CN104342593A - Copper-zinc-aluminum memory alloy for improving phase transformation point stability under hot and cold cycles - Google Patents
Copper-zinc-aluminum memory alloy for improving phase transformation point stability under hot and cold cycles Download PDFInfo
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- CN104342593A CN104342593A CN201310334086.7A CN201310334086A CN104342593A CN 104342593 A CN104342593 A CN 104342593A CN 201310334086 A CN201310334086 A CN 201310334086A CN 104342593 A CN104342593 A CN 104342593A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/01—Shape memory effect
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Abstract
The invention discloses a copper-zinc-aluminum shape memory alloy for improving phase transformation point stability under hot and cold cycles, and belongs to the technical field of preparation of copper-based memory alloys. The copper-zinc-aluminum memory alloy is characterized in that 25-26 wt% of Zn, 3.5-4 wt% of Al, 0.2-1.0 wt% of composite additives and the balance of Cu, serving as raw materials, are smelted in a medium-frequency inductive smelting furnace, and are cast to ingots with diameters of phi 80*150 mm at the temperature of 1280-1300 DEG C; the annealing treatment of the ingots is as follows: when the ingots are heated up to the temperature of 820-840 DEG C for 24 hours, the ingots are cooled along with the furnace; then, 2-3 mm of dezincification layers on the surfaces are removed; and after the ingots are insulated for 2 hours at the temperature of 820-840 DEG C, the ingots are forged to bars of 40*40 mm. Finally, the oil quenching and the ageing are performed, that is, the bars are quenched in room-temperature machine oil after being insulated for 2 hours at the temperature of 830-850 DEG C; and then, after the bars are insulated for 0.5 hour in boiled water prepared beforehand, the bars are taken out for air cooling to the room temperature. A phase transformation point test is performed for prepared samples.
Description
Technical field
The invention belongs to copper-based memory alloy preparing technical field, refer in particular to a kind of CuZnAl shape memory alloy improving transformation temperature stability under cold cycling.
Background technology
After the Delat memory metal company of Britain finds copper-based memory alloy, the research of copper-based memory alloy launches rapidly.At present, in memory alloy material, the ratio that copper-based memory alloy material accounts for is maximum, finds that there is good shape memory effect at the tens of kinds of copper base alloys such as Cu-Zn, Cu-Zn-Al, Cu-Sn, Cu-Al-Ni, Cu-Al-Be, Cu-Sn-Si, Cu-Zn-Ga at present.What in copper-based memory alloy, most study had also been applied is Cu-Zn-Al and Cu-Al-Ni alloy.CuZnAl shape memory alloy is as one of alloy with practical value of most in copper-based memory alloy, there is production technique simple, (price is only 1/10th of Ni-Ti system alloy) with low cost, there is good memory performance (being only second to Ni-Ti system alloy), its transformation temperature can regulate within the scope of-100 DEG C ~ 200 DEG C, and application prospect is boundless.
CuZnAl shape memory alloy is in cold cycling process, inner generation is just against thermoelastic martensitic transformation, between martensite and parent phase, phase interface moves repeatedly with the change of outside temperature, Interfacial Dislocations constantly increases in transition process, dislocation desity reaches capacity value very soon, thus impact is just against the transformation amount of thermoelastic martensitic transformation.In cold cycling process, transformation temperature, martensitic stucture, mechanical property and shape memory effect all can change a lot.Transformation temperature is the most basic factor of memorial alloy phase-change characteristic, and all characteristics of alloy and behavior and transformation temperature are undivided.Usually the alloy by preparing certain ingredients controls the transformation temperature of alloy, then is regulated the microrelief of transformation temperature by suitable thermal treatment.
The present invention develops a kind of CuZnAl shape memory alloy improving transformation temperature stability under cold cycling.
