Multi-scale memory alloy / aerogel / polymer damping composite material and preparation method thereof

Abstract

The invention discloses a multi-scale memory alloy / aerogel / polymer damping composite material and a preparation method thereof. The multi-scale memory alloy / aerogel / polymer damping composite material comprises a porous CuAlMn memory alloy skeleton; the NiTiPt-coated CNT + NiTi + SA aerogel is formed in pores of the porous CuAlMn memory alloy framework through freeze drying; and the polymer is filled in a gap between the porous CuAlMn memory alloy skeleton and the NiTiPt-coated CNT + NiTi + SA aerogel. The damping composite material disclosed by the invention shows excellent damping performance in similar materials, and has the high loss factor of a polymer-based composite material and the high energy storage modulus of a metal-based material. According to the invention, the requirements of low density, certain strength and relatively high damping performance in a specific temperature range are met.

Description

Technical Field

[0001] The present invention belongs to the technical field of damping material preparation, and particularly relates to a multi-scale shape memory alloy / aerogel / polymer damping composite material and a preparation method thereof. Background Art

[0002] With the continuous development of scientific and technological progress and industrial application requirements, in the fields of aerospace, military, precision instruments, and new energy vehicles, the requirements for energy dissipation and vibration suppression are constantly increasing to reduce the impacts brought by structural fatigue and noise. Currently, the requirements for damping materials not only need to provide high damping performance within a certain working temperature range, but also must have low density and a certain strength to meet the needs of lightweight and durability. This poses a higher challenge to the selection and optimization of damping materials.

[0003] Currently, typical shock absorption methods include active damping, passive damping, and structural damping. Designing a lightweight new passive damping material is the key to optimizing the system dynamic response, improving the energy utilization efficiency, and meeting the requirement of extending the service life of devices. The passive damping of materials can be decomposed into the intrinsic damping of each phase of the composite material and the interfacial damping between the phases. Shape memory alloys (such as CuAlMn, NiTi, TiNb, etc.) have a unique martensitic phase transformation mechanism, forming a rich variety of martensite variants and phase interfaces within the alloy, which gives them broad application prospects in the field of damping materials. Common damping materials developed based on the principle of synergistic effect, such as polymer-filled porous shape memory alloys, can combine the strength of the alloy and the lightweight characteristics of the polymer, and utilize the glass transition of the polymer and the metal-polymer matrix interface to enhance the damping performance. However, limited by the porosity of the porous alloy and the polymer penetration ability, the damping contribution provided by the interface in such materials is still insufficient to meet the requirements of current high-performance applications.

[0004] Adding new particles to the polymer to further stack new interfaces and damping sources is an effective means to enhance the damping performance of porous alloy-polymer composite materials. Among them, due to their high specific surface area and high strength, nano-carbon materials are often added to the polymer as fillers to enhance the damping performance of the composite material. For example, in CN111253710B, graphene is introduced into the polymer, and in CN109277571B, carbon nanotubes are directly mixed with the polymer and then infiltrated into the porous CuAlMn framework. However, the types and dimensions of these filler particles are limited, and limited by the fluidity of the polymer, the interface damping of the material cannot be maximally improved. Therefore, a preparation method that can utilize the interface properties at multiple scales to strengthen the damping performance of the composite material needs to be developed. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies and defects mentioned in the above background technology, and provide a multi-scale shape memory alloy / aerogel / polymer damping composite material and a preparation method thereof.

[0006] To solve the above technical problem, the technical solution proposed by the present invention is as follows:

[0007] A multi-scale shape memory alloy / aerogel / polymer damping composite material, which includes:

[0008] A porous CuAlMn shape memory alloy skeleton;

[0009] A NiTiPt@CNT+NiTi+SA aerogel formed by freeze-drying in the pores of the porous CuAlMn shape memory alloy skeleton; in the NiTiPt@CNT+NiTi+SA aerogel, the porous network composed of SA aerogel sheets wraps NiTiPt@CNT therein, and NiTi spherical particles are embedded on the surface of the SA aerogel; wherein NiTiPt@CNT is a carbon nanotube surface-loaded with NiTiPt nanoalloy particles.

[0010] And a polymer filled in the voids between the porous CuAlMn shape memory alloy skeleton and the NiTiPt@CNT+NiTi+SA aerogel.

[0011] As a further improvement, the size of the NiTiPt nanoalloy particles surface-loaded on the NiTiPt@CNT is 5-10 nm, and the atomic percentages of Ni, Ti, and Pt are 20%-20.7%, 11.9%-12.2%, and 67.1-68.1% respectively.

