CN111187945A - TiNb/NiTi memory material containing Nb layer and preparation method - Google Patents
TiNb/NiTi memory material containing Nb layer and preparation method Download PDFInfo
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Abstract
The invention relates to the technical field of biomedical shape memory composite materials, in particular to a TiNb-coated NiTi shape memory composite material containing an Nb transition layer and a preparation method thereof, the composite material prepared by the method has good biocompatibility, higher stress-induced martensite phase transition critical stress and large recoverable strain, is expected to solve the problems that the existing single biomedical shape memory alloy, such as NiTi-based alloy and Ni-free β titanium alloy, cannot have good biocompatibility, higher stress-induced martensite phase transition critical stress and large recoverable strain at the same time, and is expected to be applied in the biomedical field.
Description
Technical Field
The invention relates to the technical field of biomedical shape memory composite materials, in particular to a TiNb-coated NiTi shape memory composite material containing an Nb transition layer and a preparation method thereof, the composite material prepared by the method has good biocompatibility, higher stress-induced martensite phase transformation critical stress and large recoverable strain, is expected to solve the problem that the existing single biomedical shape memory alloy (such as NiTi-based alloy and Ni-free β titanium alloy) cannot have good biocompatibility, higher stress-induced martensite phase transformation critical stress and large recoverable strain at the same time, and is expected to be applied in the biomedical field.
Background
NiTi shape memory alloy is gradually becoming the leading line of academic research and application research in the field of advanced functional materials due to its excellent shape memory effect and super elasticity, good corrosion resistance and high damping property, at present, NiTi shape memory alloy has become the most widely applied shape memory material in the biomedical field, such as being used as orthodontic wire, stent graft and minimally invasive surgical instrument, etc.
It is well known that the shape memory effect and superelasticity of Ni-free β titanium alloy and NiTi alloy are due to thermoelastic martensitic phase transformation, but β titanium alloy and NiTi alloy are of the type that thermoelastic martensitic phase transformation doesNot the same, the former is β (body centered cubic mother phase)
(orthorhombic martensite) phase transformation, the latter being B2 (body centered cubic parent phase)
(monoclinic martensite) phase transformation. Due to the fact that
And
the intrinsic difference of the crystallographic characteristics (such as crystal structure, transformation habit plane, shear direction and the like) of the two types of martensitic transformation, β stress-induced martensitic transformation critical stress sigma of titanium alloySIMIn addition, as an important reference index for the design and application of shape memory alloys, β titanium alloy has a maximum recoverable strain epsilon (about 2.5%) when it exhibits superelasticity that is much lower than the maximum recoverable strain epsilon (about 10%) when it exhibits superelasticity, thus, although β titanium alloy has biocompatibility significantly better than that of NiTi alloy, its lower stress-induced martensitic transformation critical stress sigma SIM and smaller recoverable strain epsilon greatly limit its application in biomedical applications.
In conclusion, both the single NiTi alloy and the β titanium alloy are difficult to simultaneously meet the comprehensive requirements of the biomedical field on the biocompatibility (no cytotoxicity), the stress-induced martensite phase transition critical stress (high critical stress sigma SIM) and the shape memory effect and the superelasticity (large recoverable strain epsilon) of the shape memory material.
Disclosure of Invention
As described above, both the NiTi alloy and the β Ti alloy are difficult to satisfy the requirements of biomedical field for biocompatibility (no cytotoxicity) and stress-induced martensite transformation critical stress (high critical stress sigma) of shape memory materialSIM) And the comprehensive requirements in the aspects of shape memory effect and super elasticity (large recoverable strain epsilon). The invention provides a TiNb-coated NiTi shape memory composite material containing an Nb transition layer and a preparation method thereof, which fully play the good biocompatibility (no cytotoxicity) of the outer-layer TiNb alloy and the excellent mechanical property (namely high stress-induced martensite phase transformation critical stress sigma) of the inner-layer NiTi alloySIMAnd a large recoverable strain epsilon), thereby obtaining the shape memory material with good biocompatibility, high stress-induced martensite phase transformation critical stress and large recoverable strain.
The technical scheme of the invention is as follows:
1) the kind of raw material.
Core base material: a commercial NiTi shape memory alloy (Ni content is 50.5-51.0%, atomic percentage) with super-elastic characteristic; surface shell material: commercial TiNb shape memory alloy (Nb content is 27.0-27.4%, atomic percent) with super-elastic characteristic; intermediate transition Nb layer: high purity Nb (99.95% by mass) to prevent poor interface reaction due to direct contact of NiTi alloy and TiNb alloy. The raw materials with the purity are not required to be imported, and the raw materials can be prepared by self or purchased in batches at home. The core material, the shell material and the intermediate transition layer finally form a sandwich-like structure as shown in fig. 1.
2) Selecting raw materials.
Core base material: the NiTi shape memory alloy has excellent hyperelasticity and can provide high stress-induced martensite phase transformation critical stress sigma for the composite materialSIMAnd a large recoverable strain amount epsilon.
Surface shell material: the TiNb shape memory alloy is composed of non-cytotoxic elements, has good biocompatibility, and can ensure that the composite material obtains good biocompatibility by coating the surface layer of the composite material.
Intermediate transition layer material: if NiTi and TiNb shape memory alloys are in direct contact, Ti will form2Ni、TiNi3Etc. to cause interfacial cracking. The Nb transition layer can avoid the direct contact of the NiTi and the TiNb shape memory alloy, and can dissolve a large amount of Ti and Ni elements without forming intermetallic compounds, so that the three are well compounded.
3) The preparation method comprises the following specific steps.
In the first step, the raw material is cut. Cutting a NiTi core material plate, two TiNb shell material plates and two pure Nb transition laminate plates from the NiTi, TiNb and pure Nb blanks by adopting an electric spark cutting method;
and secondly, cleaning the raw materials. Sequentially mechanically polishing the surfaces of the NiTi core material plate, the TiNb shell material plate and the pure Nb transition laminate plate obtained after cutting to a mirror surface by 400#, 800# and 1200# abrasive paper, then respectively putting the mirror surface into alcohol and acetone for ultrasonic cleaning, drying and storing in a sealing bag for later use;
and step three, manufacturing a sheath and lap-rolled bag. Sequentially and regularly stacking the raw materials in a titanium alloy (TC4) sheath according to the sequence of TiNb shell plate/pure Nb transition laminate plate/NiTi core plate/pure Nb transition laminate plate/TiNb shell plate, welding and sealing, and pumping the interior of the sheath to vacuum (the vacuum degree is 5 multiplied by 10)-1-1×10-2Pa), sealing, and finally preparing the sheath and the pack-rolling package.
Fourthly, rolling and compounding. And heating the completely sheathed pack rolling ladle to 600-700 ℃, preserving the heat for 30min, performing primary rolling with the reduction rate of 50-70% for compounding, performing secondary rolling with the reduction rate of 40-60% and final rolling with the reduction rate of 30-40% to obtain the TiNb/Nb/NiTi composite plate.
And fifthly, post-rolling treatment. After the pack rolling deformation, removing the outer sheath layer by wire cutting to take out the TiNb/Nb/NiTi composite board, and then annealing by a heat treatment process of heat preservation at 400 ℃ for 10-20min at 300-.
The invention has the advantages that:
1. the TiNb-coated NiTi shape memory composite material containing the Nb transition layer has good biocompatibility, and the biocompatibility is superior to that of NiTi shape memory alloy. Meanwhile, the TiNb-coated NiTi shape memory composite material containing the Nb transition layer also has high stress-induced martensite phase transformation critical stress sigmaSIMAnd large recoverable strain epsilon, and the mechanical property of the composite material is obviously superior to that of the typical representative non-cytotoxic β titanium alloy in the existing non-Ni shape memory alloy, therefore, the composite material has good biocompatibility (provided by the non-cytotoxic TiNb alloy at the outer layer), and high stress-induced martensite phase transformation critical stress sigmaSIMAnd a large recoverable strain epsilon, can well meet the comprehensive requirements of the biomedical field on shape memory materials, and is expected to be applied in the biomedical field.
2. The preparation method of the TiNb-coated NiTi shape memory composite material containing the Nb transition layer is obviously different from the method of modifying the surface of the NiTi shape memory alloy by the traditional coating method, oxidation method and the like so as to obtain the modified coating. The modified coatings prepared by the coating method and the oxidation method have the problems of pores, cracks, looseness and the like, the clad plate after the clad and pack rolling has the defects of good quality, compact and uniform surface, no pores, cracks and the like, and the clad and pack rolling process is simple and has high reliability. The TiNb-coated NiTi shape memory composite material containing the Nb transition layer expands the variety of biomedical materials and provides a new choice for biomedical implants.
Drawings
FIG. 1 is a schematic structural diagram of a TiNb/NiTi memory material with an Nb layer.
FIG. 2 shows Ti prepared in example 173.0Nb27.0/Nb/Ni50.5Ti49.5Scanning electron micrographs of the shape memory composite.
FIG. 3 shows Ti prepared in example 173.0Nb27.0/Nb/Ni50.5Ti49.5Stress-strain curves of shape memory composites.
FIG. 4Is Ti prepared in example 173.0Nb27.0/Nb/Ni50.5Ti49.5Shape memory composite and Ni50.5Ti49.5Comparative graph of L-929 cytotoxicity test of alloy.
FIG. 5 shows Ti prepared in example 272.8Nb27.2/Nb/Ni50.8Ti49.2Scanning electron micrographs of the shape memory composite.
FIG. 6 shows Ti prepared in example 272.8Nb27.2/Nb/Ni50.8Ti49.2Stress-strain curves of shape memory composites.
FIG. 7 shows Ti prepared in example 272.8Nb27.2/Nb/Ni50.8Ti49.2Shape memory composite and Ni50.8Ti49.2Comparative graph of L-929 cytotoxicity test of alloy.
FIG. 8 is Ti prepared in example 372.6Nb27.4/Nb/Ni51.0Ti49.0Scanning electron micrographs of the shape memory composite.
FIG. 9 is Ti prepared in example 372.6Nb27.4/Nb/Ni51.0Ti49.0Stress-strain curves of shape memory composites.
FIG. 10 is Ti prepared in example 372.6Nb27.4/Nb/Ni51.0Ti49.0Shape memory composite and Ni51.0Ti49.0Comparative graph of L-929 cytotoxicity test of alloy.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1:
this example was prepared by the following steps:
(1) selecting raw materials.
Core material: ni50.5Ti49.5Alloying; surface shell material: ti73.0Nb27.0Alloying; transition layer material: high purity Nb (99.95% by mass).
(2) Ti containing Nb transition layer73.0Nb27.0Cladding Ni50.5Ti49.5And preparing the shape memory composite material.
① cutting raw material, adopting electric spark cutting method to cut from Ni50.5Ti49.5、Ti73.0Nb27.0Cutting a NiTi core material plate with the length of 60mm multiplied by 4.5mm, a TiNb shell material plate with the length of 60mm multiplied by 0.8mm and a pure Nb transition laminate plate with the length of 60mm multiplied by 0.2mm on the pure Nb blank;
② cleaning raw materials, mechanically polishing the surfaces of the NiTi alloy plate, the TiNb alloy plate and the pure Nb plate obtained after cutting by 400#, 800# and 1200# abrasive paper in sequence to a mirror surface, then respectively putting the mirror surface into alcohol and acetone for ultrasonic cleaning, drying and storing in a sealing bag for later use;
③ making a sheath pack-rolling bag, orderly stacking the raw materials in a titanium alloy (TC4) sheath according to the sequence of the TiNb upper cladding plate/the pure Nb upper cladding plate/the NiTi core material plate/the pure Nb lower cladding plate/the TiNb lower cladding plate, then welding and sealing, and pumping the interior of the sheath to vacuum (the vacuum degree is 5 multiplied by 10) through the pumping holes reserved at the edges of the sheath-1Pa), sealing, and finally preparing the sheath and the pack-rolling package.
④ performing pack rolling compounding, heating the fully wrapped pack rolling package to 600 ℃, preserving heat for 30min, performing primary rolling with a reduction rate of 50% to compound, performing secondary rolling with a reduction rate of 40% and final rolling with a reduction rate of 30% to obtain Ti73.0Nb27.0/Nb/Ni50.5Ti49.5A composite panel.
⑤ post-rolling treatment, after rolling deformation, removing the outer sheath layer by wire cutting to take out Ti73.0Nb27.0/Nb/Ni50.5Ti49.5Annealing the composite board by using a heat treatment process of keeping the temperature at 300 ℃ for 10min to obtain the Ti containing the Nb transition layer73.0Nb27.0Cladding Ni50.5Ti49.5A shape memory composite material.
(3) And (6) alloy detection.
After the sheath is overlapped and rolled, the coating containsTi of Nb transition layer73.0Nb27.0Cladding Ni50.5Ti49.5The shape memory composite material is observed under a JSM-7001F field emission scanning electron microscope for interface combination, and is subjected to tensile mechanical property test on an Instron-8801 type universal testing machine, the measured tensile strength is 500MPa, and the recoverable strain is about 4.0 percent. FIG. 2 is a SEM photograph of example 1; FIG. 3 is a stress-strain curve of example 1; FIG. 4 is a diagram showing the cytotoxicity test of L-929 in example 1. By the above tests and characterization, it was found that Ti containing Nb transition layer73.0Nb27.0Cladding Ni50.5Ti49.5The shape memory composite material has good biocompatibility and high stress-induced martensite phase transformation critical stress sigmaSIM(about 500MPa) and a large recoverable strain epsilon (about 4.0 percent), and is expected to be applied in the biomedical field. Ti containing Nb transition layer prepared in this example73.0Nb27.0Cladding Ni50.5Ti49.5The performance of the shape memory composite material versus the existing NiTi alloy and β titanium alloy is as follows:
example 2:
this example was prepared by the following steps:
(1) selecting raw materials.
Core material: ni50.8Ti49.2Alloying; surface shell material: ti72.8Nb27.2Alloying; transition layer material: high purity Nb (99.95% by mass).
(2) Ti containing Nb transition layer72.8Nb27.2Cladding Ni50.8Ti49.2And preparing the shape memory composite material.
① cutting raw material, adopting electric spark cutting method to cut from Ni50.8Ti49.2、Ti72.8Nb27.2Cutting a NiTi core material plate with the length of 65mm multiplied by 5mm, two TiNb shell material plates with the length of 65mm multiplied by 1mm and two pure Nb transition laminated plates with the length of 65mm multiplied by 0.25mm on the pure Nb blank;
② cleaning raw materials, mechanically polishing the surfaces of the NiTi alloy plate, the TiNb alloy plate and the pure Nb plate obtained after cutting by 400#, 800# and 1200# abrasive paper in sequence to a mirror surface, then respectively putting the mirror surface into alcohol and acetone for ultrasonic cleaning, drying and storing in a sealing bag for later use;
③ making a sheath pack-rolling bag, orderly stacking the raw materials in a titanium alloy (TC4) sheath according to the sequence of the TiNb upper cladding plate/the pure Nb upper cladding plate/the NiTi core material plate/the pure Nb lower cladding plate/the TiNb lower cladding plate, then welding and sealing, and pumping the interior of the sheath to vacuum (the vacuum degree is 3 multiplied by 10) through the pumping holes reserved at the edges of the sheath-1Pa), sealing, and finally preparing the sheath and the pack-rolling package.
④ rolling and compounding, heating the completely wrapped pack to 650 deg.C, keeping the temperature for 30min, compounding by primary rolling with 60% reduction ratio, secondary rolling with 50% reduction ratio and final rolling with 35% reduction ratio to obtain Ti72.8Nb27.2/Nb/Ni50.8Ti49.2A composite panel.
⑤ post-rolling treatment, after rolling deformation, removing the outer sheath layer by wire cutting to take out Ti72.8Nb27.2/Nb/Ni50.8Ti49.2Annealing the composite board by using a heat treatment process of keeping the temperature at 350 ℃ for 15min to obtain the Ti containing the Nb transition layer72.8Nb27.2Cladding Ni50.8Ti49.2A shape memory composite material.
(3) And (6) alloy detection.
The Ti containing the Nb transition layer after sheath lap rolling72.8Nb27.2Cladding Ni50.8Ti49.2The shape memory composite material is observed under a JSM-7001F field emission scanning electron microscope for interface combination, and is subjected to tensile mechanical property test on an Instron-8801 type universal testing machine, the measured tensile strength is 515MPa, and the recoverable strain is about 4.0 percent. FIG. 5 is a SEM photograph of example 2; FIG. 6 is a stress-strain curve of example 2; FIG. 7 is a diagram showing the cytotoxicity test of L-929 in example 2. By the above tests and characterization, it was found that Ti containing Nb transition layer72.8Nb27.2Cladding Ni50.8Ti49.2The shape memory composite material has good biocompatibility and high stress-induced martensite phase transformation critical stress sigmaSIM(about 515MPa) and a large recoverable strain epsilon (about 4.0 percent), and is expected to be applied in the biomedical field. Ti containing Nb transition layer prepared in this example72.8Nb27.2Cladding Ni50.8Ti49.2The performance of the shape memory composite material versus the existing NiTi alloy and β titanium alloy is as follows:
example 3:
this example was prepared by the following steps:
(1) selecting raw materials.
Core material: ni51.0Ti49.0Alloying; surface shell material: ti72.6Nb27.4Alloying; transition layer material: high purity Nb (99.95% by mass).
(2) Ti containing Nb transition layer72.6Nb27.4Cladding Ni51.0Ti49.0And preparing the shape memory composite material.
① cutting raw material, adopting electric spark cutting method to cut from Ni51.0Ti49.0、Ti72.6Nb27.4And pure Nb blank, cutting into a NiTi core plate with the length of 70mm multiplied by 5.5mm, two TiNb shell plates with the length of 70mm multiplied by 1.2mm and two pure Nb transition laminate plates with the length of 70mm multiplied by 0.3 mm;
② cleaning raw materials, mechanically polishing the surfaces of the NiTi alloy plate, the TiNb alloy plate and the pure Nb plate obtained after cutting by 400#, 800# and 1200# abrasive paper in sequence to a mirror surface, then respectively putting the mirror surface into alcohol and acetone for ultrasonic cleaning, drying and storing in a sealing bag for later use;
③ making wrapping and rolling bag, sequentially stacking the raw materials in a titanium alloy (TC4) wrapping bag in sequence according to the sequence of TiNb upper cladding plate/pure Nb upper cladding plate/NiTi core material plate/pure Nb lower cladding plate/TiNb lower cladding plate, welding and sealing, and pumping the inner part of the wrapping bag through pumping holes reserved at the edge of the wrapping bagThe vacuum degree is 1X 10-2Pa), sealing, and finally preparing the sheath and the pack-rolling package.
④ rolling and compounding, heating the completely wrapped pack to 700 deg.C, keeping the temperature for 30min, compounding by primary rolling with 70% reduction ratio, secondary rolling with 60% reduction ratio and final rolling with 40% reduction ratio to obtain Ti72.6Nb27.4/Nb/Ni51.0Ti49.0A composite panel.
⑤ post-rolling treatment, after rolling deformation, removing the outer sheath layer by wire cutting to take out Ti72.6Nb27.4/Nb/Ni51.0Ti49.0Annealing the composite board by using a heat treatment process of preserving heat at 400 ℃ for 20min to obtain Ti containing the Nb transition layer72.6Nb27.4Cladding Ni51.0Ti49.0A shape memory composite material.
(3) And (6) alloy detection.
The Ti containing the Nb transition layer after sheath lap rolling72.6Nb27.4Cladding Ni51.0Ti49.0The shape memory composite material is observed under a JSM-7001F field emission scanning electron microscope for interface combination, and is subjected to tensile mechanical property test on an Instron-8801 type universal testing machine, the tensile strength is measured to be 520MPa, and the recoverable strain is about 4.4%. FIG. 8 is a SEM photograph of example 3; FIG. 9 is a stress-strain curve of example 3; FIG. 10 is a diagram showing the cytotoxicity test of L-929 in example 3. By the above tests and characterization, it was found that Ti containing Nb transition layer72.6Nb27.4Cladding Ni51.0Ti49.0The shape memory composite material has good biocompatibility and high stress-induced martensite phase transformation critical stress sigmaSIM(about 520MPa) and a large recoverable strain epsilon (about 4.4 percent), and is expected to be applied in the biomedical field. Ti containing Nb transition layer prepared in this example72.6Nb27.4Cladding Ni51.0Ti49.0The performance of the shape memory composite material versus the existing NiTi alloy and β titanium alloy is as follows:
[1]K.Otsuka,X.Ren,Physical metallurgy of Ti-Ni-based shape memoryalloys,Progress in Materials Science 50(2005)511-678.
