a kind of excellent performance and the bell metal of nickeliferous, the silicon of suitable processing.
Above-mentioned purpose of the present invention is achieved through the following technical solutions: a kind of bell metal of nickeliferous, silicon, the weave construction of described bell metal is mainly matrix phase and the precipitated phase of Dispersed precipitate on described matrix phase, described matrix phase is face-centered cubic type sosoloid, mass ratio 94.5-99.9% shared by described matrix phase, mass ratio shared by described precipitated phase is 0.1-5.5%, and described precipitated phase is mainly Ni
2si, Cr
3si and Cu
3zr, and 2≤Ni
2si/Cr
3si≤25.
Cu
3zr phase is precipitation strength phase main in bell metal of the present invention, and it all dissolves in Copper substrate and forms supersaturated solid solution after alloy solid solution process, and separate out from Copper substrate in ag(e)ing process subsequently, Dispersed precipitate is in alloy.Cu
3zr phase plays pinning effect to dislocation after separating out, thus promotes intensity and the hardness of Copper substrate, and simultaneously because it is separated out, make Copper substrate become pure, reduce the inhibition of electronics, resistivity reduces and electric conductivity is significantly promoted.Ni
2si phase and Cu
3zr phase formation mechenism is similar, significantly can promote the intensity of alloy, hardness and conductivity.Cr
3si phase is primary phase in the alloy, produces in alloy liquid and crystallisation process, and it at high temperature has stable structure and performance, still can keep primary formation and not dissolve, therefore significantly can promote the high temperature resistance softening power of alloy at 800 DEG C.
By Ni
2si and Cr
3the ratio control of Si, at 2-25, ensure that two-phase forms strengthening phase more fast, uniformly, and more Dispersed precipitate, in Copper substrate, makes alloy be strengthened greatly.Cr
3si phase is primary phase, generates in alloy melting and process of setting, and the Cr first generated
3si phase can be used as Ni in alloy aging process
2the forming core of Si phase separates out center, increases nucleating center, suppresses Ni
2si phase is too grown up, and therefore obtains the Ni of more fine uniform distribution
2si phase.And the strengthening phase of more small and dispersed distribution is the key of alloy strengthening.
In the bell metal of above-mentioned a kind of nickeliferous, silicon, the composition of described bell metal comprises by mass percentage: nickel: 2.5-4.5%, silicon: 0.5-1.5%, chromium: 0.1-0.5%, zirconium: 0.05-0.3%, surplus is copper and inevitable impurity, total content >=99% of Qi Zhongtong, nickel and silicon.
In bell metal, nickel and copper are unlimited solid solution element, can form unlimited solid solution with copper, strengthening Copper substrate, promote intensity and the hardness of copper alloy; Silicon has certain solid solubility in copper, can strengthened copper alloy matrix, but comparatively large on the electric conductivity impact of copper, significantly can reduce the electric conductivity of copper alloy.But after adding nickel and silicon with certain proportion in copper alloy, and heat-treat, can obtain the Compound Phase of nickel and silicon, molecular formula is Ni
2si, it is the second-phase formal distribution of disperse in Copper substrate, to the effect of dislocation nail nipping bundle, thus promote intensity and the hardness of Copper substrate, simultaneously because it is separated out, make Copper substrate become pure, reduce the inhibition of electronics, resistivity reduces and electric conductivity improves.Bell metal nickel content 2.5-4.5%, silicone content 0.5-1.5% of the present invention.If lower than this scope, Ni in alloy substrate
2si phase amount is on the low side, does not have the effect of strengthening, and if higher than this scope, then too much, the precipitation that impact is overall, very easily causes Ni to the second-phase quantity in copper sosoloid
2si phase is assembled, alligatoring, reduces alloy property on the contrary.