[0012] The preparation method of the multi-scale shape memory alloy / aerogel / polymer damping composite material provided by the present invention includes the following steps:

[0013] Mix NiTiPt@CNT, NiTi spherical particles with sodium alginate solution to obtain a mixed solution, then place the porous CuAlMn shape memory alloy skeleton in the mixed solution, and generate NiTiPt@CNT+NiTi+SA aerogel in the pores of the CuAlMn alloy by freeze-drying to obtain a porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material;

[0014] Add the porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material to the resin solution, infiltrate the polymer into the voids of the material by vacuum infiltration, and then cure to obtain the multi-scale shape memory alloy / aerogel / polymer damping composite material.

[0015] As a further improvement, the preparation method of the NiTiPt@CNT includes:

[0016] Prepare a mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinate and hydrochloric acid to obtain a hydrochloric acid-acidified metal salt solution. Mix the hydrochloric acid-acidified metal salt solution with carbon nanotubes, and obtain a uniform mixture of Ni, Ti, Pt metal salts / CNT through ultrasonic stirring and drying.

[0017] Place the uniform mixture of Ni, Ti, Pt metal salts / CNT in a reducing atmosphere and keep it at 250 - 300 °C for heat preservation, then wash with water and dry. Heat the obtained powder at 850 - 950 °C for heat preservation, and then quench to obtain NiTiPt@CNT.

[0018] As a further improvement, the total metal particle concentration in the hydrochloric acid-acidified metal salt solution is 0.03 - 0.05 M, and the molar ratio of nickel nitrate, titanium sulfate, and potassium chloroplatinate is (1.5 - 2.5):(0.8 - 1.2):1.

[0019] As a further improvement, the concentration of carbon nanotubes in the solution after mixing the hydrochloric acid-acidified metal salt solution with carbon nanotubes is 3 - 6 mg / mL.

[0020] As a further improvement, the atomic ratio of Ni to Ti in the NiTi spherical particles is (50 - 55):(45 - 50).

[0021] As a further improvement, in the mixed solution obtained by mixing NiTiPt@CNT, NiTi spherical particles and sodium alginate solution, the concentration of NiTiPt@CNT is 0.5 - 1 wt%, the concentration of NiTi spherical particles is 0.025 - 0.05 g / mL, and the concentration of sodium alginate is 0.03 - 0.05 g / mL.

[0022] As a further improvement, the polymer is epoxy resin.

[0023] As a further improvement, the curing process is: first keep it at 55 - 65 °C for 4 - 6 h, then keep it at 120 - 140 °C for 5 - 7 h, and then keep it at 200 - 240 °C for 1 - 3 h.

[0024] Compared with the prior art, the beneficial effects of the present invention are:

[0025] In the present invention, sodium alginate SA, NiTiPt@CNT, and NiTi micron particles are further formed into an interconnected NiTiPt@CNT+NiTi+SA aerogel network in a porous CuAlMn alloy skeleton by freeze-drying, and a polymer is infiltrated into the pores, forming a quadruple interface superposition from the nanoscale to the millimeter scale, from the microscale to the macroscale, increasing the total interface volume of the material, and introducing multiple intrinsic damping mechanisms such as multi-scale shape memory alloys and polymers, so as to achieve the combination of high storage modulus and high loss factor within a certain temperature range, while ensuring the lightweight and strength requirements of the material.

[0026] Moreover, the CNT modified by NiTiPt nanoalloy particles strengthens the radial strength of the CNT, increases the specific surface area and surface roughness of the CNT, and greatly improves the damping performance.

[0027] The damping composite material of the present invention exhibits excellent damping performance among similar materials (metal-polymer interpenetrating composite materials), combining the high loss factor of polymer-based composite materials and the high storage modulus of metal-based materials. At the same time, the present invention meets the requirements of low density, certain strength, and high damping performance within a specific temperature range. The damping composite material of the present invention has a material density of 2.1-2.5 g / cm 3 , the loss factor is greater than 0.045 at room temperature, the compressive strength is greater than 54.4 MPa, the loss factor of the material is greater than 0.29 at 100-150 degrees Celsius, its peak loss factor is greater than 0.52, and the storage modulus is higher than 1500 MPa.

[0028] In terms of the preparation method, compared with the traditional method of directly infiltrating the filler CNT into the polymer, the present invention adopts a multi-step composite method, reducing the dosage of CNT, which effectively improves the fluidity of the polymer before curing, and then introduces more interfaces in the composite material, enhances the damping performance of the material, and has a simple preparation process and good industrialization prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0030] Figure 1Schematic diagram of the structure and preparation process of the multi-scale shape memory alloy / aerogel / polymer damping composite material of the present invention, where (a) is the porous CuAlMn shape memory alloy skeleton, (b) is the aerogel filled in the pores of the CuAlMn alloy, (c) is the composite material obtained by infiltrating epoxy resin into the voids, (d) is the multi-layer aerogel in (b) with NiTi particles embedded in the aerogel, and (e) is the single-layer aerogel in (b).

