CN103031460A - Preparation method and application of hyperelastic porous CuAlNi high temperature shape memory alloy - Google Patents

Preparation method and application of hyperelastic porous CuAlNi high temperature shape memory alloy Download PDF

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CN103031460A
CN103031460A CN 201210546004 CN201210546004A CN103031460A CN 103031460 A CN103031460 A CN 103031460A CN 201210546004 CN201210546004 CN 201210546004 CN 201210546004 A CN201210546004 A CN 201210546004A CN 103031460 A CN103031460 A CN 103031460A
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porous
ualni
cualni
naalo
shape memory
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袁斌
郑佩琪
戴维杜南
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South China University of Technology SCUT
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Abstract

The invention discloses a preparation method of a hyperelastic porous CuAlNi high temperature shape memory alloy, which comprises the following steps: preparing a CuAlNi alloy ingot by adopting an electric arc melting or induction melting method; pressing NaAlO2 powder into a green body and sintering the green body in the air atmosphere to obtain an NaAlO2 block body; placing the NaAlO2 block body into the bottom of a tubular furnace capable of moving up and down, placing the CuAlNi alloy ingot on the NaAlO2 block body and carrying out heat preservation in the vacuum atmosphere; and then filling protection gas, keeping filling the protection gas, removing the tubular furnace downwards out of a heating region, cooling the obtained product, immersing the cooled product into weak acid to carry out ultrasonic oscillation, then placing the product into a vacuum furnace, carrying out heat treatment on the product in the protection atmosphere and quenching into ice water to obtain the hyperelastic porous CuAlNi high temperature shape memory alloy. The porous CuAlNi shape memory alloy prepared by the preparation method has excellent hyperelasticity and mechanical property at high temperature and also shows excellent cycling stability.

Description

A kind of preparation method and application thereof of super-elasticity porous C uAlNi high-temperature shape memory alloy
Technical field
The present invention relates to porous C uAlNi high-temperature shape memory alloy field, particularly a kind of preparation method and application thereof of super-elasticity porous C uAlNi high-temperature shape memory alloy.
Background technology
Porous marmem can show numerous excellent properties that only just possess in shape memory alloy and porous material, such as shape memory effect and super-elasticity, light weight, regulatable mechanical property, high-specific surface area and the damping characteristic of uniqueness.Therefore, porous marmem has huge application prospect in a lot of fields, such as sclerous tissues's replacement, energy absorption device and battery electrode material etc.In several porous marmems of having prepared (comprising that NiTi is basic, Cu is basic and the Fe yl), the porous NiTi memorial alloy is considered to a kind of of tool using value, and this is because it has stable shape memory effect and super-elasticity, good biocompatibility and mechanical property.This so that the porous NiTi memorial alloy at biomedical sector, particularly there is the huge applications prospect hard tissue repair and replacement aspect.Yet, its on the high side and low transformation temperature (100 ~ 100 ° of C), this has limited it in the application of some scale operation or high working temperature occasion.On the contrary, porous C u base memorial alloy is low-cost and high transformation temperature owing to it, so that it has huge advantage in automobile, manufacturing and energy-absorbing damping industry.
Except the NiTi memorial alloy, the Cu base memorial alloy is present most widely used commercial shape memory alloy.Mainly contain two large class binary alloy: CuZn and CuAl at the Cu base memorial alloy, wherein CuAl binary memorial alloy is considered to have most the high temperature shape memory alloy of application potential, be not only because it shows high transformation temperature, also because it has more excellent microtexture stability than CuZn alloy.In order to prevent the decomposition of parent phase in the CuAl binary memorial alloy, usually add the Ni element and form the CuAlNi ternary alloy.Because the essential coarse grain characteristic of CuAlNi alloy is so that the shape memory effect of polycrystalline CuAlNi memorial alloy and mechanical property will be lower than polycrystalline NiTi memorial alloy out and away.But monocrystalline CuAlNi memorial alloy but can show very high super-elasticity, even surpasses the NiTi alloy.For example, at CuAl 14Ni 4.2(wt.%) [001] monocrystalline can show complete super-elasticity up to 17% at 205 ° of C.Polycrystalline CuAlNi alloy since the fragility γ that its large grain-size (1mm) and grain boundaries are separated out mutually so that its easy generation transgranular fracture causes its shape memory effect (less than 1%) and toughness very poor.In fact, it is very difficult to prepare large single crystal samples, and with high costs.In order to improve the performance of CuAlNi alloy, effective means adds some crystal grain thinning elements exactly, such as Ti, Mn, V and B etc., perhaps forms orientation texture by rolling method, such as CuAl 12Ni 4Mn 4B 0.04Alloy deformation 5% under 150 ° of C, but 4.5% recovery strain can be produced.
