Shape memory alloy hollow micro-lattice material and preparation method thereof
阅读说明：本技术 一种形状记忆合金中空微点阵材料及其制备方法 (Shape memory alloy hollow micro-lattice material and preparation method thereof ) 是由 王永静 吴雨豪 朱晓东 陈亚奇 于 2021-10-14 设计创作，主要内容包括：本发明公开了一种形状记忆合金中空微点阵材料及其制备方法,配方包括：等原子比的NiTi合金,组分的重量百分比是：100％的NiTi合金；制备方法,包括步骤一,聚合物掩模加工；步骤二,NiTi合金膜层溅射成型；步骤三,中空微点阵材料获取；步骤四,具有记忆效应的NiTi合金中空微点阵材料获取；该发明所制备的中空微点阵材料的结构可设计性强；得到形状记忆合金膜中空微点阵材料的方法简便、易行,可通过控制溅射时间控制膜层厚度,可实现了管壁厚度在50nm～20μm之间的调控；本发明所制备的微点阵材料具有轻质、超弹性、突出的记忆效应、高阻尼、能量吸收和生物相容性；相对于其他沉积方法,通过磁控溅射技术的使用,材料选择广泛和膜层均匀性较好。(The invention discloses a shape memory alloy hollow micro-lattice material and a preparation method thereof, and the formula comprises the following components: the NiTi alloy with equal atomic ratio comprises the following components in percentage by weight: 100% of NiTi alloy; the preparation method comprises the steps of firstly, processing a polymer mask; step two, sputtering and forming the NiTi alloy film layer; step three, obtaining a hollow micro-lattice material; step four, obtaining a NiTi alloy hollow micro-lattice material with a memory effect; the structure of the hollow micro-lattice material prepared by the invention is strong in designability; the method for obtaining the hollow microarray material of the shape memory alloy membrane is simple and easy to implement, the thickness of the membrane layer can be controlled by controlling the sputtering time, and the regulation and control of the thickness of the tube wall between 50nm and 20 mu m can be realized; the microarray material prepared by the invention has light weight, super elasticity, outstanding memory effect, high damping, energy absorption and biocompatibility; compared with other deposition methods, the method has the advantages that the material selection is wide and the uniformity of the film layer is good through the use of the magnetron sputtering technology.)
1. A shape memory alloy hollow micro-lattice material comprises the following components: the NiTi alloy with equal atomic ratio is characterized in that: the weight percentages of the components are as follows: 100% NiTi alloy.
2. A preparation method of a shape memory alloy hollow microarray material comprises the steps of firstly, processing a polymer mask; step two, sputtering and forming the NiTi alloy film layer; step three, obtaining a hollow micro-lattice material; step four, obtaining a NiTi alloy hollow micro-lattice material with a memory effect; the method is characterized in that:
firstly, establishing a micro-lattice material model through CAD software, then converting the CAD file into an STL format file, then importing the STL format file into 3D printing equipment, and processing a polymer mask by utilizing a rapid prototyping technology;
in the second step, a NiTi alloy film layer with a certain thickness is deposited on the polymer mask through a magnetron sputtering technology;
removing the polymer mask by using a chemical erosion or high-temperature ablation method to obtain a hollow micro-lattice material of the NiTi alloy film;
and in the fourth step, the NiTi alloy hollow micro-lattice material is placed in a vacuum tube furnace for annealing treatment to obtain the NiTi alloy hollow micro-lattice material with the memory effect.
3. The method for preparing a shape memory alloy hollow microarray material according to claim 2, wherein the method comprises the following steps: in the first step, the structure of the micro-lattice material model is one of an octahedron, an edge-center cube, a face-center cube, a diamond cube, a rhombic dodecahedron or a spiral icosahedron structure.
