CN100532599C - Fatigue resistant Cu-Ti alloy and producing method thereof - Google Patents
Fatigue resistant Cu-Ti alloy and producing method thereof Download PDFInfo
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Abstract
An anti-fatigue CuTi alloy and its production are both disclosed herewith. The alloy contains Ti 2.5-5.0 wt%; Cr, Co, V, Zr, B and Ni 0.01-0.5 wt%, at least one of them; and mixed rare earth 0.1-0.5 wt%. It is produced by: smelting in presence of initial gases, hot rolling and extruding at 850-950 deg.C, temperature keeping for 20-40 min., cold rolling and drawing with deformation larger than 80% before quenching at the temperature, which concentration of Ti in Cu corresponds to that of Ti solubility curve or so, cooling quickly, cold rolling and drawing with deformation of 10-50% of total with aging for 5-20h and at 350-450 deg.C. It has excellent anti-fatigue performance by optimized components, smelting process and special heat treating process to control phase structure and grain zise.
Description
Technical field
The present invention relates to the Cu-Ti alloy, relate in particular to high-performance Cu-Ti alloy and the production method thereof that are applied to elasticity interconnecting devices and power spring, belong to the non-ferrous metal technical field with excellent fatigue strength.
Background technology
The Cu-Ti alloy also has the excellent elasticity performance except that having higher mechanical property and good thermotolerance, solidity to corrosion, can be used for the elastic element of instrument, instrument and various test sets; In addition, copper-titanium alloy also has electric conductivity preferably, also can be used for various power springs.Along with modern industry and science and technology development, the elasticity interconnecting devices have been proposed the more requirement of Gao Gengxin, as have precision height, high temperature resistant, corrosion-resistant and anti-high-intensity magnetic field, fatigue property to be requirement such as to increase the service life preferably.It is berylliumbronze that elasticity interconnecting devices and power spring are used more alloy, but berylliumbronze since the severe toxicity of beryllium will be eliminated gradually.Copper-titanium alloy can not substitute electric conductivity and the too late beraloy of anti-fatigue performance that the major cause of beraloy is a copper-titanium alloy fully at present.As elasticity interconnecting devices and power spring material, the quality of fatigue property will directly influence the work-ing life of material.Therefore, develop a kind of both had higher mechanical property and electric conductivity, the copper titanium resilient material that has excellent fatigue property again is significant.
Except alloying element and metallurgical imperfection, the microtexture of material also has material impact to fatigue property.Because the phase transition process of Cu-Ti alloy is very complicated, carry out timeliness at low temperature and will produce the spinodal decomposition tissue, reach in overaging the reaction of born of the same parents' shape at high temperature will take place, generate the Wei Shi lamellar structure.When generating lamellar structure, the degradation of alloy.How controlling chemical ingredients, the minimizing metallurgical imperfection of copper-titanium alloy, and adopt rational controlling of production process microtexture, will be to obtain to have the key link of better fatigue property copper-titanium alloy.
Alloying element that adds and impurity element have material impact to the fatigue property of copper alloy, the alloy part element plays solution strengthening or dispersion-strengthened action, improve the distortion of materials drag, stop the formation and the cracking of cycle slip band, thereby stop the germinating of fatigue cracking and improve fatigue strength.The alloy part element can influence fatigue strength by hardening capacity that improves material and the obdurability that improves material.In copper-titanium alloy, the reasonable interpolation of the addition of Ti element and other alloying element all can have influence on the fatigue property of copper-titanium alloy, is one of key link that improves copper-titanium alloy fatigue strength.
Formation mechanism from fatigue cracking along second phase or inclusion, non-metallic inclusion also is a factor that reduces fatigue strength.Reduce the quantity of inclusion and the fatigue strength that size can both improve alloy effectively.Also metallurgical imperfections such as pore, shrinkage cavity, segregation, white point can be produced in the fusion process simultaneously, also fatigue strength can be reduced.
