CN113352707B - 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
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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 an Mo interlayer and a preparation method thereof.
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 the human mouth in the global range, 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 alloys are all non-cytotoxic elements, the alloys 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 plane and shear direction), 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 NiTi alloy and the novel beta titanium alloy composed of non-cytotoxic elements can not 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 an Mo interlayer and a preparation method thereof.
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 with 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 to 5.8 percent) 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 Ti 2 Ni、TiNi 3 And Ti 3 Ni 4 Etc., 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 composite rolling treatment, the composite material has large linear-like elasticity (stress is approximately linearly increased along with the increase of strain, and simultaneously has large elastic strain capacity) by virtue of martensite phase change regulated and controlled by 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 a TiMo shell layer and a NiTi core layer, so that poor 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 easily formed at the interlayer interface of the composite material, and the TiMo-NiTi layered composite plate with excellent metallurgical bonding is favorably obtained finally.
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;
the step of sheathing the sample comprises the steps of manufacturing a sheath (comprising a middle frame, an upper cover plate and a lower cover plate) by adopting titanium alloy (Ti-6 Al-4V), 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, 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, placing the two pieces of TiMo shell materials, the NiTi core material and the two pieces of high-purity Mo interlayers in the sheath middle frame regularly, fixing and welding the sheath, the lower cover plate and the middle frame, and vacuumizing the sheath through the reserved air exhaust hole (the vacuum degree range is 1 multiplied by 10, the vacuum degree range is 1 multiplied by 10, and the vacuum degree is matched -2 ～5×10 -3 Pa) post-sealing to obtain a jacketed sample;
a step of overlapping rolling and compounding, which comprises the steps of annealing heat treatment (heating to 600-700 ℃ and preserving heat for 0.5 h) of the sheathed sample, and then adopting a double-roller asynchronous rolling mill to carry out four-pass rolling and compounding on the sheathed sample, 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 the sheathed laminar composite plate with the accumulated deformation of 80-90% is obtained;
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 single-body NiTi alloy (poor biocompatibility) and beta titanium alloy (small linear elasticity) cannot simultaneously have excellent biocompatibility and large linear elasticity, realize the preparation of a novel layered composite material which is urgently needed in certain 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 view of the structure of a large class linear elastic composite plate of TiMo-NiTi comprising a Mo interlayer according to the present invention.
FIG. 2 is a Ti containing Mo interlayer prepared in example 1 according to this invention 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 Scanning electron microscope photographs of the cross sections of the large class of linear elastic composite plates.
FIG. 3 is a Ti containing Mo interlayer prepared in example 1 according to this invention 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 Stress-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 invention 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 Class I linear elastic composite board and Ni 50.0 Ti 50.0 The cytotoxicity test results of the alloys are compared with each other.
FIG. 5 is a Ti containing Mo interlayer prepared in example 2 according to this invention 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 Scanning electron microscope photographs of the cross sections of the large class of linear elastic composite plates.
FIG. 6 is a Ti with Mo interlayer prepared in example 2 according to this invention 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 Stress-strain curves for a large class of linear elastic composite sheets.
FIG. 7 is a Ti with Mo interlayer prepared in example 2 according to this invention 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 Class I linear elastic composite board and Ni 50.3 Ti 49.7 The cytotoxicity test results of the alloys are compared with each other.
FIG. 8 is a Ti containing Mo interlayer prepared in example 3 according to this invention 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 And 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 invention 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 Stress-strain curves for large class of linear elastic composite sheets.
