CN100540700C - A kind of rare earth titanium-copper alloy and manufacture method thereof - Google Patents
A kind of rare earth titanium-copper alloy and manufacture method thereof Download PDFInfo
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Abstract
The invention provides a rare earth titanium-copper alloy and manufacture method, Cu:93.4～97.8wt% in the copper alloy, Ti:2.0～5.0wt%, RE:0.01～1.5wt%; Its method for making: at first main raw material and auxiliary material are injected mold after 1200～1300 ℃ of fusions, in the temperature range of liquidus temperature to 400 ℃, cool off with 80 ℃/ speed of cooling more than the min; The strand that obtains is carried out the hot rolling calendering in the Heating temperature below 1000 ℃; Again the hot rolled band that obtains is carried out repeatedly cold rolling calendering and 600 ℃～900 ℃ short-cycle annealings; Carry out cold rolling rolling processing at last its amounts of thickness variation is reached more than 40%, carry out the low-temperature annealing below 500 ℃ again, obtain the band finished product.This copper alloy has good hot workability, helps manufacturing, and especially has characteristics such as good tensile strength, yield strength, microhardness, unit elongation and specific conductivity, is the excellent materials of producing component such as connector.
Description
Technical field
The present invention relates to copper alloy, relate in particular to a kind of connector, belong to the non-ferrous metal technical field with rare earth titanium-copper alloy and manufacture method thereof.
Background technology
Along with progress of science and technology, the electronic product volume becomes more and more littler, and weight is also more and more lighter, and electronic component is miniaturization thereupon, lightness also; Therefore, the thickness of connector is more and more thinner, and contact area is more and more littler.It is more and more higher that this just docks performance requriementss such as the mechanicalness of insert material and electroconductibility.Berylliumbronze is widely used in making connector and wearing piece etc. owing to have very high intensity, well elasticity, favorable conductive, heat conduction and premium properties such as wear-resisting.But because the manufacturing process more complicated of berylliumbronze, involve great expense, toxic side effect is big, very is necessary to develop other alloy system that can substitute berylliumbronze.Along with connector is more and more higher to the performance requriements of material, connector material that some were commonly used originally such as tin-phosphor bronze, brass can not satisfy the requirement of high-end product, and titanium copper is with low cost and performance and berylliumbronze are very approaching, at aspects such as the connector assembly of important circuit, switch, relay spring, instrument diaphragm, alternative berylliumbronze.
In general, the production process of CTB alloy comprises: melting-solid solution-hot rolling-cold rolling-process annealing-finish rolling-technologies such as timeliness.But make CTB alloy and have two technical problems: the one, phase transition process is very complicated, can produce the spinodal decomposition tissue at low temperature aging, this tissue is metastable, will form lamellar structure under overaging and high-temperature condition, when generating lamellar structure, the degradation of alloy; The 2nd, the alloy deformation difficulty, difficulty of processing is big.Therefore, how to control alloy organizing and to improve the cold and hot working performance be key link in the CTB alloy manufacturing processed in process of production.
Summary of the invention
The present invention is from alloying constituent and two angles of processing method, a kind of rare earth titanium-copper alloy and manufacture method thereof are provided, and characteristics such as its tensile strength of alloys, yield strength, microhardness, unit elongation and specific conductivity all can satisfy the many requirement of each industrial circle to material property preferably.
Purpose of the present invention is achieved through the following technical solutions:
A kind of rare earth titanium-copper alloy is characterized in that: the quality percentage composition of its composition is as follows---
Cu 93.4～97.8wt％，
Ti 2.0～5.0wt％，
RE 0.01～1.5wt％，
All the other components of this copper alloy are unavoidable impurities.
Further, above-mentioned a kind of rare earth titanium-copper alloy, described rare earth titanium-copper alloy also contain in As, Sb, Bi, Pb, Sn, the Ni element at least a above element and total amount less than 0.05wt%, and S content is below 25ppm.The tensile strength of described rare earth titanium-copper alloy is that 1000MPa is above, yield strength 900MPa above, microhardness 300Hv is above, specific conductivity 12%IACS is above, unit elongation is more than 7%.
