CN104232950A - Composite rare-earth modifier capable of improving thermal fatigue performance of copper-zinc-aluminium memory alloy - Google Patents
Composite rare-earth modifier capable of improving thermal fatigue performance of copper-zinc-aluminium memory alloy Download PDFInfo
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- CN104232950A CN104232950A CN201310234494.5A CN201310234494A CN104232950A CN 104232950 A CN104232950 A CN 104232950A CN 201310234494 A CN201310234494 A CN 201310234494A CN 104232950 A CN104232950 A CN 104232950A
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Abstract
A composite rare-earth modifier capable of improving the thermal fatigue performance of copper-zinc-aluminium memory alloy is disclosed and belongs to the technical field of memory alloy preparation. The composite rare-earth modifier is characterized by comprising, 10-15 wt% of Nd, 10-15 wt% of La, 8-12 wt% of Y, 8-12 wt% of Ce, 5-8 wt% of Tb, 5-8 wt% of Gd, 10-20 wt% of Pr+Sc+Eu+Ho+Er+Tm+Lu, 3-6 wt% of Zr, 2-5 wt% of Ti, 2-5 wt% of B, and the balance copper. The composite rare-earth modifier is alloy blocks and has the melting point scope of 850-1150 DEG C, and addition scope of the composite rare-earth modifier is 0.2-1.0 wt%.
Description
Technical field
The invention belongs to memorial alloy preparing technical field, refer in particular to a kind of composite rare-earth modifier improving CuZnAl shape memory alloy thermal fatigue property.
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 alloy material accounts for is maximum.Although some characteristic of copper-based memory alloy is not as good as NiTi alloy, due to handling ease, raw material sources is extensive, (only reaching 1/10 of NiTi alloy) with low cost, and is subject to the favor of large quantities of investigator.The ratio that copper base alloy accounts in the memorial alloy found is maximum, and mainly can be divided into the large class of Cu-Zn and Cu-Al two, what wherein most was with practical value is CuZnAl system and CuAlNi system.In recent years CuAlMn system has been developed again.Although copper-based memory alloy has good shape memory effect and cheap price, prospect is very tempting, but in practical process, discovery exist martensite stabilization, ductility poor, easily there is intercrystalline failure, and the problem such as fatigue lifetime is short, therefore it is only not high at performance requriements and require to use when reducing costs.Cu base memorial alloy easily occurs that the roughly flexible anisotropy factor of reason of intercrystalline failure is excessive, grain-size is excessive, grain boundaries has segregation, causes crystal boundary self embrittlement etc.In order to improve ductility, suppress intercrystalline failure, improve fatigue lifetime, main approach is crystal grain thinning.Main method has: 1. add alloying element, 2. rapid solidification method, 3. powder metallurgic method.Usual use first method, namely add in copper base alloy one or more solubleness very little or can and alloy in the element of certain element formation miniaturization compound, in process of setting, promote that tiny equiax crystal is formed, or stop grain growth in hot-work and heat treatment process, thus obtain fine grained texture.
The present invention develops a kind of composite rare-earth modifier improving CuZnAl shape memory alloy thermal fatigue property.
Summary of the invention
The present invention develops a kind of composite rare-earth modifier improving CuZnAl shape memory alloy thermal fatigue property, it is characterized by Nd 10 ~ 15wt%, La 10 ~ 15 wt%, Y 8 ~ 12wt%, Ce 8 ~ 12wt%, Tb 5 ~ 8 wt%, Gd 5 ~ 8 wt%, Pr+Sc+Eu+Ho+Er+Tm+Lu be 10 ~ 20wt%, Zr 3 ~ 6wt%, Ti 2 ~ 5wt%, B 2 ~ 5wt%, Yu Weitong.Described composite rare-earth modifier is bulk alloy, melting range 850 ~ 1150 DEG C, and composite rare-earth modifier add-on scope is 0.2 ~ 1.0wt%.
Mentioned component can be optimized for: Nd 12 ~ 13wt%, La 12 ~ 13 wt%, Y 10 ~ 11wt%, Ce 10 ~ 11wt%, Tb 6 ~ 7 wt%, Gd 6 ~ 7 wt%, Pr+Sc+Eu+Ho+Er+Tm+Lu be 14 ~ 16wt%, Zr 4 ~ 5wt%, Ti 3 ~ 4wt%, B 3 ~ 4wt%, Yu Weitong.Composite rare-earth modifier optimal addn scope is 0.7wt%.