The microstructure of alloy also has a strong impact on fatigue strength, can improve the fatigue strength of alloy as crystal grain thinning.Reason is a crystal grain thinning, and the inner crystal boundary of alloy is increased, and can hinder crackle and expand along crystal boundary, and crystal grain thinning also can improve the distortion of materials drag simultaneously, suppresses the formation and the cracking of cycle slip band, increases the crystal boundary resistance of crack propagation, improves fatigue strength; But the too little raising that also is unfavorable for fatigue strength of grain-size.In addition, the quench aging precipitated phase of alloy also is the important factor that influences fatigue property.How the microstructure that obtains to have better fatigue property by processing and thermal treatment will be the another key link of raising copper-titanium alloy fatigue strength.
Summary of the invention
The purpose of this invention is to provide a kind of high-performance Cu-Ti alloy and production method thereof with excellent fatigue strength, start with from chemical ingredients, melting technology and the unique links such as thermal treatment process of optimizing alloy, by control phase structure and grain-size, thereby can obtain the copper-titanium alloy of excelling in fatigue property.
Purpose of the present invention is achieved through the following technical solutions:
A kind of Cu-Ti alloy of antifatigue, it is characterized in that: the Ti that contains 2.5～5.0wt% in the alloy, contain at least a among Cr, Co, V, Zr, B and the Ni of 0.01～0.5wt%, micro-mishmetal 0.1～0.5wt%, all the other components are Cu and unavoidable impurities.
Further, the Cu-Ti alloy of above-mentioned a kind of antifatigue, described Cu-Ti tensile strength of alloys is 1000Mpa～1200Mpa, and unit elongation is greater than 14.8%, and electric conductivity is greater than 15.2%IACS, and fatigue resistance is greater than 260Mpa.
Further, the Cu-Ti alloy of above-mentioned a kind of antifatigue, the content of Ti is 3.0～4.0wt% in the described Cu-Ti alloy.
Again further, the production method of the Cu-Ti alloy of above-mentioned a kind of antifatigue is characterized in that may further comprise the steps---
1. antivacuum founding: at first main raw material and auxiliary material are dropped in the antivacuum medium-frequency induction furnace, under the protection of inert gas condition, carry out founding;
2. hot rolling and extruding: the heating and temperature control of hot rolling and extruding is incubated 20～40 minutes at 850 ℃～950 ℃;
3. the cold rolling and drawing before quenching: total deformation is greater than more than 80%;
4. quench: quenching temperature is controlled at about the solubility curve temperature of the pairing Ti of concentration of Ti among the Cu, and cooling fast;
5. the cold rolling and drawing after quenching: the cold rolling and total drawing deformation after the quenching is controlled at 10～50%;
6. timeliness: aging temp is at 350 ℃～450 ℃, and aging time is at 5～20 hours, in addition, in the timeliness process of cooling, is not higher than 50 ℃/hour from the speed of cooling of aging temp to 200 ℃.
Again further, the production method of the Cu-Ti alloy of above-mentioned a kind of antifatigue, step 4. quenching technology control crystal grain diameter at 2～20 μ m.
Again further, the production method of the Cu-Ti alloy of above-mentioned a kind of antifatigue, the cold rolling and total drawing deformation after 5. step quenches is controlled at 20～40%.
The outstanding substantive distinguishing features and the obvious improvement of technical solution of the present invention is mainly reflected in:
(1) technical solution of the present invention adopts non-vacuum melting technique, start with from chemical ingredients, melting technology and the unique links such as thermal treatment process of optimizing alloy, by control phase structure and grain-size, thereby can obtain the copper-titanium alloy of superior in quality excelling in fatigue property;
(2) the present invention is by suitable production technique, and the phase constitution structure and the grain-size of control alloy have obviously improved the alloy over-all properties, greatly reduce production cost, have optimized production technique, have good application prospects.
Embodiment
The high-performance Cu-Ti alloy of fatigue strength excellence of the present invention, the Ti that contains 2.5～5.0wt%, contain among Cr, Co, V, Zr, B and the Ni of 0.01～0.5wt% more than one, the micro-mishmetal of 0.1～0.5wt%, all the other are made of copper and unavoidable impurities.Wherein tensile strength of alloys is 1000Mpa～1200Mpa, and unit elongation is greater than 14.8%, and electric conductivity is greater than 15.2%IACS, and fatigue resistance is greater than 260MPa.
