CN113352707A - TiMo-NiTi large-class linear elastic composite board and preparation method thereof - Google Patents
TiMo-NiTi large-class linear elastic composite board and preparation method thereof Download PDFInfo
- Publication number
- CN113352707A CN113352707A CN202110410765.2A CN202110410765A CN113352707A CN 113352707 A CN113352707 A CN 113352707A CN 202110410765 A CN202110410765 A CN 202110410765A CN 113352707 A CN113352707 A CN 113352707A
- Authority
- CN
- China
- Prior art keywords
- plate
- timo
- niti
- alloy
- purity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 112
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 97
- 239000000956 alloy Substances 0.000 claims abstract description 97
- 239000011229 interlayer Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 15
- 230000005489 elastic deformation Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims description 121
- 238000005096 rolling process Methods 0.000 claims description 53
- 239000010410 layer Substances 0.000 claims description 25
- 239000011257 shell material Substances 0.000 claims description 23
- 239000011162 core material Substances 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 20
- 238000005520 cutting process Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 230000009466 transformation Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910000734 martensite Inorganic materials 0.000 claims description 7
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 231100000065 noncytotoxic Toxicity 0.000 claims description 6
- 230000002020 noncytotoxic effect Effects 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000883 Ti6Al4V Inorganic materials 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 239000002932 luster Substances 0.000 claims description 5
- 238000003466 welding Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 2
- 239000012792 core layer Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims 3
- 238000004140 cleaning Methods 0.000 claims 2
- 230000009286 beneficial effect Effects 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 claims 1
- 229910001040 Beta-titanium Inorganic materials 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 18
- 238000002386 leaching Methods 0.000 description 15
- 238000000576 coating method Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 230000035882 stress Effects 0.000 description 9
- 238000005498 polishing Methods 0.000 description 7
- AZKSAVLVSZKNRD-UHFFFAOYSA-M 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide Chemical compound [Br-].S1C(C)=C(C)N=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 AZKSAVLVSZKNRD-UHFFFAOYSA-M 0.000 description 6
- 230000003013 cytotoxicity Effects 0.000 description 6
- 231100000135 cytotoxicity Toxicity 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- 230000004083 survival effect Effects 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004113 cell culture Methods 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 238000012258 culturing Methods 0.000 description 3
- 231100000263 cytotoxicity test Toxicity 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012894 fetal calf serum Substances 0.000 description 3
- 210000002950 fibroblast Anatomy 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000012781 shape memory material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 208000005623 Carcinogenesis Diseases 0.000 description 2
- 229910000979 O alloy Inorganic materials 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000036952 cancer formation Effects 0.000 description 2
- 231100000504 carcinogenesis Toxicity 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 231100001083 no cytotoxicity Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 229910009972 Ti2Ni Inorganic materials 0.000 description 1
- 229910010381 TiNi3 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/162—Cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
- B32B2038/0016—Abrading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
- B32B2038/0048—Annealing, relaxing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2535/00—Medical equipment, e.g. bandage, prostheses or catheter
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to the technical field of medical large-class linear elastic composite materials with excellent biocompatibility, in particular to a TiMo-NiTi large-class linear elastic composite plate with a Mo interlayer and a preparation method thereof, the method realizes the preparation of the layered composite material with excellent biocompatibility, linear-like elastic deformation and large elastic strain capacity, can solve the performance bottleneck that the existing monomer NiTi alloy (poor biocompatibility) and beta titanium alloy (small linear-like elasticity) cannot simultaneously have excellent biocompatibility and large linear elasticity (namely stress is approximately linearly increased along with the increase of strain and accompanied with large elastic strain capacity), meets the comprehensive performance requirements of biomedical components (such as self-expanding stents, intelligent drivers, sensors and the like) on the biocompatibility and linear-like elastic deformation capacity of the material, and has wide application prospect in the field of biomedical.
Description
Technical Field
The invention relates to the technical field of medical large-class linear elastic composite materials with excellent biocompatibility, in particular to a TiMo-NiTi large-class linear elastic composite plate with a Mo interlayer and a preparation method thereof.
Background
With the coming of the aging of human mouth worldwide, the incidence rate of degenerative diseases related to aging is increasing, and a series of new challenges are brought to human health. The design and research of biomedical materials with excellent biocompatibility (no cytotoxicity) and large linear elasticity (namely, stress is approximately linearly increased along with the increase of strain, and simultaneously, the biomedical materials have large elastic strain) are of great significance to the development of the biomedical field (such as the fields of intelligent drivers, sensors, self-expanding stents and the like).
At present, materials which can be used for manufacturing biomedical intelligent drivers, sensors and self-expanding stents are mainly divided into two types of NiTi alloys and beta titanium alloys. The NiTi alloy can regulate the martensite transformation characteristics of the NiTi alloy by introducing micro defects (including high-density grain boundaries, twin crystals and the like), and obtains large linear-like elasticity (the linear-like elastic strain can reach 4%). However, as a biomedical implant material, the poor biocompatibility of NiTi alloy, i.e. the cytotoxicity of Ni element in NiTi alloy is liable to cause the implantation problems such as sensitization, teratogenicity and even carcinogenesis, has received wide attention from medical workers and material scientists worldwide. To solve the biocompatibility problem, since the end of the last century, the materials researchers in developed countries in the united states have begun to develop novel beta titanium alloys composed of non-cytotoxic elements (such as Ti, Nb, Ta, Mo, Zr, etc.). Since the constituent elements of such an alloy are all non-cytotoxic elements, the alloy can exhibit excellent biocompatibility. However, due to the limitation of the self crystal structure and the martensite transformation intrinsic characteristics (such as crystal structure, transformation habit, shear direction, etc.), the elastic strain amount is at a lower level (the linear-like elastic strain amount is between 0.5% and 2%) when the linear-like elastic deformation is presented, and the performance requirements of the novel biomedical material on the large linear elasticity are difficult to meet.
Therefore, both the single-body NiTi alloy and the novel beta titanium alloy composed of non-cytotoxic elements can not simultaneously meet the comprehensive performance requirements of the biomedical field on the materials in the aspects of excellent biocompatibility and large linear elasticity. Based on the above, the invention aims to provide a large-class linear elastic composite plate of TiMo-NiTi containing a Mo interlayer and a preparation method thereof, and a novel layered composite material which is urgently needed in some biomedical fields and has excellent biocompatibility and large-class linear elasticity is prepared by means of the excellent biocompatibility (no cytotoxicity) of an outer-layer TiMo alloy and the large-class linear elasticity of an inner-layer NiTi alloy, so that the composite plate has important significance for promoting the rapid and healthy development of the biomedical fields (such as intelligent drivers, sensors, self-expanding stents and the like).