[0031] Figure 2 Appearance diagram of the multi-scale shape memory alloy / aerogel / polymer damping composite material in Example 1, where (a) is the CuAlMn skeleton and (b) is the final morphology after infiltrating the polymer.

[0032] Figure 3 TEM photograph and EDS results of NiTiPt@CNT in Example 1, where (a)(b) are the TEM images of NiTiPt@CNT, (b) is the enlarged view of the red box part in (a), (c) is its EDS result, and (c1-c3) represent Ni, Ti, and Pt elements respectively.

[0033] Figure 4 Microstructure morphology of the porous CuAlMn skeleton before and after infiltrating the polymer in Example 1, where (a) is the SEM of the SA aerogel and (b) is the SEM of the infiltrated polymer.

[0034] Figure 5 Microstructure morphology of the porous CuAlMn skeleton before and after infiltrating the polymer in Comparative Example 1, where (a) is the SEM of the SA aerogel and (b) is the SEM of the infiltrated polymer. Detailed implementation manners

[0035] For the convenience of understanding the present invention, the following will describe the present invention more comprehensively and meticulously in conjunction with the accompanying drawings of the specification and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0036] Unless otherwise defined, all professional terms used hereinafter have the same meaning as commonly understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present invention.

[0037] Unless otherwise specifically stated, various raw materials, reagents, instruments, and equipment used in the present invention can be obtained through market purchases or can be prepared by existing methods.

[0038] The multi-scale shape memory alloy / aerogel / polymer damping composite material of the present invention includes:

[0039] Porous CuAlMn shape memory alloy skeleton;

[0040] The NiTiPt@CNT+NiTi+SA aerogel formed in the pores of the porous CuAlMn memory alloy skeleton. In the NiTiPt@CNT+NiTi+SA aerogel, the SA aerogel sheets form a porous network that wraps NiTiPt@CNT, and NiTi particles are embedded on the surface of the SA aerogel. Here, NiTiPt@CNT is a carbon nanotube surface-loaded with NiTiPt nanoalloy particles.

[0041] And a polymer filled in the voids between the porous CuAlMn memory alloy skeleton and the NiTiPt@CNT+NiTi+SA aerogel.

[0042] Such as Figure 1 , the present invention adopts a quadruple composite mechanism, namely:

[0043] 1# The composite of NiTiPt@CNT and SA aerogel, where NiTiPt@CNT is the filler and SA aerogel is the matrix.

[0044] 2# The composite of NiTi spherical particles and epoxy polymer, where NiTi spherical particles are the filler and epoxy polymer is the matrix.

[0045] 3# The composite of the 1# composite and the 2# composite, where the 1# composite is the filler and the 2# composite is the matrix.

[0046] 4# The composite of the 3# composite and the porous CuAlMn skeleton, where the 3# composite is the filler and the porous CuAlMn skeleton is the matrix.

[0047] In the present invention, inside the CuAlMn skeleton, an aerogel including NiTiPt@CNT, NiTi, and SA is grown by freeze-drying. In it, the porous network formed by SA aerogel sheets wraps NiTiPt@CNT, and NiTi particles are grown on the surface of the SA aerogel in an embedded manner. And epoxy resin is infiltrated into it, forming a multi-level nested interface including micro, meso, and macro levels, and introducing multiple damping sources such as shape memory alloys, glass transition polymers, and aerogels at multiple scales.

[0048] The infiltrated NiTiPt particles enhance the radial strength of CNTs, introduce the interfaces between CNTs and nano-NiTiPt particles as well as between nano-particles and SA aerogel, increase the specific surface area and surface roughness of CNTs, and enhance the interfacial dissipation capacity in the composite material. At the same time, the NiTiPt alloy on the surface of NiTiPt@CNT is an ordered nano-alloy with a martensitic phase transformation effect. The internal friction energy between nano-scale martensite variants in the alloy introduces a new phase transformation mechanism at the microscale of the composite material, thereby improving the damping performance of the material. The damping performance of the sample with the same concentration of NiTiPt@CNT added is improved by 131% compared to the sample with unmodified CNTs added.