Blanketing with inert gas replaces the method founding of vacuum; avoid the effect of oxygen, nitrogen in alloying element and the air, when melting and cast, gas shield is arranged all, realize the continuous production of Cu-Ti alloy; control inclusion content in the fusion process simultaneously, reduce the appearance of metallurgical imperfection.The production of alloy product can be adopted dual mode, and a kind of is the band production technique: hot rolling-solid solution-cold rolling-quenching-cold rolling-timeliness; A kind of is line, pole stock production technique: extruding-solid solution-drawing-quenching-drawing-timeliness.Solid solubility temperature behind thermal deformation process (hot rolling or extruding), and the quenching temperature in the cold deformation (cold rolling or drawing) will be a little more than the solvus of alloy, make alloying element as far as possible solid solution in matrix, avoid alloy in this process, to generate lamellar structure.During the copper-titanium alloy timeliness, with the raising of temperature, spinodal decomposition will take place in Ti, generate the amplitude modulation tissue, and the amplitude modulation structural transformation becomes Cu
4The metastable coherence phase of Ti continues to improve temperature, and precipitated phase is thick lamellar structure stable phase Cu
3Ti.The amplitude modulation structural transformation becomes Cu in alloy
4The metastable coherence phase time of Ti, intensity is the highest, and fatigue property is best, and electric conductivity is also higher, and this moment, the over-all properties of alloy was best.Therefore, improve the fatigue strength of copper-titanium alloy, should strict control aging temp and soaking time when timeliness, prevent separating out of thick lamellar structure in the copper-titanium alloy.
1) alloying constituent control
The high-performance Cu-Ti alloy of excelling in fatigue property contains the Ti of 2.5～5.0wt%, more than one among the Cr of 0.01～0.5wt%, Co, V, Zr, B and the Ni, and micro-mishmetal 0.1～0.5wt%, all the other are made of copper and unavoidable impurities.
When copper-titanium alloy is carried out ageing treatment, cause the titanium spinodal decomposition, form modulation structure and can obtain higher intensity.Titanium content is difficult to satisfy the requirement of higher-strength and fatigue strength during less than 2.5wt%, and the fatigue strength of alloy is relatively poor; On the other hand, when titanium content surpasses 5.0wt%, be difficult to obtain higher specific conductivity, after carrying out overaging for the acquisition high conductance, can produce thick Cu-Ti intermetallic compound and separate out mutually, the intensity of material and fatigue property reduce.Therefore reasonably choose Ti content and both can make copper-titanium alloy obtain the high-performance of high strength, better specific conductivity, can obtain excellent fatigue strength, the Ti of the preferred 3.0～4.0wt% of alloy of the present invention by processing and thermal treatment again.
In order to delay the grain growth in the recrystallization annealing process, suppress Cu
3Separating out of Ti phase is necessary to add the 3rd an amount of groups of elements and forms the 2nd phase particle.The adding of this element does not influence the formation of amplitude modulation tissue.The formed second phase particle is not to be purpose with the precipitation-hardening, but with suppress crystal grain grow up and overaging is a purpose.Here said the 3rd groups of elements contains among Cr, Co, V, Zr, B and the Ni of 0.01～0.5wt% more than one.
2) non-vacuum melting
Owing to contain the Ti of 2.5～5.0wt% in the Cu-Ti alloy, titanium is more than 650 ℃, oxygen will spread in titanium, form the hard zone of oxidation of one deck, at nitrogen and titanium more than 700 ℃ violent effect will take place in addition, form TiN, if melting in atmosphere, will produce problems such as air-breathing, oxygen uptake, nonmetal inclusion, in addition, in the open type casting process, also easily produce similar problem, influence the performance of material.The tradition casting method is to carry out in vacuum oven.And the present invention adopts undercurrent type Cu-Ti alloy horizontal continuous-casting technology, this technology adopts undercurrent type to mend process for copper on the basis of traditional horizontal continuous-casting technology, and chute and smelting furnace are sealed fully, and charge into rare gas element, guarantee that melt and air are isolated fully.Avoid in melting, chute and casting process defectives such as the melt generation is air-breathing, slag inclusion.Can feed in raw material at any time by charge cavity in process of production, adjust alloying constituent, both can realize the continuous production of Cu-Ti alloy, can control inclusion content in the fusion process again, reduce the appearance of metallurgical imperfection.