Disclosure of Invention
The invention relates to the technical field of medical large-class linear elastic composite materials with excellent biocompatibility, in particular to a TiMo-NiTi large-class linear elastic composite plate with a Mo interlayer and a preparation method thereof, the method realizes the preparation of the layered composite material with excellent biocompatibility, linear-like elastic deformation and large elastic strain capacity, can solve the performance bottleneck that the existing monomer NiTi alloy (poor biocompatibility) and beta titanium alloy (small linear-like elasticity) cannot simultaneously have excellent biocompatibility and large linear elasticity (namely stress is approximately linearly increased along with the increase of strain and accompanied with large elastic strain capacity), meets the comprehensive performance requirements of biomedical components (such as self-expanding stents, intelligent drivers, sensors and the like) on the biocompatibility and linear-like elastic deformation capacity of the material, and has wide application prospect in the field of biomedical.
In order to solve the performance bottleneck that the existing monomer NiTi alloy (poor biocompatibility) and beta titanium alloy (small linear elasticity) cannot simultaneously have excellent biocompatibility and large linear elasticity, the invention provides a TiMo-NiTi large linear elasticity composite plate containing a Mo interlayer and a preparation method thereof.
The raw materials of the TiMo-NiTi large-class linear elastic composite plate containing the Mo interlayer comprise:
the outer shell material is a TiMo alloy plate (wherein the Mo atom percentage content is 4.7-5.8%) composed of non-cytotoxic elements;
the inner core material is a NiTi alloy plate with the characteristic of large linear elastic deformation (wherein the percentage content of Ni atoms is 50.0-50.5%);
the interlayer is a high-purity Mo plate (the mass percentage of Mo is more than 99.5 percent) and is used for isolating the direct contact of the TiMo layer and the NiTi layer and avoiding the poor interface reaction (the poor interface reaction means that the direct contact of the TiMo layer and the NiTi layer can form a brittle intermetallic compound, such as Ti2Ni、TiNi3And Ti3Ni4Etc., causing cracking at the composite sheet interface).
The raw materials with the purity can be prepared by self without import, and can also be purchased in batches at home. The stack of the TiMo shell material, the NiTi core material and the Mo interlayer belongs to a shell-core composite structure containing an interlayer.
In the large class of linear elastic composite panels of TiMo-NiTi containing interlayers according to the present invention:
the outer shell material is a TiMo alloy plate (wherein, the percentage content of Mo atom is 4.7% -5.8%). The TiMo alloy is completely composed of non-cytotoxic elements, can present excellent biocompatibility, and is mainly used as an outer shell material to endow the composite material with excellent biocompatibility. In addition, the martensite transformation characteristic of the TiMo alloy plate also contributes to the final realization of large wire-like elastic deformation of the composite material.
The inner core material is NiTi alloy plate (wherein the Ni atom percentage is 50.0-50.5%). After the NiTi alloy is subjected to subsequent pack rolling composite treatment, the composite material has large linear-like elasticity (stress is increased approximately linearly along with the increase of strain and has large elastic strain amount) by virtue of martensite phase transformation under the regulation and control of microscopic defects (including high-density grain boundaries, twin crystals and the like) and reversible movement of internal twin crystals.
The interlayer material is a high-purity Mo plate (the mass percentage of Mo is more than 99.5%). A trace amount of high-purity Mo plate is used as a transition layer between the TiMo shell layer and the NiTi core layer, so that adverse interface reaction caused by direct contact of TiMo and NiTi alloy can be effectively avoided. In addition, the transition layer Mo has good bonding capacity for Ti and Ni elements, metallurgical bonding is easy to form at the interlayer interface of the composite material, and the TiMo-NiTi layered composite plate with excellent metallurgical bonding is favorably finally obtained.
According to another aspect of the invention, a preparation method of a TiMo-NiTi large-class linear elastic composite plate containing a Mo interlayer is provided, which is characterized by comprising the following steps:
a raw material cutting step, which comprises cutting original plates (a TiMo alloy plate, a NiTi alloy plate and a high-purity Mo plate) into a rectangular blank by using a wire cut electrical discharge machine, wherein each composite plate needs two TiMo plates as a shell material, one NiTi plate as a core material and two high-purity Mo plates as interlayers;
the method comprises the steps of raw material pretreatment, wherein the TiMo alloy plate, the NiTi alloy plate and the high-purity Mo plate which are cut in the steps are respectively and sequentially mechanically ground on 400#, 800# and 1200# abrasive paper, so that the surface of a sample is smooth and presents metal luster, then the sample is respectively ultrasonically cleaned by acetone and absolute ethyl alcohol, and the sample is dried and then placed in a dust-free sealing bag for later use;
a step of sheathing a sample, which comprises the steps of adopting titanium alloy (Ti-6Al-4V) to manufacture a sheath (comprising a middle frame, an upper cover plate and a lower cover plate), reserving an air exhaust hole on the side surface of the middle frame in the manufacturing process, polishing the surfaces of the upper cover plate and the lower cover plate which are contacted with the sample, then sequentially stacking two pieces of TiMo shell materials, a NiTi core material and two high-purity Mo interlayers which are subjected to pretreatment according to the sequence of TiMo-Mo-NiTi-Mo-TiMo, and then placing the two pieces of TiMo shell materials, the NiTi core material and the two high-purity Mo interlayersSleeving the middle frame, fixing the upper and lower cover plates with the middle frame, welding, and vacuumizing the bag via the reserved air exhaust holes (vacuum degree of 1 × 10)-2～5×10-3Pa) post-sealing to obtain a jacketed sample;
performing annealing heat treatment on the sheathed sample (heating to 600-700 ℃ and preserving heat for 0.5h), and then performing four-pass rolling compounding on the sheathed sample by adopting a double-roller asynchronous rolling mill, wherein the rolling reduction rate of the first pass is 50-60%, the rolling reduction rate of the second pass is 40-50%, the rolling reduction rate of the third pass is 20-30%, the rolling reduction rate of the final pass is 10-20%, and finally obtaining the sheathed laminar composite plate with the accumulated deformation of 80-90%;
and a post-rolling treatment step, which comprises the steps of separating the laminated composite plate after the rolling deformation from a sheath on the surface layer, and removing the uneven parts at the two ends and the edge of the rolled plate by using a wire cut electrical discharge machine, thereby finally completing the preparation of the TiMo-NiTi large-class wire elastic composite plate containing the Mo interlayer.
