CN115927915B - Ti-Ni-Zr shape memory alloy and preparation method thereof - Google Patents
Ti-Ni-Zr 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 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000956 alloy Substances 0.000 claims abstract description 83
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 75
- 238000005242 forging Methods 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000005096 rolling process Methods 0.000 claims abstract description 25
- 239000004615 ingredient Substances 0.000 claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 230000006698 induction Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims description 45
- 238000003723 Smelting Methods 0.000 claims description 22
- 230000032683 aging Effects 0.000 claims description 17
- 238000010622 cold drawing Methods 0.000 claims description 15
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 238000000265 homogenisation Methods 0.000 claims description 6
- 238000005098 hot rolling Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000012856 weighed raw material Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000005097 cold rolling Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910004337 Ti-Ni Inorganic materials 0.000 abstract description 23
- 229910011209 Ti—Ni Inorganic materials 0.000 abstract description 23
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 abstract description 23
- 230000007704 transition Effects 0.000 abstract description 11
- 241001062472 Stokellia anisodon Species 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 74
- 239000010936 titanium Substances 0.000 description 67
- 239000000463 material Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 19
- 238000001816 cooling Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 230000006399 behavior Effects 0.000 description 9
- 230000009466 transformation Effects 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 230000003446 memory effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000734 martensite Inorganic materials 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910010380 TiNi Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention belongs to the technical field of Ti-Ni-based shape memory alloy, in particular to a Ti-Ni-Zr shape memory alloy and a preparation method thereof, and solves the problems of high cost, poor processability, poor phase transition temperature, memory characteristic and mechanical property controllability of the existing Ti-Ni-based shape memory alloy. The alloy is characterized by comprising the following components in percentage by atom: ni50.5% -50.8%; zr0.1% -1.0%; the balance being Ti. The preparation method is characterized by comprising the following steps: firstly, weighing Ti, ni and Zr according to atomic percentage, and uniformly mixing to obtain ingredients; step two, placing the ingredients into an intermediate frequency vacuum induction furnace to smelt ingot blanks; step three, placing the ingot blank into a vacuum furnace, vacuumizing, homogenizing at high temperature, and obtaining a blank for forging; step four: forging, rolling and drawing a blank for forging to obtain an alloy section; step five: and (5) performing heat treatment to obtain a shape memory alloy material finished product.
Description
Technical Field
The invention belongs to the technical field of Ti-Ni-based shape memory alloy, and particularly relates to a Ti-Ni-Zr shape memory alloy and a preparation method thereof.
Background
The Ti-Ni based shape memory alloy has shown remarkable application value since discovery. With the recent intensive research and achievement transformation, various shape memory alloy products appear on the market, and the application range relates to the engineering and civil fields of aerospace, biomedicine, mechano-electronics, chemical energy and the like.
Ti-Ni shape memory alloys, while having many advantages, also have the disadvantages of high raw material cost, difficult processing and self-properties affected by alloy composition, processing process, heat treatment process, deformation temperature, etc. In order to improve the performance and reduce the cost of the Ti-Ni shape memory alloy, studies have been made on alloy components, heat treatment processes, experimental conditions, and the like, wherein the Ti-Ni alloy as a base body, the performance of which is improved by doping a third component and assisting the heat treatment process, has been widely used.
However, the existing Ti-Ni-based shape memory alloy doped with the third component has good workability but high cost; some are low cost but have poor processability; and the phase transition temperature, the memory characteristic and the mechanical property of the composite material are poor in controllability.
Disclosure of Invention
The invention aims to provide a Ti-Ni-Zr shape memory alloy and a preparation method thereof, which are used for solving the technical problems of higher cost, poorer processability, and poorer phase transition temperature, memory characteristic and mechanical property controllability of the existing Ti-Ni-based shape memory alloy.
The technical scheme adopted by the invention is that the Ti-Ni-Zr shape memory alloy is characterized by comprising the following components in percentage by atom:
Ni：50.5％～50.8％；
Zr：0.1％～1.0％；
The balance being Ti.
Further, the Ti 49.1Ni50.8Zr0.1.Ti49.1Ni50.8Zr0.1 shape memory alloy has good cold and hot workability, and the martensite reverse phase transformation ending temperature Af after complete annealing is about minus 17 ℃; the tensile strength is 1136 MPa-1489 MPa, the elongation is 11.6% -13.3% after low-temperature annealing, the superelastic stress platform is about 500MPa after high-temperature annealing, and the superelastic strain exceeds 7%; the functional characteristic parameters can completely meet the requirements of practical application.
