CN117512391A - CuAlMnNiCr shape memory alloy and preparation method thereof - Google Patents
CuAlMnNiCr shape memory alloy and preparation method thereof Download PDFInfo
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- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000956 alloy Substances 0.000 claims abstract description 76
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 75
- 238000004321 preservation Methods 0.000 claims abstract description 19
- 238000010791 quenching Methods 0.000 claims abstract description 16
- 230000000171 quenching effect Effects 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000003723 Smelting Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 34
- 238000011534 incubation Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000011651 chromium Substances 0.000 abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 24
- 239000013078 crystal Substances 0.000 abstract description 18
- 229910052804 chromium Inorganic materials 0.000 abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 28
- 239000011572 manganese Substances 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 copper-aluminum-manganese Chemical compound 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
- C22F1/006—Resulting in heat recoverable alloys with a memory effect
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a CuAlMnNiCr shape memory alloy, which has a grain structure exceeding 1.5cm, wherein the chemical formula of the alloy is as follows: cu (Cu) x Al y Mn z Cr j Ni k The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 9 and less than or equal to 18,0, j is more than or equal to 2, k is more than 0 and less than or equal to 6, and x+y+z+j+k=100; the alloy ingot obtained by smelting the alloy is subjected to temperature T 1 Is subjected to first constant temperature heat preservation and gradient cooling to T 2 The second constant temperature is maintained, and the temperature is increased to T in a gradient way 1 Is subjected to constant temperature heat preservation and quenching to obtain the product; the T is 1 Not lower than 800 ℃ and not higher than the melting point of the alloy ingot; the T is 2 Not lower than 350 ℃. In the alloy, chromium and nickel are matched, and the grain size is multipliedAnd the single crystal grain is not smaller than 1.5cm and can reach 13cm at maximum.
Description
Technical Field
The invention relates to a CuAlMnNiCr shape memory alloy and also relates to a preparation method of the CuAlMnNiCr shape memory alloy, belonging to the technical field of copper-based alloys.
Background
In the prior research, the Cu-based shape memory alloy workpiece with the single crystal structure can obviously improve the fatigue strength and the super-elasticity of the polycrystalline Cu-based shape memory alloy, has excellent mechanical property and longer service life, so that the preparation of the Cu-based shape memory alloy with the large-size single crystal is convenient and efficient, and is one of main research directions for improving the comprehensive performance of the alloy and realizing large-scale engineering application at present.
In order to conveniently and efficiently realize the preparation of large-size grains, one of the main technical means is to add a proper amount of other alloy elements into a CuAlMn alloy system to obtain a new alloy system, thereby obtaining higher grain boundary migration driving force or reducing the driving force required by grain boundary migration and rapidly realizing the acquisition of large-size single crystals. The invention patent application with publication number of CN 108277535A discloses a copper-aluminum-manganese-based single crystal alloy material, which has a centimeter-level oversized crystal grain structure and is obtained by annealing and quenching an as-cast alloy with a polycrystalline structure for 1-30 hours in a single-phase region at 800-950 ℃, wherein the as-cast alloy comprises the following components in percentage by weight: 70-82% of copper, 10-16% of aluminum, 5-12% of manganese, 0.2-3% of a fourth alloy element, and the fourth alloy element is molybdenum, tungsten, vanadium or chromium; the fourth alloy element has a liquid phase and two phases separated from copper, has a body-centered cubic structure or can form a body-centered cubic structure with manganese and aluminum, and can cause the phase separation phenomenon of the body-centered cubic of the alloy. In the invention, the aluminum content is between 10 and 16 percent, and the obtained single crystal alloy has highly ordered Heusler-L2 1 (Cu 2 AlMn) structure, the addition of optional metals causes phase separation of the alloy, except L2 1 In addition to the phases, there are very fine precipitated phases rich in optional metallic elements, the presence of which promotes the formation of oversized grains of the alloy upon high temperature heat treatment. By this means, a bulk single crystal size of up to 4cm is obtained, but only when the metal of choice is chromiumAbout 1cm. The invention patent application of publication No. CN 113862508A discloses a CuAlMnCoNi shape memory alloy and a preparation method thereof. The chemical formula of the memory alloy is as follows: cu (Cu) x Al y Mn z Co j Ni k The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is more than or equal to 12 and less than or equal to 18, z is more than or equal to 8 and less than or equal to 15, j is more than or equal to 0.5 and less than or equal to 5, k is more than or equal to 0.5 and less than or equal to 5, x+y+z+j+k=100, and x and y, z, j, k represent the molar percentage content. In the invention, co is added to promote secondary recrystallization, co and Ni are matched to accelerate the migration rate of grain boundaries, the maximum grain size after two times of cyclic heat treatment is 3.5cm, in the scheme, the preparation efficiency of single crystals is relatively improved, but the growth efficiency of the grains and the grain size still have room for improvement.
