CN104073686B - A kind of deformation dilute copper alloy material riveted and application thereof - Google Patents

A kind of deformation dilute copper alloy material riveted and application thereof Download PDF

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Publication number
CN104073686B
CN104073686B CN201410269844.6A CN201410269844A CN104073686B CN 104073686 B CN104073686 B CN 104073686B CN 201410269844 A CN201410269844 A CN 201410269844A CN 104073686 B CN104073686 B CN 104073686B
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copper alloy
alloy
dilute copper
deformation
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CN104073686A (en
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孙文声
郜晓彬
余惺
杨澍
周宏渤
张明
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Ningbo Powerway Alloy Material Co Ltd
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Ningbo Powerway Alloy Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • C22C18/04Alloys based on zinc with aluminium as the next major constituent

Abstract

A kind of deformation dilute copper alloy material riveted and application thereof.Dilute copper alloy material disclosed by the invention is made up of Al, Cu, M, Zn and inevitable impurity, M is at least one element in Ni, V, Ti, Zr, La, Ce, Pr, Nd, Mo, Si, Be, Cr, Mn, Co and Mg, and impurity includes at least one element in Fe, Pb, Sn, Sb and Cd;In the percentage by weight composition of this dilute copper alloy material: content z=0.001 1.0 wt% of content y=0.1 4.0 wt%, M of content x=0.1 6.0 wt%, Cu of Al, the total amount≤0.1 wt % of impurity, surplus is Zn;The content sum of Al Yu Cu meets: the ratio of the content of 0.5 wt%≤x+y≤9.0 wt%, Al and Cu meets: 1≤x/y≤4.This alloy can be applicable to the attaching plug of household electrical appliance etc. need to carry out to rivet, the parts of punch process.

Description

A kind of deformation dilute copper alloy material riveted and application thereof
Technical field
The present invention relates to dilute copper alloy material and applied technical field thereof, be specifically related to a kind of deformation dilute copper alloy material riveted And application, this alloy material can be applicable to the attaching plug of household electrical appliance etc. need to carry out to rivet, the parts of punch process.
Background technology
Copper and copper alloy are one of non-ferrous metals most widely used, that consumption is maximum, the consumption in electronic apparatus industry account for half with On.Although in great demand to copper, but China's copper resource critical shortage, Domestic Resources supply rate is less than 25%, and copper valency also continues Keep a high position.Further, the copper content of copper alloy is higher, and typically more than 55%, and copper raw material price generally accounts for copper alloy price 85-90%, therefore copper valency is extremely serious on the Capital Flow of Copper fabrication enterprise and the impact of relation between market supply and demand.The day of copper resource Short and the lasting high-copper valency of benefit makes the fact that people have to accept: copper and copper alloy have become rare material.Therefore, for Tackling world economic situation complicated and changeable, developing novel low-cost alloy material replacement copper alloy has become non-ferrous metal and has added The future developing trend of the industries such as work.
Zinc-containing alloy is another kind of important non-ferrous alloy, have that fusing point is low, good fluidity, conduct electricity very well, raw material low The feature such as honest and clean, uses generally as die casting and gravitational casting product.The alloy that pressure and gravitational casting obtain is as-cast structure, often Existing with dendritic form, tissue topography is thick, and owing to zinc is hexagonal structure crystal, during room temperature, slip system is less, and casting is closed Gold is in fragility, and elongation percentage is the lowest, it is impossible to carry out riveting, deep processing that the deflection such as crimping is bigger.
Due to the cost advantage of zinc-containing alloy, in recent years in the prevailing application of some copper alloy, cast zinc alloy The most progressively instead of some copper alloys.But the kirsite using extrusion process to produce can not carry out following process deformation, and die casting The profile of zinc alloy product is limited to mould, often there is the defects such as spue line, affects following process, therefore uses cast zinc to close Gold substitutes the popularization and application of copper alloy and is subject to bigger restriction, all the more so for deformation zinc alloy.
Attaching plug is relatively conventional household electrical appliance parts, and its usage amount is big, and range is wide.Currently manufactured attaching plug Raw material in the majority with brass alloys, such as H59, H62 etc., but relatively costly, add the resource-constrained of copper, will necessarily be to family The future development of electrical appliance causes restriction.