The invention also provides a preparation method of the Ti-Ni-Zr shape memory alloy, which is characterized by comprising the following steps:
Step one: weighing Ti, ni and Zr raw materials according to the atomic percentage ratio, and uniformly mixing the weighed raw materials to obtain an alloy ingredient;
step two: putting the alloy ingredients obtained in the step one into a medium-frequency vacuum induction furnace, and smelting a Ti-Ni-Zr alloy ingot casting blank;
Step three: putting the Ti-Ni-Zr alloy ingot casting blank obtained by smelting in the second step into a vacuum furnace, and vacuumizing to ensure that the vacuum degree is less than 1 multiplied by 10 -2 Pa; then preserving heat for 6-12 h at 850-1050 ℃ to carry out high-temperature homogenization treatment; finally, mechanically removing surface oxide skin and riser to obtain a blank for forging the Ti-Ni-Zr alloy;
step four: forging the blank for forging the Ti-Ni-Zr alloy obtained in the step three, or forging and then rolling the blank, or forging, rolling and drawing the blank in sequence to obtain a Ti-Ni-Zr shape memory alloy section;
Step five: and (3) annealing the Ti-Ni-Zr shape memory alloy section obtained in the step four at 350-700 ℃, or carrying out solution treatment at 750-850 ℃ first, and then carrying out aging treatment at 300-600 ℃ to obtain a Ti-Ni-Zr shape memory alloy material finished product, wherein the preparation of the Ti-Ni-Zr shape memory alloy is completed.
Further, in order to make the impurities of the prepared Ti-Ni-Zr shape memory alloy material finished product less, the purity of the Ti, ni and Zr raw materials in the first step is as follows: 99.9wt.% or more of Ti, 99.99wt.% or more of Ni, and 99.9wt.% or more of Zr.
Further, in order to improve the purity and uniformity of the Ti-Ni-Zr alloy ingot casting blank obtained by smelting, in the second step, when the alloy ingredients obtained in the first step are put into an intermediate frequency vacuum induction furnace for smelting, the vacuum degree is less than 1X 10 -3 Pa, the smelting temperature is controlled to 1250-1360 ℃, the smelting time is controlled to 15-25 min, the crucible is a water-cooled copper crucible, and the crucible diameter is 100-300 mm.
Further, the forging temperature in the fourth step is controlled to be 750-900 ℃.
Further, the temperature of the rolling in the fourth step is controlled to be 750-900 ℃.
The forging and rolling temperatures in the fourth step are controlled to be 750-900 ℃, and the temperature is controlled to be within the range as follows: the temperature is too high, so that a plurality of coarse precipitated phases are formed in the material, the oxidation of the material is accelerated, the forging and rolling performances of the material are finally reduced, and the impurity elements of the alloy are increased, so that the control of the alloy components is not facilitated; too low a temperature can result in too high a material strength and insufficient workability, while the alloy is relatively sensitive to cracking and too low a temperature can result in cracking of the material forge crack.
Further, the rolling in the fourth step is hot rolling or cold rolling after hot rolling and then recrystallization annealing.
Further, in the fourth step, the drawing is hot drawing, or hot drawing is performed first, and then drawing is performed again;
the hot drawing temperature is controlled at 600-850 ℃;
in the cold drawing, intermediate annealing treatment at 650-800 ℃ is required when the total deformation reaches 40-55%.
Thus, the drawing mode can be selected according to the size specification of the required finished product, for example, when the diameter of the required finished product is 4-6 mm, a single hot drawing mode can be selected; when the diameter of the required finished product is 0.5-2 mm, a mode of firstly carrying out hot drawing and then carrying out cold drawing can be selected; the cold drawing can improve the performance of the material, and the hardness, tensile strength, super elasticity and memory property of the material are improved. The temperature of the hot drawing is controlled within a temperature range of 600-850 ℃, because the material is in a recrystallization annealing state at 600-850 ℃, the material has good plasticity, good processability and easy deformation, and is beneficial to drawing. In cold drawing, the intermediate annealing treatment at 650-800 ℃ is needed when the total deformation reaches 40-55%, because the material is too hard and difficult to draw when the total deformation reaches 40-55%, and the intermediate annealing treatment at 650-800 ℃ can soften the material, which is beneficial to drawing; if the total deformation is too small, the intermediate annealing treatment is carried out at 650-800 ℃, and the drawing efficiency is too low.