Chromium is also the main component in alloy of the present invention.Solid solubility under chromium normal temperature in copper is very little, but during high temperature, solid solubility is relatively large, and therefore chromium is precipitation strength type element main in copper alloy of the present invention.In copper alloy, utilize thermal treatment can obtain the strengthening phase particle of simple substance Cr, strengthening effect is formed to matrix.When chromium joins in Corson alloy, a Cr part forms simple substance strengthening phase particle, and in a part of Cr and Copper substrate, the Si of solid solution on a small quantity forms Cr
3si compound.Find Cr after deliberation
3si compound is high-temperature stable Compound Phase, even if also can not dissolve under 800 DEG C of high temperature, therefore it is high temperature resistant softening very competent.So add the Cr of certain content in Corson alloy, high-temperature stable phase Cr can be produced
3si.Bell metal chromium content of the present invention is 0.1-0.5%, if chromium content is less than this scope, Cr and Si is difficult to form Cr
3si, even if formed, quantity is also few, can not play due effect, and if chromium content is greater than this scope, chromium by cause in conjunction with silicon forms compound in a large number nickel can in conjunction with silicone content significantly reduce, and Cr
3si Main Function is high-temperature behavior and is not exclusively strengthening, so nickel causes Ni less in conjunction with silicon
2si phase is few, and the over-all properties of material is deteriorated.
The 0.05-0.3% zirconium added by mass percentage has in copper alloy must solubleness, not only can improve the recrystallization temperature of Copper substrate, promotes the resistance to softening at high temperature energy of copper alloy, also can form Cu with copper
3zr intermediate compound, plays strengthening effect to Copper substrate, promotes the electrical property of copper alloy simultaneously.Bell metal zirconium content of the present invention, at 0.05-0.3%, if lower than this scope, then do not have effect, and higher than this scope, though alloy can play strengthening effect, greatly can fall low-alloyed electroconductibility, affect the over-all properties of alloy.
As preferably, the massfraction of Ni+Si and the Cr in described bell metal meets 5≤(Ni+Si)/Cr≤32.
Suitable (Ni+Si)/Cr can ensure that two kinds of strengthening phases reasonably separated out by alloy, and alloy plays biphase strengthening effect.Ni+Si and Cr is controlled when 5≤(Ni+Si)/Cr≤32, Ni
2si and Cr
3si forms the second strengthening phase of fine uniform.If higher than this ratio, Ni
2si phase is far more than Cr
3si phase, Cr
3si phase cannot play the effect of nucleating center, if lower than this ratio, and Ni
2then very little, alloy cannot play strengthening effect to Si phase, then alloy strength is not high.And in this ratio, Ni
2si phasor is applicable to, and can play enough strengthening effects by alloy, simultaneously rational Cr
3si phase can be Ni
2si phase is separated out and is provided nucleating center, contributes to forming strengthening phase that is tiny, Dispersed precipitate.
In the bell metal of above-mentioned a kind of nickeliferous, silicon, the composition of described bell metal also comprises the magnesium of 0.005-0.3% by mass percentage.0.005-0.1% magnesium is added in bell metal, while less on the conductivity impact of bell metal, be solid-solution in Copper substrate on the one hand, strengthening effect is risen to bell metal, effectively can eliminate the oxygen in bell metal on the other hand, reduce the oxygen level of bell metal, promote the quality of alloy.Bell metal Mg content of the present invention, at 0.005-0.3%, if lower than this scope, then do not have effect, and higher than this scope, though alloy can play strengthening effect, can reduce the mobility of alloy solution, and alloy processing causes difficulty.
In the bell metal of above-mentioned a kind of nickeliferous, silicon, the composition of described alloy also comprises the cerium of 0.01-0.1% by mass percentage.The cerium of 0.01-0.1% is added in bell metal of the present invention, can refining alloy crystal grain, improve recrystallization temperature, promote the intensity hardness of bell metal, thermotolerance, high temperature resistance softening power and matrix purity.Bell metal cerium content of the present invention, at 0.01-0.1%, if lower than this scope, does not then have the effect promoting material property, and higher than this scope, unnecessary cerium can react with the oxygen etc. in matrix, cause oxide inclusion, make alloy strength decline on the contrary, be unfavorable for that product quality controls.