Disclosure of Invention
The invention aims to: the invention aims to provide a CuAlMnNiCr shape memory alloy capable of forming large-size grains, and another aim of the invention is to provide a preparation method which is helpful for promoting the growth of the sizes of the grains of the CuAlMnNiCr shape memory alloy.
The technical scheme is as follows: the CuAlMnNiCr shape memory alloy is characterized by the following chemical formula: cu (Cu) x Al y Mn z Cr j Ni k The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 9 and less than or equal to 18,0, j is more than or equal to 2, k is more than 0 and less than or equal to 6, and x+y+z+j+k=100; the alloy ingot obtained by smelting the alloy is subjected to temperature T 1 Is subjected to first constant temperature heat preservation and gradient cooling to T 2 The second constant temperature is maintained, and the temperature is increased to T in a gradient way 1 Is subjected to constant temperature heat preservation and quenching to obtain the product; the T is 1 Not lower than 750 ℃ and not higher than the melting point of the alloy ingot; the T is 2 Not lower than 350 ℃. In the alloy, chromium and nickel are matched, the grain size is multiplied, and the grain size is not less than 1.5cm.
In the Cu-Al-based alloy, the alloy has good cold workability when the Al content is less than 18.0%, and the best combination property can be obtained when the Al content is 17%, so that in the present invention, al is preferably 10.0 to 20.0%, for example, 12%, 14%, 16%, 18%. The addition of a certain amount of Mn to the Cu-Al alloy can expand the beta phase region to a region where the Al content is low, thereby improving the alloy properties, so that the Mn content is preferably 9.0 to 18.0%, for example, 10%, 12%, 14%, 16%. The addition of a proper amount of Cr can refine the size of the sub-crystal grains, increase the area of the sub-crystal boundary, and provide more driving force for the migration of the crystal boundary and promote the abnormal growth of the crystal grains. However, when the Cr content is too high, the grain growth is suppressed, so that the Cr content is preferably 0.1% to 2.0%, for example, 0.3%, 0.5%, 0.8%, 1.0%, 1.5%. The addition of a proper amount of Ni is favorable for obtaining texture and improving the ductility of the system, thereby improving the mechanical properties of the alloy, and the preferred orientation of the texture is utilized for promoting the migration of grain boundaries, but when the addition amount is too large, the content of brittle Ni of the alloy is increased to be preferably 0.1-6.0%, for example 0.5%, 1.0%, 2.0%, 3.0%, 4.0% and 5.0%.
Experiments show that Cr is singly added in the CuAlMn alloy without Ni, and the obtained four-component alloy cast ingot is subjected to temperature T 1 Is subjected to constant temperature heat treatment and is cooled down to T in a gradient way 2 Is subjected to first short-time heat preservation, and is subjected to gradient heat recovery to T 1 After quenching treatment, there is no obvious difference in single crystal grains compared with the heat treated alloy ingot in which the single phase region of 800-950 deg.c is annealed for 1-30 hr in the prior art. After Ni addition, the grains continue to grow in accordance with the treatment scheme of the present invention. The combination of Cr and Ni increases the single crystal size in the alloy by multiple times. Preferably, the alloy has the formula: cu (Cu) x Al y Mn z Ni j Cr k The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is more than or equal to 14 and less than or equal to 20, z is more than or equal to 9 and less than or equal to 14, j is more than or equal to 0 and less than or equal to 3, k is more than or equal to 0 and less than or equal to 1, x+y+z+j+k=100, and the addition of Ni is not too much, and too much is not beneficial to grain growth.