Further, in the fourth step, the heating devices used in the forging, rolling and drawing processes are all resistance furnaces. Thus, when heating is performed by using a gas furnace, impurities containing elements such as carbon, hydrogen, oxygen and the like generated by gas combustion are prevented from entering the material at high temperature, and if the impurities enter the material, the impurities are increased, the alloy composition is changed, and the alloy performance is further deteriorated.
The beneficial effects of the invention are as follows:
(1) The Ti-Ni-Zr shape memory alloy comprises the following components in percentage by atom: ni:50.5 to 50.8 percent; zr:0.1 to 1.0 percent; the balance being Ti. As can be seen from the atomic percentage ratio, the Ti-Ni-Zr shape memory alloy belongs to the Ti-Ni shape memory alloy rich in Ni. The Ti-Ni shape memory alloy rich in Ni has better memory property than the Ti-Ni shape memory alloy lean in Ni and the Ti-Ni shape memory alloy near to the equal atomic ratio, and the property of the Ti-Ni shape memory alloy is easier to regulate; the Ni-rich precipitates such as Ti 3Ni4 and the like do not exist in the Ni-lean Ti-Ni alloy after heat treatment, so that the heat treatment has little influence on microstructure and phase change behavior of the Ni-lean Ti-Ni alloy, and the potential of improving the performance of the Ni-lean Ti-Ni alloy through the heat treatment is little; the Ti 3Ni4 phase which is coherent with the matrix can be separated out from the structure of the Ti-Ni alloy rich in Ni after heat treatment, and the appearance of the phase is favorable for improving the strength of the alloy on one hand, and can reduce the Ni content in the matrix on the other hand, thereby influencing the phase transition temperature and deformation behavior of the alloy. Therefore, if a ternary shape memory alloy with adjustable phase transition temperature, memory characteristics and mechanical properties is to be obtained, the addition of the third component to the Ni-rich Ti-Ni alloy is more suitable. Zr is added into the Ti-Ni alloy rich in Ni, and in the preparation process, the Ti-Ni-Zr shape memory alloy section obtained by shaping the alloy is matched with heat treatment with different systems, so that the phase transition temperature, the memory behavior, the tensile strength and the like of the alloy are regulated and controlled; meanwhile, zr is low in price, the cold and hot processing performance of the alloy with specific components is good, after a small amount of Zr is added into the Ti-Ni alloy rich in Ni, the phase transition temperature of the alloy is reduced and then increased, and the performances such as strength, elongation, shape memory recovery rate and the like are improved; therefore, the Ti-Ni-Zr shape memory alloy has the advantages of lower preparation cost, good processability and good memory property; therefore, the invention solves the technical problems of higher cost, poorer processability, poorer phase transition temperature, memory characteristic and mechanical property controllability of the existing Ti-Ni-based shape memory alloy. The Ti-Ni-Zr shape memory alloy of the invention is a Ti-Ni-based shape memory alloy with very good application prospect.
(2) The Ti-Ni-Zr shape memory alloy has good cold and hot workability, and the martensite reverse phase transformation ending temperature Af after complete annealing is about-17 ℃; the tensile strength is 1136 MPa-1489 MPa, the elongation is 11.6% -13.3% after low-temperature annealing, the superelastic stress platform is about 500MPa after high-temperature annealing, and the superelastic strain exceeds 7%; the functional characteristic parameters can completely meet the requirements of practical application.
(3) The Ti-Ni-Zr shape memory alloy is prepared by adopting the preparation method of the Ti-Ni-Zr shape memory alloy, and the process is simple; the prepared Ti-Ni-Zr shape memory alloy has good plastic processing capability and good memory property, and the maximum super-elastic strain is more than 7%; the Ti-Ni-Zr shape memory alloy section obtained by shaping the alloy (forging in the step four, forging and rolling firstly, or forging, rolling and drawing sequentially) is matched with heat treatment of different systems (annealing treatment at 350-700 ℃ in the step five, or solution treatment at 750-850 ℃ firstly, and aging treatment at 300-600 ℃) to regulate and control the phase transition temperature, super elasticity, memory effect, mechanical property and microstructure of the finally obtained Ti-Ni-Zr shape memory alloy material finished product.