The free-electron model under certain condition need to be met as the material of attaching plug must not occur damaging and after energising in the stipulated time Temperature rise must not exceed 45K.IEC60884-1 " family expenses and the similar applications plugs and sockets of International Electrotechnical Commission (IEC) 1 part: General Requirement " standard regulation: if sample is without flexible-cable, weight be less than 100g, free-electron model 1000 times, Must not there is infringement in surface;After being energized 1 hour, the temperature rise of latch must not exceed 45K.Except free-electron model and the requirement of temperature rise Outward, material also needs to meet the requirement in terms of other machinings, and the most suitable intensity, hardness and plasticity, to meet subsequent power The processing requests such as riveting in plug manufacture process, punching press.Cast zinc alloy cannot meet requirements above, uses deformation zinc alloy Report is currently also rarely had as attaching plug.
The deformation zinc alloy of present stage most study is Zn-Al system alloy, but this alloy exists, and cutting ability is poor, intercrystalline corrosion The shortcomings such as tendency is serious, dimensional stability is low, it is impossible to meet the attaching plug manufacturing property such as easily processing and can rivet to material Can requirement.
JP Laid-Open 10-168533A discloses a kind of kirsite, and this kirsite contains: 0.1-4.5%Mg, and remaining is Zn and not Evitable impurity.If it is necessary, at least one element is selected from Cu, Ni, Mn, total amount≤7%, and/or≤10%Al, and / or at least one element selected from Ti, Zr, Cr, Co, Li, Be, Si and La series of elements, total amount≤2%, this alloy is at height There is under temperature hot strength and the creep-resistant property of excellence, but this alloy is cast zinc alloy, it is adaptable to chill casting, hot-die casting Make, the casting method such as injection moulding.
CN102277517A discloses a kind of high strength weldable kirsite, and this alloy consists of: aluminium 8~12%;Copper 0.5~3%; Titanium 0.05~0.5%;Magnesium 0.02~0.2%;Chromium 0.03~0.15%;Rare earth 0.1~0.25%;Surplus is that zinc is with inevitable Impurity;Impurity content≤0.05%.As a kind of Zn-Al base deformation zinc alloy, the tensile strength of this alloy at more than 360MPa, And elongation percentage only≤10%, it is impossible to meet the requirement to riveting processing of the attaching plug kirsite.
Summary of the invention
The technical problem to be solved is, for the deficiencies in the prior art, it is provided that a kind of deformation dilute copper alloy riveted Material, this alloy material can be applicable to the attaching plug of household electrical appliance etc. need to carry out to rivet, the parts of punch process.
The present invention solves the technical scheme that above-mentioned technical problem used: a kind of deformation dilute copper alloy material riveted, this is low Cu alloy material by Al, Cu, M, Zn and inevitably impurity form, wherein M be Ni, V, Ti, Zr, La, Ce, At least one element in Pr, Nd, Mo, Si, Be, Cr, Mn, Co and Mg, impurity includes Fe, Pb, Sn, Sb With at least one element in Cd, the microstructure of this dilute copper alloy material contains the aluminium zinc-copper ternary eutectic tissue rich in aluminium;
In the percentage by weight composition of this dilute copper alloy material: the content y=0.1-5.0 of the content x=0.1-6.0wt%, Cu of Al The content z=0.001-1.0wt% of wt%, M, the total amount≤0.1wt% of impurity, surplus is Zn;The content sum of Al Yu Cu Meet: the ratio of the content of 0.5wt%≤x+y≤9.0wt%, Al and Cu meets: 1≤x/y≤4.
Al forms primary α dendrite and eutectic α phase with the α-Al solid solution thereof rich in aluminium, and a small amount of Al is solid-solution in η-Zn solid solution In body, acting primarily as invigoration effect in the alloy, along with the raising of Al content, the intensity of alloy, hardness improve, but plasticity reduces. Although the Al of proper content can improve the mobility of alloy casting, anti-oxidation, and improves pressure machining characteristics, but zinc-aluminium Base deformation zinc alloy, when carrying out riveting and punch process, owing to impact flexibility is poor, easily ftractures, so such alloy is uncomfortable Share in riveting processing.But the present inventor is found by lot of experiments, zinc-aluminum based alloy adds a certain amount of copper, can be formed The netted aluminium zinc-copper ternary eutectic tissue rich in aluminium, this ternary eutectic tissue makes the riveting of alloy and pressworkability obtain Bigger improvement, cracking phenomena substantially reduces.And being formed of this netted ternary eutectic tissue needs suitable aluminium, copper proportioning, this In invention, the content ratio of Al/Cu controls at 1-4, and aluminium content controls at 0.1-6.0wt%.