Add magnesium and cerium in bell metal of the present invention simultaneously, except the effects such as solution strengthening, degasification deoxidation, crystal grain thinning, also can form high melting compound between two kinds of elements, this high melting compound can form extra nucleating center, further refinement matrix, promotes the performance of bell metal.
As preferably, the composition of described bell metal comprises by mass percentage: nickel: 3.0-3.5%, silicon: 0.7-1.0%, chromium: 0.2-0.4%, magnesium: 0.005-0.05%, zirconium: 0.08-0.28%, cerium 0.03-0.08%, surplus is copper and inevitable impurity, total content >=99% of Qi Zhongtong, nickel and silicon.
In the bell metal of above-mentioned a kind of nickeliferous, silicon, described bell metal also comprises one or more compositions be selected from Co, Zn, Mn, Fe, Sn element, and each elementary composition meets 0.01-2.5% by mass percentage, and summation is no more than 3.5%.
The present invention is nickeliferous, the preparation method of the bell metal of silicon comprises: batching, melting, ingot casting, machine-shaping and thermal treatment, and wherein said thermal treatment comprises ageing treatment:
When preparing the Bronze alloy bar of nickeliferous, silicon, aging temperature is 420-520 DEG C;
When preparing the bell metal band of nickeliferous, silicon, aging temperature is 400-500 DEG C.
As preferably, when preparing the bell metal of nickeliferous, silicon, ageing treatment carries out ageing treatment for being warming up to 420 DEG C-500 DEG C with the average heating speed of 1-30 DEG C/min, and the soaking time of ageing treatment is 1-6h (this programme is applicable to Bronze alloy bar and the band of nickeliferous, silicon simultaneously).
Bell metal of the present invention is a kind of ageing strengthening type alloy containing multiple precipitated phase, the precipitation of each precipitated phase, distribution and impact are each other the key factors determining this alloy material performance, and ensure that the precipitation of each precipitated phase and the major control means of distribution are the thermal treatment process of this material.
During the ageing treatment of bell metal of the present invention, heat up with the average heating speed of 1-30 DEG C/min, if heat-up rate is excessively slow, be less than 1 DEG C/min, heat treatment time is long, affects production efficiency, increasing energy consumption; If heat-up rate is too fast, be greater than 30 DEG C/min, then material rises to high temperature at short notice, and material internal stress concentration discharges, and can cause material cracks.
During the ageing treatment of bell metal of the present invention, be advisable with 1-6h soaking time, scope inside holding at this moment, material properties is excellent.If soaking time is less than 1h, then material ages is insufficient, and separate out not exclusively, material lack time effect, material hardness and electroconductibility are all bad; If soaking time is greater than 6h, then material produces overaging, though the good hardness of electroconductibility is not good, and can causes and organizes coarse grains, locally even burning.
Tensile strength >=the 750MPa of above-mentioned bell metal alloy, yield strength/tensile strength >=85%, stress relaxation rate < 12%, electric conductivity >=30%IACS at 100 DEG C, under 50% yield strength initial stress, 1000h condition, anti-softening temperature >=580 DEG C.
The invention still further relates to a kind of electronic equipments parts, described electronic equipments parts are made up of above-mentioned bell metal that is nickeliferous, silicon.
As preferably, described electronic equipments parts can be lead frame, junctor, welding apparatus etc.Further preferably, described electronic equipments parts are lead frame.
With alloy phase ratio of the prior art, bell metal of the present invention is on the basis of copper nisiloy, by adding a certain amount of chromium, zirconium, also have magnesium, cerium, with even crystal grain thinning, ensureing, under the excellent prerequisite of electrical property, to promote the intensity, high temperature resistance softening performance, pressworkability etc. of material, solving copper alloy with high strength and high conductivity intensity and electrical property can not compatibility and copper alloy high temperature resistance softening performance and the general problem of pressworkability.This invention also solves a difficult problem of how to work in coordination with between multiple precipitated phase, fill up the blank of current techniques.The present invention is nickeliferous, the bell metal of silicon has high strength, snappiness, good electrical property, the excellent high temperature resistance property of softening and have excellent pressworkability, is particularly suitable for the lead frame in industrial circle, junctor, welding apparatus etc.