FIG. 10 is a schematic view ofTi containing Mo interlayer prepared in example 3 according to the invention 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 Class I linear elastic composite board and Ni 50.5 Ti 49.5 The 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, including:
outer shell material: selecting Ti with the thickness of 0.6mm 95.3 Mo 4.7 An alloy plate;
inner layer core material: selecting Ni with the thickness of 4.0mm 50.0 Ti 50.0 An 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 interlayer 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 Preparation of a large class of linear elastic composite panels comprising:
(1) a raw material cutting step comprising cutting a raw plate (Ti) by a wire electric discharge machine 95.3 Mo 4.7 Alloy plate, ni 50.0 Ti 50.0 Alloy plate and high-purity Mo plate) into rectangular blanks (the length is 70mm multiplied by 50 mm), 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;
(2) the method comprises the steps of raw material pretreatment, wherein the raw material pretreatment comprises the steps of mechanically grinding a cut TiMo alloy plate, a cut NiTi alloy plate and a high-purity Mo plate on 400#, 800# and 1200# abrasive paper respectively in sequence to enable the surface of a sample to be flat and to present metal luster, then respectively carrying out ultrasonic cleaning on the sample by using acetone and absolute ethyl alcohol, drying the sample and placing the sample in a dust-free sealing bag for later use;
(3) a step of sheathing a sample, which comprises the steps of manufacturing a sheath (comprising a middle frame, an upper cover plate and a lower cover plate) by adopting titanium alloy (Ti-6 Al-4V), 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 in contact 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 -3 Pa) post-sealing to obtain a jacketed sample;
(4) the step of overlapping rolling and compounding comprises the steps of carrying out annealing heat treatment on the sheathed sample (heating to 600 ℃ and preserving heat for 0.5 h), then carrying out four-pass rolling and compounding by adopting a double-roller asynchronous rolling mill, wherein the rolling reduction rate of the first pass is about 50%, the rolling reduction rate of the second pass is about 40%, the rolling reduction rate of the third pass is about 20%, the rolling reduction rate of the final pass is about 10%, and finally obtaining the sheathed Ti with the accumulated deformation of about 80% 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 A layered composite panel;
(5) a post-rolling treatment step, which comprises the step of rolling the Ti containing the Mo interlayer after the stack rolling deformation 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 Separating the composite plate from the sheath of the surface layer, removing the uneven parts at two ends and the edge of the rolled plate by using a wire cut electrical discharge machine, and finally finishing the Ti-containing interlayer 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 And (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 microscope 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 The 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 Performance tester. Adopting a tensile sample with the gauge length of 30mm, and removing the composite material through mechanical grinding and polishingRough cutting marks on the surface of the plate and oxide scale (avoidance of outer Ti) 95.3 Mo 4.7 Excessive wear of the alloy) followed by washing and drying, followed by rolling in a direction parallel to the specimen at 1 × 10 -3 s -1 The tensile test was performed using an electronic extensometer with a gauge length of 25mm to accurately measure the true strain value during the test, 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 observed 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 The 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, ti 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 Composite sheet and Ni 50.0 Ti 50.0 Alloy in 3cm 2 The leaching ratio of each ml is respectively put into serum-free Du's modified medium (DMEM) containing 5 percent (volume fraction) of CO 2 Performing a leaching liquor test for 3 days in a sterile environment of (1), thereby obtaining two leaching liquors; then, mouse fibroblast L929 cells were cultured in DMEM medium containing 10% fetal bovine serum at 3X 10 4 Placing 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) colorimetry 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 Composite board leach liquor and Ni 50.0 Ti 50.0 The 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 at different times in Ti 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 The survival rate of the composite board leaching liquor is higher than that of Ni 50.0 Ti 50.0 Impregnation of alloysIn the extract, i.e. Ti 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 The composite board has better biocompatibility.