The advantages of the invention include:
1. the TiMo-NiTi large-class linear elastic composite plate containing the Mo interlayer, provided by the invention, takes the TiMo alloy without cytotoxicity as an outer shell material, so that the implantation problems of sensitization, teratogenesis, carcinogenesis and the like caused by the cytotoxicity of Ni and Ni ions escaping from the surface of the inner NiTi alloy can be effectively avoided, and the composite plate is endowed with excellent biocompatibility. Meanwhile, after the NiTi core material is subjected to the rolling and compounding treatment, the composite material is endowed with large linear-like elasticity by virtue of martensite phase transformation and reversible movement of internal twin crystals. In conclusion, the invention can effectively solve the performance bottleneck that the existing monomer NiTi alloy (poor biocompatibility) and beta titanium alloy (small linear elasticity) cannot simultaneously have excellent biocompatibility and large linear elasticity, realizes the preparation of the novel layered composite material which is urgently needed in some biomedical fields and has excellent biocompatibility and large linear elasticity, and has important application prospect in the biomedical field.
2. Compared with the modified coating prepared by the traditional coating method and the oxidation method, the TiMo-NiTi layered composite material containing the Mo interlayer obtained by the method has firm interlayer interface combination and uniform surface compactness, does not have the defects of pores, cracks and the like, and effectively solves the problems that the surface of the coating prepared by the traditional modified coating process is easy to have pores, cracks and poor compactness. In addition, the interface between each layer of the prepared TiMo-NiTi layered composite board is firmly combined, the thickness of the TiMo on the surface layer in the composite material can be freely adjusted by regulating and controlling the initial thickness of the TiMo shell material before the pack rolling (namely the thickness of the TiMo layer in the composite material can be thin and thick), and the problem that the coating surface is easy to crack when a thick coating is prepared by the traditional modified coating process can be effectively solved. Meanwhile, the preparation process of the TiMo-NiTi large-class linear elastic composite plate containing the Mo interlayer is simple and controllable, is suitable for industrial large-scale production, and can meet the batch preparation requirement of the material in the biomedical field.
Drawings
Fig. 1 is a schematic structural view of a large class of linear elastic composite plates of TiMo-NiTi containing a Mo interlayer according to the present invention.
FIG. 2 is a Ti containing Mo interlayer prepared in example 1 according to this invention95.3Mo4.7-Ni50.0Ti50.0And scanning electron microscope photographs of the cross sections of the large-class linear elastic composite plates.
FIG. 3 is a Ti containing Mo interlayer prepared in example 1 according to this invention95.3Mo4.7-Ni50.0Ti50.0Stress-strain curves for a large class of linear elastic composite sheets.
FIG. 4 is a Ti containing Mo interlayer prepared in example 1 according to this invention95.3Mo4.7-Ni50.0Ti50.0Class I linear elastic composite board and Ni50.0Ti50.0The cytotoxicity test results of the alloys are compared.
FIG. 5 is a Ti containing Mo interlayer prepared in example 2 according to this invention94.8Mo5.2-Ni50.3Ti49.7And scanning electron microscope photographs of the cross sections of the large-class linear elastic composite plates.
FIG. 6 is a Ti containing Mo interlayer prepared in example 2 according to this invention94.8Mo5.2-Ni50.3Ti49.7Stress-strain curves for a large class of linear elastic composite sheets.
FIG. 7 is a Ti containing Mo interlayer prepared in example 2 according to this invention94.8Mo5.2-Ni50.3Ti49.7Class I linear elastic composite board and Ni50.3Ti49.7The cytotoxicity test results of the alloys are compared.
FIG. 8 is a Ti containing Mo interlayer prepared in example 3 according to this invention94.2Mo5.8-Ni50.5Ti49.5And scanning electron microscope photographs of the cross sections of the large-class linear elastic composite plates.
FIG. 9 is a Ti containing Mo interlayer prepared in example 3 according to this invention94.2Mo5.8-Ni50.5Ti49.5Stress-strain curves for a large class of linear elastic composite sheets.
FIG. 10 is a Ti with Mo interlayer prepared in example 3 according to this invention94.2Mo5.8-Ni50.5Ti49.5Class I linear elastic composite board and Ni50.5Ti49.5The cytotoxicity test results of the alloys are compared.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples, so as to understand the objects, features and advantages of the present invention. It should be noted that the following examples are only for illustrating the present invention and are not intended to limit the implementable scope of the present invention.
Example 1:
the present example performed the following operations:
(1) selecting raw materials, comprising:
outer shell material: selecting Ti with the thickness of 0.6mm95.3Mo4.7An alloy plate;
inner layer core material: selecting Ni with the thickness of 4.0mm50.0Ti50.0An alloy plate;
an intermediate layer: high purity Mo plates (Mo content 99.95 wt.%) with a thickness of 0.15mm were chosen.