4. The method for preparing a shape memory alloy hollow microarray material according to claim 2, wherein the method comprises the following steps: in the first step, the polymer mask is a photosensitive resin material; the relative density of the micro-lattice mask is 1-15%, and the unit rod diameter is 0.1-0.5 mm; the rapid forming technology is a photocuring three-dimensional forming technology and a digital light processing technology, the technological parameters of the photocuring three-dimensional forming technology are ultraviolet laser with the wavelength of 355nm or 405nm, the scanning speed is 100-300 mm, the scanning interval is 0.1-0.6 mm, the spot compensation diameter is 0.1-0.3 mm, the interlayer waiting time is 1-5 s, and the lifting speed of a workbench is 1-10 mm/s; the technical parameters of the digital light processing technology are 768 multiplied by 480 of projection resolution, 300-500 nm of projection light wave band, 20-100 m of slice thickness, 1-10 s of exposure time of each layer and 1-5 s of lifting time of a workbench.
5. The method for preparing a shape memory alloy hollow microarray material according to claim 2, wherein the method comprises the following steps: in the second step, the thickness of the NiTi alloy film layer is 50 nm-10 m; the magnetron sputtering process parameter for preparing the NiTi alloy film is 1 x 10 of background vacuum degree-4The substrate temperature is more than 25 ℃, the distance between the substrate and the sputtering target is 50-80 mm, and the sputtering vacuum degree is 4-10 x 10-2Pa or more, the rotating speed of the template is 10-20r/min, and the pressure of argon is 4-10 x 10-4Pa, sputteringThe power is 50-200W, the sputtering voltage is 200-400V, the sputtering current is 0.2-1A, the pre-sputtering time is 10-30 min, and the sputtering time is 30-120 min, so that a NiTi alloy film layer with the Ni content of 0.48-0.53 is obtained; the target material is NiTi alloy with equal atomic ratio.
6. The method for preparing a shape memory alloy hollow microarray material according to claim 2, wherein the method comprises the following steps: in the third step, the photosensitive resin mask is removed by a chemical etching method, wherein the chemical etching process parameters are that methanol and water are mixed according to the volume ratio of 1:1 to form a mixed solution, the mixed solution is used as a solvent to prepare a sodium hydroxide solution with the concentration of 3mol/L, and then the photosensitive resin mask is removed under the condition that the temperature of the sodium hydroxide solution is 60 ℃.
7. The method for preparing a shape memory alloy hollow microarray material according to claim 2, wherein the method comprises the following steps: in the fourth step, the annealing treatment process parameter of the hollow micro-lattice material is that the vacuum degree is 1.5 multiplied by 10-3Pa, annealing at 450-650 ℃ for 1 h.
Technical Field
The invention relates to the technical field of a micro-lattice material, in particular to a shape memory alloy hollow micro-lattice material and a preparation method thereof.
Background
Because the performance requirements of the fields of aerospace, energy chemical industry, biomedicine and the like on the materials are higher and higher, the low-density materials are more and more valued by people; due to the fact that the micro-lattice material is multi-scale, the micro-lattice material has excellent mechanical property, high designability and extraordinary multifunctionality; by optimally designing the geometric configuration of the unit structure of the micro-lattice material, the integration of low density and high strength of the material can be realized by regulating and controlling the multi-level scale of the structural elements of the material, the elastic modulus and the strength of the material are far superior to those of other existing ultra-light materials such as carbon nano tubes, graphene, metal foam, silicon aerogel and the like with the same density, the performance limitation of a disordered structure is broken through, and the material is a structural efficient material with a great development prospect; NiTi shape memory alloy materials are receiving more and more attention due to excellent super-elasticity, recoverability and biocompatibility; the porous NiTi shape memory alloy is a good energy absorption material, and compared with a solid lattice material, the hollow lattice material has the characteristics of light weight, high specific strength, high specific energy absorption and the like; the NiTi shape memory alloy material is used as a matrix material of the hollow lattice material, so that a lighter and structure-function integrated micro lattice material can be obtained; therefore, certain requirements are provided for some NiTi shape memory alloy hollow micro-lattice materials and preparation methods thereof in the market; however, at present, no NiTi shape memory alloy hollow micro-lattice material with strong related designability and simple and feasible preparation method exists; therefore, the invention of a shape memory alloy hollow microarray material and a preparation method thereof is very necessary at the present stage.
Disclosure of Invention
The invention aims to provide a shape memory alloy hollow microarray material and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a shape memory alloy hollow micro-lattice material comprises the following components: the NiTi alloy with equal atomic ratio comprises the following components in percentage by weight: 100% NiTi alloy.