Based on the above studies, it can be seen that Ti containing Mo interlayer 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 The 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 example 95.3 Mo 4.7 -Ni 50.0 Ti 50.0 The performance of the large class of 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 1.0mm 94.8 Mo 5.2 An alloy plate;
inner layer core material: selecting Ni with the thickness of 5.0mm 50.3 Ti 49.7 An 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 interlayer 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 Preparation of a large class of linear elastic composite plates, comprising:
(1) a raw material cutting step comprising cutting a raw plate (Ti) by a wire electric discharge machine 94.8 Mo 5.2 Alloy plate, ni 50.3 Ti 49.7 Alloy plate and high-purity Mo plate) into rectangular blanks (length multiplied by width is 80mm multiplied by 60 mm), wherein each composite plate needs two TiMo plates with the length multiplied by 60mm multiplied by 1.0mm as a shell material, one NiTi plate with the length multiplied by 60mm multiplied by 5.0mm as a core material and two high-purity Mo plates with the length multiplied by 60mm multiplied by 0.2mmThe plate is used as an interlayer;
(2) 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 treatment 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;
(3) a step of sheathing a sample, which comprises the steps of manufacturing a sheath (comprising a middle frame, an upper cover plate and a lower cover plate) by adopting a titanium alloy (Ti-6 Al-4V), 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 in contact 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 -3 Pa) post-sealing to obtain a jacketed sample;
(4) the step of overlapping rolling and compounding comprises the steps of carrying out annealing heat treatment on the sheathed sample (heating to 650 ℃ and keeping the temperature for 0.5 h), and then carrying out four-pass rolling and compounding by adopting a double-roller asynchronous rolling mill, wherein the rolling reduction rate of the first pass is about 55%, the rolling reduction rate of the second pass is about 45%, the rolling reduction rate of the third pass is about 25%, the rolling reduction rate of the final pass is about 15%, and finally the sheathed Ti with the accumulated deformation of about 85% is obtained 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 A layered composite board;
(5) a post-rolling treatment step, which comprises the step of subjecting the Ti containing the Mo interlayer after the pack rolling deformation to 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 Separating the composite plate from the sheath of the surface layer, removing the uneven parts at two ends and the edge of the rolled plate by using a wire cut electrical discharge machine, and finally finishing the Ti-containing interlayer 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 And (3) preparing a large class of linear elastic composite plate.
(3) Alloy detection
Ti containing Mo interlayer is researched by adopting JSM-7001F type scanning electron microscope 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 The 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 polishing 94.8 Mo 5.2 Excessive wear of the alloy) followed by washing and drying, then rolling in a direction parallel to the specimen at 1 × 10 -3 s -1 The 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 observed 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 The 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 samples, their cytotoxicity was determined by means of in vitro cell experiments. Firstly, ti 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 Composite sheet and Ni 50.3 Ti 49.7 Alloy in 3cm 2 The leaching ratio of each ml is put into serum-free Du's modified medium (DMEM) containing 5% (volume fraction) CO 2 Performing a leaching liquor test for 3 days in a sterile environment of (1), thereby obtaining two leaching liquors; then, mouse fibroblast L929 cells were cultured in DMEM medium containing 10% fetal bovine serum at 3X 10 4 Placing 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) colorimetry 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 Composite board leach liquor and Ni 50.3 Ti 49.7 The 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 times 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 The survival rate of the composite board leaching liquor is higher than that of Ni 50.3 Ti 49.7 In leach solutions of alloys, i.e. Ti 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 The composite plate has better biocompatibility.
Based on the above studies, it can be seen that Ti containing Mo interlayer 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 The 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 of the Mo-containing interlayer prepared in this example 94.8 Mo 5.2 -Ni 50.3 Ti 49.7 The 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 1.4mm 94.2 Mo 5.8 An alloy plate;
inner layer core material: selecting Ni with the thickness of 6.0mm 50.5 Ti 49.5 An alloy plate;
an intermediate layer: high purity Mo plates (Mo content 99.99 wt.%) with a thickness of 0.25mm were selected.
