CN100491558C - High-performance yttrium-base heavy rare earth copper alloy die material and preparation method thereof - Google Patents

High-performance yttrium-base heavy rare earth copper alloy die material and preparation method thereof Download PDF

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CN100491558C
CN100491558C CNB200710051881XA CN200710051881A CN100491558C CN 100491558 C CN100491558 C CN 100491558C CN B200710051881X A CNB200710051881X A CN B200710051881XA CN 200710051881 A CN200710051881 A CN 200710051881A CN 100491558 C CN100491558 C CN 100491558C
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alloy
yttrium
rare earth
copper
base heavy
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CN101148717A (en
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陈乐平
周全
庄建平
张剑平
黄松
彭新元
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NANCHANG AVIATION INDUSTRY COLLEGE
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NANCHANG AVIATION INDUSTRY COLLEGE
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Abstract

The present invention relates to preparation process of high performance copper alloy mold material, and is especially preparation process of high performance yttrium-base heavy RE copper alloy mold material. The high performance yttrium-base heavy RE copper alloy mold material has small amount of yttrium-base heavy RE added into traditional NBC alloy, and is prepared through hot forging, solid solution treatment, cold forging, ageing treatment and other steps. It has balanced comprehensive performance, obviously raised conductivity and wear resistance compared with traditional NBC alloy. It may be applied widely in electronic sealing mold, pressure casting mold, injection molding mold, etc.