Recently, there is research to find that the polycrystalline CuAlNi B alloy wire of the micro-meter scale that the hot candied legal system of employing melting is standby at room temperature can show the complete super-elasticity up to 6.6%, this is mainly owing to forming brilliant (bamboo-like structure) structure of class ring, be that the brilliant silk of whole alloy is as a bamboo, one of them crystal grain is just as a joint bamboo, only have two ends to contact with another one crystal grain, other face all is the free surface.This structure helps to discharge the stress that martensitic transformation causes, so performance improves significantly, and near the performance of monocrystalline.Based on this principle, there is the investigator to adopt and infiltrates the standby porous NiMnGa magnetic memorial alloy that goes out to have class ring crystal structure of precipitation legal system, only adjacent with a crystal grain about each crystal grain, other face all joins with hole wall, the magnetic memory performance of this Polycrystalline and monocrystalline approach, yet the porosity of this porous alloy generally all is greater than 50%, and this must limit its range of application.Therefore, can the characteristic that utilize the crystal grain of CuAlNi alloy easily to grow up be prepared the porous C uAlNi memorial alloy that all has complete class bamboo shape crystal structure under any porosity, and at high temperature shown preferably super-elasticity, and this will be very significant.
Summary of the invention
For the shortcoming and deficiency that overcomes prior art, the object of the present invention is to provide a kind of preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy, (〉 200 ° of C at high temperature) show better mechanical property and super-elasticity, and good high temperature circulation stability.Another object of the present invention is to provide the application of the super-elasticity porous C uAlNi high-temperature shape memory alloy that aforesaid method obtains.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy may further comprise the steps:
(1) adopt arc melting or induction melting to prepare the CuAlNi alloy pig; The mass ratio of each element is Cu:Al:Ni=(100-x-y): x:y in the described CuAlNi alloy pig, and wherein x is that 13 ~ 15, y is 3 ~ 5;
(2) with pore-forming material NaAlO 2Powder is pressed into green compact, carries out sintering under air atmosphere, obtains NaAlO 2Block;
(3) step (2) gained NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into step (1) gained CuAlNi alloy pig on the block, in vacuum, temperature is 1150 ℃ ~ 1250 ℃ lower insulation 0.5h～5h; Then charged pressure is 1.2 * 10 5Pa ~ 2 * 10 5The shielding gas of Pa and keep 1h～5h after, tube furnace is shifted out the heating zone downwards, obtain CuAlNi and NaAlO after the cooling 2Matrix material;
(4) CuAlNi and the NaAlO of step (3) gained 2Matrix material immerse sonic oscillation in the weak acid, NaAlO is removed in dissolving 2, obtain porous C uAlNi alloy;
(5) step (4) gained porous C uAlNi alloy is put into vacuum oven, under protective atmosphere, heat-treat, then be quenched in the frozen water, obtain hyperelastic porous C uAlNi high temperature shape memory alloy.
The described NaAlO of step (2) 2The particle size of powder is 50～1500 μ m.
The described sintering of step (2), actual conditions is: temperature is 1350 ℃ ~ 1500 ℃, and the time is 10h ~ 24h.
The described compacting of step (2), actual conditions is: pressure is 5～600MPa, and temperature is 30～100 ℃, and the time is 5 minutes～1 hour.
The described vacuum of step (3), vacuum tightness is 1 * 10 -2Pa ~ 1 * 10 -3Pa.
Described shielding gas is argon gas or nitrogen.
Step (3) is described to shift out the heating zone downwards with tube furnace, is specially:
Speed with 0.5mm/min ~ 20mm/min shifts out the heating zone downwards with tube furnace.