(2) Ti with Mo interlayer95.3Mo4.7-Ni50.0Ti50.0Preparation of a large class of linear elastic composite panels comprising:
cutting raw materialComprising cutting a raw sheet material (Ti) by a wire electric discharge machine95.3Mo4.7Alloy plate, Ni50.0Ti50.0Alloy plate and high-purity Mo plate) into rectangular blanks (the length is 70mm multiplied by 50mm), wherein each composite plate needs two TiMo plates with the length of 70mm multiplied by 50mm multiplied by 0.6mm as a shell material, one NiTi plate with the length of 70mm multiplied by 50mm multiplied by 4.0mm as a core material and two high-purity Mo plates with the length of 70mm multiplied by 50mm multiplied by 0.15mm as interlayers;
secondly, a raw material pretreatment step, which comprises the steps of mechanically grinding the cut TiMo alloy plate, NiTi alloy plate and high-purity Mo plate on 400#, 800# and 1200# abrasive paper respectively in sequence to ensure that the surface of a sample is smooth and presents metallic luster, then carrying out ultrasonic cleaning by acetone and absolute ethyl alcohol respectively, drying and placing in a dust-free sealing bag for later use;
step three, coating the sample, which comprises the steps of adopting titanium alloy (Ti-6Al-4V) to manufacture a coating (comprising a middle frame, an upper cover plate and a lower cover plate), reserving an air suction hole on the side surface of the middle frame in the manufacturing process, and polishing the surfaces of the upper cover plate and the lower cover plate which are contacted with the sample; then, sequentially stacking two pretreated TiMo shell materials, a NiTi core material and two high-purity Mo interlayers according to the sequence of TiMo-Mo-NiTi-Mo-TiMo (the arrangement sequence is shown in figure 1), then placing the stack in a sheath middle frame in a regular manner, and fixing and welding the sheath upper cover plate and the sheath lower cover plate with the middle frame; the bag is vacuumized through the reserved air exhaust holes (to the vacuum degree range of 1 multiplied by 10)-2～5×10-3Pa) post-sealing to obtain a jacketed sample;
fourthly, a step of rolling and laminating, which comprises the steps of annealing heat treatment (heating to 600 ℃ and preserving heat for 0.5h) of the sheathed sample, and then rolling and laminating the sheathed sample by adopting a double-roller asynchronous rolling mill for four times, wherein the rolling reduction rate of the first time is about 50 percent, the rolling reduction rate of the second time is about 40 percent, the rolling reduction rate of the third time is about 20 percent, the rolling reduction rate of the final time is about 10 percent, and finally the sheathed Ti with the accumulated deformation of about 80 percent is obtained95.3Mo4.7-Ni50.0Ti50.0A layered composite board;
fifthly, post-rolling treatment step, which comprises the step of subjecting the Ti containing Mo interlayer after the pack rolling deformation95.3Mo4.7-Ni50.0Ti50.0Separating the composite board from the sheath of the surface layer, removing the uneven parts at two ends and the edge of the rolled board by using a wire cut electrical discharge machine, and finally finishing the Ti containing the Mo interlayer95.3Mo4.7-Ni50.0Ti50.0And (4) preparing a large class of linear elastic composite board.
(3) Alloy detection
Ti containing Mo interlayer is researched by adopting JSM-7001F type scanning electron microscope95.3Mo4.7-Ni50.0Ti50.0The result of the interfacial bonding state of the large class of linear elastic composite plates is shown in fig. 2.
Tensile testing was performed on an Instron-8801 mechanical property tester. Adopting a tensile sample with the gauge length of 30mm, and removing rough cutting marks and oxide skin on the surface of the composite plate (avoiding outer Ti layer) through mechanical grinding and polishing95.3Mo4.7Excessive wear of the alloy) followed by washing and drying, followed by rolling in a direction parallel to the specimen at 1 × 10-3s-1The strain rate of (a) was subjected to a tensile test, during which an electronic extensometer with a gauge length of 25mm was used to accurately measure the true strain value, and finally the stress-strain curve as shown in fig. 3 was plotted using Origin software according to the test results. From FIG. 3, Ti can be observed95.3Mo4.7-Ni50.0Ti50.0The composite plate exhibits an approximately linear increase in stress with increasing strain during stretching and an approximately linear decrease in stress with decreasing strain upon unloading, indicating that the composite plate undergoes a linear-like elastic deformation. Also, it is noted that the strain is fully recovered after the tensile strain is relieved to 3.5%, indicating that the amount of linear elastic-like strain in the composite panel is about 3.5%.
To evaluate the biocompatibility of the composite material samples, their cytotoxicity was determined by means of in vitro cell experiments. Firstly, Ti95.3Mo4.7-Ni50.0Ti50.0Composite sheet and Ni50.0Ti50.0Alloy in 3cm2The leaching ratio of each ml is put into serum-free Du's modified medium (DMEM) containing 5% (volume fraction) CO2Performing a leaching liquor test for 3 days in a sterile environment of (1), thereby obtaining two leaching liquors; then will beMouse fibroblast L929 cells and DMEM medium containing 10% fetal calf serum according to 3X 104Placing the cells with the concentration of each ml on a 96-hole cell culture plate for culturing for 1 day, pouring out the original culture solution after the cells adhere to the wall, and adding different leaching solutions to respectively culture for 1 day, 7 days and 14 days; analysis of L929 cells at Ti by Thiazolyl blue (MTT) colorimetry95.3Mo4.7-Ni50.0Ti50.0Composite board leach liquor and Ni50.0Ti50.0The survival rates of the alloy leach liquor at different culture times finally obtained the results shown in fig. 4. It can be seen from FIG. 4 that the L929 cells were cultured in Ti at different times95.3Mo4.7-Ni50.0Ti50.0The survival rate of the composite board leaching liquor is higher than that of Ni50.0Ti50.0In leach solutions of alloys, i.e. Ti95.3Mo4.7-Ni50.0Ti50.0The composite plate has better biocompatibility.
Based on the above studies, it can be seen that Ti containing Mo interlayer95.3Mo4.7-Ni50.0Ti50.0The large class linear elastic composite plate can have excellent biocompatibility, linear elastic deformation and large elastic strain (about 3.5 percent), and is expected to solve the problem of practical application of shape memory materials in the field of biomedicine.
Table 1 shows the Ti containing Mo interlayers prepared in this example95.3Mo4.7-Ni50.0Ti50.0The performance of the large-class linear elastic composite plate is compared with that of the existing single-body NiTi and beta titanium alloy:
TABLE 1
Example 2:
the present embodiment performs the following operations:
(1) selecting raw materials, wherein:
outer shell material: selecting Ti with the thickness of 1.0mm94.8Mo5.2An alloy plate;
inner layer core material: selecting Ni with the thickness of 5.0mm50.3Ti49.7An alloy plate;
an intermediate layer: high purity Mo plates (Mo content 99.97 wt.%) with a thickness of 0.2mm were chosen.