Summary of the invention
The present invention develops a kind of CuZnAl shape memory alloy improving transformation temperature stability under cold cycling, it is characterized by: with electrolytic copper, No. 0, zinc ingot metal, No. A00, industrial aluminium ingot, composite additive (wherein: Ni8 ~ 12 wt%, Ti8 ~ 12 wt%, Ce7 ~ 10wt%, La7 ~ 10wt%, V6 ~ 9wt%, Ba6 ~ 9wt%, Zr5 ~ 7wt%, Tb 4 ~ 6wt%, Nd 4 ~ 6wt%, Pr 2 ~ 4wt%, B2 ~ 4wt%, remaining for Cu.) be raw material, namely Zn25-26wt%, Al3.5-4wt%, composite additive 0.2-1.0wt%, surplus are meltings in medium frequency induction melting furnace after the ratio of Cu is weighed.Melting technology is: first add preheated electrolytic copper, zinc ingot metal, aluminium ingot, composite additive, will add the borax of weight alloy 0.2% between melting period.After material all melts, be warming up to 1280-1300 DEG C and pour into the ingot casting that diameter is φ 80 × 150mm.Anneal is heated to 820-840 DEG C of insulation furnace cooling after 24 hours, then removes the dezincify layer of surperficial 2-3mm, then ingot casting is forged into the bar of 40 × 40mm 820-840 DEG C of insulation after 2 hours.Finally heat-treat: oil quenching adds timeliness, namely 830-850 DEG C of insulation is quenched in room temperature machine oil for 2 hours, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared boiling water.CuZnAl shape memory alloy transformation temperature stability prepared by the method is significantly improved.
Bar is processed into national standard coupon, room temperature tensile Mechanics Performance Testing is carried out on WE-10 type fluid pressure type tensile testing machine, records memorial alloy tensile strength 695.5MPa, elongation 9.5%, Brinell hardness 186HB after this processing method process.Sample on bar, go out cold cycling sample by linear cutter, cold cycling sample final size is long 40 mm, wide 10 mm, high 5mm.Resistance furnace heating is adopted to carry out thermal cycling test from constraint thermal cycling test machine.Plate tensile sample is installed on four sides of cube jig, ensures that the heating of every block sample is consistent with cool position, and by the upper and lower vertical movement of transmission mechanism, thus the automatization reaching sample heating and cooling completes.Automatic control when employing is established, thermocouple measurement control temperature, sample carries out the thermal cycling of heating Yu cooling between room temperature 20 DEG C to 300 DEG C, 400 DEG C, 500 DEG C, adopts counter to carry out Auto-counting, adjust and keep furnace temperature accurate, water temperature 20 DEG C (flowing tap water).Rapid heating sample, heating, cooling are once as a circulation, and each circulating-heating time is 120s, and entering the water cooling time is 15s, until predetermined cycle index.Every cycle sets number of times, takes off sample, and surface film oxide is removed in polishing, the transformation temperature of beta alloy sample, comprises martensitic transformation and changes beginning temperature M
s, martensitic transformation changes end temp M
f, martensite reverse transformation change start temperature A
send temp A is changed with martensite reverse transformation
f.
embodiment
embodiment 1
With electrolytic copper, No. 0, zinc ingot metal, No. A00, industrial aluminium ingot, composite additive (wherein: Ni8 ~ 12 wt%, Ti8 ~ 12 wt%, Ce7 ~ 10wt%, La7 ~ 10wt%, V6 ~ 9wt%, Ba6 ~ 9wt%, Zr5 ~ 7wt%, Tb 4 ~ 6wt%, Nd 4 ~ 6wt%, Pr 2 ~ 4wt%, B2 ~ 4wt%, remaining for Cu.) be raw material, namely Zn25wt%, Al3.5wt%, composite additive 0.7wt%, surplus are meltings in medium frequency induction melting furnace after the ratio of Cu is weighed.Melting technology is: first add preheated electrolytic copper, zinc ingot metal, aluminium ingot, composite additive, will add the borax of weight alloy 0.2% between melting period.After material all melts, be warming up to 1280-1300 DEG C and pour into the ingot casting that diameter is φ 80 × 150mm.Anneal is heated to 820-840 DEG C of insulation furnace cooling after 24 hours, then removes the dezincify layer of surperficial 2-3mm, then ingot casting is forged into the bar of 40 × 40mm 820-840 DEG C of insulation after 2 hours.Finally heat-treat: oil quenching adds timeliness, namely 830-850 DEG C of insulation is quenched in room temperature machine oil for 2 hours, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared boiling water.CuZnAl shape memory alloy transformation temperature stability