Composite rare-earth modifier of the present invention is aided with multiple rare earth element and other element, avoid improving unconspicuous shortcoming to material over-all properties when being used alone a kind of rare earth element or other element a kind of, there is mutual and metamorphism in composite rare-earth modifier and CuZnAl shape memory alloy element, reach purification aluminium alloy, remove impurity, crystal grain thinning, strengthening crystal boundary, tissue is optimized, CuZnAl shape memory alloy thermal fatigue property can be increased substantially.
accompanying drawing explanation
Fig. 1 thermal fatigue specimen size figure
Fig. 2 composite rare-earth modifier add-on is on the impact of CuZnAl shape memory alloy thermal fatigue property
█ composite rare-earth modifier add-on is 0.2 wt %, and ▲ composite rare-earth modifier add-on is 0.7 wt %, ● composite rare-earth modifier add-on is 1.0 wt %, as can be seen from Figure 2, sample marking is ▲ thermal fatigue property best.
embodiment 1
With electrolytic copper, No. 0 zinc ingot metal, A00 aluminium ingot, No. 1 electrolytic nickel, composite rare-earth modifier (composition of optimization) for raw material.Composition weigh in the ratio that Zn25.25 wt %, Al3.75wt %, Ni0.9 wt %, composite rare-earth modifier 0.2 wt %, surplus are Cu after melting in medium frequency induction melting furnace.Melting technology is: first add preheated electrolytic copper, electrolytic nickel, aluminium ingot, after add zinc ingot metal and composite rare-earth modifier, to add in fusion process a small amount of borax cover, add-on is 0.15 wt % of molten metal.After material all melts, be warming up to 1280 DEG C-1300 DEG C, pour into the ingot casting that diameter is φ 80 × 150mm.Anneal is heated to 820 DEG C of insulations furnace cooling after 24 hours, and then the dezincify layer of surperficial 2-3mm is removed in turning, then ingot casting is forged into the bar of 45 × 45mm after 840 DEG C of insulation half an hour.Finally carry out the thermal treatment of two-stage timeliness, namely 820-840 DEG C of insulation is quenched in room temperature machine oil for 1 hour, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared 100 DEG C of boiling water, then takes out air cooling to room temperature be incubated 0.5 hour in 50 DEG C of water after.Go out thermal fatigue sample by linear cutter, thermal fatigue specimen size is long 40 mm, wide 10 mm, high 5mm, sample top with v-notch, as shown in Figure 1.Resistance furnace heating is adopted to carry out thermal fatigue test from constraint thermal fatigue tester.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 surface measurements crack length, sample marking is █, and thermal fatigue property is shown in Fig. 2.
embodiment 2
With electrolytic copper, No. 0 zinc ingot metal, A00 aluminium ingot, No. 1 electrolytic nickel, composite rare-earth modifier (composition of optimization) for raw material.Composition weigh in the ratio that Zn25.25 wt %, Al3.75wt %, Ni0.9 wt %, composite rare-earth modifier 0.7 wt %, surplus are Cu after melting in medium frequency induction melting furnace.Melting technology is: first add preheated electrolytic copper, electrolytic nickel, aluminium ingot, after add zinc ingot metal and composite rare-earth modifier, to add in fusion process a small amount of borax cover, add-on is 0.15 wt % of molten metal.After material all melts, be warming up to 1280 DEG C-1300 DEG C, pour into the ingot casting that diameter is φ 80 × 150mm.Anneal is heated to 820 DEG C of insulations furnace cooling after 24 hours, and then the dezincify layer of surperficial 2-3mm is removed in turning, then ingot casting is forged into the bar of 45 × 45mm after 840 DEG C of insulation half an hour.Finally carry out the thermal treatment of two-stage timeliness, namely 820-840 DEG C of insulation is quenched in room temperature machine oil for 1 hour, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared 100 DEG C of boiling water, then takes out air cooling to room temperature be incubated 0.5 hour in 50 DEG C of water after.Go out thermal fatigue sample by linear cutter, thermal fatigue specimen size is long 40 mm, wide 10 mm, high 5mm, sample top with v-notch, as shown in Figure 1.Resistance furnace heating is adopted to carry out thermal fatigue test from constraint thermal fatigue tester.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, surface measurements crack length, and sample marking is ▲, thermal fatigue property is shown in Fig. 2.