3) quench treatment in the deformation process
The Cu-Ti alloy carries out a kind of special quenching processing technology after through cold deformation to a certain degree can make grain refining, and this intensity and fatigue property to alloy all is highly profitable.Inner crystal boundary increases because grain refining makes alloy; can hinder crackle expands along crystal boundary; crystal grain thinning also can improve the distortion of materials drag simultaneously; the formation and the cracking that suppress the cycle slip band; increase the crystal boundary resistance of crack propagation; improve fatigue strength, this link is the key link that copper-titanium alloy obtains excellent fatigue property.Quenching temperature should be controlled at about the solubility curve temperature of the pairing Ti of concentration of Ti among the Cu, and should cool off fast.Quenching more than the temperature far above this, grain-size can be grown up fast, and intensity and fatigue property are descended; Quench under far below this temperature, grain-size is minimum, and intensity is very high, but too tiny crystal grain is harmful to fatigue property equally, the too for a short time inhibition that loses fatigue cracking of crystal grain, and fatigue property descends.Reasonably grain-size should make the grain-size on the cross section be controlled between 2～20 μ m.If be lower than 2 μ m or surpass 20 μ m, all can not reach the requirement that improves fatigue property.
In addition, this quench treatment approaches solution treatment because its temperature is higher than the solid solubility line of Ti in Cu.The Cu-Ti alloy forms oversaturated sosoloid by solution treatment, when this state carries out low temperature aging, generate metastable amplitude modulation tissue, alloy significantly hardens in a certain period in this process, to produce overaging when continuing timeliness, finally separate out stable phase Cu
3Ti, and make alloy softening.On the other hand, under the inadequate condition of solid solution, titanium will be with Cu completely in solid solution
3The state of Ti remains in the parent phase, therefore is necessary to make Cu in the solution treatment of its preceding operation in order to reach the sclerosis under the timeliness to greatest extent
3The completely dissolve of Ti phase.In other words, titanium is solid-solubilized in the parent phase fully, therefore, is necessary to be heated to the temperature that the solid solution limit that makes titanium surpasses the titanium amount.
4) ageing treatment
Aging temp should be lower than 350 ℃ at 350 ℃～450 ℃, and then the Cu-Ti intermetallic compound is separated out insufficiently mutually, can not obtain high intensity and specific conductivity; If be higher than 450 ℃, then the Cu-Ti intermetallic compound is easy to thickization mutually, and is easy to overaging, causes alloy strength to reduce.Aging time was at 5～20 hours.In addition, in the timeliness process of cooling, in order to cause fully separating out of Cu-Ti intermetallic compound phase, should not be higher than 50 ℃/hour from the speed of cooling of aging temp to 200 ℃
During the copper-titanium alloy timeliness, spinodal decomposition will take place at low temperature in Ti in short-term, generate the amplitude modulation tissue, and this moment, the intensity of alloy can improve rapidly, and electric conductivity also can increase sharply.Obtain higher intensity and specific conductivity, must allow Ti separate out as much as possible, be incubated for a long time.Improve aging temp, the amplitude modulation structural transformation becomes Cu
4The metastable coherence phase of Ti, can obtain intensity and specific conductivity preferably this moment.Continue to improve temperature, precipitated phase is thick lamellar structure stable phase Cu
3Ti, the intensity variation, this thick lamellar structure is unfavorable for the raising of fatigue property simultaneously.The amplitude modulation structural transformation becomes Cu in the alloy
4The metastable coherence phase time of Ti, intensity is the highest, and fatigue property is best, and electric conductivity is also higher, and this moment, the over-all properties of alloy was best.Therefore, improve the fatigue strength of copper-titanium alloy, should strict control aging temp and soaking time when timeliness, prevent separating out of thick lamellar structure in the copper-titanium alloy.Preferred aging temp is 360 ℃～430 ℃, is incubated 5～20 hours.