Drawings
FIG. 1 is a photograph of a microstructure of a Ti 49.1Ni50.8Zr0.1 shape memory alloy prepared in example 1 of the present invention; other preparation conditions of (a), (b), (c) and (d) in fig. 1 are the same, except that the annealing temperature is different in the fifth step, in which:
(a) The annealing treatment temperature is 400 ℃;
(b) The annealing treatment temperature is 500 ℃;
(c) The annealing treatment temperature is 600 ℃;
(d) The annealing treatment temperature is 700 ℃;
FIG. 2 is a graph showing the tensile strength and elongation of the Ti 49.1Ni50.8Zr0.1 shape memory alloy prepared in example 1 of the present invention;
FIG. 3 is a graph showing the superelasticity and memory effect of the Ti 49.1Ni50.8Zr0.1 shape memory alloy prepared in example 1 of the present invention;
FIG. 4 is a phase change behavior curve of the Ti 49.1Ni50.8Zr0.1 shape memory alloy prepared under the condition that the heat treatment system in the fifth step of the embodiment 1 of the invention is changed from annealing treatment at 350-700 ℃ to solid solution treatment at 800 ℃ for 1h, water cooling, aging at 300-600 ℃ for 1 h-50 h, and other preparation steps are unchanged; other preparation conditions of (e) and (f) in fig. 4 are the same, except that the aging temperature in step five is different, wherein:
(e) The aging treatment temperature is 400 ℃;
(f) The aging treatment temperature is 500 ℃;
FIG. 5 is a graph showing the mechanical properties of the Ti 48.5Ni50.5Zr1 shape memory alloy prepared in example 2 of the present invention;
FIG. 6 is a graph showing the superelastic properties of the Ti 48.8Ni50.7Zr0.5 shape memory alloy prepared in example 3 of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a Ti-Ni-Zr shape memory alloy, which comprises the following components in percentage by atom: ni:50.5 to 50.8 percent; zr:0.1 to 1.0 percent; the balance being Ti.
The Ti-Ni-Zr shape memory alloy has the preferable chemical formula of Ti 49.1Ni50.8Zr0.1.Ti49.1Ni50.8Zr0.1 shape memory alloy with good cold and hot processing performance, and the martensite reverse phase transformation ending temperature Af after complete annealing is about minus 17 ℃; the tensile strength is 1136 MPa-1489 MPa, the elongation is 11.6% -13.3% after low-temperature annealing, the superelastic stress platform is about 500MPa after high-temperature annealing, and the superelastic strain exceeds 7%; the functional characteristic parameters can completely meet the requirements of practical application.
The invention also provides a preparation method of the Ti-Ni-Zr shape memory alloy, which comprises the following steps:
step one: weighing Ti, ni and Zr raw materials according to the atomic percentage ratio, and uniformly mixing the weighed raw materials to obtain an alloy ingredient;
step two: putting the alloy ingredients obtained in the step one into a medium-frequency vacuum induction furnace, and smelting a Ti-Ni-Zr alloy ingot casting blank;
Step three: putting the Ti-Ni-Zr alloy ingot casting blank obtained by smelting in the second step into a vacuum furnace, and vacuumizing to ensure that the vacuum degree is less than 1 multiplied by 10 -2 Pa; then preserving heat for 6-12 h at 850-1050 ℃ to carry out high-temperature homogenization treatment; finally, mechanically removing surface oxide skin and riser to obtain a blank for forging the Ti-Ni-Zr alloy;
step four: forging the blank for forging the Ti-Ni-Zr alloy obtained in the step three, or forging and then rolling the blank, or forging, rolling and drawing the blank in sequence to obtain a Ti-Ni-Zr shape memory alloy section;
Step five: and (3) annealing the Ti-Ni-Zr shape memory alloy section obtained in the step four at 350-700 ℃, or carrying out solution treatment at 750-850 ℃ first, and then carrying out aging treatment at 300-600 ℃ to obtain a Ti-Ni-Zr shape memory alloy material finished product, wherein the preparation of the Ti-Ni-Zr shape memory alloy is completed.
In order to make the prepared Ti-Ni-Zr shape memory alloy material finished product have less impurities, preferably, the purity of the Ti, ni and Zr raw materials in the first step is: 99.9wt.% or more of Ti, 99.99wt.% or more of Ni, and 99.9wt.% or more of Zr.
In order to improve the purity and uniformity of the Ti-Ni-Zr alloy ingot casting blank obtained by smelting, when the alloy ingredients obtained in the step one are put into a medium-frequency vacuum induction furnace for smelting, the vacuum degree is preferably less than 1X 10 -3 Pa, the smelting temperature is controlled to 1250-1360 ℃, the smelting time is controlled to 15-25 min, the crucible is a water-cooled copper crucible, and the crucible diameter is 100-300 mm.