Preferably, in the alloy ingot, the molar ratio of Al is: y is more than or equal to 16.4 and less than or equal to 17, and the mole ratio of Mn is as follows: z is more than or equal to 11.1 and less than or equal to 11.4, and the mole ratio of Ni is as follows: j is more than or equal to 2 and less than or equal to 3, and the molar ratio of Cr is as follows: k is more than or equal to 0.1 and less than or equal to 0.7, and the grain size of the obtained shape memory alloy monocrystal is not less than 3.5cm.
Preferably, said T 1 At a temperature of not lower than 850 ℃ and not higher than 900 ℃, the shape of the invention is based on the alloy which is mainly in a beta single-phase region and has a small part of alpha phase, and the interface between the alpha phase and the beta phase is in a semi-coherent structure, and the interface can be generated in the transformation processThe micro stress generates dislocation, promotes the precipitation of sub-crystals, and is unfavorable for the generation of the transformation and the generation of single crystals due to the excessively low temperature.
Preferably, the duration of the first constant temperature heat preservation, the second constant temperature heat preservation and the third constant temperature heat preservation is 1-120 minutes.
Preferably, the gradient of the gradient cooling is 3-15 ℃/min, and the gradient of the gradient tempering is 5-15 ℃/min. More preferably, the gradient of the gradient cooling is 3-5 ℃/min, and the gradient of the gradient heating is 8-10 ℃/min.
Preferably, the duration of the first, second and third constant temperature incubations is 1-60 minutes.
The invention relates to a preparation method of a CuAlMnNiCr shape memory alloy, which is characterized by comprising the following steps:
(1) Proportioning according to the chemical formula of the partial alloy, and smelting to obtain an alloy cast ingot;
(2) Shaping the alloy ingot at a temperature T 1 Carrying out first constant temperature heat preservation for 1-60 minutes, wherein the T is as follows 1 Not lower than 850 ℃ and not higher than 900 ℃;
(3) Cooling the alloy cast ingot obtained in the step (2) to a temperature T at a gradient of 3-15 ℃/min 2 Performing a second constant temperature heat preservation for 1 to 60 minutes, wherein the T is as follows 2 Not lower than 350 ℃;
(4) Heating the alloy ingot obtained in the step (3) to a temperature T at a gradient of 8-15 ℃/min 1 Carrying out a third constant temperature heat preservation for 1-60 minutes;
(5) Quenching the alloy cast ingot obtained in the step (4) to obtain a shape memory alloy;
the steps (3) and (4) are carried out for 1 to 7 times, and the grain growth is facilitated to approach the limit through a plurality of heat cycle processes.
Preferably, steps (3) and (4) are performed 1 to 5 times. In the experiment, the grain size and the thermal cycle times are not in a direct proportion relation, when the times are 6 times, the grain growth approaches to the limit, the cycle times of the steps (3) and (4) are further increased, and the grains are not obviously changed.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: 1. the grain size of the chromium-containing copper-base alloy monocrystal is obviously improved, the grain size obtained by one-time heat cycle treatment exceeds 4cm, and the maximum grain size can reach 13cm under the condition of multiple heat cycles; 2. the comprehensive performance of the alloy is obviously improved, and the maximum recoverable strain is 10%; 3. the preparation method is simple, and the grain size can be increased by one thermal cycle.