Further, a kind of manufacture method of rare earth titanium-copper alloy is characterized in that may further comprise the steps---
1. at first main raw material and auxiliary material are injected mold after 1200～1300 ℃ of fusions, in the temperature range of liquidus temperature to 400 ℃, cool off with 80 ℃/ speed of cooling more than the min, control component content Cu is 93.4～97.8wt% in manufacturing processed, Ti is 2.0～5.0wt%, RE is 0.01～1.5wt%, and all the other components are inevitable impurity;
2. the strand that obtains is carried out the hot rolling calendering in the Heating temperature below 1000 ℃, control component content Cu is 93.4～97.8wt% in manufacturing processed, and Ti is 2.0～5.0wt%, and RE is 0.01～1.5wt%, and all the other components are inevitable impurity;
3. the hot rolled band that obtains is carried out repeatedly cold rolling calendering and 600 ℃～900 ℃ short-cycle annealings, control component content Cu is 93.4～97.8wt% in manufacturing processed, and Ti is 2.0～5.0wt%, and RE is 0.01～1.5wt%, and all the other components are inevitable impurity;
4. carrying out cold rolling rolling processing reaches more than 40% its amounts of thickness variation, carry out the low-temperature annealing below 500 ℃ again, obtain the band finished product, control component content Cu is 93.4～97.8wt% in manufacturing processed, Ti is 2.0～5.0wt%, RE is 0.01～1.5wt%, and all the other components are inevitable impurity.
Again further, 2. the manufacture method of above-mentioned a kind of rare earth titanium-copper alloy controls the crystal grain diameter of band less than 50 μ m in the hot rolling calendering course of processing in step.Step 2. hot-rolled temperature is 920 ℃.The crystal grain diameter of control band is less than 50 μ m in the 3. cold rolled annealed course of processing of step.
Again further, the manufacture method of above-mentioned a kind of rare earth titanium-copper alloy, step 2. strand to make its thickness through hot rolling calendering be 6mm, 3. step carries out hot rolled band cold rolling calendering repeatedly, and to make its thickness be 1mm, it is 0.5mm that the 4. cold rolling calendering of step makes its thickness.
Again further, the manufacture method of above-mentioned a kind of rare earth titanium-copper alloy, described main raw material is No. 1 electrolytic copper, auxiliary material is pure titanium and mishmetal.
The outstanding substantive distinguishing features and the obvious improvement of technical solution of the present invention is mainly reflected in:
(1) copper alloy over-all properties of the present invention is superior, alloy structure even, the control precipitated phase is the amplitude modulation tissue, avoids forming thick lamellar structure;
(2) tensile strength of alloy finished product reaches that 1000MPa is above, yield strength reaches more than the 900MPa, and microhardness 300Hv is above, specific conductivity 12%IACS is above, unit elongation is more than 7%, can satisfy the many requirement of each industrial circle to material property preferably;
(3) rare earth titanium-copper alloy price of the present invention is relatively low, compares with berylliumbronze to have tangible absolute predominance; Also having good cold and hot working in addition, help manufacturing, is the best materials of producing component such as connector.
Embodiment
The invention provides a kind of rare earth titanium-copper alloy and manufacture method thereof, select best Ti and the component concentration of RE, process means with advanced persons such as the rolling processing conditions of only strand cooling conditions, strand and heat-treat conditions is manufactured, and the alloy that manufactures can ideal satisfy component such as connector with desired kind of specific character of material.