In the present invention, addition Cu is in addition to being solid-solution in α phase and η phase, primarily forms ε phase (i.e. CuZn5).Cu is to metastable state β phase in version play inhibitory action, it is provided that the mobile performance of intensity, hardness, corrosion resistance and aluminium alloy that alloy is high, reduce close The Susceptibility To Intergranular Corrosion of gold.Copper maximum solid solution degree in zinc is 2.7wt%, along with the reduction of temperature, separates out ε phase, at copper In the case of content is relatively low, the quantity that ε phase separates out is few, size is little, and alloy is under keeping relatively small intensity amplification, and percentage elongation increases, Hardness is held essentially constant, and suitably carries high copper content, is conducive to refining the matrix of zinc-aluminum based alloy, improves consistency, Reduce shrinkage cavity shrinkage porosity tendency.In the present invention, η phase, α phase, ε phase three separate out jointly, form the aluminium zinc-copper three rich in aluminium Unit's eutectic structure, this precipitation is organized in while significantly reducing intensity, contributes to the riveting of subsequent material, punch process, suitable Profit rolling lenticular wire.But copper content is unsuitable too high, and too high copper content can separate out substantial amounts of ε phase, although intensity, hardness increase, But elongation percentage is greatly reduced, therefore the present invention by copper content control at 0.1-5wt%.
Preferably, in the percentage by weight composition of this dilute copper alloy material: x=0.5-4.5wt%, y=0.5-3.0wt%, 1≤x/y ≤2.5。
Preferably, in the percentage by weight composition of this dilute copper alloy material: x=4.6-6.0wt%, y=0.3-3.5wt%, 1≤x/y ≤3。
Preferably, the tensile strength of this dilute copper alloy material is 290-400MPa, and hardness is 90-110HV5, elongation percentage >=15%. After dilute copper alloy material of the present invention makes the round wires of Ф 4.8 or Ф 4.0, it is machined into contact pin, by riveting equipment by power line Link together with plug, i.e. make AC/DC plug.Power line generally uses T2 copper, for realizing dilute copper alloy plug and electricity Source line preferably connects, and both mechanical performances should be close, and it is 290-400MPa that present aspect controls the tensile strength of dilute copper alloy, Hardness is 90-110HV5, elongation percentage >=15%, to realize the more preferable matching connection of dilute copper alloy plug and power line.
Preferably, the content of described Ni is 0.001-0.1wt%, and the content of described Mg is 0.001-0.1wt%, described The content of Mn be 0.001-0.1wt%.Ni, Mg have a small amount of solid solubility in zinc, are solid-solution in η phase and β phase, can The transformation of suppression β phase, is just improved the effect of intensity when both additions in dilute copper alloy are more than 0.001%, and can Put forward heavy alloyed intergranular corrosion resistance performance, but along with the increase of both content, although the intensity of alloy, hardness improve, but simultaneously Plasticity reduces, and increases hot tearing and cold cracking performance, makes riveting and punching performance be deteriorated.Consider both impacts on alloy property, In the present invention, the content of Ni, Mg and Mn controls respectively at 0.001-0.1wt%.
Preferably, the content of described V is 0.001-0.1wt%, and the content of described Ti is 0.001-0.1wt%, described Zr Content be 0.001-0.1wt%.Zr, V, Ti solubility in dilute copper alloy is the lowest, and three can be combined with Zn, Cu, Al Generate the particle of small and dispersed, play refining alloy crystal grain, the effect of raising intensity, the TiZn formed such as Ti Yu Zn3Can refine The crystal grain of alloy, thus put forward heavy alloyed mechanical property and recrystallization temperature, but too high content easily causes the fragility of alloy, no Being beneficial to follow-up riveting processing, therefore addition controls respectively at 0.001-0.1wt%.