Description

A kind of high-performance yttrium-base heavy rare earth copper alloy die material and preparation method thereof
Affiliated technical field
The present invention relates to moulding stock, especially a kind of high-performance yttrium-base heavy rare earth copper alloy and preparation method thereof.
Background technology
At present, domestic a lot of enterprises still adopt tungsten copper to do the soldering and sealing material, and most of foreign capitals and joint venture then depend on from external Imported High-performance copper alloy and be used for soldering and sealing mould.On the other hand, be applied to the die casting die head, present domestic die casting die head generally adopts cast iron, and its injection life-span is no more than 3000 times.And the external high property copper alloy that contains beryllium that all adopts, its life-span is above 15000 times, improved work-ing life greatly, reducing when changing die head causes die casting to scrap, and because of containing the lubricant film that the beryllium die surfaces forms one deck densification, avoided the wearing and tearing of expensive injection chamber, significantly reduced its number of rewelding, its comprehensive benefit is highly significant also.Abroad, being applied to the die casting die head for high property copper alloy has special development, manufacturing enterprise, as U.S. SEMCO company.At home, the nineties is ground zero, and its product result of use and external gap are also very big, are in low level, low-level state.The third aspect, abroad in the precise injection molding mould, high property copper alloy is applied to moulding stock thermal center point, because of it has good characteristic, increase the radiating rate at mold hot node place, guaranteed the mold integral cooling evenly, the service efficiency and the life-span of having improved mould, injection moulding speed has improved 2 times, and the moulding surface quality also increases.Though domesticly also possess some special knowledge in this respect and put into practice, also some problem on the few and material capability because of the material choice, result of use is not ideal.At present domestic mainly is with general berylliumbronze series product as an alternative, but the kind of domestic berylliumbronze has only the 2-3 kind, in the practical application life-span short, cause production efficiency of equipment low, a follow-up mouthful like product has a long way to go; Kind surplus reaching 20 abroad.External main manufacturer U.S. Brushwallman, day is chanted by Korea S, river, family, Japanese river Special Metal Co., Ltd. etc., their professional division is all very thin.Domestic main manufacturer is mineral office the 6th smeltery, mountain, the mouth of a river, east tantalum industry company limited, but the kind that they produce repeats, and those professional very strong kinds are difficult to tissue production.Therefore, exploitation high property copper alloy moulding stock is directions of non-ferrous metal industry development with the needs that adapt to market.
The preparation method of high property copper alloy moulding stock mainly contains alloying, matrix material method and rapid solidification method at present.The high property copper alloy of artificial composite material method preparation, can make the intensity of copper obtain to improve greatly, but, cause conductivity to worsen often because material internal defect is serious, add preparation technology's restriction, this method only is applicable to the manufacturing of high-strength high-conductivity copper small articles.Though inner thinking of a way certainly solved wild phase and the non-wetted problem of matrix preferably, needs to solve the homogenizing and the alligatoring problem of wild phase.The rapid solidification method complex process, the production cost height.The high property copper alloy moulding stock that conventional alloying is produced; can directly combine with particularly continuous casting technology of routine casting; can reduce the production cost of copper alloy significantly; be fit to large-scale production; its product not only can be used as functional materials; and can be used as structured material, thereby still demonstrate great vitality.Most of copper alloy die materials of present exploitation, then electrical and thermal conductivity is not good enough as the intensity height, as well insufficient strength ideal then of electrical and thermal conductivity, this is because the intensity and the electroconductibility of material are a pair of contradiction, and this just makes that technical difficulty of preparation high-strength highly-conductive material is very big.In metallurgical industry, rare earth often b referred to as " VITAMIN " of metallic substance.The effect of rare earth in copper alloy mainly contains: deoxidation, desulfurization, dehydrogenation and remove harmful element such as lead purify the composition of copper alloy; Eliminate dendritic crystalline substance, crystal grain thinning improves plasticity and intensity, reduces surface crack and defective; Improve the hot workability of copper and alloy thereof; Improve electroconductibility, heat resistance, oxidation-resistance and the welding property of copper and alloy thereof.Rare earth is confirmed by a large amount of experiment to the improvement of copper alloy performance, as: add the copper bar that a certain amount of rare earth can be produced high conductivity in common electrolytic copper, indexs such as its electric conductivity, tensile strength, unit elongation, hot mastication temperature all are better than common red copper row; In copper alloy, add a certain amount of cerium, can obviously improve the rotproofness and the anti-local corrosion ability of alloy; Add rare earth elements such as being no more than 0.5% iridium, lanthanum and can make strength of alloy reach 570Mpa in the Cu-Cr alloy, specific conductivity reaches 90%IACS; The rare earth of adding about 0.05% can make its electric conductivity reach 1031ACS in fine copper.
ZL02148648.4 has announced a kind of high-strength high conductivities such as lead frame, electrode metal and microelectronic packaging material copper alloy and manufacturing technology thereof of being used for.This invention is to add trace alloying element La, Zn and Fe (or Co) and Ti on the basis of traditional CuCrZr alloy.ZL200510096378.7 discloses a kind of Copper-based High Intensity And High Guide Material And Its Preparation Method, and it is to be matrix with copper, adds iron, phosphorus, boron and rare earth or lucium, thereby makes copper base high-strength highly-conductive material.ZL96120446.X discloses a kind of copper base alloy, contains RE (La+Ce) 0.05-0.25% during its chemistry becomes.Though the application of relevant rare earth in copper alloy all has report both at home and abroad, but do not see document and patent report in the application of high property copper alloy moulding stock about the rare earth application in the high property copper alloy moulding stock, particularly yttrium-base heavy rare earth.
Summary of the invention
The objective of the invention is to propose a kind of high property copper alloy moulding stock and preparation method thereof that has, on the basis of traditional NBC (berylliumbronze of nickeliferous, beryllium and cobalt) alloy, add the micro aluminate based heavy rare earths, and by technologies such as forge hot, solution treatment, cold forging, timeliness, make the over-all properties of its alloy reach balance, its specific conductivity and wear resistance and traditional NBC alloy phase ratio are significantly improved.Its preparation method is simple, and raw materials cost is low, high life, thus realize its widespread use in fields such as electronics soldering and sealing mould, die casting die head, injection mold thermal center points.