Drawings
FIG. 1 is a photograph of the grain size of example 1;
FIG. 2 is a metallographic view of the subgrain precipitation during the cyclic heat treatment of example 1;
FIG. 3 is a stress-strain curve for example 1; the abscissa in the figure is engineering strain, and the ordinate in the figure is engineering stress;
FIG. 4 is a photograph of the grain size of example 2;
FIG. 5 is a stress-strain curve of example 2, with the abscissa in the graph being engineering strain and the ordinate in the graph being engineering stress;
FIG. 6 is a photograph of the grain size of comparative example 1;
FIG. 7 is a metallographic view showing the precipitation of sub-crystals during the cyclic heat treatment of comparative example 1;
FIG. 8 is a stress-strain curve of comparative example 1; the abscissa in the figure is engineering strain and the ordinate in the figure is engineering stress.
Detailed Description
The invention is further illustrated and described below in connection with the following drawings and specific embodiments, which, however, should not be construed as unduly limiting the scope of the invention.
Example 1: in this example, the alloy has the formula Cu in mole percent 69.1 Al 16.6 Mn 11.1 Ni 2 Cr 0.5 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion, then smelting is carried out to obtain an alloy ingot, and the ingot is hot rolled to a thickness of 2mm at 800 ℃. The rolled plate is put into a heat treatment furnace for heat treatment, and is firstly kept at 900 DEG C30min, cooling to 500 ℃ at a cooling rate of 3 ℃/min, preserving heat for 15min, heating to 900 ℃ at a heating rate of 10 ℃/min, preserving heat for 1h, taking out the workpiece, and quenching. The grain size is shown in FIG. 1, and the maximum grain size obtained is 4.3cm. The subgrain precipitation metallographic photograph during the cyclic heat treatment is shown in fig. 2, the average size is 43 μm, the stress-strain curve is shown in fig. 3, and the maximum recoverable strain is 10%.
Example 2: in this example, the alloy has the formula Cu in mole percent 68.9 Al 16.4 Mn 11 Ni 3 Cr 0.7 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion, then smelting is carried out to obtain an alloy ingot, and the ingot is hot rolled to 2mm at 800 ℃. Placing the rolled plate into a heat treatment furnace for heat treatment, (1) firstly preserving heat at 850 ℃ for 30min, (2) reducing the temperature to 450 ℃ at a temperature reduction rate of 5 ℃/min, preserving heat for 5min, (3) raising the temperature to 900 ℃ at a temperature rise rate of 8 ℃/min, preserving heat for 30min, repeating the processes (2) and (3) for 4 times, taking out the workpiece, and quenching. The grain size is shown in FIG. 4, and the maximum grain size obtained is 13cm. The stress-strain curve is shown in FIG. 5, with a maximum recoverable strain of 9%.
Example 3: in this example, the alloy has the formula Cu in mole percent 69.5 Al 17 Mn 11.4 Ni 2 Cr 0.1 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion, then smelting is carried out to obtain an alloy ingot, and the ingot is hot rolled to a thickness of 2mm at 800 ℃. Placing the rolled plate into a heat treatment furnace for heat treatment, (1) firstly preserving heat at 900 ℃ for 30min, (2) reducing the temperature to 500 ℃ at a temperature reduction rate of 3 ℃/min, preserving heat for 60min, (3) raising the temperature to 900 ℃ at a temperature rise rate of 10 ℃/min, preserving heat for 1h, repeating the processes (2) and (3) for 4 times, taking out the workpiece, and quenching. The maximum grain size obtained was 3.9cm and the maximum recoverable strain was 4.3%.
Example 4: in this example, the alloy has the formula Cu in mole percent 67.6 Al 17 Mn 11.4 Ni 2 Cr 2 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion,then smelting to obtain an alloy ingot, and hot-rolling the ingot to a thickness of 2mm at 800 ℃. Placing the rolled plate into a heat treatment furnace for heat treatment, (1) firstly preserving heat at 900 ℃ for 30min, (2) reducing the temperature to 500 ℃ at a temperature reduction rate of 3 ℃/min, preserving heat for 45min, (3) raising the temperature to 900 ℃ at a temperature rise rate of 10 ℃/min, preserving heat for 1h, repeating the processes (2) and (3) for 4 times, taking out the workpiece, and quenching. The maximum grain size obtained was 1.7cm and the recoverable strain was 3.6%.