Preferably, the forging temperature in the fourth step is controlled to be 750-900 ℃. The temperature of rolling in the fourth step is controlled between 750 ℃ and 900 ℃. The rolling is hot rolling or cold rolling after hot rolling and then recrystallization annealing. The reason why the forging and rolling temperatures in the fourth step are controlled to be within the range of 750 ℃ to 900 ℃ is that: the temperature is too high, so that a plurality of coarse precipitated phases are formed in the material, the oxidation of the material is accelerated, the forging and rolling performances of the material are finally reduced, and the impurity elements of the alloy are increased, so that the control of the alloy components is not facilitated; too low a temperature can result in too high a material strength and insufficient workability, while the alloy is relatively sensitive to cracking and too low a temperature can result in cracking of the material forge crack.
Preferably, the drawing in the fourth step is hot drawing, or hot drawing is performed first and then drawing is performed again; the hot drawing temperature is controlled at 600-850 ℃; in cold drawing, intermediate annealing treatment at 650-800 deg.c is required when the total deformation reaches 40-55%. Thus, the drawing mode can be selected according to the size specification of the required finished product, for example, when the diameter of the required finished product is 4-6 mm, a single hot drawing mode can be selected; when the diameter of the required finished product is 0.5-2 mm, a mode of firstly carrying out hot drawing and then carrying out cold drawing can be selected; the cold drawing can improve the performance of the material, and the hardness, tensile strength, super elasticity and memory property of the material are improved. The temperature of the hot drawing is controlled within a temperature range of 600-850 ℃, because the material is in a recrystallization annealing state at 600-850 ℃, the material has good plasticity, good processability and easy deformation, and is beneficial to drawing. In cold drawing, the intermediate annealing treatment at 650-800 ℃ is needed when the total deformation reaches 40-55%, because the material is too hard and difficult to draw when the total deformation reaches 40-55%, and the intermediate annealing treatment at 650-800 ℃ can soften the material, which is beneficial to drawing; if the total deformation is too small, the intermediate annealing treatment is carried out at 650-800 ℃, and the drawing efficiency is too low.
The heating devices used in the forging, rolling and drawing processes in the fourth step are preferably electric resistance furnaces. Thus, when heating is performed by using a gas furnace, impurities containing elements such as carbon, hydrogen, oxygen and the like generated by gas combustion are prevented from entering the material at high temperature, and if the impurities enter the material, the impurities are increased, the alloy composition is changed, and the alloy performance is further deteriorated.
Example 1:
a preparation method of a Ti 49.1Ni50.8Zr0.1 shape memory alloy wire comprises the following steps:
step one: weighing 99.9wt.% zirconium, 99.99wt.% nickel and 99.9wt.% titanium according to the proportion of 0.1at.% Zr, 50.8at.% Ni and 49.1at.% Ti based on the total weight of 15Kg Ti 49.1Ni50.8Zr0.1 shape memory alloy, and mixing the weighed raw materials uniformly to obtain alloy mixture;
Step two: and (3) placing the alloy ingredients obtained in the step one into an intermediate frequency vacuum induction furnace, vacuumizing to ensure that the vacuum degree is 0.5 multiplied by 10 -3 Pa, and introducing argon for protection. Heating to a smelting temperature of 1360 ℃, refining for 15min, and cooling to obtain a Ti 49.1Ni50.8Zr0.1 alloy ingot casting blank; the weight of the alloy ingot casting blank is about 15kg;
Step three: placing the Ti 49.1Ni50.8Zr0.1 alloy ingot casting blank obtained by smelting in the second step into a vacuum furnace, vacuumizing to ensure that the vacuum degree is 0.2 multiplied by 10 -2 Pa, then carrying out high-temperature homogenization treatment at 900 ℃ for 10 hours, cooling the furnace after the heat preservation time is up, and mechanically adding and removing surface oxide skin, defects and riser after the furnace is taken out to obtain a blank for forging the Ti 49.1Ni50.8Zr0.1 alloy;
Step four: heating the blank for forging the Ti 49.1Ni50.8Zr0.1 alloy obtained in the step three to 850 ℃, preserving heat for 4 hours, forging and then rolling into an alloy wire blank with the diameter of 9 mm; carrying out hot drawing on an alloy wire blank with the diameter of 9mm, controlling the hot drawing temperature to be 700 ℃, controlling the pass deformation to be 10% -20% until the drawing is carried out until the diameter is 3mm, carrying out cold drawing, carrying out intermediate annealing treatment at 700 ℃ when the total deformation reaches 40% -55% in the cold drawing, and finally processing into a Ti 49.1Ni50.8Zr0.1 shape memory alloy wire section with the diameter of 1 mm;
Step five: and (3) annealing the Ti 49.1Ni50.8Zr0.1 shape memory alloy wire section obtained in the step four at 350-700 ℃ for 20min, cooling along with a furnace to obtain a Ti 49.1Ni50.8Zr0.1 shape memory alloy wire finished product, and completing the preparation of the Ti 49.1Ni50.8Zr0.1 shape memory alloy.