[0049] Among the CNT-modified NiTiPt nano-alloy particles, NiTi micron particles, and the porous CuAlMn alloy skeleton with millimeter-sized pores, all three are martensitic phase transformation alloys. The martensite variant friction existing in the internal microstructure of the alloys and the martensitic effect of the alloys introduce a brand-new damping mechanism into the composite material.

[0050] The present invention uses a porous CuAlMn alloy as the skeleton, and the composite material formed by the epoxy interpenetration with infiltrated NiTiPt@CNT + NiTi + SA aerogel makes up for the strength defect of the polymer while ensuring the lightweight of the material.

[0051] In some embodiments, as Figure 1 shown, the preparation method of the multi-scale shape memory alloy / aerogel / polymer damping composite material of the present invention includes the following steps:

[0052] (1) Provide a porous CuAlMn shape memory alloy skeleton.

[0053] In some embodiments, the pore diameter of the porous CuAlMn shape memory alloy skeleton is 1 - 1.6 mm, and the porosity is 70 - 90%;

[0054] An existing porous CuAlMn shape memory alloy skeleton can be used, or a porous CuAlMn shape memory alloy skeleton can be prepared by known methods. For example, a porous CuAlMn shape memory alloy skeleton is prepared by a sintering evaporation process. In some embodiments, the specific steps are as follows:

[0055] 1.1) High-temperature melt the CuAlMn alloy to obtain a CuAlMn alloy melt, and atomize the alloy melt by using high-purity Ar gas to obtain CuAlMn alloy powder, and screen out the powder particles with a particle size less than 60 μm;

[0056] 1.2) Mix NaCl particles with a size of 1 - 1.5 mm thoroughly with CuAlMn alloy powder, and perform vacuum high-temperature sintering at 750 °C through a hot press, with the pressure controlled at 30 - 35 MPa to obtain a composite initial hot-pressed blank of the mixed powder;

[0057] 1.3) Unload the pressure of the hot press, raise the temperature of the initial blank to the vaporization point of NaCl, and completely remove the NaCl particles to obtain a porous skeleton of CuAlMn alloy, with the mass percentages of Cu, Al, and Mn being 85.6 wt%: 11.9 wt%: 2.5 wt%, the porosity of the porous alloy skeleton being 80%, and the pore diameter being 1.5 mm.

[0058] (2) Load NiTiPt nanoalloy particles on the surface of carbon nanotubes (CNT) to obtain NiTiPt@CNT.

[0059] The present invention prepares NiTiPt@CNT by the solution impregnation method. In some embodiments, the specific steps are as follows:

[0060] 2.1) Prepare a mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinate, and hydrochloric acid to obtain a hydrochloric acid-acidified metal salt solution. Then mix the hydrochloric acid-acidified metal salt solution with carbon nanotubes (CNT), and after ultrasonic stirring and drying, obtain a uniform mixture of Ni, Ti, Pt metal salts / CNT.

[0061] In some embodiments, the total metal particle concentration in the hydrochloric acid-acidified metal salt solution is 0.03 - 0.05 M, preferably 0.04 M, the molar ratio of nickel nitrate, titanium sulfate, and potassium chloroplatinate is (1.5 - 2.5): (0.8 - 1.2): 1, preferably 2: 1: 1, and the hydrochloric acid concentration is 0.008 - 0.012 M, preferably 0.01 M. The hydrochloric acid therein improves the oxidation ability and increases the activation sites of CNT.

[0062] In some embodiments, the CNT concentration is 3 - 6 mg / mL, preferably 5 mg / mL.

[0063] 2.2) Place the uniform mixture of Ni, Ti, Pt metal salts / CNT in a reducing atmosphere (such as H2 / Ar atmosphere, with the hydrogen-argon volume ratio preferably 1:9), keep it at 250 - 300 °C (preferably 300 °C) for a certain period of time (preferably keep it for 1 - 2 hours), then wash with water and dry. Then keep the powder in a reducing atmosphere (such as H2 / Ar atmosphere) at 850 - 950 °C (preferably 900 °C) for a certain period of time (preferably keep it for 2 - 3 hours), and then perform quenching to obtain NiTiPt@CNT.

[0064] The heat preservation at 250 - 300 °C is for the nucleation to generate the metal precursor on the CNT, and the heat preservation at 850 - 950 °C is for the precursor to grow into nanoparticles and enhance the order degree of the nanoparticles, which can enhance the stability of the particles. Compared with the method of reducing by NaBH4, this method has fewer steps, lower cost, higher yield, and the solution impregnation method can make the nanoparticles on the CNT distribute more uniformly.