Step (4) described CuAlNi and NaAlO with step (3) gained 2Matrix material enter sonic oscillation in the weak acid, be specially:
CuAlNi and NaAlO with step (3) gained 2Matrix material to immerse solubility be 5% ~ 15% HCl or H 2SO 4Middle sonic oscillation, the time of sonic oscillation is 15h ~ 30h, temperature is 30 ℃ ~ 80 ℃.
The described thermal treatment of step (5) is specially: thermal treatment temp is 850 ℃ ~ 950 ℃, and heat treatment time is 0.5h ~ 5h.
The elasticity porous C uAlNi high-temperature shape memory alloy that aforesaid method obtains is for the preparation of the energy-absorbing in automobile, the space flight and driving element, or as the electrode materials of battery.
Principle of the present invention is: use NaAlO 2Powder sinters the NaAlO with certain porosity into as pore-forming material 2Block, then the CuAlNi alloy with melting infiltrates NaAlO under the help of high pressure gas 2In the space between the particle, obtain NaAlO 2Matrix material with CuAlNi; Then utilize directional freeze, obtain the very thick CuAlNi alloy of crystal grain; Utilize NaAlO 2Solubleness is very large in weak acid, and the CuAlNi alloy is then very little, can remove NaAlO 2, obtain the porous C uAlNi alloy of coarse grains; Through after the quenching heat treatment so that it shows the super-elasticity of high temperature.And, utilize the variable grain degree can control NaAlO with different pressing forces 2The porosity of block and pore size, thus porosity, pore size and the connectedness of porous C uAlNi alloy can be adjusted.Different directional freeze speed can be controlled the grain-size of different sizes, thereby can obtain the complete class bamboo joint structure at different porosities.In weak acid, soak different time, can also further adjust porosity and the pore size of porous C uAlNi.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the super-elasticity porous C uAlNi high-temperature shape memory alloy of the present invention's preparation has the porous C uAlNi shape memory alloy of class ring crystal structure, not only under high porosity, can obtain the complete class bamboo joint structure, and under low porosity (＜10%), also can obtain the porous C uAlNi high-temperature shape memory alloy of class ring crystal structure.
(2) invention porous C uAlNi memorial alloy is (〉 200 ° of C at high temperature) show better mechanical property and super-elasticity, and good high temperature circulation stability.
(3) the present invention can control the grain-size of different sizes by different directional freeze speed, thereby can obtain the complete class bamboo joint structure at different porosities.Can also be controlled at and soak different time in the weak acid, further adjust porosity and the pore size of porous C uAlNi.
Description of drawings
Fig. 1 is that embodiment 1 does not remove NaAlO 2The stereoscan photograph of porous C uAlNi alloy.
Fig. 2 is that embodiment 1 removes NaAlO 2The stereoscan photograph of porous C uAlNi alloy.
Fig. 3 is that embodiment 1 is the Metallograph of the porous C uAlNi alloy after the corrosion.
Fig. 4 is the DSC curve of embodiment 1 porous C uAlNi alloy heating and cooling.
Fig. 5 is the compressive stress strain curve figure (260 ° of C of probe temperature, through 6 compression cycle, prestrain increases gradually) of embodiment 1 porous C uAlNi alloy.
Fig. 6 is the stress-strain curve (probe temperature is 260 ° of C) of embodiment 1 porous C uAlNi alloy.
Fig. 7 is that the recovery of shape rate of embodiment 1 porous C uAlNi alloy is 260 ° of C with the change curve probe temperature of cycle index).
Fig. 8 is that embodiment 2 does not remove NaAlO 2The stereoscan photograph of porous C uAlNi alloy.
Fig. 9 is that embodiment 2 removes NaAlO 2The stereoscan photograph of porous C uAlNi alloy.
Figure 10 is the Metallograph of the porous C uAlNi alloy after embodiment 2 corrosion.
Figure 11 is the DSC curve of embodiment 2 porous C uAlNi alloy heating and cooling.
Figure 12 is the compressive stress strain curve figure (260 ° of C of probe temperature, through 3 compression cycle, prestrain increases gradually) of embodiment 2 porous C uAlNi alloys.
Figure 13 is the Metallograph of the CuAlNi alloy after embodiment 3 corrosion.