Embodiment
Be below specific embodiments of the invention, technical scheme of the present invention is further described, but the present invention is not limited to these embodiments.
Table 1: the present invention is nickeliferous, the composition of the bell metal of silicon and mass percent (%) thereof
Embodiment 21-40
Press composition and the mass percent batching thereof of the bell metal of nickeliferous, the silicon described in table 1 embodiment 1-20 respectively, then through melting, ingot casting, machine-shaping, finally being warming up to 420 DEG C-500 DEG C with the average heating speed of 1-30 DEG C/min carries out ageing treatment, insulation 1-6h, obtains that the present invention is nickeliferous, the bell metal finished product of silicon.
Analyze the heterogeneous microstructure of the bell metal finished product of nickeliferous in embodiment 21-40, silicon, result is as shown in table 2.
The bell metal of nickeliferous in embodiment of the present invention 21-40, silicon is mainly through added various alloying element and specific ageing treatment, form microcosmic mesophase spherule of different nature and simple substance, these microcosmic phase disperses be distributed in Copper substrate, the various performances of copper alloy are effectively improved, embodiment of the present invention 21-40 is nickeliferous, the relevant phase of the bell metal of silicon and content thereof is in table 2.
Table 2: the mesophase spherule of the bell metal of nickeliferous in embodiment of the present invention 21-40, silicon and content thereof
Embodiment 41-60
Press composition and the mass percent batching thereof of the bell metal of nickeliferous described in table 1 embodiment 1-20, silicon respectively; then the method melting of Alloying Treatment and covering protection refining is adopted; and ingot casting is cast as at 1150-1350 DEG C; ingot casting is first heated at 850-950 DEG C; again through large extrusion ratio extrusion blooming; then solution treatment at 850-950 DEG C; and through the cold deformation of 20-60% working modulus; then aging strengthening model at 420-520 DEG C, finishing tough becomes the Bronze alloy bar finished product of nickeliferous, the silicon of Ф 8.
Detect by concerned countries and industry standard prescriptive procedure that embodiment of the present invention 41-60 is nickeliferous, tensile strength, yield strength, gravitation-resistant relaxation property, electric conductivity, the softening temperature of the Bronze alloy bar of silicon, test-results is in table 3.Wherein, tensile test at room temperature carries out on electronic universal testing machine for mechanical properties according to " GB/T228.1-2010 metal material stretching test part 1: room temperature test method ", and sample adoption rate coefficient is the circular cross section proportional test bar of 5.65.Stress relaxation ability test is carried out according to " GB/T10120-1996 metal stresses relaxation test method ".Conductivity test is according to " GB/T3048-2007 electric wire electrical performance test method part 2: metallic substance resistivity test ", and this test apparatus is ZFD micro computer electric bridge instrument for measuring DC resistance, and sample length is 1000mm, represents with %IACS.According to " HB5420-89 resistance welding electrode and supplementary unit Copper and its alloy ", softening temperature test requires that method is tested.
Table 3: the performance test results of the Bronze alloy bar of nickeliferous in embodiment of the present invention 41-60, silicon
Embodiment 61-80
Nickeliferous in embodiment 61-80, identical with embodiment 41-60 of the composition of the bell metal of silicon and mass percent thereof, namely press described in table 1 embodiment 1-20 nickeliferous respectively, the composition of the bell metal of silicon and mass percent batching thereof, then the method melting of Alloying Treatment and covering protection refining is adopted, and ingot casting is cast as at 1150-1350 DEG C, ingot casting is first heated at 850-950 DEG C, again through 60-95% working modulus hot rolling cogging, then solution treatment at 750-900 DEG C, and through the cold deformation of 20-80% working modulus, then aging strengthening model at 400-500 DEG C, finishing tough becomes that 0.2mm's is nickeliferous, the bell metal band finished product of silicon.