(2) Ti with Mo interlayer94.8Mo5.2-Ni50.3Ti49.7Preparation of a large class of linear elastic composite panels comprising:
a raw material cutting step including cutting a raw sheet material (Ti) by a wire electric discharge machine94.8Mo5.2Alloy plate, Ni50.3Ti49.7Alloy plate and high-purity Mo plate) into rectangular blanks (the length is 80mm multiplied by 60mm), wherein each composite plate needs two TiMo plates with the length being 80mm multiplied by 60mm multiplied by 1.0mm as a shell material, one NiTi plate with the length being 80mm multiplied by 60mm multiplied by 5.0mm as a core material and two high-purity Mo plates with the length being 80mm multiplied by 60mm multiplied by 0.2mm as interlayers;
secondly, a raw material pretreatment step, which comprises the steps of respectively and sequentially mechanically grinding the TiMo alloy plate, the NiTi alloy plate and the high-purity Mo plate which are cut in the treatment process on 400#, 800# and 1200# abrasive paper, respectively, carrying out ultrasonic cleaning on the samples respectively by using acetone and absolute ethyl alcohol after the surfaces of the samples are smooth and present metal luster, drying and placing the samples in a dust-free sealing bag for later use;
step three, coating the sample, which comprises the steps of adopting titanium alloy (Ti-6Al-4V) to manufacture a coating (comprising a middle frame, an upper cover plate and a lower cover plate), reserving an air suction hole on the side surface of the middle frame in the manufacturing process, and polishing the surfaces of the upper cover plate and the lower cover plate which are contacted with the sample; then, sequentially stacking two pretreated TiMo shell materials, a NiTi core material and two high-purity Mo interlayers according to the sequence of TiMo-Mo-NiTi-Mo-TiMo (the arrangement sequence is shown in figure 1), then placing the stack in a sheath middle frame in a regular manner, and fixing and welding the sheath upper cover plate and the sheath lower cover plate with the middle frame; the bag is vacuumized through the reserved air exhaust holes (to the vacuum degree range of 1 multiplied by 10)-2～5×10-3Pa) post-sealing to obtain a jacketed sample;
a step of rolling and laminating, which comprises annealing heat treatment (heating to 650 ℃ and preserving heat for 0.5h) of the sheathed sample, then rolling and laminating the sheathed sample for four times by adopting a double-roller asynchronous rolling mill, wherein the rolling reduction rate of the first time is about 55 percent, the rolling reduction rate of the second time is about 45 percent,the third rolling reduction is about 25 percent, the final rolling reduction is about 15 percent, and finally the sheathed Ti with the accumulated deformation of about 85 percent is obtained94.8Mo5.2-Ni50.3Ti49.7A layered composite board;
fifthly, post-rolling treatment step, which comprises the step of subjecting the Ti containing Mo interlayer after the pack rolling deformation94.8Mo5.2-Ni50.3Ti49.7Separating the composite board from the sheath of the surface layer, removing the uneven parts at two ends and the edge of the rolled board by using a wire cut electrical discharge machine, and finally finishing the Ti containing the Mo interlayer94.8Mo5.2-Ni50.3Ti49.7And (4) preparing a large class of linear elastic composite board.
(3) Alloy detection
Ti containing Mo interlayer is researched by adopting JSM-7001F type scanning electron microscope94.8Mo5.2-Ni50.3Ti49.7The results obtained for the interfacial bonding state of the large class of linear elastic composite panels are shown in fig. 5.
Tensile testing was performed on an Instron-8801 mechanical property tester. Adopting a tensile sample with the gauge length of 30mm, and removing rough cutting marks and oxide skin on the surface of the composite plate (avoiding outer Ti layer) through mechanical grinding and polishing94.8Mo5.2Excessive wear of the alloy) followed by washing and drying, followed by rolling in a direction parallel to the specimen at 1 × 10-3s-1The strain rate of (a) was subjected to a tensile test, during which an electronic extensometer with a gauge length of 25mm was used to accurately measure the true strain value, and finally the stress-strain curve as shown in fig. 6 was plotted using Origin software according to the test results. From this curve, Ti can be observed94.8Mo5.2-Ni50.3Ti49.7The composite plate exhibits an approximately linear increase in stress with increasing strain during stretching and an approximately linear decrease in stress with decreasing strain upon unloading, indicating that the composite plate undergoes a linear-like elastic deformation. Also, it is noted that the strain is substantially fully recovered after the tensile strain is relieved to 3.7%, indicating that the linear-like elastic strain of the composite panel is about 3.7%.
To evaluate the biocompatibility of the composite material sampleThe cytotoxicity of the compound is determined by an in vitro cell experiment. Firstly, Ti94.8Mo5.2-Ni50.3Ti49.7Composite sheet and Ni50.3Ti49.7Alloy in 3cm2The leaching ratio of each ml is put into serum-free Du's modified medium (DMEM) containing 5% (volume fraction) CO2Performing a leaching liquor test for 3 days in a sterile environment of (1), thereby obtaining two leaching liquors; then mouse fibroblast L929 cells and DMEM medium containing 10% fetal calf serum are mixed according to the ratio of 3 x 104Placing the cells with the concentration of each ml on a 96-hole cell culture plate for culturing for 1 day, pouring out the original culture solution after the cells adhere to the wall, and adding different leaching solutions to respectively culture for 1 day, 7 days and 14 days; analysis of L929 cells at Ti by Thiazolyl blue (MTT) colorimetry94.8Mo5.2-Ni50.3Ti49.7Composite board leach liquor and Ni50.3Ti49.7The survival rates of the alloy leach liquor at different culture times finally obtained the results shown in fig. 7. It can be seen from FIG. 7 that the L929 cells were cultured in Ti at different times94.8Mo5.2-Ni50.3Ti49.7The survival rate of the composite board leaching liquor is higher than that of Ni50.3Ti49.7In leach solutions of alloys, i.e. Ti94.8Mo5.2-Ni50.3Ti49.7The composite plate has better biocompatibility.
Based on the above studies, it can be seen that Ti containing Mo interlayer94.8Mo5.2-Ni50.3Ti49.7The large class linear elastic composite plate can have excellent biocompatibility, linear elastic deformation and large elastic strain (about 3.7 percent), and is expected to solve the problem of practical application of shape memory materials in the field of biomedicine.
Table 2 shows the Ti containing Mo interlayers prepared in this example94.8Mo5.2-Ni50.3Ti49.7The performance of the large-class linear elastic composite plate is compared with that of the existing single-body NiTi and beta titanium alloy:
TABLE 2
Example 3:
the present example performed the following operations:
(1) selecting raw materials, comprising:
outer shell material: selecting Ti with the thickness of 1.4mm94.2Mo5.8An alloy plate;
inner layer core material: selecting Ni with the thickness of 6.0mm50.5Ti49.5An alloy plate;
an intermediate layer: high purity Mo plates (Mo content 99.99 wt.%) with a thickness of 0.25mm were chosen.