Figure 14 is the compressive stress strain curve figure (210 ° of C of probe temperature, through 9 compression cycle, prestrain increases gradually) of embodiment 3CuAlNi alloy.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) adopt arc melting to prepare Cu 81.5Al 14.5Ni 4(wt.%) alloy pig;
(2) with purity 99%, particle size is the NaAlO of 350 ~ 510 μ m 2Powder is pressed into green compact, and pressing force is 10MPa, and temperature is 30 ℃, and the time is 10 minutes; Carry out sintering under air atmosphere, sintering temperature is 1400 ℃, and sintering time is 12 hours, obtains NaAlO 2Block;
(3) NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into Cu on the block 81.5Al 14.5Ni 4Alloy pig is 5 * 10 -3Under the Pa vacuum, at 1200 ℃ of lower insulation 0.5h, then be filled with 1.2 * 10 5The argon gas of Pa also keeps 2h, and then tube furnace is shifted out the heating zone downwards with the speed of 5mm/min, obtains Cu after the cooling 81.5Al 14.5Ni 4And NaAlO 2Matrix material;
This matrix material is cut, find that the CuAlNi alloy infiltrates by NaAlO fully 2In the space between the particle (as shown in Figure 1), and NaAlO 2Basically identical before granular size and the sintering.
(4) to immerse solubility be among 10% the weak HCl to the gained matrix material, sonic oscillation 20h, and temperature is 60 ℃; NaAlO is removed in dissolving 2Behind the particle, obtain porous C u 81.5Al 14.5Ni 4Alloy (such as Fig. 2).Its hole all is interconnected, and pore size is 300 ~ 550 μ m, and porosity is 60%.
(5) porous C u 81.5Al 14.5Ni 4Alloy is heated to 900 ℃ under argon shield, be cooled fast in the frozen water behind the insulation 0.5h, obtains the porous C uAlNi alloy of high transition temperature.
To the porous C u after the thermal treatment 81.5Al 14.5Ni 4The Metallograph of alloy after corrosion found only to observe several crystal boundaries in whole sample as shown in Figure 3, and the crystal boundary two ends must link to each other with hole, forms completely class ring crystal structure.It all is the martensite bar in the whole sample.Also to porous C u 81.5Al 14.5Ni 4Alloy carries out transformation behavior and characterizes (as shown in Figure 4), when finding heating and cooling obvious neither endothermic nor exothermic peak is arranged, and this shows that martensitic transformation has occured sample, and measures its A fTemperature (martensite reverses to become and finishes temperature) is 255 ℃.
By to porous C u 81.5Al 14.5Ni 4Alloy carries out compression verification at 260 ℃, finds that it can reply under less than 2.5% prestrain fully, shows complete super-elasticity.Under 3.9% prestrain, can also keep 80% recovery of shape rate, as shown in Figure 5.Its compressive strength limit can reach 40MPa, and Young's modulus is 2.8GPa.And it is carried out compression cycle test under 260 ℃, prestrain is 2.6%, finds that it shows good high temperature circulation stability, as shown in Figure 6.And except the recovery of shape rate of for the first time circulation is 94%, all be stabilized in about 98%, as shown in Figure 7 afterwards.
The elasticity porous C uAlNi high-temperature shape memory alloy of present embodiment preparation can be used for preparing energy-absorbing and the driving element in automobile, the space flight, or as the electrode materials of battery.
Embodiment 2
(1) adopt arc melting to prepare Cu 83Al 13Ni 4(wt.%) alloy pig;
(2) with purity 99%, particle size is the NaAlO of 300 ~ 450 μ m 2Powder is pressed into green compact, and pressing force is 50MPa, and temperature is 50 ℃, and the time is 5 minutes; Carry out sintering under air atmosphere, sintering temperature is 1500 ℃, and sintering time is 15 hours, obtains NaAlO 2Block;
(3) NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into the CuAlNi alloy pig on the block, 2 * 10 -3Under the Pa vacuum, at 1250 ℃ of lower insulation 5h, then be filled with 2 * 10 5The argon gas of Pa also keeps 5h, and then tube furnace is shifted out the heating zone downwards with the speed of 1mm/min, obtains CuAlNi and NaAlO after the cooling 2Matrix material;
This matrix material is cut, find that the CuAlNi alloy infiltrates by NaAlO fully 2In the space between the particle (as shown in Figure 8), and NaAlO 2Basically identical before granular size and the sintering.