Example 5: in this example, the alloy has the formula Cu in mole percent 71 Al 17 Mn 11.4 Ni 0.1 Cr 0.5 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion, weighed according to the molar mass ratio, then smelted to obtain an alloy ingot, and the ingot is hot rolled to a thickness of 2mm at 800 ℃. And (3) placing the rolled plate into a heat treatment furnace for heat treatment, firstly preserving heat at 750 ℃ for 1min, then cooling to 350 ℃ at a cooling rate of 1 ℃/min, preserving heat for 1min, then raising to 750 ℃ at a heating rate of 1 ℃/min, preserving heat for 1min, and taking out a workpiece for quenching. The maximum grain size obtained was 1.5cm and the recoverable strain was 3.1%.
Example 6: in this example, the alloy has the formula Cu in mole percent 66.1 Al 17 Mn 11.4 Ni 5 Cr 0.5 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion, then smelting is carried out to obtain an alloy ingot, and the ingot is hot rolled to a thickness of 2mm at 800 ℃. Placing the rolled plate into a heat treatment furnace for heat treatment, (1) firstly preserving heat at 900 ℃ for 600min, (2) reducing the temperature to 690 ℃ at a temperature reduction rate of 15 ℃/min, preserving heat for 120min, (3) raising the temperature to 900 ℃ at a temperature increase rate of 15 ℃/min, preserving heat for 120min, repeating the processes (2) and (3) for 5 times, taking out the workpiece, and quenching. The maximum grain size obtained was 2.7cm and the maximum recoverable strain was 4.3%.
Example 7: in this example, the alloy has the formula Cu in mole percent 61.8 Al 20 Mn 15 Ni 2 Cr 0.5 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion, and then smelting is carried out to obtainAnd (3) obtaining an alloy ingot, and hot-rolling the ingot to a thickness of 2mm at 800 ℃. Placing the rolled plate into a heat treatment furnace for heat treatment, firstly preserving heat at 900 ℃ for 30min, then cooling to 500 ℃ at a cooling rate of 3 ℃/min, preserving heat for 180min, then raising to 900 ℃ at a heating rate of 15 ℃/min, preserving heat for 180min, taking out a workpiece, and quenching. The maximum grain size exceeds 1.5cm.
Comparative example 1: in this example, the alloy has the formula Cu in mole percent 71.6 Al 17 Mn 11.4 . Cu, al and Mn are selected as raw materials according to the chemical formula proportion, then smelting is carried out to obtain an alloy ingot, and the ingot is hot rolled to a thickness of 2mm at 800 ℃. And (3) placing the rolled plate into a heat treatment furnace for heat treatment, firstly preserving the heat at 900 ℃ for 30min, then reducing the temperature to 500 ℃ at a temperature reduction rate of 3 ℃/min, preserving the heat for 15min, then raising the temperature to 900 ℃ at a temperature rise rate of 10 ℃/min, preserving the heat for 1h, taking out the workpiece, and quenching. The grain size is shown in FIG. 6, and the maximum grain size obtained is 1.5cm. The subgrain precipitation metallographic photograph during the cyclic heat treatment is shown in fig. 7, the average size is 71 μm, the stress-strain curve is shown in fig. 8, and the maximum recoverable strain is 5.2%.
Comparative example 2: in this example, the alloy has the formula Cu in mole percent 81.8 Al 10 Mn 5 Ni 2 Cr 0.5 . Cu, al, mn, ni and Cr are selected as raw materials according to the chemical formula proportion, then smelting is carried out to obtain an alloy ingot, and the ingot is hot rolled to a thickness of 2mm at 800 ℃. And (3) placing the rolled plate into a heat treatment furnace for heat treatment, firstly preserving the heat at 900 ℃ for 30min, then reducing the temperature to 500 ℃ at a temperature reduction rate of 3 ℃/min, preserving the heat for 15min, then raising the temperature to 900 ℃ at a temperature rise rate of 10 ℃/min, preserving the heat for 1h, taking out the workpiece, and quenching. The maximum grain size exceeds 1cm.
Claims (10)
1. A cualmnnnicr shape memory alloy characterized by: the alloy has the chemical formula as follows in mole percent: cu (Cu) x Al y Mn z Ni j Cr k The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is more than or equal to 10 and less than or equal to 20, z is more than or equal to 9 and less than or equal to 18,0, j is more than or equal to 6, k is more than 0 and less than or equal to 2, and x+y+z+j+k=100; the alloy is melted byThe alloy cast ingot obtained by smelting is subjected to temperature T 1 Is subjected to first constant temperature heat preservation and gradient cooling to T 2 The second constant temperature is maintained, and the temperature is increased to T in a gradient way 1 Is subjected to constant temperature heat preservation and quenching to obtain the product; the T is 1 Not lower than 750 ℃ and not higher than the melting point of the alloy ingot; the T is 2 Not lower than 350 ℃.
2. The cualmnnnicr shape memory alloy of claim 1, wherein the alloy has the formula, in mole percent: cu (Cu) x Al y Mn z Ni j Cr k The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is more than or equal to 14 and less than or equal to 20, z is more than or equal to 9 and less than or equal to 14, j is more than or equal to 0 and less than or equal to 3, k is more than or equal to 0 and less than or equal to 1, and x+y+z+j+k=100.
3. The cualmnnnicr shape memory alloy according to claim 1 or 2, wherein the molar ratio of Al in the alloy ingot is: y is more than or equal to 16.4 and less than or equal to 17, and the mole ratio of Mn is as follows: z is more than or equal to 11.1 and less than or equal to 11.4.
4. The cualmnnnicr shape memory alloy according to claim 1 or 2, wherein the molar ratio of Ni in the alloy ingot is: j is more than or equal to 2 and less than or equal to 3, and the molar ratio of Cr is as follows: k is more than or equal to 0.1 and less than or equal to 0.7.
5. The cualmnnnicr shape memory alloy according to claim 1, wherein said T 1 The temperature is not lower than 850 ℃ and not higher than 900 ℃, and the duration time of the first constant temperature heat preservation, the second constant temperature heat preservation and the third constant temperature heat preservation is 1-120 minutes.
6. The cualmnnnicr shape memory alloy according to claim 1, wherein the gradient of the gradient cooling is 1-15 ℃/min and the gradient of the gradient heating is 3-15 ℃/min.
7. The cualmnnnicr shape memory alloy according to claim 1 or 6, wherein the gradient of the gradient cooling is 2-5 ℃/min and the gradient of the gradient heating is 7-13 ℃/min.
8. The cualmnnnicr shape memory alloy according to claim 1 or 5, wherein the first, second and third constant temperature incubation are of a duration of 1 to 60 minutes.
9. The preparation method of the CuAlMnNiCr shape memory alloy is characterized by comprising the following steps of:
(1) Proportioning according to the chemical formula of the alloy of claim 1, and smelting to obtain an alloy ingot;
(2) Shaping the alloy ingot at a temperature T 1 Carrying out first constant temperature heat preservation for 1-60 minutes, wherein the T is as follows 1 Not lower than 800 ℃ and not higher than 950 ℃;
(3) Cooling the alloy cast ingot obtained in the step (2) to a temperature T at a gradient of 3-15 ℃/min 2 Performing a second constant temperature heat preservation for 1 to 60 minutes, wherein the T is as follows 2 Not lower than 350 ℃;
(4) Heating the alloy ingot obtained in the step (3) to a temperature T at a gradient of 8-15 ℃/min 1 Carrying out a third constant temperature heat preservation for 1-60 minutes;
(5) Quenching the alloy cast ingot obtained in the step (4) to obtain a shape memory alloy;
the steps (3) and (4) are carried out 1 to 7 times.
10. The method of preparing a cualmnnnicr shape memory alloy according to claim 9, wherein said steps (3) and (4) are performed 1 to 5 times.
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