A preparation method of a shape memory alloy hollow microarray material comprises the steps of firstly, processing a polymer mask; step two, sputtering and forming the NiTi alloy film layer; step three, obtaining a hollow micro-lattice material; step four, obtaining a NiTi alloy hollow micro-lattice material with a memory effect;
firstly, establishing a micro-lattice material model through CAD software, then converting the CAD file into an STL format file, then importing the STL format file into 3D printing equipment, and processing a polymer mask by utilizing a rapid prototyping technology;
in the second step, a NiTi alloy film layer with a certain thickness is deposited on the polymer mask through a magnetron sputtering technology;
removing the polymer mask by using a chemical erosion or high-temperature ablation method to obtain a hollow micro-lattice material of the NiTi alloy film;
and in the fourth step, the NiTi alloy hollow micro-lattice material is placed in a vacuum tube furnace for annealing treatment to obtain the NiTi alloy hollow micro-lattice material with the memory effect.
Preferably, in the first step, the model structure of the microarray material is one of an octahedron, an edge-center cube, a face-center cube, a diamond cube, a rhombic dodecahedron or a spiral icosahedron structure.
Preferably, in the first step, the polymer mask is a photosensitive resin material; the relative density of the micro-lattice mask is 1-15%, and the unit rod diameter is 0.1-0.5 mm; the rapid forming technology is a photocuring three-dimensional forming technology and a digital light processing technology, the technological parameters of the photocuring three-dimensional forming technology are ultraviolet laser with the wavelength of 355nm or 405nm, the scanning speed is 100-300 mm, the scanning interval is 0.1-0.6 mm, the spot compensation diameter is 0.1-0.3 mm, the interlayer waiting time is 1-5 s, and the lifting speed of a workbench is 1-10 mm/s; the technical parameters of the digital light processing technology are 768 multiplied by 480 of projection resolution, 300-500 nm of projection light wave band, 20-100 m of slice thickness, 1-10 s of exposure time of each layer and 1-5 s of lifting time of a workbench.
Preferably, in the second step, the thickness of the NiTi alloy film layer is 50 nm-10 m; the magnetron sputtering process parameter for preparing the NiTi alloy film is 1 x 10 of background vacuum degree-4The substrate temperature is more than 25 ℃, the distance between the substrate and the sputtering target is 50-80 mm, and the sputtering vacuum degree is 4-10 x 10-2Pa or more, the rotating speed of the template is 10-20r/min, and the pressure of argon is 4-10 x 10-4Pa, sputtering power of 50-200W, sputtering voltage of 200-400V, sputtering current of 0.2-1A, pre-sputtering time of 10-30 min and sputtering time of 30-120 min to obtain a NiTi alloy film layer with Ni content of 0.48-0.53; the target material is NiTi alloy with equal atomic ratio.
Preferably, in the third step, the photosensitive resin mask is removed by a chemical etching method, wherein the chemical etching process parameter is to mix methanol and water in a volume ratio of 1:1 to form a mixed solution, the mixed solution is used as a solvent to prepare a sodium hydroxide solution with a concentration of 3mol/L, and then the photosensitive resin mask is removed under the condition that the temperature of the sodium hydroxide solution is 60 ℃.
Preferably, in the fourth step, the annealing treatment process parameter of the hollow microarray material is 1.5 × 10 of vacuum degree-3Pa, annealing at 450-650 ℃ for 1 h.
Compared with the prior art, the invention has the beneficial effects that: the structure of the hollow micro-lattice material of the shape memory alloy membrane prepared by the invention has strong designability; the method for obtaining the hollow microarray material of the shape memory alloy membrane is simple and easy to implement, the thickness of the membrane layer can be controlled by controlling the sputtering time, and the regulation and control of the thickness of the tube wall between 50nm and 20 mu m can be realized; the microarray material prepared by the invention has light weight, super elasticity, better memory effect, high damping, energy absorption and biocompatibility; compared with other deposition methods, the magnetron sputtering technology used in the invention has the advantages of wide material selection and better film uniformity.