A kind of rare earth titanium-copper alloy, Cu:93.4～97.8wt%, Ti:2.0～5.0wt%, RE:0.01～1.5wt%, all the other components of this copper alloy are unavoidable impurities.Rare earth titanium-copper alloy also contains in As, Sb, Bi, Pb, Sn, the Ni element at least a above element and total amount less than 0.05wt%, and S content is below 25ppm.The tensile strength of this rare earth titanium-copper alloy is that 1000MPa is above, yield strength 900MPa above, microhardness 300Hv is above, specific conductivity 12%IACS is above, unit elongation is more than 7%.
Ti is main strengthening element in the rare earth titanium-copper alloy of the present invention, and alloy is through after the suitable ageing treatment, and the Ti element forms tiny Cu with spinodal decomposition mechanism
4Ti plays the ageing strengthening effect mutually.
The main effect of mixed rare-earth elements RE is:
(1) deoxidation dehydrogenation: the chemically reactive of rare earth is very strong, with the avidity of the oxygen avidity much larger than copper and oxygen, and generates fusing point than copper height, rare earth oxide that density is littler than copper, plays good desoxydatoin; Rare earth and hydrogen are combined into the little hydride of density, float to copper liquid surface, at high temperature decompose again, discharge hydrogen, or oxidizedly enter slag and be removed;
(2) cleaning molten: rare earth to the effect that removes of other harmful element also clearly, these dystectic rare earth compounds will keep solid state to discharge from liquid copper with slag, thereby reach the effect that removes detrimental impurity, rare earth especially can be removed the crystal boundary impurity element significantly, increase the significant quantity of Ti element after impurity element is removed, can increase substantially the intensity of alloy;
(3) crystal grain thinning: add RE in alloy, obvious crystal grain thinning in the making processes greatly improves alloy plasticity after follow-up thermomechanical treatment;
(4) promote strengthening phase to separate out: after in alloy, adding RE, tiny, the disperse of strengthening phase in the band, wavelength is below 100nm; In addition, can improve the recrystallization temperature of alloy behind the interpolation RE, thereby improve the resistance to elevated temperatures of alloy, suitable addition 0.01～1.5wt% of mishmetal RE.
In technical solution of the present invention, based on sulphur in the main raw material impurity to the influence of technology and product, its main raw material is selected electrolytic copper for use No. 1, sulfur-bearing as few as possible not only in the impurity, and will prevent punch process the time owing to oil pollution is sneaked into sulphur, even the deformation performance that a spot of sulphur also can make hot rolling add man-hour sharply descends, the content of control sulphur, workpiece cracking in the time of can avoiding hot rolling.Usually, the content of sulphur must be less than 0.0025wt%, and ideal value is less than 0.0015wt%.
A kind of manufacturing process of rare earth titanium-copper alloy: 1. at first with No. 1 electrolytic copper 1200～1300 ℃ of fusings, carry out the minitype vertical type semicontinuous casting after adding fusions such as pure titanium and mishmetal, utilize mold once to cool off and utilize water spray to carry out the secondary cooling, make in the temperature range of liquidus line to 400 ℃ speed of cooling 80 ℃/more than the min, control component content Cu is 93.4～97.8wt% in manufacturing processed, Ti is 2.0～5.0wt%, RE is 0.01～1.5wt%, and all the other components are inevitable impurity; 2. strand (920 ℃ of ideal temperatures) in 900～1000 ℃ temperature range makes its thickness reach 6mm through the hot rolling calendering, the finishing temperature of hot rolling calendering is high as far as possible, make grain-size less than 50 μ m by chilling, control component content Cu is 93.4～97.8wt% in manufacturing processed, Ti is 2.0～5.0wt%, RE is 0.01～1.5wt%, and all the other components are inevitable impurity; 3. hot rolled band being carried out repeatedly cold rolling calendering, to make its thickness be 1mm, in 600 ℃～900 ℃ temperature range, carry out short-cycle annealing, the crystal grain diameter that makes the calendering band after the annealing is less than 50 μ m, control component content Cu is 93.4～97.8wt% in manufacturing processed, Ti is 2.0～5.0wt%, RE is 0.01～1.5wt%, and all the other components are inevitable impurity; 4. cold rolling calendering makes thickness reach 0.5mm, carries out low-temperature annealing again, obtains the band finished product; Control component content Cu is 93.4～97.8wt% in manufacturing processed, and Ti is 2.0～5.0wt%, and RE is 0.01～1.5wt%, and all the other components are inevitable impurity.
In the manufacturing process of the present invention: alloy raw material is No. 1 electrolytic copper, pure titanium and mishmetal, adopts the medium-frequency induction furnace melting.
For best, also can by semicontinuous casting with continuous casting for casting technique after the raw material fusing.In the temperature range of liquidus line to 400 ℃, cool off in the castingprocesses with the speed of cooling that 80 ℃/min is above.When speed of cooling is lower than 80 ℃/min, elements segregation can take place, the hot rolling processibility of postorder is brought adverse influence, and cause the reduction of production efficiency.Controlled chilling speed, the temperature range of preferred liquid phase line temperature to 400 ℃; Below 400 ℃, the length of cooling time changes the excessive segregation that can not cause alloying element during casting.
Behind the melt-casting, carry out hot-work.Hot worked Heating temperature should be 900～1000 ℃ scope, if temperature surpasses ceiling temperature, it is overheated to take place, and causes the hot rolling cracking, reduces production efficiency.In 900～1000 ℃ temperature range, carry out hot rolling and add man-hour, small segregation and cast structure will disappear, in the content range of Ti of the present invention and RE, can obtain the rolled strip of homogeneous microstructure, better hot rolling processing temperature is about 920 ℃, and hot rolling processing back crystal grain diameter is below 50 μ m.
After the hot rolling processing, carry out surfacing cut as required, carry out the short-cycle annealing in the temperature range of cold rolling processing and 600～900 ℃ thereafter repeatedly.Short-cycle annealing can reach control grain-size (crystal grain diameter is less than 50 μ m) and improve the purpose of the processing characteristics of high-intensity rare earth titanium-copper alloy.When temperature was lower than 600 ℃, it was longer to carry out the required time of structure property control; Surpass 900 ℃, crystal grain will become thick in the short period of time.If the crystallization crystal grain after the annealing greater than 50 μ m, can make mechanical characteristics and processing characteristics reductions such as tensile strength.The present invention makes crystal grain diameter less than 50 μ m, and desirable crystal grain diameter is less than 25 μ m.
Resulting annealed material, carrying out cold rolling rolling processing reaches more than 40% its amounts of thickness variation, also carry out the low-temperature annealing below 500 ℃, obtain that tensile strength 1000MPa is above, yield strength 900MPa above, microhardness 300Hv is above, specific conductivity 12%IACS is above, the rare earth titanium-copper alloy of unit elongation more than 7%.Discontented 40% o'clock of cold rolling working modulus, meeting can not improve mechanical characteristics fully because of the insufficient strength that work hardening produces.Therefore the ideal working modulus is more than 50%.In order further to improve tensile strength of alloys, yield strength, hardness, unit elongation, especially characteristic such as specific conductivity, low temperature annealing process is very necessary, be higher than under 500 ℃ the temperature, because of thermal capacity excessive, make material soften at short notice, and no matter adopt intermittent type or continous way, all be easy to generate the characteristic inequality of material internal; Be higher than 500 ℃ of annealing, alloy is easy to occur overaging, forms thick lamellar structure, reduces the over-all properties of alloy.Low-temperature annealing of the present invention is below 500 ℃.
Embodiment:
The copper alloy № 1～5 of composition as shown in table 1 (wt%),
Table 1
In the fusion process of alloy, each element all has scaling loss in various degree, its burn out rate Ti:4～15%, RE:30～50%; In the process of batching, should supply.Add electrolytic copper when melting begins earlier, begin heating, treat that its fusing back adds mishmetal insulation 1～3min of 1/3 earlier; Treat its fusing back insulation 3～5min, add the mishmetal of pure titanium and residue 2/3 again, insulation 10min casting behind the fine melt; Use the strand of minitype vertical type semicontinuous caster casting 70 * 180 * 1000 (mm), utilize mold once to cool off and utilize the water spray to carry out the secondary cooling, make in the temperature range of liquidus line to 400 ℃ speed of cooling 80 ℃/more than the min.Thereafter, each strand in 900～1000 ℃ temperature range after (920 ℃ of the preferred temperature of one) heating, through hot rolling calendering so that its thickness is 6mm, from the surface and the crackle at edge estimate the hot rolling processibility.After overpickling, the experiment material that does not observe crackle under 50 times opticmicroscope is evaluated as, and it is poor that the experiment material that can observe crackle is evaluated as.The end temp of hot rolling calendering is high as far as possible, by chilling grain-size is controlled at about 50 μ m.Carrying out cold rolling calendering then, to make its thickness be 1mm, in 600～900 ℃ temperature range, carry out short-cycle annealing, impel alloy generation recrystallize to change the processing characteristics of improving alloy, carrying out cold rolling calendering afterwards again, to make its thickness be 0.5mm, carry out the low-temperature annealing below 500 ℃ at last, kind and shape by precipitated phase in the low-temperature annealing control alloy reach the purpose that improves alloy property.
Clip test film from the above resulting band carries out the mensuration of tensile strength, yield strength, microhardness, unit elongation and specific conductivity, and every performance index are all measured according to GB and relevant regulations.More than resulting outcome record in table 2.
Table 2
| Embodiment | Tensile strength (MPa) | Yield strength (MPa) | Hardness (Hv) | Unit elongation (%) | Specific conductivity (%IACS) | The hot rolling processing characteristics |
| 1 | 1053 | 921 | 330 | 7.5 | 14 | Good |
| 2 | 1066 | 938 | 352 | 8.1 | 15 | Good |
| 3 | 1056 | 928 | 346 | 7.8 | 13 | Good |
| 4 | 1060 | 918 | 333 | 7.6 | 16 | Good |
| 5 | 1061 | 930 | 347 | 8.0 | 13 | Good |
Obviously, rare earth titanium-copper alloy has good hot workability, helps manufacturing, and especially has characteristics such as good tensile strength, yield strength, microhardness, unit elongation and specific conductivity, is the excellent materials of producing component such as connector.
More than by specific embodiment technical solution of the present invention has been done to further specify, the example that provides only is an exemplary applications, can not be interpreted as a kind of restriction to claim protection domain of the present invention.
Claims (7)
1. rare earth titanium-copper alloy, it is characterized in that: the quality percentage composition of its composition is as follows---
Cu 93.4～97.8wt％，
Ti 3.7～5.0wt％，
RE 0.01～1.5wt％，
All the other components of this copper alloy are unavoidable impurities;
The tensile strength of described rare earth titanium-copper alloy is that 1000MPa is above, yield strength 900MPa above, microhardness 300Hv is above, specific conductivity 12%IACS is above, unit elongation is more than 7%.
2. a kind of rare earth titanium-copper alloy according to claim 1 is characterized in that: described rare earth titanium-copper alloy also contains in As, Sb, Bi, Pb, Sn, the Ni element at least a above element and total amount less than 0.05wt%, and S content is below 25ppm.