(2) Ti with Mo interlayer94.2Mo5.8-Ni50.5Ti49.5Preparation of a large class of linear elastic composite panels comprising:
a raw material cutting step including cutting a raw sheet material (Ti) by a wire electric discharge machine94.2Mo5.8Alloy plate, Ni50.5Ti49.5Alloy plate and high-purity Mo plate) into rectangular blanks (the length is 90mm multiplied by 70mm), wherein each composite plate needs two TiMo plates with the length being 90mm multiplied by 70mm multiplied by 1.4mm as a shell material, one NiTi plate with the length being 90mm multiplied by 70mm multiplied by 6.0mm as a core material and two high-purity Mo plates with the length being 90mm multiplied by 70mm multiplied by 0.25mm as interlayers;
secondly, a raw material pretreatment step, which comprises the steps of mechanically grinding the cut TiMo alloy plate, the cut NiTi alloy plate and the high-purity Mo plate on 400#, 800# and 1200# abrasive paper respectively in sequence to ensure that the surface of a sample is smooth and presents metallic luster, then carrying out ultrasonic cleaning by using acetone and absolute ethyl alcohol respectively, drying and placing in a dust-free sealing bag for later use;
step three, coating the sample, which comprises the steps of adopting titanium alloy (Ti-6Al-4V) to manufacture a coating (comprising a middle frame, an upper cover plate and a lower cover plate), reserving an air suction hole on the side surface of the middle frame in the manufacturing process, and polishing the surfaces of the upper cover plate and the lower cover plate which are contacted with the sample; then, sequentially stacking two pretreated TiMo shell materials, a NiTi core material and two high-purity Mo interlayers according to the sequence of TiMo-Mo-NiTi-Mo-TiMo (the arrangement sequence is shown in figure 1), then placing the stack in a sheath middle frame in a regular manner, and fixing and welding the sheath upper cover plate and the sheath lower cover plate with the middle frame; vacuumizing the bag sleeve through the reserved air exhaust hole (to the vacuum degree)Range 1 × 10-2～5×10-3Pa) post-sealing to obtain a jacketed sample;
fourthly, a step of rolling and laminating, which comprises the steps of annealing heat treatment (heating to 700 ℃ and preserving heat for 0.5h) of the sheathed sample, and then rolling and laminating the sheathed sample by adopting a double-roller asynchronous rolling mill for four times, wherein the rolling reduction rate of the first time is about 60 percent, the rolling reduction rate of the second time is about 50 percent, the rolling reduction rate of the third time is about 30 percent, the rolling reduction rate of the final time is about 20 percent, and finally the sheathed Ti with the accumulated deformation of about 90 percent is obtained94.2Mo5.8-Ni50.5Ti49.5A layered composite board;
fifthly, post-rolling treatment step, which comprises the step of subjecting the Ti containing Mo interlayer after the pack rolling deformation94.2Mo5.8-Ni50.5Ti49.5Separating the composite board from the sheath of the surface layer, removing the uneven parts at two ends and the edge of the rolled board by using a wire cut electrical discharge machine, and finally finishing the Ti containing the Mo interlayer94.2Mo5.8-Ni50.5Ti49.5And (4) preparing a large class of linear elastic composite board.
(3) Alloy detection
Ti containing Mo interlayer is researched by adopting JSM-7001F type scanning electron microscope94.2Mo5.8-Ni50.5Ti49.5The result of the interfacial bonding state of the large class of linear elastic composite plates is shown in fig. 8.
Tensile testing was performed on an Instron-8801 mechanical property tester. Adopting a tensile sample with the gauge length of 30mm, and removing rough cutting marks and oxide skin on the surface of the composite plate (avoiding outer Ti layer) through mechanical grinding and polishing94.2Mo5.8Excessive wear of the alloy) followed by washing and drying, followed by rolling in a direction parallel to the specimen at 1 × 10-3s-1The strain rate of (a) was subjected to a tensile test, during which an electronic extensometer with a gauge length of 25mm was used to accurately measure the true strain value, and finally the stress-strain curve as shown in fig. 9 was plotted using Origin software according to the test results. From this curve, Ti can be observed94.2Mo5.8-Ni50.5Ti49.5The stress of the composite board in the stretching process is close to that of the composite board along with the increase of the strainA quasi-linear increase in strain and a nearly linear decrease in stress with decreasing strain upon unloading indicates that the composite panel undergoes a linear-like elastic deformation, while it is noted that the strain is substantially fully recovered after the tensile strain reaches 3.9% unloading, indicating that the amount of linear-like elastic strain in the composite panel is about 3.9%.
To evaluate the biocompatibility of the composite material samples, their cytotoxicity was determined by means of in vitro cell experiments. Firstly, Ti94.2Mo5.8-Ni50.5Ti49.5Composite sheet and Ni50.5Ti49.5Alloy in 3cm2The leaching ratio of each ml is put into serum-free Du's modified medium (DMEM) containing 5% (volume fraction) CO2Performing a leaching liquor test for 3 days in a sterile environment of (1), thereby obtaining two leaching liquors; then mouse fibroblast L929 cells and DMEM medium containing 10% fetal calf serum are mixed according to the ratio of 3 x 104Placing the cells with the concentration of each ml on a 96-hole cell culture plate for culturing for 1 day, pouring out the original culture solution after the cells adhere to the wall, and adding different leaching solutions to respectively culture for 1 day, 7 days and 14 days; analysis of L929 cells at Ti by Thiazolyl blue (MTT) colorimetry94.2Mo5.8-Ni50.5Ti49.5Composite board leach liquor and Ni50.5Ti49.5The survival rates of the alloy leach liquor at different culture times finally obtained the results shown in fig. 10. From FIG. 10, it can be seen that the L929 cells were cultured in Ti at various times94.2Mo5.8-Ni50.5Ti49.5The survival rate of the composite board leaching liquor is higher than that of Ni50.5Ti49.5In leach solutions of alloys, i.e. Ti94.2Mo5.8-Ni50.5Ti49.5The composite plate has better biocompatibility.
Based on the above studies, it can be seen that Ti containing Mo interlayer94.2Mo5.8-Ni50.5Ti49.5The large class linear elastic composite plate can have excellent biocompatibility, linear elastic deformation and large elastic strain (about 3.9 percent), and is expected to solve the problem of practical application of shape memory materials in the field of biomedicine.