(2) Ti with Mo interlayer 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 Preparation of a large class of linear elastic composite panels comprising:
(1) a raw material cutting step comprising cutting a raw plate (Ti) by a wire electric discharge machine 94.2 Mo 5.8 Alloy plate, ni 50.5 Ti 49.5 Alloy plate and high-purity Mo plate) into a rectangular blank (the length multiplied by the width is 90mm multiplied by 70 mm), wherein each composite plate needs two TiMo plates with the length multiplied by 70mm multiplied by 1.4mm as a shell material, one NiTi plate with the length multiplied by 70mm multiplied by 6.0mm as a core material and two high-purity Mo plates with the length multiplied by 70mm multiplied by 0.25mm as interlayers;
(2) the method comprises the following steps of raw material pretreatment, wherein the raw material pretreatment comprises the steps of mechanically grinding a cut TiMo alloy plate, a cut NiTi alloy plate and a 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;
(3) a step of sheathing a sample, which comprises the steps of manufacturing a sheath (comprising a middle frame, an upper cover plate and a lower cover plate) by adopting a titanium alloy (Ti-6 Al-4V), 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 in contact 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 land preparation 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 -3 Pa) post-sealing to obtain a jacketed sample;
(4) the step of overlapping rolling and compounding comprises the steps of carrying out annealing heat treatment on the sheathed sample (heating to 700 ℃ and keeping the temperature for 0.5 h), then carrying out four-pass rolling and compounding by adopting a double-roller asynchronous rolling mill, wherein the rolling reduction rate of the first pass is about 60%, the rolling reduction rate of the second pass is about 50%, the rolling reduction rate of the third pass is about 30%, the rolling reduction rate of the final pass is about 20%, and finally the sheathed Ti with the accumulated deformation of about 90% is obtained 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 A layered composite board;
(5) a post-rolling treatment step, which comprises the step of subjecting the Ti containing the Mo interlayer after the pack rolling deformation to 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 Separating 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 interlayer 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 And (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 microscope 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 The 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 polishing 94.2 Mo 5.8 Excessive wear of the alloy) followed by washing and drying, followed by rolling in a direction parallel to the specimen at 1 × 10 -3 s -1 The 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 observed 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 While the composite panel exhibited an approximately linear increase in stress with increasing strain during stretching and an approximately linear decrease in stress with decreasing strain when unloaded, indicating that the composite panel had undergone a linear-like elastic deformation, it was noted that the strain was substantially completely recovered after the tensile strain was unloaded to 3.9%, indicating that the amount of linear-like elastic strain in the composite panel was about 3.9%.
To evaluate the biocompatibility of the composite material samples, their cytotoxicity was determined by means of in vitro cell experiments. Firstly, ti 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 Composite sheet and Ni 50.5 Ti 49.5 Alloy with a thickness of 3cm 2 The leaching ratio of each ml is put into serum-free Du's modified medium (DMEM) containing 5% (volume fraction) CO 2 Is carried out for 3 days under the sterilization environmentTesting to obtain two kinds of leaching liquor; then mouse fibroblast L929 cells and DMEM medium containing 10% fetal calf serum are mixed according to the ratio of 3 x 10 4 Placing 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) colorimetry 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 Composite board leach liquor and Ni 50.5 Ti 49.5 The survival rates of the alloy leach liquor at different culture times finally obtained the results shown in fig. 10. It can be seen from FIG. 10 that the L929 cells were cultured in Ti at different times 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 The survival rate of the composite board leaching liquor is higher than that of Ni 50.5 Ti 49.5 Leaching solutions of alloys, i.e. Ti 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 The composite plate has better biocompatibility.
Based on the above studies, it can be seen that Ti containing Mo interlayer 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 The 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 example 94.2 Mo 5.8 -Ni 50.5 Ti 49.5 The 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 Ni 4 Ti 3 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 (7)
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, 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) The step of overlapping rolling and compounding comprises the step of annealing heat treatment of the sheathed sample, wherein the annealing heat treatment comprises heating to 600-700 ℃ and preserving heat for 0.5h, and then four-pass rolling and compounding are carried out 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 that the sheathed laminated composite plate with the accumulated deformation of 80-90% is obtained;
d) The post-rolling treatment step comprises the step of separating the laminated composite plate after the stack rolling deformation from a sheath on the surface layer, thereby obtaining the TiMo-NiTi large-class linear elastic composite plate with a Mo interlayer, which comprises the following steps:
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%.
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 production method according to claim 1, characterized in that:
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 production method according to claim 1, characterized in that:
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 -3 Vacuum 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. A TiMo-NiTi bulk linear elastic composite panel comprising a Mo interlayer prepared by the preparation method according to one of claims 1 to 5.
7. The TiMo-NiTi generic wire elastic composite panel with a Mo-containing interlayer of claim 6, 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.
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