[2]L.Wang,C.Fu,Y.D.Wu,R.G.Li,X.D.Hui,Y.D.Wang,Superelastic effect inTi-rich high entropy alloys via stress-induced martensitic transformation,Scripta Materialia 162(2019)1359-6462.
[3]M.Tahara,H.Y.Kim,H.Hosoda,S.Miyazaki,Cyclic deformation behaviorof a Ti-26at.％Nb alloy,Acta Materialia 57(2009)2461-2469.
[4]A.Biesiekierski,J.Wang,M.A.Gepreel,C.Wen,A new look at biomedicalTi-based shape memory alloys,Acta Biomaterialia 8(2012)1661-1669.
[5]Y.Al-Zain,H.Y.Kim,H.Hosoda,T.H.Nam,S.Miyazaki,Shape memoryproperties of Ti-Nb-Mo biomedical alloys,Acta Materialia 58(2010)4212-4223.
Claims (7)
1. the TiNb/NiTi memory material containing the Nb layer is characterized in that the composite material is of a sandwich-like structure, namely NiTi shape memory alloy serving as a core substrate material, a middle transition layer Nb coated on the upper surface and the lower surface of the NiTi shape memory alloy and a shell material TiNb shape memory alloy coated on the surface of the middle transition layer Nb.
2. The TiNb/NiTi memory material with the Nb layer as recited in claim 1, wherein the Ni content in the NiTi shape memory alloy is 50.5 to 51.0 atomic percent; nb is high-purity Nb with the mass purity of 99.95 percent; in the TiNb shape memory alloy, the Nb content is 27.0 to 27.4 percent by atom percent.
3. The method for preparing the TiNb/NiTi memory material containing the Nb layer according to claim 1, which is characterized by comprising the following specific preparation steps:
step one, cutting raw materials: cutting a NiTi core material plate, two TiNb shell material plates and two pure Nb transition laminate plates from the NiTi, TiNb and pure Nb blanks by adopting an electric spark cutting method;
step two, raw material cleaning: polishing the surfaces of the NiTi core material plate, the TiNb shell material plate and the pure Nb transition laminate plate obtained after cutting to a mirror surface, respectively cleaning, drying and storing in a sealing bag for later use;
thirdly, manufacturing a sheath and lap-rolled bag: sequentially and regularly stacking raw materials in a titanium alloy sheath according to the sequence of a TiNb shell plate/a pure Nb transition laminate plate/a NiTi core plate/a pure Nb transition laminate plate/a TiNb shell plate, then welding and sealing, vacuumizing the interior of the sheath to be vacuum through a reserved air suction hole at the edge of the sheath, and finally preparing a sheath pack-rolling bag;
fourthly, rolling and compounding: heating and insulating the completely sheathed pack rolling ladle, and rolling for three times to obtain a TiNb/Nb/NiTi composite plate;
step five, post-rolling treatment: after the pack rolling deformation, the external sheath layer is removed by wire cutting to take out the TiNb/Nb/NiTi composite board, and then annealing is carried out to obtain the TiNb-coated NiTi shape memory composite material containing the Nb transition layer.
4. The method for preparing a TiNb/NiTi memory material with Nb layer according to claim 3, wherein in the second step, the surfaces of the NiTi core plate, the TiNb shell plate and the pure Nb transition layer plate obtained after cutting are mechanically polished to a mirror surface by 400#, 800# and 1200# sandpaper in sequence, and then are respectively put into alcohol and acetone for ultrasonic cleaning.
5. The method of claim 3, wherein the vacuum degree after vacuuming is 5 x 10 in the third step-1-1×10-2Pa。
6. The method for preparing a TiNb/NiTi memory material with Nb layer as in claim 3, wherein in the fourth step, the temperature is raised to 600-700 ℃ for 30 min; the third rolling is that the first rolling with the reduction ratio of 50-70% is firstly carried out for compounding, and then the second rolling with the reduction ratio of 40-60% and the final rolling with the reduction ratio of 30-40% are carried out.
7. The method for preparing a TiNb/NiTi memory material with Nb layer as claimed in claim 3, wherein in the fifth step, the annealing is a heat treatment process with a temperature of 300-400 ℃ for 10-20 min.
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| CN113352707A (en) * | 2021-04-14 | 2021-09-07 | 江苏大学 | TiMo-NiTi large-class linear elastic composite board and preparation method thereof |
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