The high property copper alloy moulding stock that the present invention proposes is the yttrium-base heavy rare earth that adds 0.01~3% weight ratio on the basis of NBC alloy, yttrium-base heavy rare earth adds with the form of copper-yttrium master alloy, traditional NBC is nickeliferous, the concrete composition of the berylliumbronze of beryllium and cobalt is: 1.8%-2.0%Ni, 0.9%-1.0%Co, 0.45%-0.5%Be, all the other are Cu.The weight ratio of the composition of master alloy is: ReO1-11%, Cu15-30%, Si30-35%, Fe20-25%, Mg0-5%, B0-5%.
The preparation method of the high property copper alloy moulding stock that the present invention proposes adds 0.01~3% yttrium-base heavy rare earth on the basis of NBC alloy, comprise the steps:
(1) melting: adopt traditional smelting copper alloy technology.The NBC alloy melting finishes, and adds the yttrium-base heavy rare earth of 0.01~3% weight ratio, and yttrium-base heavy rare earth adds with the form of copper-yttrium master alloy, the weight ratio of the composition of master alloy is: ReO1-11%, Cu15-30%, Si30-35%, Fe20-25%, Mg0-5%, B0-5%.Melting was poured into a mould after 1~4 minute.
(2) forge hot: the alloy pig of above-mentioned cast is incubated 0.5~4 hour at 850~950 ℃, on warm forming machine, carries out 40~80% distortion then and forge.
(3) solution treatment: the sheet material after the forge hot is packed in the heat treatment furnace,, its alloying element is fully dissolved in the copper matrix, carry out quench treatment then 950~1050 ℃ of insulations 2~5 hours down.
(4) cold forging: the alloy after will quenching carries out 40~90% cold deformation processing.
(5) ageing treatment: alloy is incubated 0.5~3 hour or adopts interrupted aging technology at 450~480 ℃.
High property copper alloy moulding stock of the present invention and preparation method thereof has following advantage: 1) the high property copper alloy moulding stock that adopts the microalloying of rare earth method to produce; can directly combine with particularly continuous casting technology of routine casting; can reduce the production cost of copper alloy die material significantly; be fit to large-scale production; its product not only can be used as functional materials, and can be used as structured material.2) good combination property of copper alloy die material.All there is the increase alloy adding in copper alloy die material, can increase substantially the over-all properties of alloy, but all can reduce conductivity greatly; And the minimizing alloy adding, conductivity then can improve, but its over-all properties is with regard to the problem of difference.Yttrium-base heavy rare earth can improve mechanical property, conductivity and the work-ing life of copper alloy die material simultaneously.3) adopt the mode of copper-yttrium master alloy to add yttrium-base heavy rare earth, can prevent that the segregation of rare earth and scaling loss are serious.
Embodiment
Below in conjunction with specific embodiment embodiments of the present invention are described further:
Embodiment 1:
The high property copper alloy moulding stock is the yttrium-base heavy rare earth that adds 2% weight ratio on the basis of NBC alloy, and NBC is nickeliferous, the weight ratio of the concrete composition of the berylliumbronze of beryllium and cobalt is: 1.8% Ni, and 0.9% Co, 0.45% Be, all the other are Cu.Yttrium-base heavy rare earth adds with the form of copper-yttrium master alloy, and the weight ratio of the composition of master alloy is: ReO10%, Cu30%, Si35%, Fe25%.
The preparation method of embodiment 1 high property copper alloy moulding stock is as follows
1) melting: adopt traditional smelting copper alloy technology that the NBC alloy melting is finished, add copper-yttrium master alloy 2%, melting was poured into a mould after 2 minutes.
2) forge hot: the alloy pig of above-mentioned cast is incubated 2 hours at 850 ℃, on warm forming machine, carries out 40% distortion then and forge.
3) solution treatment: alloy pig is packed in the heat treatment furnace,, carry out quench treatment then 980 ℃ of insulations 3 hours down.
4) cold forging: the alloy after will quenching carries out 40% cold deformation processing.
5) ageing treatment: alloy is incubated 3 hours at 480 ℃.
Rare-earth copper alloy and common NBC alloy phase ratio, performance improves as follows: the electric conductivity of material has improved 19.4%, and improved 21% the work-ing life of electronics soldering and sealing mould, and the soldering and sealing qualification rate of material has improved 0.3%.
Embodiment 2:
The high property copper alloy moulding stock is the yttrium-base heavy rare earth that adds 1% weight ratio on the basis of NBC alloy, and NBC is nickeliferous, the weight ratio of the concrete composition of the berylliumbronze of beryllium and cobalt is: 1.9% Ni, and 0.9% Co, 0.5% Be, all the other are Cu.Yttrium-base heavy rare earth adds with the form of copper-yttrium master alloy, and the weight ratio of the composition of master alloy is: ReO11%, Cu30%, Si35%, Fe24%.
The preparation method of embodiment 2 high property copper alloy moulding stock is as follows:
1) melting: adopt traditional smelting copper alloy technology that the NBC alloy melting is finished, add copper-yttrium master alloy 1%, melting was poured into a mould after 1 minute.
2) forge hot: the alloy pig of above-mentioned cast is incubated 2 hours at 900 ℃, on warm forming machine, carries out 60% distortion then and forge.
3) solution treatment: alloy pig is packed in the heat treatment furnace,, carry out quench treatment then 980 ℃ of insulations 3 hours down.
4) cold forging: the alloy after will quenching carries out 50% cold deformation processing.
5) ageing treatment: alloy is incubated 3 hours at 480 ℃.
Rare-earth copper alloy and common NBC alloy phase ratio, performance improves as follows: electric conductivity has improved 14.6%, and improved 19% the work-ing life of electronics soldering and sealing mould, and the soldering and sealing qualification rate of material has improved 0.25%.
Embodiment 3:
The high property copper alloy moulding stock is the yttrium-base heavy rare earth that adds 0.5% weight ratio on the basis of NBC alloy, and NBC is nickeliferous, the weight ratio of the concrete composition of the berylliumbronze of beryllium and cobalt is: 2% Ni, and 01% Co, 0.45% Be, all the other are Cu.Yttrium-base heavy rare earth adds with the form of copper-yttrium master alloy, and the weight ratio of the composition of master alloy is: ReO5%, Cu30%, Si35%, Fe25%, Mg2%, B3%.
The preparation method of embodiment 3 high property copper alloy moulding stock is as follows
1) melting: adopt traditional smelting copper alloy technology that the NBC alloy melting is finished, add copper-yttrium master alloy 0.5%, melting was poured into a mould after 2 minutes.
2) forge hot: the alloy pig of above-mentioned cast is incubated 3 hours at 950 ℃, on warm forming machine, carries out 80% distortion then and forge.
3) solution treatment: alloy pig is packed in the heat treatment furnace,, carry out quench treatment then 980 ℃ of insulations 3 hours down.
4) cold forging: the alloy after will quenching carries out 80% cold deformation processing.
5) ageing treatment: 440 ℃ of ageing treatment 1h30min+480 ℃ of ageing treatment 1h30min rare-earth copper alloys and common NBC alloy phase ratio, performance improves as follows: hardness has improved 11.93%, wear resisting property has improved 15 times, and corrosion resistance nature has improved 29.6%, and electric conductivity has improved 11.55%.

Claims (2)

1. high-performance yttrium-base heavy rare earth copper alloy is characterized in that: include the yttrium-base heavy rare earth of 0.01~3% weight ratio in the beraloy of nickeliferous, beryllium and cobalt, the weight ratio of the concrete composition of the berylliumbronze of nickeliferous, beryllium and cobalt is:
1.8%-2.0%Ni, 0.9%-1.0%Co, 0.45%-0.5%Be, all the other are Cu; Yttrium-base heavy rare earth adds with the form of copper-yttrium master alloy, and the composition of master alloy is: ReO1-11%, Cu15-30%, Si30-35%, Fe20-25%, Mg0-5%, B0-5%.
2, a kind of preparation method of high-performance yttrium-base heavy rare earth copper alloy is to prepare as follows:
(1) melting: adopt traditional smelting copper alloy technology; The beraloy melting of nickeliferous, beryllium and cobalt finishes, add the yttrium-base heavy rare earth of 0.01~3% weight ratio, yttrium-base heavy rare earth adds with the form of copper-yttrium master alloy, the weight ratio of the composition of master alloy is: ReO1-11%, Cu15-30%, Si30-35%, Fe20-25%, Mg0-5%, B0-5%, melting was poured into a mould after 1~4 minute;
(2) forge hot: the alloy pig of above-mentioned cast is incubated 0.5~4 hour at 850~950 ℃, on warm forming machine, carries out 40~80% distortion then and forge;
(3) solution treatment: the sheet material after the forge hot is packed in the heat treatment furnace,, its alloying element is fully dissolved in the copper matrix, carry out quench treatment then 950~1050 ℃ of insulations 2~5 hours down;
(4) cold forging: the alloy after will quenching carries out 40~90% cold deformation processing;
(5) ageing treatment: alloy is incubated 0.5~3 hour or adopts interrupted aging technology at 450~480 ℃.
CNB200710051881XA 2007-04-12 2007-04-12 High-performance yttrium-base heavy rare earth copper alloy die material and preparation method thereof Expired - Fee Related CN100491558C (en)

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CN101981211B (en) * 2008-03-28 2012-12-12 日本碍子株式会社 Forged beryllium-copper bulk material
CN102688966B (en) * 2011-03-24 2015-06-24 比亚迪股份有限公司 Cold forging method and metal housing processing method
CN103436725A (en) * 2013-08-24 2013-12-11 浙江东亚机电有限公司 Preparation method of copper-based rear earth composite material
CN105112713A (en) * 2015-08-28 2015-12-02 苏州莱特复合材料有限公司 Rare earth copper-based composite and preparation method thereof
CN105803258A (en) * 2016-04-18 2016-07-27 宁波乌中远景新材料科技有限公司 High-strength high-toughness titanium alloy
CN106566946A (en) * 2016-10-19 2017-04-19 苏州东方模具科技股份有限公司 Rare earth-copper alloy glass mold and preparation method thereof

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