The finished Ti 49.1Ni50.8Zr0.1 shape memory alloy material prepared in example 1 was used as a sample for microstructure observation, mechanical property and memory property testing. FIG. 1 is a photograph of a microstructure of a sample, and it can be seen from (a), (b), (c) and (d) in FIG. 1 that as the annealing temperature increases, the structure of the alloy changes from fibrous to equiaxed; FIG. 2 is a graph of tensile strength and elongation for a sample, and it can be seen from FIG. 2 that as the annealing temperature increases, both the tensile strength R m and the elongation delta of the alloy change; FIG. 3 shows the superelasticity and memory effect curves of the samples, and it can be seen from FIG. 3 that as the annealing temperature increases, the alloy characteristics are changed from superelasticity to shape memory effect and then to superelasticity, and the platform stress of the alloy is reduced and then increased.
FIG. 4 is a graph showing the phase change behavior of the Ti 49.1Ni50.8Zr0.1 shape memory alloy prepared by changing the heat treatment system in the fifth step of example 1 from 350-700 ℃ annealing treatment to 800 ℃ solid solution for 1h, water cooling, 300-600 ℃ aging for 1 h-50 h, and other preparation steps unchanged; other preparation conditions of (e) and (f) in fig. 4 are the same, except that the aging temperature in step five is different, wherein: (e) aging treatment temperature is 400 ℃; (f) aging treatment temperature is 500 ℃; after ageing for 1-50 h, testing the phase transformation behavior on NETZSCH DSC, wherein in FIG. 4, M represents martensite, R represents R phase, R' represents R reverse phase transformation, and A represents austenite; as can be seen from fig. 4, the phase transformation behavior, the phase transformation temperature, and the aging time of the alloy are continuously changed with the increase of the aging temperature. Compared with a heat treatment system which only carries out solution treatment, the heat treatment system which carries out solution treatment and then aging treatment can lead to precipitation of Ni-rich phases in the alloy after aging, and the occurrence of the precipitation phases can influence metallographic phase change, memory property and mechanical property.
In conclusion, the Ti 49.1Ni50.8Zr0.1 shape memory alloy has good cold and hot workability, and microstructure, memory behavior (super elasticity and memory effect) and phase transition temperature can be regulated and controlled by matching different heat treatment systems after drawing, namely the alloy is TiNi-based shape memory alloy with good application prospect.
Example 2:
a preparation method of a Ti 48.5Ni50.5Zr1 shape memory alloy wire comprises the following steps:
Step one: weighing zirconium with the purity of 99.9 wt%, nickel with the purity of 99.99 wt% and titanium with the purity of 99.9 wt% according to the proportion of 1 at% of Zr, 50.5 at% of Ni and 48.5 at% of Ti based on the total weight of the Ti 48.5Ni50.5Zr1 shape memory alloy with the weight of 25Kg, and mixing the weighed raw materials uniformly to obtain an alloy mixture;
Step two: and (3) placing the alloy ingredients obtained in the step one into an intermediate frequency vacuum induction furnace, vacuumizing to ensure that the vacuum degree is 0.7X10 -3 Pa, and then introducing argon for protection. Heating to a smelting temperature of 1320 ℃, refining for 25min, and cooling to obtain a Ti 48.5Ni50.5Zr1 alloy ingot blank, wherein the weight of the alloy ingot blank is about 25Kg;
Step three: placing the Ti 48.5Ni50.5Zr1 alloy ingot casting blank obtained by smelting in the second step into a vacuum furnace, vacuumizing to ensure that the vacuum degree is 0.4x10 -2 Pa, then carrying out high-temperature homogenization treatment at 950 ℃ for 6 hours, cooling the furnace after the heat preservation time is up, and mechanically adding and removing surface oxide skin, defects and riser after the furnace is taken out to obtain a blank for forging the Ti 48.5Ni50.5Zr1 alloy;
Step four: heating the blank for forging the Ti 48.5Ni50.5Zr1 alloy obtained in the step three to 800 ℃, preserving heat for 10 hours, forging and then rolling into an alloy wire blank with the diameter of 9 mm; carrying out hot drawing on an alloy wire blank with the diameter of 9mm, controlling the hot drawing temperature to be 750 ℃, controlling the pass deformation to be 10% -20% until the drawing is carried out to the diameter of 3mm, then carrying out cold drawing, carrying out intermediate annealing treatment at 700 ℃ when the total deformation reaches 40% -55% in the cold drawing, and finally processing into a Ti 48.5Ni50.5Zr1 shape memory alloy wire section with the diameter of 0.8 mm;
Step five: and (3) annealing the Ti 48.5Ni50.5Zr1 shape memory alloy wire section obtained in the step four at 650 ℃ for 20min, cooling along with a furnace to obtain a Ti 48.5Ni50.5Zr1 shape memory alloy wire finished product, and completing the preparation of the Ti 48.5Ni50.5Zr1 shape memory alloy.