(4) the gained matrix material immerses 15% weak H 2SO 4In, sonic oscillation 30h, temperature is 80 ℃; NaAlO is removed in dissolving 2Behind the particle, obtain porous C uAlNi alloy (as shown in Figure 9).Its hole all is interconnected, and pore size is 300 ~ 450 μ m, and porosity is 50%.
(5) porous C uAlNi alloy is heated to 950 ℃ under nitrogen protection, is cooled fast in the frozen water behind the insulation 5h, obtains the porous C uAlNi alloy of high transition temperature.
To the Metallograph of the porous C uAlNi alloy after the thermal treatment after corrosion as shown in figure 10, find in whole sample, only to observe several crystal boundaries, and the crystal boundary two ends must link to each other with hole, form completely class ring crystal structure.It all is the martensite bar in the whole sample.Also porous C uAlNi alloy is carried out transformation behavior and characterize (as shown in figure 11), and measure its A fTemperature is 225 ℃.
By porous C uAlNi alloy is carried out compression verification at 260 ℃, find that it can reply fully under less than 1% prestrain, show complete super-elasticity.Under 1.88% prestrain, the recovery of shape rate is 69%, as shown in figure 12.Its compressive strength limit can reach 35MPa, and Young's modulus is 3.2GPa.
Embodiment 3
(1) adopt arc melting to prepare Cu 81.5Al 14Ni 4.5(wt.%) alloy pig;
(2) with purity 99%, particle size is the NaAlO of 50 μ m 2Powder is pressed into green compact, and pressing force is 600MPa, and temperature is 100 ℃, and the time is 1 hour; Carry out sintering under air atmosphere, sintering temperature is 1500 ℃, and sintering time is 24 hours, obtains NaAlO 2Block;
(3) NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into the CuAlNi alloy pig on the block, 1 * 10 -3Under the Pa vacuum, at 1200 ℃ of lower insulation 2h, then be filled with 2 * 10 5The argon gas of Pa also keeps 5h, and then tube furnace is shifted out the heating zone downwards with the speed of 5mm/min, obtains CuAlNi and NaAlO after the cooling 2Matrix material;
This matrix material is cut, find that the CuAlNi alloy does not infiltrate NaAlO substantially 2In the space between the particle, NaAlO 2The division is clearly demarcated for block and CuAlNi.
(4) among the weak HCl of gained matrix material immersion 5%, sonic oscillation 15h, temperature is 60 ℃; NaAlO is removed in dissolving 2Behind the particle, obtain porous C uAlNi alloy, its porosity only is 1%.
(5) porous C uAlNi alloy is heated to 950 ℃ under argon shield, is cooled fast in the frozen water behind the insulation 0.5h, obtains the porous C uAlNi alloy of high transition temperature.
To the Metallograph of the porous C uAlNi alloy after the thermal treatment after corrosion as shown in figure 13, find only to observe several crystal grain in whole sample, grain-size is 4-5mm, and each crystal grain is basic only adjacent with 1-2 crystal grain, forms class ring crystal structure.It all is the martensite bar in the whole sample.Also measure its A fTemperature is 190 ℃.
By this CuAlNi alloy is carried out compression verification at 210 ℃, find that it can reply substantially fully under less than 6.64% prestrain, show complete super-elasticity.Under 7.7% prestrain, the recovery of shape rate can also reach 86%, as shown in figure 14.Its compressive strength limit can reach 850MPa, and Young's modulus is 17.2GPa.And, under 210 ℃, can show extraordinary cyclical stability.
Embodiment 4
(1) adopt arc melting to prepare Cu 81.5Al 14Ni 4.5(wt.%) alloy pig;
(2) with purity 99%, particle size is the NaAlO of 500 ~ 750 μ m 2Powder is pressed into green compact, and pressing force is 5MPa, and temperature is 30 ℃, and the time is 5 minutes; Carry out sintering under air atmosphere, sintering temperature is 1400 ℃, and sintering time is 24 hours, obtains NaAlO 2Block;
(3) NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into the CuAlNi alloy pig on the block, 6 * 10 -3Under the Pa vacuum, at 1200 ℃ of lower insulation 3h, then be filled with 1.5 * 10 5The argon gas of Pa also keeps 3h, and then tube furnace is shifted out the heating zone downwards with the speed of 10mm/min, obtains CuAlNi and NaAlO after the cooling 2Matrix material;
This matrix material is cut, find that the CuAlNi alloy infiltrates by NaAlO fully 2In the space between the particle, and NaAlO 2Basically identical before granular size and the sintering.