prepared by the method is significantly improved.Bar is processed into national standard coupon, room temperature tensile Mechanics Performance Testing is carried out on WE-10 type fluid pressure type tensile testing machine, records memorial alloy tensile strength 695.5MPa, elongation 9.5%, Brinell hardness 186HB after this processing method process.Sample on bar, go out cold cycling sample by linear cutter, cold cycling sample final size is long 40 mm, wide 10 mm, high 5mm.Resistance furnace heating is adopted to carry out thermal cycling test from constraint thermal cycling test machine.Plate tensile sample is installed on four sides of cube jig, ensures that the heating of every block sample is consistent with cool position, and by the upper and lower vertical movement of transmission mechanism, thus the automatization reaching sample heating and cooling completes.Automatic control when employing is established, thermocouple measurement control temperature, sample carries out the thermal cycling of heating Yu cooling between room temperature 20 DEG C to 300 DEG C, adopts counter to carry out Auto-counting, adjust and keeps furnace temperature accurately, water temperature 20 DEG C (flowing tap water).Rapid heating sample, heating, cooling are once as a circulation, and each circulating-heating time is 120s, and entering the water cooling time is 15s, until predetermined cycle index.Every cycle sets number of times, takes off sample, and surface film oxide is removed in polishing, and the transformation temperature of beta alloy sample is as shown in table 1.
The transformation temperature (K) of alloy before and after the circulation of 20 DEG C-300 DEG C, table 1
embodiment 2
With electrolytic copper, No. 0, zinc ingot metal, No. A00, industrial aluminium ingot, composite additive (wherein: Ni8 ~ 12 wt%, Ti8 ~ 12 wt%, Ce7 ~ 10wt%, La7 ~ 10wt%, V6 ~ 9wt%, Ba6 ~ 9wt%, Zr5 ~ 7wt%, Tb 4 ~ 6wt%, Nd 4 ~ 6wt%, Pr 2 ~ 4wt%, B2 ~ 4wt%, remaining for Cu.) be raw material, namely Zn25.5wt%, Al3.7wt%, composite additive 0.7wt%, surplus are meltings in medium frequency induction melting furnace after the ratio of Cu is weighed.Melting technology is: first add preheated electrolytic copper, zinc ingot metal, aluminium ingot, composite additive, will add the borax of weight alloy 0.2% between melting period.After material all melts, be warming up to 1280-1300 DEG C and pour into the ingot casting that diameter is φ 80 × 150mm.Anneal is heated to 820-840 DEG C of insulation furnace cooling after 24 hours, then removes the dezincify layer of surperficial 2-3mm, then ingot casting is forged into the bar of 40 × 40mm 820-840 DEG C of insulation after 2 hours.Finally heat-treat: oil quenching adds timeliness, namely 830-850 DEG C of insulation is quenched in room temperature machine oil for 2 hours, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared boiling water.CuZnAl shape memory alloy transformation temperature stability prepared by the method is significantly improved.Bar is processed into national standard coupon, room temperature tensile Mechanics Performance Testing is carried out on WE-10 type fluid pressure type tensile testing machine, records memorial alloy tensile strength 695.5MPa, elongation 9.5%, Brinell hardness 186HB after this processing method process.Sample on bar, go out cold cycling sample by linear cutter, cold cycling sample final size is long 40 mm, wide 10 mm, high 5mm.Resistance furnace heating is adopted to carry out thermal cycling test from constraint thermal cycling test machine.Plate tensile sample is installed on four sides of cube jig, ensures that the heating of every block sample is consistent with cool position, and by the upper and lower vertical movement of transmission mechanism, thus the automatization reaching sample heating and cooling completes.Automatic control when employing is established, thermocouple measurement control temperature, sample carries out the thermal cycling of heating Yu cooling between room temperature 20 DEG C to 400 DEG C, adopts counter to carry out Auto-counting, adjust and keeps furnace temperature accurately, water temperature 20 DEG C (flowing tap water).Rapid heating sample, heating, cooling are once as a circulation, and each circulating-heating time is 120s, and entering the water cooling time is 15s, until predetermined cycle index.Every cycle sets number of times, takes off sample, and surface film oxide is removed in polishing, and the transformation temperature of beta alloy sample is as shown in table 2.
The transformation temperature (K) of alloy before and after table 2 20 DEG C of-400 DEG C of thermal cyclings
embodiment 3
With electrolytic copper, No. 0, zinc ingot metal, No. A00, industrial aluminium ingot, composite additive (wherein: Ni8 ~ 12 wt%, Ti8 ~ 12 wt%, Ce7 ~ 10wt%, La7 ~ 10wt%, V6 ~ 9wt%, Ba6 ~ 9wt%, Zr5 ~ 7wt%, Tb 4 ~ 6wt%, Nd 4 ~ 6wt%, Pr 2 ~ 4wt%, B2 ~ 4wt%, remaining for Cu.) be raw material, namely Zn26wt%, Al4wt%, composite additive 0.7wt%, surplus are meltings in medium frequency induction melting furnace after the ratio of Cu is weighed.Melting technology is: first add preheated electrolytic copper, zinc ingot metal, aluminium ingot, composite additive, will add the borax of weight alloy 0.2% between melting period.After material all melts, be warming up to 1280-1300 DEG C and pour into the ingot casting that diameter is φ 80 × 150mm.Anneal is heated to 820-840 DEG C of insulation furnace cooling after 24 hours, then removes the dezincify layer of surperficial 2-3mm, then ingot casting is forged into the bar of 40 × 40mm 820-840 DEG C of insulation after 2 hours.Finally heat-treat: oil quenching adds timeliness, namely 830-850 DEG C of insulation is quenched in room temperature machine oil for 2 hours, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared boiling water.CuZnAl shape memory alloy transformation temperature stability prepared by the method is significantly improved.
The transformation temperature (K) of alloy before and after table 3 20 DEG C of-500 DEG C of thermal cyclings
| Before non-cold cycling | 308 | 320 | 311 | 303 |
| After reaching stable response rate | 307 | 324 | 315 | 301 |
| Cold cycling 500 times | 306 | 326 | 316 | 299 |
| Cold cycling 1000 times | 306 | 326 | 317 | 298 |
| Cold cycling 3000 times | 305 | 327 | 317 | 297 |
| Cold cycling 5000 times | 305 | 328 | 318 | 296 |
| Cold cycling 7000 times | 304 | 330 | 319 | 295 |
Bar is processed into national standard coupon, room temperature tensile Mechanics Performance Testing is carried out on WE-10 type fluid pressure type tensile testing machine, records memorial alloy tensile strength 695.5MPa, elongation 9.5%, Brinell hardness 186HB after this processing method process.Sample on bar, go out cold cycling sample by linear cutter, cold cycling sample final size is long 40 mm, wide 10 mm, high 5mm.Resistance furnace heating is adopted to carry out thermal cycling test from constraint thermal cycling test machine.Plate tensile sample is installed on four sides of cube jig, ensures that the heating of every block sample is consistent with cool position, and by the upper and lower vertical movement of transmission mechanism, thus the automatization reaching sample heating and cooling completes.Automatic control when employing is established, thermocouple measurement control temperature, sample carries out the thermal cycling of heating Yu cooling between room temperature 20 DEG C to 500 DEG C, adopts counter to carry out Auto-counting, adjust and keeps furnace temperature accurately, water temperature 20 DEG C (flowing tap water).Rapid heating sample, heating, cooling are once as a circulation, and each circulating-heating time is 120s, and entering the water cooling time is 15s, until predetermined cycle index.Every cycle sets number of times, takes off sample, and surface film oxide is removed in polishing, and the transformation temperature of beta alloy sample is as shown in table 3.
Claims (3)
1. one kind is improved the CuZnAl shape memory alloy of transformation temperature stability under cold cycling, it is characterized by: with electrolytic copper, No. 0, zinc ingot metal, industry No. A00, aluminium ingot, composite additive, wherein: Ni8 ~ 12 wt%, Ti8 ~ 12 wt%, Ce7 ~ 10wt%, La7 ~ 10wt%, V6 ~ 9wt%, Ba6 ~ 9wt%, Zr5 ~ 7wt%, Tb 4 ~ 6wt%, Nd 4 ~ 6wt%, Pr 2 ~ 4wt%, B2 ~ 4wt%, remaining is Cu, for raw material, i.e. Zn25-26wt%, Al3.5-4wt%, composite additive 0.2-1.0wt%, surplus is melting in medium frequency induction melting furnace after the ratio of Cu is weighed, melting technology is: first add preheated electrolytic copper, zinc ingot metal, aluminium ingot, composite additive, will add the borax of weight alloy 0.2% between melting period, after material all melts, be warming up to 1280-1300 DEG C and pour into the ingot casting that diameter is φ 80 × 150mm, anneal is heated to 820-840 DEG C of insulation furnace cooling after 24 hours, then removes the dezincify layer of surperficial 2-3mm, then ingot casting is forged into the bar of 40 × 40mm 820-840 DEG C of insulation after 2 hours, finally heat-treat: oil quenching adds timeliness, namely 830-850 DEG C of insulation is quenched in room temperature machine oil for 2 hours, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared boiling water, CuZnAl shape memory alloy transformation temperature stability prepared by the method is significantly improved, bar is processed into national standard coupon, room temperature tensile Mechanics Performance Testing is carried out on WE-10 type fluid pressure type tensile testing machine, records memorial alloy tensile strength 695.5MPa, elongation 9.5%, Brinell hardness 186HB after this processing method process, sample on bar, go out cold cycling sample by linear cutter, cold cycling sample final size is long 40 mm, wide 10 mm, high 5mm, resistance furnace heating is adopted to carry out thermal cycling test from constraint thermal cycling test machine, plate tensile sample is installed on four sides of cube jig, ensures that the heating of every block sample is consistent with cool position, and by the upper and lower vertical movement of transmission mechanism, thus the automatization reaching sample heating and cooling completes, automatic control when employing is established, thermocouple measurement control temperature, sample carries out the thermal cycling of heating Yu cooling between room temperature 20 DEG C to 300 DEG C, 400 DEG C, 500 DEG C, adopts counter to carry out Auto-counting, adjust and keeps furnace temperature accurate, and water temperature 20 DEG C flows tap water, rapid heating sample, heating, cooling are once as a circulation, and each circulating-heating time is 120s, and entering the water cooling time is 15s, until predetermined cycle index, every cycle sets number of times, takes off sample, and surface film oxide is removed in polishing, the transformation temperature of beta alloy sample, comprises martensitic transformation and changes beginning temperature M
s, martensitic transformation changes end temp M
f, martensite reverse transformation change start temperature A
send temp A is changed with martensite reverse transformation
f.
2. a kind of copper-zinc-aluminum shape memory alloy that can improve transformation temperature stability under cold cycling according to claim 1, when adding composite additive 0.7wt%, this alloy cold cycling, transformation temperature stability is excellent.
3. a kind of copper-zinc-aluminum shape memory alloy that can improve transformation temperature stability under cold cycling according to claim 1, this alloy room temperature 20 DEG C to 400 DEG C and following carry out cold cycling time transformation temperature stability excellent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105861863A (en) * | 2016-05-18 | 2016-08-17 | 太仓鸿鑫精密压铸有限公司 | Heat treatment technology for high-strength aluminum alloy |
| CN105973930A (en) * | 2016-04-27 | 2016-09-28 | 山东大学 | Detection method of copper-based memory alloy martensite contravariant phase transformation energy |
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2013
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105973930A (en) * | 2016-04-27 | 2016-09-28 | 山东大学 | Detection method of copper-based memory alloy martensite contravariant phase transformation energy |
| CN105861863A (en) * | 2016-05-18 | 2016-08-17 | 太仓鸿鑫精密压铸有限公司 | Heat treatment technology for high-strength aluminum alloy |
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Application publication date: 20150211 |