Drawings
FIG. 1 is a schematic view of a hollow microarray material of a shape memory alloy membrane;
FIG. 2 is a flow chart of the method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-2, a technical solution provided by the present invention is:
example 1:
a shape memory alloy hollow micro-lattice material comprises the following components: the NiTi alloy with equal atomic ratio comprises the following components in percentage by weight: 100% NiTi alloy.
A preparation method of a shape memory alloy hollow microarray material comprises the steps of firstly, processing a polymer mask; step two, sputtering and forming the NiTi alloy film layer; step three, obtaining a hollow micro-lattice material; step four, obtaining a NiTi alloy hollow micro-lattice material with a memory effect;
firstly, establishing a micro-lattice material model with the relative density of 5% and the unit rod diameter of 0.1mm by CAD software, then converting the CAD file into an STL format file, then introducing the STL format file into 3D printing equipment, and processing a PR48 photosensitive resin octahedral micro-lattice material mask by utilizing a digital light processing technology; the process parameters are that the projection resolution is 768 multiplied by 480, the projection light wave band is 350nm, the slice thickness is 50um, the exposure time of each layer is 5s, and the lifting time of the workbench is 3 s;
in the second step, the polymer template is placed into acetone for ultrasonic cleaning for 15min, deionized water for ultrasonic cleaning for 15min, ethanol for ultrasonic cleaning for 15min, and natural drying is carried out; putting the NiTi alloy target material with equal atomic ratio and the cleaned polymer template into magnetron sputteringA chamber with a substrate temperature of more than 25 deg.C, a substrate-sputtering target distance of 60mm, and a vacuum degree of 10-4The rotating speed of the template is 15r/min, the argon pressure is 0.5Pa, the sputtering power is 200W, the sputtering voltage is 220V, the sputtering current is 0.5A, the pre-sputtering time is 30min, the sputtering time is 30min, and the Ni with the thickness of 500nm is obtained51.6Ti48.4An alloy film layer;
in the third step, the sample piece obtained in the second step is placed into a reactor, methanol and water are mixed according to the volume ratio of 1:1 to form a mixed solution, the mixed solution is used as a solvent to prepare a sodium hydroxide solution with the concentration of 3mol/L, and then the photosensitive resin mask is removed under the condition that the temperature of the sodium hydroxide solution is 60 ℃ to obtain the NiTi alloy membrane octahedron hollow micro-lattice material;
in the fourth step, the NiTi alloy membrane octahedron hollow micro-lattice material obtained in the third step is put into a vacuum tube furnace for annealing treatment, and the vacuum degree is 1.5 multiplied by 10-3Pa, annealing for 1h at 450 ℃ to obtain the NiTi alloy octahedral hollow micro-lattice material with the memory effect.
Example 2:
a shape memory alloy hollow micro-lattice material comprises the following components: the NiTi alloy comprises the following components in percentage by weight: 100% NiTi alloy.
A preparation method of a shape memory alloy hollow microarray material comprises the steps of firstly, processing a polymer mask; step two, sputtering and forming the NiTi alloy film layer; step three, obtaining a hollow micro-lattice material; step four, obtaining a NiTi alloy hollow micro-lattice material with a memory effect;
firstly, establishing a micro-lattice material model with the relative density of 10% and the unit rod diameter of 0.2mm by CAD software, then converting the CAD file into an STL format file, then introducing the STL format file into 3D printing equipment, and processing a composite EX-200 type photosensitive resin material face-centered cubic micro-lattice material mask by using a digital light processing technology; the technological parameters are ultraviolet laser 355nm, scanning speed 300mm/s, scanning interval 0.3mm, light spot compensation diameter 0.3mm, interlayer waiting time 3s and workbench lifting speed 5 mm/s;
in the second step, the polymer template is placed into acetone for ultrasonic cleaning for 10min, deionized water for ultrasonic cleaning for 10min, ethanol for ultrasonic cleaning for 10min, and natural drying is carried out; putting the NiTi alloy target material with equal atomic ratio and the cleaned polymer template into a magnetron sputtering chamber, wherein the substrate temperature is more than 25 ℃, the distance between the substrate and the sputtering target is 10mm, and the vacuum degree is 10-4The rotating speed of the template is 20r/min, the argon pressure is 0.4Pa, the sputtering power is 300W, the sputtering voltage is 220V, the sputtering current is 0.5A, the pre-sputtering time is 30min, the sputtering time is 60min, and the Ni with the thickness of 1000nm is obtained51.1Ti48.9An alloy film layer;
in the third step, the sample piece obtained in the second step is placed into a reactor, methanol and water are mixed according to the volume ratio of 1:1 to form a mixed solution, the mixed solution is used as a solvent to prepare a sodium hydroxide solution with the concentration of 3mol/L, and then the photosensitive resin mask is removed under the condition that the sodium hydroxide solution is at 60 ℃ to obtain the NiTi alloy film face-centered cubic hollow micro-lattice material;
in the fourth step, the hollow micro-lattice material of the NiTi alloy film face-core cube obtained in the third step is put into a vacuum tube furnace for annealing treatment, and the vacuum degree is 1.5 multiplied by 10-3Pa, annealing for 1h at 650 ℃ to obtain the NiTi alloy face-centered cubic hollow micro-lattice material with the memory effect.
Example 3:
a shape memory alloy hollow micro-lattice material comprises the following components: the NiTi alloy comprises the following components in percentage by weight: 100% NiTi alloy.
A preparation method of a shape memory alloy hollow microarray material comprises the steps of firstly, processing a polymer mask; step two, sputtering and forming the NiTi alloy film layer; step three, obtaining a hollow micro-lattice material; step four, obtaining a NiTi alloy hollow micro-lattice material with a memory effect;
firstly, establishing a micro-lattice material model with the relative density of 5% and the unit rod diameter of 0.1mm by CAD software, then converting the CAD file into an STL format file, then introducing the STL format file into 3D printing equipment, and processing a composite EX-200 type photosensitive resin material rhombic dodecahedron micro-lattice material mask by utilizing a digital light processing technology; the technological parameters are ultraviolet laser 355nm, scanning speed 300mm/s, scanning interval 0.3mm, light spot compensation diameter 0.3mm, interlayer waiting time 3s and workbench lifting speed 5 mm/s;
in the second step, the polymer template is placed into acetone for ultrasonic cleaning for 15min, deionized water for ultrasonic cleaning for 10min, ethanol for ultrasonic cleaning for 10min, and natural drying is carried out; putting the NiTi alloy target material with equal atomic ratio and the cleaned polymer template into a magnetron sputtering chamber, wherein the substrate temperature is more than 25 ℃, the distance between the substrate and the sputtering target is 10mm, and the vacuum degree is 10-4The rotating speed of the template is 10-20r/min, the argon pressure is 0.3Pa, the sputtering power is 200W, the sputtering voltage is 300V, the sputtering current is 0.5A, the pre-sputtering time is 30min, the sputtering time is 60min, and the Ni with the thickness of 1000nm is obtained50.8Ti49.2An alloy film layer;
in the third step, the sample piece obtained in the second step is placed into a mixed solution formed by mixing methanol and water according to the volume ratio of 1:1, the mixed solution is used as a solvent to prepare a sodium hydroxide solution with the concentration of 3mol/L, and then the photosensitive resin mask is removed under the condition that the temperature of the sodium hydroxide solution is 60 ℃ to obtain the NiTi alloy film rhombic dodecahedron hollow microarray material;
in the fourth step, the NiTi alloy film rhombic dodecahedron hollow micro-lattice material obtained in the third step is put into a vacuum tube furnace for annealing treatment, and the vacuum degree is 1.5 multiplied by 10-3Pa, annealing for 1h at 650 ℃ to obtain the NiTi alloy rhombic dodecahedron hollow micro-lattice material with the memory effect.
The properties of the examples are compared in the following table:
based on the above, the invention has the advantages that: the hollow micro-lattice material prepared by the method has strong designability, and is convenient for producing and preparing hollow micro-lattice materials with various complex structures; the preparation method is simple, convenient and feasible, the thickness of the film layer is conveniently controlled by using the magnetron sputtering technology, the regulation and control of the thickness of the tube wall between 50nm and 20 mu m can be realized, the material selection is wide, and the uniformity of the film layer is better; the microarray material prepared by the invention has various excellent performances of light weight, hyperelasticity, memory effect, high damping, energy absorption and biocompatibility.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.