(4) the gained matrix material immerses 10% weak H 2SO 4In, sonic oscillation 18h, temperature is 60 ℃; NaAlO is removed in dissolving 2Behind the particle, obtain porous C uAlNi alloy.Its hole all is interconnected, and pore size is 550 ~ 800 μ m, and porosity is 70%.
(5) porous C uAlNi alloy is heated to 950 ℃ under nitrogen protection, is cooled fast in the frozen water behind the insulation 3h, obtains the porous C uAlNi alloy of high transition temperature.
Several crystal boundaries are only observed in discovery in whole sample, and the crystal boundary two ends must link to each other with hole, form completely class ring crystal structure, all are the martensite bars in the whole sample, and measure its A fTemperature is 245 ℃.
By porous C uAlNi alloy is carried out compression verification at 260 ℃, find that it can reply fully under less than 2% prestrain, show complete super-elasticity.
Embodiment 5
(1) adopt arc melting to prepare Cu 82Al 13Ni 5(wt.%) alloy pig;
(2) with purity 99%, particle size is the NaAlO of 1000 ~ 1500 μ m 2Powder is pressed into green compact, and pressing force is 50MPa, and temperature is 30 ℃, and the time is 10 minutes; Carry out sintering under air atmosphere, sintering temperature is 1400 ℃, and sintering time is 20 hours, obtains NaAlO 2Block;
(3) NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into the CuAlNi alloy pig on the block, 4 * 10 -3Under the Pa vacuum, at 1150 ℃ of lower insulation 3h, then be filled with 1.5 * 10 5The argon gas of Pa also keeps 2h, and then tube furnace is shifted out the heating zone downwards with the speed of 4mm/min, obtains CuAlNi and NaAlO after the cooling 2Matrix material;
This matrix material is cut, find that the CuAlNi alloy infiltrates by NaAlO fully 2In the space between the particle, and NaAlO 2Basically identical before granular size and the sintering.
(4) among the weak HCl of gained matrix material immersion 15%, sonic oscillation 24h, temperature is 40 ℃; NaAlO is removed in dissolving 2Behind the particle, obtain porous C uAlNi alloy.Its hole all is interconnected, and pore size is 1000 ~ 1500 μ m, and porosity is 85%.
(5) porous C uAlNi alloy is heated to 900 ℃ under argon shield, is cooled fast in the frozen water behind the insulation 1h, obtains the porous C uAlNi alloy of high transition temperature.
Embodiment 6
(1) adopt arc melting to prepare Cu 82Al 15Ni 3(wt.%) alloy pig;
(2) with purity 99%, particle size is the NaAlO of 550 ~ 750 μ m 2Powder is pressed into green compact, and pressing force is 200MPa, and temperature is 30 ℃, and the time is 30 minutes; Carry out sintering under air atmosphere, sintering temperature is 1400 ℃, and sintering time is 12 hours, obtains NaAlO 2Block;
(3) NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into the CuAlNi alloy pig on the block, 7 * 10 -3Under the Pa vacuum, at 1200 ℃ of lower insulation 1h, then be filled with 5 * 10 5The argon gas of Pa also keeps 2h, and then tube furnace is shifted out the heating zone downwards with the speed of 6mm/min, obtains CuAlNi and NaAlO after the cooling 2Matrix material;
(4) the gained matrix material immerses 12% weak H 2SO 4In, sonic oscillation 30h, temperature is 80 ℃; NaAlO is removed in dissolving 2Behind the particle, obtain porous C uAlNi alloy.Its hole all is interconnected, and pore size is 600 ~ 800 μ m, and porosity is 65%.