6) production and processing method
According to the difference that copper-titanium alloy is used, the production of its product can be adopted dual mode, and a kind of is the band production technique: founding-hot rolling-solid solution-cold rolling-quenching-cold rolling-timeliness; A kind of is line, pole stock production technique: founding-extruding-solid solution-drawing-quenching-drawing-timeliness.
I. non-vacuum melting
Alloy after Composition Control is qualified, pours into the copper-titanium alloy ingot under gas shield in the non-vacuum melting stove.Production of copper titanium band is then poured into a mould the copper-titanium alloy slab ingot, and production line, pole stock are then poured into a mould the copper-titanium alloy billet.
II. hot rolling and extruding
Heating temperature generally is controlled at 850 ℃～950 ℃ when the hot rolling of copper-titanium alloy and extruding, is incubated about 30 minutes, and the thick intermetallic compound that forms when making casting is solidly soluted in the matrix.
III. the cold rolling and drawing before quenching
When copper-titanium alloy carries out quench treatment, store a large amount of energy of deformation in defectives such as before this dislocation that cold deformation produced, rooms, when recrystallize, can promote the formation of nucleus, the deflection of this cold deformation (cold rolling and drawing) is big more, the generation of recrystallize nucleus is remarkable more, growing up of crystal grain can to a certain degree be suppressed, and obtains fine crystal grain.General this total deformation can obtain the median size about 10 μ m greater than more than 80%.
IV. the quenching in the cold deformation process
Quenching temperature should be controlled at about the solubility curve temperature of the pairing Ti of concentration of Ti among the Cu, and should cool off fast.Reasonably grain-size should make the grain-size on the cross section be controlled between 2～20 μ m.
V. the cold rolling and drawing after quenching
Cold rolling and drawing after the quenching its objective is the intensity and the fatigue strength that improve the back alloy product that quenches.Its deflection can not improve the intensity and the fatigue property of alloy by work hardening less than 10% o'clock; Deflection was greater than 50% o'clock, and alloy causes internal modification inhomogeneous because of deflection is excessive, stress raisers occur, added unavoidable impurities and metallurgical imperfection, and the fatigue property of alloy is sharply descended.Therefore the cold rolling and total drawing deformation after quenching should be controlled at 10～50%, preferred 20～40%.
The VI timeliness
Aging temp should be at 350 ℃～450 ℃, and aging time is between 5～20 hours.In addition, in the timeliness process of cooling, in order to make fully separating out of Cu-Ti intermetallic compound phase, should not be higher than 50 ℃/hour from the speed of cooling of aging temp to 200 ℃.In order to improve the fatigue strength of copper-titanium alloy, control aging temp and soaking time when timeliness make that precipitated phase is metastable coherence phase Cu in the alloy
4Ti, prevent with reduce copper-titanium alloy in thick lamellar structure Cu mutually
3Ti separates out.Preferred aging temp is 360 ℃～430 ℃, is incubated 5～20 hours.
[embodiment]
With industrial electrolysis copper, titanium sponge and other trace alloying element is raw material, in the antivacuum medium-frequency induction furnace of gas shield, adopts the plumbago crucible melting.Ingot casting (the slab ingot: 50 * 100 * 500mm of cast 20Kg
3, billet: Φ 120mm), by icp analysis, alloying constituent sees Table 1.Then, ingot casting carries out hot rolling or extruding at 850 ℃, after the hot rolling 860 ℃ of solution treatment of carrying out 1h.
Sheet metal thickness after the solid solution is 10mm, mill carry out behind the face cold rolling, rolling 1.5mm band; quenching behind the insulation 5min under 820 ℃ of argon shield conditions; after sheet material after the quenching was cold-rolled to 1mm again, last 380 ℃ of ageing treatment 10h tested the performance of alloy.Line shank diameter after the solid solution is Φ 20mm, is drawn to Φ 8mm, is drawn to Φ 6mm test performance after the quenching, the results are shown in Table 1.
The composition of table 1 alloy and final state property energy
Embodiment shows, technical solution of the present invention adopts non-vacuum melting technique, start with from chemical ingredients, melting technology and the unique links such as thermal treatment process of optimizing alloy, by control phase structure and grain-size, obtain the copper-titanium alloy of superior in quality excelling in fatigue property, can be widely used in elasticity interconnecting devices and power spring.
Need to prove that except that above-mentioned embodiment, the present invention still has other numerous embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop within the scope of protection of present invention.
Claims (5)
1. the Cu-Ti alloy of an antifatigue, it is characterized in that: the Ti that contains 2.5～5.0wt% in the alloy, contain at least a among Cr, Co, V, Zr, B and the Ni of 0.01～0.5wt%, the mishmetal of 0.1～0.5wt%, all the other components are Cu and unavoidable impurities; Described Cu-Ti tensile strength of alloys is 1000Mpa～1200Mpa, and unit elongation is greater than 14.8%, and electric conductivity is greater than 15.2%IACS, and fatigue resistance is greater than 260Mpa.
2. the Cu-Ti alloy of a kind of antifatigue according to claim 1, it is characterized in that: the content of Ti is 3.0～4.0wt% in the described Cu-Ti alloy.
3. the method for the Cu-Ti alloy of the described a kind of antifatigue of production claim 1 is characterized in that may further comprise the steps---
1. antivacuum founding: at first main raw material and auxiliary material are dropped in the antivacuum medium-frequency induction furnace, under the protection of inert gas condition, carry out founding;
2. hot rolling and extruding: the heating and temperature control of hot rolling and extruding is incubated 20～40 minutes at 850 ℃～950 ℃;
3. the cold rolling and drawing before quenching: total deformation is greater than more than 80%;
4. quench: quenching temperature is controlled at about the solubility curve temperature of the pairing Ti of concentration of Ti among the Cu, and cooling fast;
5. the cold rolling and drawing after quenching: the cold rolling and total drawing deformation after the quenching is controlled at 10～50%;
6. timeliness: aging temp is at 350 ℃～450 ℃, and aging time is at 5～20 hours, in addition, in the timeliness process of cooling, is not higher than 50 ℃/hour from the speed of cooling of aging temp to 200 ℃.
4. the production method of the Cu-Ti alloy of a kind of antifatigue according to claim 3 is characterized in that: step 4. quenching technology control crystal grain diameter at 2～20 μ m.
5. the production method of the Cu-Ti alloy of a kind of antifatigue according to claim 3, it is characterized in that: the total deformation of the cold rolling and drawing after 5. step quenches is controlled at 20～40%.
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| JP5718436B1 (en) * | 2013-11-18 | 2015-05-13 | Jx日鉱日石金属株式会社 | Titanium copper for electronic parts |
| JP5632063B1 (en) * | 2013-11-19 | 2014-11-26 | Jx日鉱日石金属株式会社 | Copper alloy plate, high-current electronic component and heat dissipation electronic component including the same |
| JP5718443B1 (en) * | 2013-12-27 | 2015-05-13 | Jx日鉱日石金属株式会社 | Titanium copper for electronic parts |
| CN109355526B (en) * | 2018-11-06 | 2020-07-17 | 有研工程技术研究院有限公司 | High-elasticity copper-titanium alloy and tissue regulation method thereof |
| CN110042270B (en) * | 2019-04-24 | 2020-05-01 | 宁波金田铜业(集团)股份有限公司 | Preparation method of ultrafine-grained copper-titanium alloy wire |
| CN110218899B (en) * | 2019-06-21 | 2020-04-10 | 灵宝金源朝辉铜业有限公司 | High-strength corrosion-resistant Cu-Ti alloy foil and preparation method thereof |
| CN110923499B (en) * | 2019-12-27 | 2021-02-05 | 宁波博威合金材料股份有限公司 | Ce and B-containing titanium bronze alloy strip and preparation method thereof |
| CN112831686B (en) * | 2021-01-07 | 2022-03-11 | 宁波金田铜业(集团)股份有限公司 | Preparation method of high-strength high-conductivity copper-chromium-zirconium bar |
| 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 |
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