Taking the Ti 48.5Ni50.5Zr1 shape memory alloy wire finished product prepared in the embodiment 2 as a sample, testing the mechanical properties of the finished product, and FIG. 5 is a mechanical property curve of the Ti 48.5Ni50.5Zr1 shape memory alloy prepared in the embodiment 2; as can be seen from FIG. 5, the Ti 48.5Ni50.5Zr1 alloy has a tensile strength of 1004MPa, an elongation of up to 30.1% after recrystallization annealing, and exhibits excellent strength and plasticity.
Example 3:
A preparation method of a Ti 48.8Ni50.7Zr0.5 shape memory alloy wire comprises the following steps:
Step one: weighing 99.9wt.% zirconium, 99.99wt.% nickel and 99.9wt.% titanium according to the proportion of 0.5at.% Zr, 50.7at.% Ni and 48.8at.% Ti based on the total weight of 20Kg Ti 48.8Ni50.7Zr0.5 shape memory alloy, and mixing the weighed raw materials uniformly to obtain alloy mixture;
Step two: and (3) placing the alloy ingredients obtained in the step one into an intermediate frequency vacuum induction furnace, vacuumizing to ensure that the vacuum degree is 0.9X10 -3 Pa, and then introducing argon for protection. Heating to a smelting temperature of 1340 ℃, refining for 20min, and cooling to obtain a Ti 48.8Ni50.7Zr0.5 alloy ingot blank, wherein the weight of the alloy ingot blank is about 20Kg;
Step three: placing the Ti 48.8Ni50.7Zr0.5 alloy ingot casting blank obtained by smelting in the second step into a vacuum furnace, vacuumizing to ensure that the vacuum degree is 0.4x10 -2 Pa, then carrying out high-temperature homogenization treatment at 940 ℃ for 8 hours, cooling the furnace after the heat preservation time is up, and mechanically adding and removing surface oxide skin, defects and riser after the furnace is taken out to obtain a blank for forging the Ti 48.8Ni50.7Zr0.5 alloy;
Step four: heating the blank for forging the Ti 48.8Ni50.7Zr0.5 alloy obtained in the step three to 870 ℃, preserving heat for 7 hours, forging and then rolling into an alloy wire blank with the diameter of 9 mm; and (3) carrying out hot drawing on the alloy wire blank with the diameter of 9mm, controlling the hot drawing temperature to 810 ℃, controlling the pass deformation to 10% -20% until the drawing is carried out to the diameter of 3mm, then carrying out cold drawing, and carrying out intermediate annealing treatment at 740 ℃ when the total deformation reaches 40% -55% in the cold drawing, thereby finally processing the Ti 48.8Ni50.7Zr0.5 shape memory alloy wire section with the diameter of 0.5 mm.
Step five: and (3) annealing the Ti 48.8Ni50.7Zr0.5 shape memory alloy wire section obtained in the step four for 20min at the temperature of 450 ℃, and cooling along with a furnace to obtain a Ti 48.8Ni50.7Zr0.5 shape memory alloy wire finished product, and completing the preparation of the Ti 48.8Ni50.7Zr0.5 shape memory alloy.