Preferably, the content of described La is 0.001-0.1wt%, and the content of described Ce is 0.001-0.1wt%, described The content of Pr be 0.001-0.1wt%, the content of described Nd is 0.001-0.1wt%;The content of described Mo is 0.001-0.1wt%, the content of described Si is 0.001-0.1wt%, and the content of described Cr is 0.001-0.1wt%, described The content of Co be 0.001-0.1wt%.Rare earth element La and Ce, Pr, Nd can play good crystal grain thinning and degasification is made With, can obviously improve the mechanical property of alloy, riveting processing and pressworkability after interpolation, but the too high meeting of addition causes base Body fragility, elongation percentage is substantially reduced.The addition of Mo, Si, Cr, Co controls at 0.001-0.1wt% respectively, Mo, Si, Cr, Co and zinc generate the second phase, are dispersed in Zinc Matrix, play second-phase strength effect.
Preferably, the content of described Be is 0.001-0.1wt%.The Be of 0.001-0.1wt% is solid-solution in Zinc Matrix, plays The effect of solution strengthening.
Dilute copper alloy of the present invention has stronger sensitiveness for impurity such as Fe, Pb, Sn, Sb and Cd.Formed containing during impurity F e FeAl3And FeZn7Meet and drop low-alloyed mobility, and the Hard Inclusion formed is unfavorable for follow-up deep processing, particularly to rear Continuous plating performance impact is very big, and product surface forms stain the most after plating.Pb is that fine particle is distributed in crystal boundary and interdendritic, Easily cause intercrystalline corrosion.Sn and zinc can form the eutectic of low melting point so that material easily becomes fragile, and is unfavorable for follow-up processing. Sb and Cd is present in solid solution, forms red brittleness, reduces corrosion resisting property.Therefore the element such as Fe, Pb, Sn, Sb and Cd is at this In invention alloy, being all to control as impurity element, overall control is at below 0.1wt%.For limiting Pb, Cd etc. further Harmful element content, meets the requirement of environmental protection, and in alloy of the present invention, the content of impurity Pb should control at below 0.005wt%, miscellaneous The content of matter Cd should control at below 0.001wt%.
Preferably, the deformation dilute copper alloy material application on attaching plug that the present invention can rivet.The riveting of dilute copper alloy of the present invention It is good with pressworkability to connect, can be applicable to the attaching plug etc. of household electrical appliance need to carry out to rivet, the parts of punch process.
Compared with prior art, it is an advantage of the current invention that:
(1) alloy of the present invention is compared with common Zn-Cu, Zn-Al base deformation zinc alloy, have suitable intensity, hardness and Elongation percentage, tensile strength is maintained between 290-400MPa, and hardness is at 90-110HV5, elongation percentage >=15%, it is possible to achieve riveting Connect, pressworkability.
(2) common variation kirsite recrystallization temperature is low, and meeting occurrence dynamics recrystallization in drawing process, when working modulus reaches 30% Time will produce work softening, but instant invention overcomes the above-mentioned deficiency of common variation kirsite, the processing of dilute copper alloy of the present invention Just there will be work softening phenomenon when rate reaches 85%, thus dilute copper alloy of the present invention has good deformation performance, it is possible to smoothly Produce round wires and lenticular wire.
(3) this invention alloy meets the attaching plug requirement to material temperature rise model, and the temperature rise after 1h is generally 15-34K, symbol Close IEC60884-1 to the performance requirement in terms of attaching plug temperature rise.
(4) this alloy is mainly used in the replacement of basis brass attaching plug, can be cost-effective, it is possible to being applied to other needs Carry out riveting, the replacement of the copper alloy element of punch process.
Accompanying drawing explanation
Fig. 1 is the SEM picture of embodiment 1 dilute copper alloy microstructure;
Fig. 2 is the EDAX results in Fig. 1 at arrow indication.
Detailed description of the invention
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail.
(comparative example 1 is closed according to JP Laid-Open 10-168533A to have chosen 20 embodiment alloys and 2 comparative example alloys Gold proportioning, comparative example 2 carries out alloy proportion according to CN102277517A), use identical process to be processed into manufacture respectively Round wires needed for AC/DC plug: produce into Φ 100-Φ 200mm ingot casting by D.C.casting or horizontal casting, ingot casting is through extruding After be sawn to the length of 400-700mm, be heated to 200-300 DEG C, squeeze out round wires by forward extrusion machine or indirect extrusion machine Base Φ 6-12, through multi-drawing with at least twice annealing aft-loaded airfoil become specification to be Φ 4.8, Φ 4.0 round wires finished product, then it is entered Row aligning.Round wires becomes contact pin after machining, then by riveting equipment, power line and plug is linked together, makes AC/DC finished product plug.Embodiment, the composition of comparative example and the performance test results are shown in Table 1.