Table 3 shows Ti containing Mo interlayers prepared in this example94.2Mo5.8-Ni50.5Ti49.5The performance of the large-class linear elastic composite plate is compared with that of the existing single-body NiTi and beta titanium alloy:
TABLE 3
Reference documents:
[1]P.Rasmussen,R.Berlia,R.Sarkar,J.Rajagopalan,Mechanical behavior of nanocrystalline and ultrafine-grained NiTi thin films,Materialia 15(2021)100994.
[2]B.Feng,X.G.Kong,S.J.Hao,Y.N.Liu,Y.Yang,H.Yang,F.M.Guo,D.Q.Jiang,T.T.Wang,Y.Ren,L.S.Cui,In-situ synchrotron high energy X-ray diffraction study of micro-mechanical behaviour of R phase reorientation in nanocrystalline NiTi alloy,Acta Materialia 194(2020)565-576.
[3]H.Yu,Y.Qiu,M.L.Young,Influence of Ni4Ti3 precipitate on pseudoelasticity of austenitic NiTi shape memory alloys deformed at high strain rate,Materials Science and Engineering A 804(2021)140753.
[4]H.Matsumoto,S.Watanabe,S.Hanada,Microstructures and mechanical properties of metastableβTiNbSn alloys cold rolled and heat treated,Journal of Alloys and Compounds439(2007)146-155.
[5]C.Y.Wang,L.W.Yang,Y.W.Cui,M.T.Pérez-Prado,High throughput analysis of solute effects on the mechanical behavior and slip activity of beta titanium alloys,Materials and Design 137(2018)371-383.
[6]Y.L.Zhou,D.M.Luo,Microstructures and mechanical properties of Ti–Mo alloys cold-rolled and heat treated,Materials Characterization 62(2011)931-937.
Claims (8)
1. a preparation method of a TiMo-NiTi large-class linear elastic composite plate containing a Mo interlayer is characterized by comprising the following steps of:
A) the method comprises the steps of pretreatment, wherein the pretreatment step comprises the steps of mechanically grinding a cut TiMo alloy plate, a cut NiTi alloy plate and a cut high-purity Mo plate respectively to enable the surfaces of the TiMo alloy plate, the cut NiTi alloy plate and the cut high-purity Mo plate to be flat and to present metal luster, then cleaning and drying the TiMo alloy plate, the cut NiTi alloy plate and the cut high-purity Mo plate, wherein the thickness of the TiMo alloy plate is 0.6-1.4 mm, the thickness of the NiTi alloy plate is 4.0-6.0 mm, and the thickness of the high-purity Mo plate is 0.15-0.25 mm;
B) a step of sheath packaging, which comprises the steps of sequentially stacking two pretreated TiMo alloy plates, a NiTi core material and two high-purity Mo interlayers according to the sequence of TiMo-Mo-NiTi-Mo-TiMo and then packaging in a sheath, wherein the sheath is made of titanium alloy and comprises a middle frame, an upper cover plate and a lower cover plate, an air exhaust hole is reserved on the side surface of the middle frame, vacuumizing is performed on the sheath through the air exhaust hole, and then the sheath is sealed;
C) performing overlapping rolling compounding, namely performing annealing heat treatment on the sheathed sample, wherein the annealing heat treatment comprises heating to 600-700 ℃, preserving heat for 0.5h, and then performing four-pass rolling compounding on the sample by adopting a double-roller asynchronous rolling mill, wherein the rolling reduction rate of the first pass is 50-60%, the rolling reduction rate of the second pass is 40-50%, the rolling reduction rate of the third pass is 20-30%, and the rolling reduction rate of the fourth pass is 10-20%, so as to obtain the sheathed layered composite plate with the accumulated deformation of 80-90%;
D) and a post-rolling treatment step, which comprises separating the laminated composite plate after the stack rolling deformation from a sheath on the surface layer, so as to obtain the TiMo-NiTi large-class linear elastic composite plate with the Mo interlayer.
2. The method of claim 1, wherein:
the TiMo alloy plate, the NiTi alloy plate and the high purity Mo plate are obtained by cutting an original plate material of the TiMo alloy plate, the NiTi alloy plate and the high purity Mo plate into a rectangular billet by a wire electric discharge machine.
3. The method of claim 1, wherein:
the mechanical grinding comprises the steps of respectively and sequentially carrying out mechanical grinding on a TiMo alloy plate, a NiTi alloy plate and a high-purity Mo plate which are cut in 400#, 800# and 1200# abrasive paper,
the cleaning comprises respectively carrying out ultrasonic cleaning on the TiMo alloy plate, the NiTi alloy plate and the high-purity Mo plate by using acetone and absolute ethyl alcohol,
and placing the dried TiMo alloy plate, the dried NiTi alloy plate and the dried high-purity Mo plate in a dust-free sealing bag for later use.
4. The method of claim 1, wherein:
the sheath is made of titanium alloy Ti-6Al-4V and comprises a middle frame, an upper cover plate and a lower cover plate, an air exhaust hole is reserved on the side surface of the middle frame,
the surfaces of the upper cover plate and the lower cover plate which are contacted with the sample are polished,
the packaging operation comprises the steps of placing two TiMo shell materials, a NiTi core material and two high-purity Mo interlayers which are stacked into a sheath middle frame in a regular manner, fixing and welding an upper cover plate and a lower cover plate with the middle frame,
the step of vacuumizing the sheath comprises vacuumizing to 1 x 10-2～5×10-3Vacuum degree range of Pa.
5. The manufacturing method according to claim 1, wherein the post-rolling treatment step further comprises removing uneven portions of both ends and edges of the laminated composite panel after the deformation by the pack rolling using a wire electric discharge machine.
6. The TiMo-NiTi large-class linear elastic composite plate containing the Mo interlayer prepared by the preparation method according to any one of claims 1 to 5.
7. A kind of TiMo-NiTi line elastic clad plate containing Mo intermediate layer, its characteristic lies in:
the NiTi alloy plate as the core material of the inner layer contains 50.0 to 50.5 percent of Ni atom,
high-purity Mo plates which are arranged on two sides of the NiTi alloy plate and are used as an intermediate interlayer, wherein the mass percentage of Mo is more than 99.5 percent,
the TiMo alloy plate is arranged on the outer side of the high-purity Mo plate and used as an outer shell material, wherein the percentage content of Mo atoms is 4.7-5.8%.