Tensile strength, yield strength, gravitation-resistant relaxation property, electric conductivity, the softening temperature of the bell metal band of nickeliferous in embodiment of the present invention 61-80, silicon, test-results is in table 4.Detection method is with reference to the detection method of embodiment of the present invention 41-60.
Table 4: the performance test results of the bell metal band of nickeliferous in embodiment of the present invention 61-80, silicon
Application Example
Bell metal Strip that is nickeliferous, silicon in the bell metal plate bar of nickeliferous, the silicon in optional embodiment 41-60 or embodiment 61-80 makes junctor.
Bell metal Strip that is nickeliferous, silicon in optional embodiment 61-80 makes lead frame.
In sum, nisiloy bell metal of the present invention not only has high strength, snappiness, good electrical property, also there is the excellent high temperature resistance property of softening and the stress relaxation-resistant ability of excellence, the industrial circle such as be particularly suitable for welding apparatus, junctor, lead frame add.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Claims (10)
1. the bell metal of nickeliferous a, silicon, it is characterized in that, the heterogeneous microstructure of described bell metal is mainly matrix phase and the precipitated phase of Dispersed precipitate on described matrix phase, described matrix phase is face-centered cubic type sosoloid, mass ratio 94.5-99.9% shared by described matrix phase, mass ratio shared by described precipitated phase is 0.1-5.5%, and described precipitated phase is mainly Ni
2si, Cr
3si and Cu
3zr, and 2≤Ni
2si/Cr
3si≤25.
2. the bell metal of a kind of nickeliferous, silicon according to claim 1, it is characterized in that, the composition of described bell metal comprises by mass percentage: nickel: 2.5-4.5%, silicon: 0.5-1.5%, chromium: 0.1-0.5%, zirconium: 0.05-0.3%, surplus is copper and inevitable impurity, total content >=99% of Qi Zhongtong, nickel and silicon.
3. the bell metal of a kind of nickeliferous, silicon according to claim 2, is characterized in that, the massfraction of Ni+Si and the Cr in described bell metal meets 5≤(Ni+Si)/Cr≤32.
4. the bell metal of a kind of nickeliferous, silicon according to claim 3, it is characterized in that, the composition of described bell metal also comprises the magnesium of 0.005-0.3% by mass percentage.
5. the bell metal of a kind of nickeliferous, the silicon according to Claims 2 or 3 or 4, it is characterized in that, the composition of described bell metal also comprises the cerium of 0.01-0.1% by mass percentage.
6. the bell metal of a kind of nickeliferous, silicon according to claim 5, it is characterized in that, the composition of described bell metal comprises by mass percentage: nickel: 3.0-3.5%, silicon: 0.7-1.0%, chromium: 0.2-0.4%, zirconium: 0.08-0.28%, magnesium: 0.005-0.05%, cerium 0.03-0.08%, surplus is copper and inevitable impurity, total content >=99% of Qi Zhongtong, nickel and silicon.
7. the bell metal of a kind of nickeliferous, silicon according to claim 6, it is characterized in that, described bell metal also comprises one or more compositions be selected from Co, Zn, Mn, Fe, Sn element, each elementary composition meets 0.01-2.5% by mass percentage, and summation is no more than 3.5%.
8. the bell metal of a kind of nickeliferous, the silicon according to any one in claim 1-4,6-7, it is characterized in that, tensile strength >=the 750MPa of described bell metal, yield strength/tensile strength >=85%, stress relaxation rate < 12% at 100 DEG C, under 50% yield strength initial stress, 1000h condition, electric conductivity >=30%IACS, anti-softening temperature >=580 DEG C.
9. the bell metal of a kind of nickeliferous, silicon according to claim 5, it is characterized in that, it is characterized in that, tensile strength >=the 750MPa of described bell metal, yield strength/tensile strength >=85%, stress relaxation rate < 12%, electric conductivity >=30%IACS at 100 DEG C, under 50% yield strength initial stress, 1000H condition, anti-softening temperature >=580 DEG C.
10. electronic equipments parts, is characterized in that, described electronic equipments parts are made up of the bell metal that is nickeliferous, silicon described in any one of claim 1-9.
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