The SEM picture of embodiment 1 dilute copper alloy microstructure is as it is shown in figure 1, EDAX results at arrow indication in Fig. 1 As in figure 2 it is shown, it is evident that alloy of the present invention has the aluminium zinc-copper ternary eutectic tissue rich in aluminium, this ternary eutectic is organized as Netted.
Carrying out free-electron model and temperature rise test according to IEC60884-1 standard, IEC60884-1 standard specifies: to being processed into finished product Plug carry out alternating current energising 1h, heat up not can exceed that 45K is qualified;Cylinder falls detection, varying in weight according to plug Plug to carry out the cylinder fall-down test of 100-1000 time, and during test, plug can not have fracture, bending.For reality Execute example and comparative example alloy carries out free-electron model and temperature rise test.The sample of free-electron model test is less than without flexible-cable, weight 100g, observes whether sample surfaces has crackle after falling 1000 times, it is judged that its intact degree.Free-electron model and the knot of temperature rise test Fruit is shown in Table 1.

Claims (9)

1. the deformation dilute copper alloy material that a kind can rivet, it is characterised in that this dilute copper alloy material is by Al, Cu, M, Zn Form with inevitable impurity, wherein M be Ni, V, Ti, Zr, La, Ce, Pr, Nd, Mo, Si, Be, Cr, At least one element in Mn, Co and Mg, impurity includes at least one element in Fe, Pb, Sn, Sb and Cd, should Containing the aluminium zinc-copper ternary eutectic tissue rich in aluminium in the microstructure of dilute copper alloy material;
In the percentage by weight composition of this dilute copper alloy material: the content y=0.1-4.0 of the content x=0.1-6.0wt%, Cu of Al The content z=0.001-1.0wt% of wt%, M, the total amount≤0.1wt% of impurity, surplus is Zn;The content sum of Al Yu Cu Meet: the ratio of the content of 0.5wt%≤x+y≤9.0wt%, Al and Cu meets: 1≤x/y≤4;Resisting of this dilute copper alloy material Tensile strength is 290-400MPa, and hardness is 90-110HV5, elongation percentage >=15%.
A kind of deformation dilute copper alloy material riveted the most according to claim 1, it is characterised in that this dilute copper alloy material Percentage by weight composition in: x=0.5-4.5wt%, y=0.5-3.0wt%, 1≤x/y≤2.5.
A kind of deformation dilute copper alloy material riveted the most according to claim 1, it is characterised in that this dilute copper alloy material Percentage by weight composition in: x=4.6-6.0wt%, y=0.3-3.5wt%, 1≤x/y≤3.
4. according to a kind of deformation dilute copper alloy material riveted according to any one of claim 1-3, it is characterised in that described The content of Ni be 0.001-0.1wt%, the content of described Mg is 0.001-0.1wt%, and the content of described Mn is 0.001-0.1wt%.
5. according to a kind of deformation dilute copper alloy material riveted according to any one of claim 1-3, it is characterised in that described The content of V be 0.001-0.1wt%, the content of described Ti is 0.001-0.1wt%, and the content of described Zr is 0.001-0.1 Wt%.
6. according to a kind of deformation dilute copper alloy material riveted according to any one of claim 1-3, it is characterised in that described The content of La be 0.001-0.1wt%, the content of described Ce is 0.001-0.1wt%, and the content of described Pr is 0.001-0.1 Wt%, the content of described Nd is 0.001-0.1wt%;The content of described Mo is 0.001-0.1wt%, described Si's Content is 0.001-0.1wt%, and the content of described Cr is 0.001-0.1wt%, and the content of described Co is 0.001-0.1wt%.
7. according to a kind of deformation dilute copper alloy material riveted according to any one of claim 1-3, it is characterised in that described The content of Be be 0.001-0.1wt%.
8. according to a kind of deformation dilute copper alloy material riveted according to any one of claim 1-3, it is characterised in that this is low The content of the impurity Pb described in Cu alloy material is below 0.005wt%, the content of described impurity Cd be 0.001wt% with Under.
9. a kind of deformation dilute copper alloy material application on attaching plug riveted according to any one of claim 1-3.
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