3. the manufacture method of the described a kind of rare earth titanium-copper alloy of claim 1 is characterized in that may further comprise the steps---
1. at first main raw material and auxiliary material are injected mold after 1200～1300 ℃ of fusions, in the temperature range of liquidus temperature to 400 ℃, cool off with 80 ℃/ speed of cooling more than the min, control component content Cu is 93.4～97.8wt% in manufacturing processed, Ti is 2.0～5.0wt%, RE is 0.01～1.5wt%, and all the other components are inevitable impurity;
2. the strand that obtains is carried out the hot rolling calendering in the Heating temperature below 1000 ℃, control component content Cu is 93.4～97.8wt% in manufacturing processed, and Ti is 2.0～5.0wt%, and RE is 0.01～1.5wt%, and all the other components are inevitable impurity;
3. the hot rolled band that obtains is carried out repeatedly cold rolling calendering and 600 ℃～900 ℃ short-cycle annealings, control component content Cu is 93.4～97.8wt% in manufacturing processed, and Ti is 2.0～5.0wt%, and RE is 0.01～1.5wt%, and all the other components are inevitable impurity;
4. carrying out cold rolling rolling processing reaches more than 40% its amounts of thickness variation, carry out the low-temperature annealing below 500 ℃ again, obtain the band finished product, control component content Cu is 93.4～97.8wt% in manufacturing processed, Ti is 2.0～5.0wt%, RE is 0.01～1.5wt%, and all the other components are inevitable impurity.
4. the manufacture method of a kind of rare earth titanium-copper alloy according to claim 3 is characterized in that: 2. control the crystal grain diameter of band less than 50 μ m in the hot rolling calendering course of processing in step.
5. the manufacture method of a kind of rare earth titanium-copper alloy according to claim 3 is characterized in that: control the crystal grain diameter of band less than 50 μ m in the 3. cold rolled annealed course of processing of step.
6. the manufacture method of a kind of rare earth titanium-copper alloy according to claim 3, it is characterized in that: step 2. strand to make its thickness through hot rolling calendering be 6mm, 3. step carries out hot rolled band cold rolling calendering repeatedly, and to make its thickness be 1mm, and it is 0.5mm that the 4. cold rolling calendering of step makes its thickness.
7. the manufacture method of a kind of rare earth titanium-copper alloy according to claim 3, it is characterized in that: described main raw material is No. 1 electrolytic copper, and auxiliary material is pure titanium and mishmetal.
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| CN104278171B (en) * | 2014-09-16 | 2016-09-07 | 中南大学 | A kind of CuTi series elastic copper alloy and preparation method thereof |
| CN105058064B (en) * | 2015-07-31 | 2017-08-25 | 中色奥博特铜铝业有限公司 | A kind of method for milling of rolled copper foil red copper strand |
| CN109487116B (en) * | 2018-11-27 | 2020-09-18 | 北京北冶功能材料有限公司 | High-strength titanium-copper alloy strip suitable for conductive elastic component and preparation method thereof |
| CN109504871B (en) * | 2018-11-27 | 2020-09-04 | 北京北冶功能材料有限公司 | High-strength titanium-copper alloy wire suitable for conductive elastic component and manufacturing method thereof |
| CN109504865B (en) * | 2018-11-27 | 2020-09-04 | 北京北冶功能材料有限公司 | High-strength titanium-copper alloy special-shaped wire suitable for conductive elastic component and preparation method thereof |
| CN110042274A (en) * | 2019-05-05 | 2019-07-23 | 陶大海 | A kind of high elastic modulus, copper alloy of stress relaxation-resistant and preparation method thereof |
| CN111118335B (en) * | 2020-01-17 | 2022-04-08 | 河北中泊防爆工具集团股份有限公司 | Titanium bronze alloy material and preparation method and application thereof |
| CN114150123B (en) * | 2021-11-24 | 2024-03-12 | 中铝科学技术研究院有限公司 | Method for effectively improving alloy strength and conductivity |
| CN114807668B (en) * | 2022-05-06 | 2022-11-01 | 浙江百川导体技术股份有限公司 | Rare earth nitride dispersion strengthening titanium-doped copper alloy and preparation method thereof |
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Effective date of registration: 20171127 Address after: 102209 Changping District City, Beiqijia, the future of science and technology in the south area of the town of Beijing Patentee after: China Aluminum Material Applied Research Institute Co Ltd Address before: Suzhou City, Jiangsu province 215021 Industrial Park No. 200 Shen Hu Road Patentee before: Suzhou Non-ferrous Metal academy Co., Ltd. |