Taking the Ti 48.8Ni50.7Zr0.5 shape memory alloy wire finished product prepared in the example 3 as a sample, testing the superelastic characteristics of the wire finished product, and FIG. 6 is the superelastic characteristic curve of the Ti 48.8Ni50.7Zr0.5 shape memory alloy prepared in the example 3; from FIG. 6, it can be seen that the Ti 48.8Ni50.7Zr0.5 alloy exhibits excellent superelastic properties after low-temperature annealing with a superelastic yield point of up to 612MPa and a superelastic strain of up to 8% and a superelastic residual strain of only 0.1%.
The 3 embodiments show that the Ti-Ni-Zr (50.5 at.% to 50.8at.% Ni, 0.1at.% to 1.0at.% Zr, and the balance Ti) shape memory alloy has good cold and hot workability, and the microstructure, the memory behavior (super elasticity and memory effect) and the phase transition temperature can be regulated and controlled by matching different heat treatment systems after drawing processing, so that the Ti-Ni-Zr shape memory alloy with excellent performance is obtained, namely the alloy is a TiNi-based shape memory alloy with good application prospect.
Claims (6)
1. The Ti-Ni-Zr shape memory alloy is characterized by comprising the following components in percentage by atom:
Ni：50.5%~50.8%；
Zr：0.1%~1.0%；
The balance being Ti;
The preparation method of the Ti-Ni-Zr shape memory alloy comprises the following steps:
Step one: weighing Ti, ni and Zr raw materials according to the atomic percentage ratio, and uniformly mixing the weighed raw materials to obtain an alloy ingredient;
step two: putting the alloy ingredients obtained in the step one into a medium-frequency vacuum induction furnace, and smelting a Ti-Ni-Zr alloy ingot casting blank;
Step three: putting the Ti-Ni-Zr alloy ingot casting blank obtained by smelting in the second step into a vacuum furnace, and vacuumizing to ensure that the vacuum degree is less than 1 multiplied by 10 -2 Pa; then carrying out heat preservation for 6-12 hours at 850-1050 ℃ and carrying out high-temperature homogenization treatment; finally, mechanically removing surface oxide skin and riser to obtain a blank for forging the Ti-Ni-Zr alloy;
step four: forging the blank for forging the Ti-Ni-Zr alloy obtained in the step three, or forging and then rolling the blank, or forging, rolling and drawing the blank in sequence to obtain a Ti-Ni-Zr shape memory alloy section;
Step five: annealing the Ti-Ni-Zr shape memory alloy section obtained in the step four at 350-700 ℃, or carrying out solution treatment at 750-850 ℃ first, and then carrying out aging treatment at 300-600 ℃ to obtain a Ti-Ni-Zr shape memory alloy material finished product, wherein the preparation of the Ti-Ni-Zr shape memory alloy is completed;
The alloy ingredients obtained in the step one are put into an intermediate frequency vacuum induction furnace to be smelted, the vacuum degree is less than 1 multiplied by 10 -3 Pa, the smelting temperature is controlled to 1250 ℃ to 1360 ℃, the smelting time is controlled to 15min to 25min, the crucible is a water-cooled copper crucible, and the diameter of the crucible is 100mm to 300mm;
In the fourth step, the drawing is hot drawing or hot drawing is performed first and then drawing is performed again;
the hot drawing temperature is controlled to be 600-850 ℃;
And in the cold drawing, intermediate annealing treatment at 650-800 ℃ is required when the total deformation reaches 40-55%.
2. The Ti-Ni-Zr shape memory alloy of claim 1, wherein: the purity of the Ti, ni and Zr raw materials in the first step is as follows: 99.9wt.% or more of Ti, 99.99wt.% or more of Ni, and 99.9wt.% or more of Zr.
3. The Ti-Ni-Zr shape memory alloy of claim 1, wherein: and in the fourth step, the forging temperature is controlled to be 750-900 ℃.
4. The Ti-Ni-Zr shape memory alloy of claim 1, wherein: and in the fourth step, the rolling temperature is controlled to be 750-900 ℃.
5. The Ti-Ni-Zr shape memory alloy of claim 1, wherein: and in the fourth step, the rolling is hot rolling or cold rolling after hot rolling and recrystallization annealing.
6. The Ti-Ni-Zr shape memory alloy according to any of claims 1 to 5, wherein: and step four, heating equipment used in forging, rolling and drawing processes is a resistance furnace.
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| JP3098587B2 (en) * | 1991-10-22 | 2000-10-16 | 古河電気工業株式会社 | Method and apparatus for manufacturing Ni-Ti based shape memory alloy wire for linear actuator |
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| DE4006076C1 (en) * | 1989-08-12 | 1990-12-13 | Fried. Krupp Gmbh, 4300 Essen, De | |
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