8. The large class wire-elastic composite plate of TiMo-NiTi containing an interlayer of claim 7, wherein:
the TiMo alloy is completely composed of non-cytotoxic elements and has good biocompatibility, thereby being used as an outer shell material to mainly endow the TiMo-NiTi large-class linear elastic composite board with good biocompatibility,
the martensite phase transformation characteristic of the TiMo alloy plate is beneficial to leading the TiMo-NiTi large-class wire elastic composite plate to present large-class wire elastic deformation,
by using a trace amount of high-purity Mo plate as a transition layer between the TiMo shell layer and the NiTi core layer, the poor interface reaction caused by the direct contact of TiMo and NiTi alloy is effectively avoided,
the transition layer Mo has good binding capacity for Ti and Ni elements, is favorable for forming metallurgical bonding at the interlayer interface of the TiMo-NiTi large-class linear elastic composite plate,
the TiMo-NiTi large-class linear elastic composite plate is subjected to rolling and compounding treatment, so that the composite material has large linear elasticity by virtue of martensite phase transformation under the regulation and control of microscopic defects including high-density crystal boundaries and twin crystals and reversible movement of internal twin crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110410765.2A CN113352707B (en) | 2021-04-14 | 2021-04-14 | TiMo-NiTi large-class linear elastic composite board and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110410765.2A CN113352707B (en) | 2021-04-14 | 2021-04-14 | TiMo-NiTi large-class linear elastic composite board and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113352707A true CN113352707A (en) | 2021-09-07 |
| CN113352707B CN113352707B (en) | 2023-02-03 |
Family
ID=77525134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110410765.2A Active CN113352707B (en) | 2021-04-14 | 2021-04-14 | TiMo-NiTi large-class linear elastic composite board and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113352707B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115852123A (en) * | 2023-02-28 | 2023-03-28 | 北京为康环保科技有限公司 | Method for processing antibacterial stainless steel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109706415A (en) * | 2019-01-25 | 2019-05-03 | 北京工业大学 | A kind of memory alloy-based nano lamellar composite material and preparation method |
| CN110293717A (en) * | 2019-05-29 | 2019-10-01 | 金川集团股份有限公司 | A kind of enhancing TiNi laminar composite and preparation method thereof |
| CN111187945A (en) * | 2020-01-15 | 2020-05-22 | 江苏大学 | TiNb/NiTi memory material containing Nb layer and preparation method |
-
2021
- 2021-04-14 CN CN202110410765.2A patent/CN113352707B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109706415A (en) * | 2019-01-25 | 2019-05-03 | 北京工业大学 | A kind of memory alloy-based nano lamellar composite material and preparation method |
| CN110293717A (en) * | 2019-05-29 | 2019-10-01 | 金川集团股份有限公司 | A kind of enhancing TiNi laminar composite and preparation method thereof |
| CN111187945A (en) * | 2020-01-15 | 2020-05-22 | 江苏大学 | TiNb/NiTi memory material containing Nb layer and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 侯泽敬，赵景涛，李嘉明: "医用钛钼合金的国内外研究概况", 《世界有色金属》, 31 May 2017 (2017-05-31), pages 130 - 131 * |
| 曹沛宇: "TiMo和NiCoMGa合金相稳定性及弹性行为第一性原理研究", 《中国优秀硕博士学位论文全文数据库（博士） 工程科技I辑》, 15 January 2021 (2021-01-15), pages 34 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115852123A (en) * | 2023-02-28 | 2023-03-28 | 北京为康环保科技有限公司 | Method for processing antibacterial stainless steel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113352707B (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105013821B (en) | Nanoscale twins mutually strengthen the accumulation ply rolling preparation method of TiNi based alloy composite boards | |
| Pérez-Prado et al. | Bulk nanocrystalline ω-Zr by high-pressure torsion | |
| CN100546732C (en) | The super plastic forming method of plate type heat converter special titanium plate | |
| CN110293717B (en) | Reinforced TiNi layered composite material and preparation method thereof | |
| CN113352707B (en) | TiMo-NiTi large-class linear elastic composite board and preparation method thereof | |
| CN109706415A (en) | A kind of memory alloy-based nano lamellar composite material and preparation method | |
| Yu et al. | Enhanced materials performance of Al/Ti/Al laminate sheets subjected to cryogenic roll bonding | |
| Wu et al. | Effect of hydrogen addition on diffusion bonding behavior of Ti-55 alloy | |
| CN105603258B (en) | A kind of high intensity zircaloy and preparation method | |
| CN109201736A (en) | A kind of asynchronous rolling method of high-entropy alloy | |
| Shri et al. | Surface characterization of TiNi deformed by high-pressure torsion | |
| CN104611673A (en) | Manufacture method of molybdenum alloy target material | |
| CN113715429B (en) | Biomedical NiTiFe-Ta composite board and preparation method thereof | |
| CN112251685B (en) | Ultrahigh-strength nanocrystalline 12Cr13Cu4Mo stainless steel and preparation method thereof | |
| CN104999085B (en) | Preparation method of nanosheet layer phase reinforced TiNi-based alloy composite plate | |
| CN113183562A (en) | Gradient isomeric titanium-tantalum layered composite material, preparation method and application thereof | |
| Ma et al. | Studies of the interfacial structure of a linear friction welded Fe/Ni joint: First principles calculation and TEM validation | |
| CN112342431B (en) | High-thermal-stability equiaxial nanocrystalline Ti6Al4V-Cu alloy and preparation method thereof | |
| Pita et al. | The effect of surface temperature and particle size on mechanical properties during accumulative roll bonding of Al 1050-H4 aluminum alloy | |
| CN112063892B (en) | High-thermal-stability equiaxial nanocrystalline Ti-Zr-Mn alloy and preparation method thereof | |
| CN111167860B (en) | Nb-coated NiTi shape memory composite material and preparation method thereof | |
| CN113634989B (en) | Zr-Ta nanosheet reinforced Ti-Mo-based composite material and preparation method thereof | |
| CA3062762A1 (en) | Titanium alloy-based sheet material for low- temperature superplastic deformation | |
| Vulcan et al. | X-RAY DIFFRACTION OF A Ti-Ta-Nb ALLOY PROCESSED BY SEVERE PLASTIC DEFORMATION | |
| CN112251644B (en) | High-thermal-stability equiaxial nanocrystalline Ti6Al4V-Ag alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |