A negative poisson's ratio composite blast mitigation material and method of making

Abstract

A negative Poisson's ratio composite explosion-proof material and its preparation method are disclosed. The material comprises a gradient chiral superstructure shape memory alloy skeleton reinforcement phase, a shear-thickening liquid filler, and a ceramic particle reinforcement phase. The shape memory alloy skeleton reinforcement phase is formed by horizontally arranging and axially stretching gradient structure negative Poisson's ratio cell units. The negative Poisson's ratio cell units are composed of a gradient array of four-ligament or six-ligament chiral honeycomb structures. A mixture of the shear-thickening liquid filler and the ceramic particle reinforcement phase is impregnated and filled into the shape memory alloy skeleton. After solidification, the negative Poisson's ratio composite explosion-proof material is formed. The volume percentage of the shape memory alloy skeleton reinforcement phase is 20%–60%, the volume percentage of the shear-thickening liquid filler is 20%–40%, and the volume percentage of the ceramic particle reinforcement phase is 10%–50%. The preparation method of this invention is scientifically sound and reasonable. The composite explosion-proof material exhibits low density, high impact strength, high fracture resistance, and good energy absorption and shock absorption properties, showing broad application prospects in explosion-proof, bulletproof, and lightweight armor protection.

Description

Technical Field

[0001] This invention belongs to the field of explosion-proof material preparation technology, and particularly relates to a negative Poisson's ratio composite explosion-proof material and its preparation method. Specifically, it relates to a gradient chiral superstructure memory alloy with negative Poisson's ratio, a shear-thickening liquid and ceramic particles composite explosion-proof material and its preparation method. Background Technology

[0002] Modern warfare places extremely high demands on the protective performance and lightweighting of ballistic materials. While traditional metal ballistic materials offer advantages such as good protection and low cost, they are generally heavy, inconvenient to wear, and severely hinder the mobility of personnel and equipment. To adapt to the high destructiveness, fast pace, and harsh battlefield environment of modern warfare, ballistic materials are developing towards lightweighting and composite materials. Countries worldwide have successively developed a series of lightweight ballistic materials, including ceramics, high-performance fibers, and new composite materials, further enhancing the survivability and mobility of personnel and equipment. Although these composite ballistic materials offer the advantage of customizable structure and function, the epoxy resins and other adhesives used in their preparation have drawbacks such as poor toughness and low bonding strength. This can prevent the composite ballistic materials from quickly transmitting stress waves, thus reducing their protective effectiveness.

[0003] Ceramic materials possess characteristics such as low density, high hardness, and high compressive strength. Combining ceramic materials with fiber-reinforced resin-based composites to prepare ceramic-reinforced resin-based explosion-proof composites can improve the explosion-proof performance of armor while reducing weight. In recent years, ceramic-reinforced resin-based explosion-proof composites have been widely used in ballistic protection fields such as individual soldier protection, armored vehicles, ships, armed helicopters, civilian personal protective equipment, and engineering protection, demonstrating significant advantages in lightweighting and high protection. However, a distinct interface exists between ceramics and fiber-reinforced resin-based composites, and the bonding performance between the interface directly affects the impact performance of the composite material. The composite of ceramics and fiber-reinforced resin-based composites involves the bonding of dissimilar materials. Since most ceramic surfaces have low activity, without ceramic surface treatment, the bonding strength with the resin-based composite material cannot be guaranteed, resulting in compromised impact performance and thus hindering the development of ceramic-reinforced resin-based explosion-proof composites.

[0004] STF liquid, also known as shear-thickening liquid, is a non-Newtonian fluid. It often exists as a concentrated colloidal suspension. Under rapidly increasing shear stress, its viscosity increases dramatically, sometimes even transforming from a liquid to a solid, and this process is reversible. This phenomenon is primarily attributed to the formation of rigid particle clusters under liquid pressure. This property of STF liquid makes it widely applicable in various technical fields, including damping and vibration reduction, hydraulic coupling devices in transmissions, vehicle suspension systems, and personal protective equipment. Protective clothing made using it is often called "liquid armor." Shear-thickening liquid penetrates fabric, normally existing in a liquid state. However, once the fabric is impacted and compressed, the shear-thickening liquid becomes a hard solid, making the fabric stronger and harder to penetrate. New types of bulletproof vests made using shear-thickening liquid are soft and comfortable under normal conditions, but become incredibly tough the moment they are struck by sharp objects like knives or stabs, or impacted by high-speed bullets or shrapnel. They also rapidly disperse the impact force along the fabric, significantly reducing the pressure per unit area. After the impact force dissipated, the "shear-thickening liquid" returned to its liquid state, and the fabric softened again. However, the protective effect of STF liquid composite fiber material under high-speed projectile impact was not ideal, and the actual projectile velocity was far greater than the shear rate under shear test conditions, reaching up to 10. 5 ~10 7 s -1 STF liquid composite materials have low protective strength. Summary of the Invention

[0005] The first technical problem to be solved by this invention is to provide a negative Poisson's ratio composite explosion-proof material that combines a gradient chiral superstructure memory alloy skeleton, a shear thickening liquid and ceramics, and has low density, high impact strength, high fracture resistance and good energy absorption and shock absorption performance.

[0006] The second technical problem to be solved by the present invention is to provide a method for preparing a negative Poisson's ratio composite explosion-proof material, which combines a gradient chiral superstructure memory alloy skeleton, a shear thickening liquid and ceramics to form a periodic structure composite material with a macroscopic negative Poisson's ratio effect, thereby significantly improving the explosion-proof capability and protective performance of the composite material.

[0007] The technical solution adopted by this invention to solve the first technical problem mentioned above is as follows: a negative Poisson's ratio composite explosion-proof material, characterized in that it comprises a gradient chiral superstructure shape memory alloy skeleton reinforcement phase, a shear thickening liquid filler, and a ceramic particle reinforcement phase. The shape memory alloy skeleton reinforcement phase is formed by horizontally arranging and axially stretching gradient structure negative Poisson's ratio cell units. The negative Poisson's ratio cell units are composed of a four-ligament or six-ligament chiral honeycomb gradient array. The shear thickening liquid filler is mixed with the ceramic particle reinforcement phase to form a mixed liquid that impregnates and completely fills the shape memory alloy skeleton. After solidification, a composite explosion-proof material with a macroscopic negative Poisson's ratio effect and a three-dimensional interconnected structure is formed. The volume percentage of the shape memory alloy skeleton reinforcement phase in the composite explosion-proof material is 20%–60%, the volume percentage of the shear thickening liquid filler is 20%–40%, and the volume percentage of the ceramic particle reinforcement phase is 10%–50%.

[0008] Preferably, the material of the shape memory alloy skeleton reinforcement phase is a nickel-titanium shape memory alloy or a high-entropy shape memory alloy.

[0009] Preferably, the material of the ceramic particle reinforcing phase is one or a mixture of any proportions of Al2O3 ceramic, B4C ceramic, SiC ceramic, TiB2 ceramic, ZrO2 ceramic, Si3N4 ceramic, TiN ceramic, and AlN ceramic; the particle size of the ceramic particles is 0.02 to 10 mm.

[0010] Preferably, the shear-thickening liquid filler comprises an organic solvent and particles, wherein the organic solvent accounts for 30-50% by weight and needs to be diluted with ethanol before use.

[0011] Furthermore, the organic solvent is one or more of polyol monomers or polyol monomer oligomers, wherein the polyol monomers are one or more of vinyl ethanol, polyethylene glycol or polypropylene glycol, and mineral oil; the molecular weight of the polyol monomer oligomers is 200-2000 g / mol; the particles are one or more of spherical or ellipsoidal organic particles and inorganic particles; the inorganic particles are one or more of silicon dioxide, titanium dioxide, aluminum trioxide, magnesium oxide, and calcium carbonate, with a particle size of 1 nm-500 nm; the organic particles are one or more of chemically synthesized PS and PMMA particles, with a particle size of 600 nm-1200 nm.

[0012] Finally, the shear-thickening liquid filler also includes a surface treatment agent, wherein the surface treatment agent for the inorganic particles is a silane coupling agent, and the amount of silane coupling agent used is 4-5% of the inorganic particles.

[0013] The technical solution adopted by the present invention to solve the second technical problem mentioned above is: a method for preparing the above-mentioned negative Poisson's ratio composite explosion-proof material, characterized by comprising the following steps:

[0014] 1) Forming gradient chiral superstructure memory alloy skeleton: The memory alloy skeleton is obtained by laser sintering layer by layer using a 3D printing molding machine;

[0015] 2) Preparation of ceramic particles and shear-thickening liquid mixture: Turn on the magnetic stirrer, slowly add the ceramic particles and shear-thickening liquid into the container and mix evenly. Place the container in an ultrasonic cleaner and agitate until the mixture is clear and free of bubbles, to obtain a uniformly dispersed ceramic particles and shear-thickening liquid mixture.

[0016] 3) Solidification and molding of composite materials: The shape memory alloy skeleton obtained in step 1) is placed into a pre-prepared mold, and then a mixture of uniformly dispersed ceramic particles and shear thickening liquid is slowly poured in. The mixture is then subjected to ultrasonic cleaning and vibration treatment. The mechanical vibration allows the mixture to penetrate into the shape memory alloy skeleton and completely fill the gaps in the skeleton. Finally, the mixture is dried in a vacuum oven at a certain temperature. After cooling and solidification, the shape memory alloy skeleton reinforcing phase, shear thickening liquid, and ceramic particle reinforcing phase are continuously and densely distributed in three-dimensional space, forming a composite material structure of a gradient chiral superstructure shape memory alloy skeleton with negative Poisson's ratio and ceramic reinforcing particles reinforcing shear thickening liquid.

[0017] Furthermore, the specific process of step 1) is as follows: first, the structural parameters of the shape memory alloy skeleton are optimized and designed, then a three-dimensional solid model of the periodic skeleton is generated using three-dimensional modeling software, and the model information is transmitted to a 3D printing molding machine to obtain the shape memory alloy skeleton by sintering layer by layer through laser sintering process.

[0018] Furthermore, the shape memory alloy skeleton obtained in step 1) needs to undergo surface etching or roughening treatment to obtain a modified shape memory alloy skeleton.

[0019] Finally, the preparation method of the shear-thickening liquid filler in step 2) is as follows:

[0020] a. Pour the organic solvent and ethanol into a beaker, dilute them at a mass ratio of 1:2 to 4, add a stir bar, and place the beaker in a magnetic stirrer;

[0021] b. Turn on the magnetic stirrer and slowly add the particles and surface treatment agent into the beaker. Place the beaker in the ultrasonic cleaner and vibrate until the mixture is clear and free of bubbles to obtain the shear thickening liquid.

[0022] The stirring speed of the magnetic stirrer is set to 100-1500 r / min; the power of the ultrasonic cleaner is 400-600 W.

[0023] Compared with the prior art, the advantages of the present invention are as follows:

[0024] 1. The gradient chiral superstructure memory alloy skeleton, shear thickening liquid, and ceramic particle composite material of the present invention are made into a metal skeleton with a three-dimensional interconnected structure of periodic regular pores by forming a memory alloy material. Then, a diluted shear thickening liquid and ceramic particle mixture is immersed in and fills the pores of the memory alloy skeleton to form a three-phase continuous and tightly bonded composite material. The three-phase composite structure formed in this way has a multi-effect explosion-proof mechanism coupling effect; the periodic three-dimensional interconnected structure has topological uniformity, which can ensure that the composite material has macroscopically consistent mechanical properties and resistance to penetration; the uniformly dispersed shear thickening liquid becomes extremely strong and tough instantly when subjected to external force, fixing the ceramic spheres and rapidly dispersing the impact force. The high-strength ceramic spheres inside are partially broken by impact, thereby absorbing energy and playing a dual protective role.

[0025] 2. The shape memory alloy skeleton is formed by horizontally arranging and axially stretching gradient structure negative Poisson's ratio cell units. Under the action of macroscopic negative Poisson's ratio characteristics, when the composite target plate is subjected to local penetration, the material in the region will shrink towards the loaded region, the local density will increase, thus exhibiting higher compressive strength and frictional energy dissipation effect, further improving the penetration resistance; moreover, the structural characteristics of negative Poisson's ratio gradient change can simultaneously improve the energy absorption stability and comprehensive energy absorption performance of the overall composite structure.

[0026] 3. The mechanical properties of shape memory alloy skeletons can be optimized through the structural parameters of periodic cells, thereby realizing the functional design of composite structural materials, making them of broad application value in the field of composite material structures in aviation, aerospace and transportation, especially in lightweight explosion protection.

[0027] 4. Combining chiral superstructure design technology and shear-thickening liquid technology, a gradient chiral superstructure memory alloy skeleton with a negative Poisson's ratio is first prepared using 3D printing technology. The shear-thickening liquid filler and ceramic particle reinforcing phase are pre-mixed uniformly through mechanical vibration and ultrasonic treatment, and then immersed into and completely filled into the memory alloy skeleton. After solidification, the gradient chiral superstructure memory alloy skeleton, shear-thickening liquid and ceramic particle reinforcing phase are continuously and densely distributed in three-dimensional space, forming a periodic structural composite material with a macroscopic negative Poisson's ratio effect, which greatly improves the explosion-proof capability and protective performance of the composite material.

[0028] The preparation method of this invention is scientific and reasonable, and the prepared composite explosion-proof material has low density, high impact strength, high fracture resistance and good energy absorption and shock absorption performance, and has broad application prospects in explosion protection, bulletproofing and lightweight armor protection. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the structural morphology of the negative Poisson's ratio composite explosion-proof material prepared by the present invention;

[0030] Figure 2 This is a schematic diagram of the gradient chiral superstructure memory alloy skeleton with negative Poisson's ratio of the present invention;

[0031] Figure 3 This is a schematic diagram of the structure of cell units, shear-thickening liquid fillers, and ceramic particles;

[0032] Figure 4 This is a flowchart illustrating the preparation process of the negative Poisson's ratio composite explosion-proof material of the present invention. Detailed Implementation

[0033] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0034] like Figures 1-3 As shown, a negative Poisson's ratio composite explosion-proof material includes a gradient chiral superstructure shape memory alloy skeleton reinforcement phase 1, a ceramic particle reinforcement phase 3, and a shear thickening liquid filler 4. The shape memory alloy skeleton reinforcement phase 1 is formed by horizontally arranging and axially stretching gradient structure negative Poisson's ratio cell units. The negative Poisson's ratio cell units are composed of a four-ligament or six-ligament chiral honeycomb gradient array. The shear thickening liquid filler 4 is mixed with the ceramic particle reinforcement phase 3 to form a shear thickening liquid and ceramic particle mixture 2. The shear thickening liquid and ceramic particle mixture 2 impregnates and completely fills the shape memory alloy skeleton reinforcement phase 1. After solidification, a composite explosion-proof material with a macroscopic negative Poisson's ratio effect and a three-dimensional interconnected structure is formed. The volume percentage of the shape memory alloy skeleton reinforcement phase 1 in the composite explosion-proof material is 20% to 60%, the volume percentage of the shear thickening liquid filler 4 is 20% to 40%, and the volume percentage of the ceramic particle reinforcement phase 3 is 10% to 50%.

[0035] In this embodiment, the material of the shape memory alloy skeleton reinforcement phase 1 is nickel-titanium shape memory alloy or TiZrNbSnMo high entropy shape memory alloy, and the material of the ceramic particle reinforcement phase 3 is a mixture of B4C ceramic and SiC ceramic uniformly mixed in a volume ratio of 1:1, and their particle sizes are all 0.05 to 0.10 mm.

[0036] The shear-thickening liquid filler 4 includes an organic solvent, particles, and a surface treatment agent. In this embodiment, the organic solvent is polypropylene glycol, which accounts for 35% by weight. The particles are a mixture of spherical silica and titanium dioxide in a volume ratio of 1:2, with a particle size of 1 nm to 20 nm. The surface treatment agent is a silane coupling agent, and the amount of silane coupling agent used is 4 to 5% of the particles.

[0037] During preparation, the shear-thickening liquid filler 4 is prepared as follows: polypropylene glycol and ethanol are diluted at a ratio of 1:3 and then mixed evenly with particles and surface treatment agent to obtain shear-thickening liquid. The mixing is carried out by oscillation with an ultrasonic cleaner and stirring with a magnetic stirrer. The stirring speed of the magnetic stirrer can be set to 100-1500 r / min; the power of the ultrasonic cleaner is 400-600W.

[0038] A method for preparing the above-mentioned negative Poisson's ratio composite explosion-proof material, the preparation process flow is as follows: Figure 4 As shown, the specific steps are as follows:

[0039] 1) Molding gradient chiral superstructure memory alloy skeleton 1: First, the structural parameters of the memory alloy skeleton are optimized and designed. Then, a three-dimensional solid model of the periodic skeleton is generated using three-dimensional modeling software. The model information is transmitted to a 3D printing machine and the memory alloy skeleton is obtained by sintering layer by layer through laser sintering process. In order to avoid the problems of bubbles and poor adhesion in the cross section when the memory skeleton is immersed in the mixture of shear thickening liquid filler and ceramic particle reinforcing phase 3, the surface of the printed memory alloy skeleton is etched or roughened to obtain a modified memory alloy skeleton.

[0040] 2) Preparation of shear-thickening liquid and ceramic particle mixture 2: Turn on the magnetic stirrer, slowly add ceramic particles and shear-thickening liquid into the container and mix evenly. Place it in an ultrasonic cleaner and vibrate until the mixture is clear and free of bubbles, to obtain a uniformly dispersed mixture of shear-thickening liquid and ceramic particles 2.

[0041] 3) Solidification and molding of composite materials: The shape memory alloy skeleton obtained in step 1) is placed into a pre-prepared mold, and then a uniformly dispersed shear thickening liquid and ceramic particle mixture 2 is slowly poured in. The mixture is then subjected to ultrasonic cleaning and vibration treatment. The mechanical vibration allows the mixture to penetrate into the shape memory alloy skeleton and completely fill the gaps in the skeleton. Finally, it is dried in a vacuum oven at a certain temperature. After cooling and solidification, the shape memory alloy skeleton reinforcing phase, shear thickening liquid and ceramic particle reinforcing phase are continuously and densely distributed in three-dimensional space, forming a composite material structure of a gradient chiral superstructure shape memory alloy skeleton with negative Poisson's ratio and ceramic reinforcing particles reinforcing the shear thickening liquid.

[0042] The preparation method of shear-thickening liquid filler 4 is as follows:

[0043] a. Pour the organic solvent and ethanol into a beaker, dilute them to a ratio of 1:2 to 4, add a stir bar, and place the beaker in a magnetic stirrer.

[0044] b. Turn on the magnetic stirrer and slowly add the particles and surface treatment agent into the beaker. Place the beaker in the ultrasonic cleaner and vibrate until the mixture is clear and free of bubbles to obtain the shear thickening liquid.

[0045] The stirring speed of the magnetic stirrer is set to 100-1500 r / min; the power of the ultrasonic cleaner is 400-600 W.

[0046] The specific components of the negative Poisson's ratio composite explosion-proof material are shown in the 11 examples in the table below. The numerical simulation explosion-proof performance parameters of the negative Poisson's ratio composite explosion-proof material in the 11 examples are shown in Table 2 below.

[0047] Table 1. Composition (volume ratio) of negative Poisson's ratio composite explosion-proof materials in each embodiment.

[0048]

[0049] The shape memory alloy skeleton reinforcement phase is one of two components.

[0050] Table 2. Numerical simulation of explosion-proof performance of negative Poisson's ratio composite explosion-proof materials in each embodiment.

[0051] Example Internal energy absorption rate / % Stress wave attenuation rate / % 1 15.8 18.4 2 45.3 19.5 3 50.8 21.4 4 55.2 28.9 5 57.8 36.9 6 62.4 39.5 7 76.3 43.8 8 79.6 56.9 9 82.4 78.4 10 85.6 85.7 11 90.5 88.2

[0052] The numerical simulation method for evaluating explosion-proof performance is based on the explosion-proof performance evaluation method in Wang Xiaowei's "Explosion-proof Performance of Polyurea Elastomer Composite Sandwich Structure" published in Engineering Plastics Applications. This method will not be described in detail in this embodiment.

[0053] It is evident that the preparation method of this invention is scientific and reasonable, and the prepared composite explosion-proof material has low density, high impact strength, high fracture resistance and good energy absorption and shock absorption performance.

[0054] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A negative Poisson's ratio composite explosion-proof material, characterized in that: The material comprises a gradient chiral superstructure shape memory alloy skeleton reinforcement phase, a shear thickening liquid filler, and a ceramic particle reinforcement phase. The shape memory alloy skeleton reinforcement phase is formed by horizontally arranging and axially stretching gradient structure negative Poisson's ratio cell units. The negative Poisson's ratio cell units are composed of a gradient array of four-ligament or six-ligament chiral honeycomb structures. The shear thickening liquid filler is mixed with the ceramic particle reinforcement phase to form a mixed liquid that infiltrates and completely fills the shape memory alloy skeleton. After solidification, a composite explosion-proof material with a three-dimensional interconnected structure exhibiting a macroscopic negative Poisson's ratio effect is formed. The volume percentage of the shape memory alloy skeleton reinforcement phase in the composite explosion-proof material is 20%–60%, the volume percentage of the shear thickening liquid filler is 20%–40%, and the volume percentage of the ceramic particle reinforcement phase is 10%–50%. The material of the shape memory alloy skeleton reinforcement phase is nickel-titanium shape memory alloy or high-entropy shape memory alloy; The ceramic particle reinforcing phase is made of one or any mixture of several of the following materials in any proportion: Al2O3 ceramic, B4C ceramic, SiC ceramic, TiB2 ceramic, ZrO2 ceramic, Si3N4 ceramic, TiN ceramic, and AlN ceramic; the particle size of the ceramic particles is 0.02–10 mm. The shear-thickening liquid filler includes an organic solvent and particles, with the organic solvent comprising 30-50% by weight. The organic solvent must be diluted with ethanol before use. The organic solvent is one or more of polyol monomers or polyol monomer oligomers, wherein the polyol monomers are one or more of vinyl ethanol, polyethylene glycol or polypropylene glycol, and mineral oil; the molecular weight of the polyol monomer oligomers is 200-2000 g / mol; the particles are one or more of spherical or ellipsoidal organic particles and inorganic particles; the inorganic particles are one or more of silicon dioxide, titanium dioxide, aluminum trioxide, magnesium oxide, and calcium carbonate, with a particle size of 1 nm-500 nm; the organic particles are one or more of chemically synthesized PS and PMMA particles, with a particle size of 600 nm-1200 nm.

2. The negative Poisson's ratio composite explosion-proof material according to claim 1, characterized in that: The shear-thickening liquid filler also includes a surface treatment agent, wherein the surface treatment agent for the inorganic particles is a silane coupling agent, and the amount of silane coupling agent used is 4 to 5% of the inorganic particles.

3. A method for preparing a negative Poisson's ratio composite explosion-proof material according to claim 1 or 2, characterized in that... Includes the following steps: 1) Forming gradient chiral superstructure memory alloy skeleton: The memory alloy skeleton is obtained by laser sintering layer by layer using a 3D printing molding machine; 2) Preparation of ceramic particles and shear-thickening liquid mixture: Turn on the magnetic stirrer, slowly add the ceramic particles and shear-thickening liquid into the container and mix evenly. Place the container in an ultrasonic cleaner and vibrate until the mixture is clear and free of bubbles, to obtain a uniformly dispersed ceramic particles and shear-thickening liquid mixture. 3) Solidification and molding of composite materials: The shape memory alloy skeleton obtained in step 1) is placed into a pre-prepared mold, and then a mixture of uniformly dispersed ceramic particles and shear thickening liquid is slowly poured in. The mixture is subjected to vibration treatment with an ultrasonic cleaner. The mechanical vibration allows the mixture to penetrate into the shape memory alloy skeleton and completely fill the gaps in the skeleton. Finally, it is dried in a vacuum oven at a certain temperature. After cooling and solidification, the shape memory alloy skeleton reinforcing phase, shear thickening liquid and ceramic particle reinforcing phase are continuously and densely distributed in three-dimensional space, forming a composite material structure of a gradient chiral superstructure shape memory alloy skeleton with negative Poisson's ratio and ceramic reinforcing particles reinforcing shear thickening liquid.

4. The preparation method according to claim 3, characterized in that: The specific process of step 1) is as follows: First, the structural parameters of the shape memory alloy skeleton are optimized and designed. Then, a three-dimensional solid model of the periodic skeleton is generated using three-dimensional modeling software. The model information is then transmitted to a 3D printing machine and the shape memory alloy skeleton is obtained by sintering layer by layer using laser sintering process.

5. The preparation method according to claim 3, characterized in that: The shape memory alloy skeleton obtained in step 1) still needs to undergo surface etching or roughening treatment to obtain a modified shape memory alloy skeleton.

6. The preparation method according to claim 3, characterized in that: The preparation method of the shear-thickening liquid filler in step 2) is as follows: a. Pour the organic solvent and ethanol into a beaker, dilute them at a mass ratio of 1:2~4, add a stir bar, and place the beaker in a magnetic stirrer; b. Turn on the magnetic stirrer and slowly add the particles and surface treatment agent into the beaker. Place the beaker in the ultrasonic cleaner and vibrate until the mixture is clear and free of bubbles to obtain the shear thickening liquid. The stirring speed of the magnetic stirrer is set to 100-1500 r / min; the power of the ultrasonic cleaner is 400~600W.

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