embodiment 3
With electrolytic copper, No. 0 zinc ingot metal, A00 aluminium ingot, No. 1 electrolytic nickel, composite rare-earth modifier (composition of optimization) for raw material.Composition weigh in the ratio that Zn25.25 wt %, Al3.75wt %, Ni0.9 wt %, composite rare-earth modifier 1.0wt %, surplus are Cu after melting in medium frequency induction melting furnace.Melting technology is: first add preheated electrolytic copper, electrolytic nickel, aluminium ingot, after add zinc ingot metal and composite rare-earth modifier, to add in fusion process a small amount of borax cover, add-on is 0.15 wt % of molten metal.After material all melts, be warming up to 1280 DEG C-1300 DEG C, pour into the ingot casting that diameter is φ 80 × 150mm.Anneal is heated to 820 DEG C of insulations furnace cooling after 24 hours, and then the dezincify layer of surperficial 2-3mm is removed in turning, then ingot casting is forged into the bar of 45 × 45mm after 840 DEG C of insulation half an hour.Finally carry out the thermal treatment of two-stage timeliness, namely 820-840 DEG C of insulation is quenched in room temperature machine oil for 1 hour, takes out air cooling to room temperature after being then incubated 0.5 hour in preprepared 100 DEG C of boiling water, then takes out air cooling to room temperature be incubated 0.5 hour in 50 DEG C of water after.Go out thermal fatigue sample by linear cutter, thermal fatigue specimen size is long 40 mm, wide 10 mm, high 5mm, sample top with v-notch, as shown in Figure 1.Resistance furnace heating is adopted to carry out thermal fatigue test from constraint thermal fatigue tester.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, surface measurements crack length, and sample marking is ●, thermal fatigue property is shown in Fig. 2.
Claims (3)
1. one kind is improved the composite rare-earth modifier of CuZnAl shape memory alloy thermal fatigue property, it is characterized by Nd 10 ~ 15wt%, La 10 ~ 15 wt%, Y 8 ~ 12wt%, Ce 8 ~ 12wt%, Tb 5 ~ 8 wt%, Gd 5 ~ 8 wt%, Pr+Sc+Eu+Ho+Er+Tm+Lu be 10 ~ 20wt%, Zr 3 ~ 6wt%, Ti 2 ~ 5wt%, B 2 ~ 5wt%, Yu Weitong; Described composite rare-earth modifier is bulk alloy, melting range 850 ~ 1150 DEG C, and composite rare-earth modifier add-on scope is 0.2 ~ 1.0wt%.
2. a kind of composite rare-earth modifier improving CuZnAl shape memory alloy thermal fatigue property according to claim 1, mentioned component can be optimized for: Nd 12 ~ 13wt%, La 12 ~ 13 wt%, Y 10 ~ 11wt%, Ce 10 ~ 11wt%, Tb 6 ~ 7 wt%, Gd 6 ~ 7 wt%, Pr+Sc+Eu+Ho+Er+Tm+Lu be 14 ~ 16wt%, Zr 4 ~ 5wt%, Ti 3 ~ 4wt%, B 3 ~ 4wt%, Yu Weitong.
3. a kind of composite rare-earth modifier improving CuZnAl shape memory alloy thermal fatigue property according to claim 1, composite rare-earth modifier optimal addn scope is 0.7wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756405A (en) * | 2016-12-01 | 2017-05-31 | 安徽枫慧金属股份有限公司 | For the combined rare earth additive that copper-based shape memory alloy is modified |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220419A (en) * | 2007-11-20 | 2008-07-16 | 江苏大学 | Composite rare earth alterative capable of appreciably improving thermal fatigue capability of aluminum copper alloy |
| CN101307401A (en) * | 2008-03-18 | 2008-11-19 | 镇江忆诺唯记忆合金有限公司 | Special composite rare-earth modifier for prevent copper zinc aluminum shape memory alloy from generating martensite stabilization |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220419A (en) * | 2007-11-20 | 2008-07-16 | 江苏大学 | Composite rare earth alterative capable of appreciably improving thermal fatigue capability of aluminum copper alloy |
| CN101307401A (en) * | 2008-03-18 | 2008-11-19 | 镇江忆诺唯记忆合金有限公司 | Special composite rare-earth modifier for prevent copper zinc aluminum shape memory alloy from generating martensite stabilization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106756405A (en) * | 2016-12-01 | 2017-05-31 | 安徽枫慧金属股份有限公司 | For the combined rare earth additive that copper-based shape memory alloy is modified |
| CN106756405B (en) * | 2016-12-01 | 2018-06-01 | 安徽枫慧金属股份有限公司 | The combined rare earth additive being modified for copper-based shape memory alloy |
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Application publication date: 20141224 |