(5) porous C uAlNi alloy is heated to 950 ℃ under nitrogen protection, is cooled fast in the frozen water behind the insulation 0.5h, obtains the porous C uAlNi alloy of high transition temperature.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. the preparation method of a super-elasticity porous C uAlNi high-temperature shape memory alloy is characterized in that, may further comprise the steps:
(1) adopt arc melting or induction melting to prepare the CuAlNi alloy pig; The mass ratio of each element is Cu:Al:Ni=(100-x-y): x:y in the described CuAlNi alloy pig, and wherein x is that 13 ~ 15, y is 3 ~ 5;
(2) with pore-forming material NaAlO 2Powder is pressed into green compact, carries out sintering under air atmosphere, obtains NaAlO 2Block;
(3) step (2) gained NaAlO 2Block is put into tube furnace moving up and down bottom, then at NaAlO 2Put into step (1) gained CuAlNi alloy pig on the block, in vacuum, temperature is 1150 ℃ ~ 1250 ℃ lower insulation 0.5h～5h; Then charged pressure is 1.2 * 10 5Pa ~ 2 * 10 5The shielding gas of Pa and keep 1h～5h after, tube furnace is shifted out the heating zone downwards, obtain CuAlNi and NaAlO after the cooling 2Matrix material;
(4) CuAlNi and the NaAlO of step (3) gained 2Matrix material immerse sonic oscillation in the weak acid, NaAlO is removed in dissolving 2, obtain porous C uAlNi alloy;
(5) step (4) gained porous C uAlNi alloy is put into vacuum oven, under protective atmosphere, heat-treat, then be quenched in the frozen water, obtain hyperelastic porous C uAlNi high temperature shape memory alloy.
2. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, the described NaAlO of step (2) 2The particle size of powder is 50～1500 μ m.
3. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, the described sintering of step (2), and actual conditions is: temperature is 1350 ℃ ~ 1500 ℃, and the time is 10h ~ 24h.
4. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, the described compacting of step (2), and actual conditions is: pressure is 5～600MPa, and temperature is 30～100 ℃, and the time is 5 minutes～1 hour.
5. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, the described vacuum of step (3), and vacuum tightness is 1 * 10 -2Pa ~ 1 * 10 -3Pa.
6. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, described shielding gas is argon gas or nitrogen.
7. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, step (3) is described to shift out the heating zone downwards with tube furnace, is specially:
Speed with 0.5mm/min ~ 20mm/min shifts out the heating zone downwards with tube furnace.
8. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, step (4) described CuAlNi and NaAlO with step (3) gained 2Matrix material enter sonic oscillation in the weak acid, be specially:
CuAlNi and NaAlO with step (3) gained 2Matrix material to enter solubility be 5% ~ 15% HCl or H 2SO 4Middle sonic oscillation, the time of sonic oscillation is 15h ~ 30h, temperature is 30 ℃ ~ 80 ℃.
9. the preparation method of super-elasticity porous C uAlNi high-temperature shape memory alloy according to claim 1 is characterized in that, the described thermal treatment of step (5) is specially: thermal treatment temp is 850 ℃ ~ 950 ℃, and heat treatment time is 0.5h ~ 5h.
10. the elasticity porous C uAlNi high-temperature shape memory alloy that obtains of each method of claim 1 ~ 9 is for the preparation of the energy-absorbing in automobile, the space flight and driving element, or as the electrode materials of battery.
CN 201210546004 2012-12-15 2012-12-15 Preparation method and application of hyperelastic porous CuAlNi high temperature shape memory alloy Withdrawn CN103031460A (en)

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CN103710570B (en) * 2013-12-19 2016-02-24 长沙理工大学 Cu-Ni-Al-Ce porous alloy and preparation method thereof
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CN106099086A (en) * 2015-12-18 2016-11-09 华南理工大学 Micro-nano Porous Cu zinc-aluminum shape memory alloy composite and preparation method and application
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CN107008905A (en) * 2017-02-25 2017-08-04 河北工业大学 The preparation method of TiNiCu marmem based damping composite materials
CN107008905B (en) * 2017-02-25 2018-08-17 河北工业大学 The preparation method of TiNiCu marmem based damping composite materials
WO2018161742A1 (en) * 2017-03-09 2018-09-13 华南理工大学 Nanoporous copper-zinc-aluminum shape memory alloy and preparation method and application thereof
CN109139766A (en) * 2017-06-15 2019-01-04 湖南尚成新材料科技有限责任公司 A kind of buffer structure of aerogel-congtg
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