[0065] In the present invention, the size of the NiTiPt particles loaded on the surface of NiTiPt@CNT is 5 - 10 nm, and the atomic percentages of Ni, Ti, and Pt are 20% - 20.7%, 11.9% - 12.2%, and 67.1 - 68.1%.

[0066] (3) Prepare NiTi spherical particles.

[0067] The NiTi spherical particles can be prepared by the melt injection method. In some embodiments, the NiTi alloy is melted to obtain a NiTi alloy melt, and then the alloy melt is atomized to obtain NiTi alloy powder. The powder particles with an average particle size of 6.5 μm are screened out and aged and heat-preserved at 450 °C for 30 minutes and then quenched. The atomic ratio (atomic number ratio) of Ni to Ti in the NiTi alloy is preferably (50 - 55):(45 - 50).

[0068] (4) Mix NiTiPt@CNT, NiTi spherical particles with sodium alginate (SA) solution to obtain a mixed solution, and then place the porous CuAlMn memory alloy skeleton in the mixed solution and freeze-dry (preferably freeze-dry at -60 °C for 24 h) to generate NiTiPt@CNT + NiTi + SA aerogel in the pores of the CuAlMn alloy, and obtain the porous CuAlMn / (NiTiPt@CNT + NiTi + SA aerogel) material.

[0069] Preferably, the concentration of NiTiPt@CNT in the mixed solution is 0.5 - 1 wt%, the concentration of NiTi spherical particles is 0.025 - 0.05 g / mL, and the concentration of sodium alginate is 0.03 - 0.05 g / mL.

[0070] (5) Add the obtained porous CuAlMn / (NiTiPt@CNT + NiTi + SA aerogel) material into the resin solution, and infiltrate the polymer into the voids of the material through vacuum infiltration to obtain the skeleton-aerogel-polymer. Then cure it to obtain the porous CuAlMn / (NiTiPt@CNT + NiTi + SA aerogel) / polymer composite material.

[0071] The resin solution, such as an epoxy resin solution, may adopt a known formula, for example, E51 type epoxy resin: curing agent MeTHPa: diluent 669: epoxy accelerator DMP-30 = 100:85:30:3 (mass ratio).

[0072] In some embodiments, curing is performed in a vacuum drying oven. The curing process is to first keep the temperature at 55-65°C for 4-6 hours, then keep the temperature at 120-140°C for 5-7 hours, and then keep the temperature at 200-240°C for 1-3 hours, preferably 60°C for 5 hours + 130°C for 6 hours + 200-240°C for 2 hours.

[0073] In the preparation method of the present invention, compared with directly infiltrating epoxy mixed with CNTs into a porous alloy skeleton, CNT / SA aerogel is first generated and embedded in a porous CuAlMn alloy skeleton, and then pure epoxy resin is infiltrated. This can reduce the amount of CNTs used, enhance the fluidity and penetration ability of epoxy, simplify the preparation process, reduce equipment requirements, and has a low cost, and has excellent industrial prospects.

[0074] Compared with patent application 202410047423.2, the advantage of the present invention lies in its outstanding peak damping. The best sample can achieve a peak loss factor close to 0.8, which is significantly higher than 202410047423.2. At the same time, it can reach a loss factor of 0.4 within a certain temperature range, ensuring that the composite material has richer application scenarios.

[0075] Example 1

[0076] The preparation method of the multi-scale memory alloy / aerogel / polymer damping composite material of this embodiment includes the following steps:

[0077] (1) preparing a porous CuAlMn alloy skeleton;

[0078] 1.1) melting a Cu-11.9Al-2.5Mn alloy at a high temperature to obtain an alloy melt; atomizing the melt by atomizing high-purity Ar gas to obtain a CuAlMn alloy powder, and screening out powder particles with a particle size of less than 60 μm;

[0079] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0080] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0081] (2) Preparation of NiTiPt@CNT by solution impregnation method;

[0082] 2.1) Prepare 50 ml of a mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinite (ratio 2:1:1) and hydrochloric acid, with a total metal particle concentration of 0.04 M and a hydrochloric acid concentration of 0.01 M. Add 250 mg of CNT to the mixed solution, and obtain a uniform mixture of Ni, Ti, Pt metal salts / CNTs through ultrasonic stirring and vacuum drying.

[0083] 2.2) The uniform mixture of Ni, Ti, Pt metal salts / CNTs in step 2.1) was placed in a H2 / Ar atmosphere at 300°C for 1 hour, taken out and repeatedly rinsed with deionized water and dried again, and then the powder was kept at 900°C for 2 hours, and then quenched with liquid nitrogen to obtain NiTiPt@CNT.

[0084] (3) preparing NiTi ball micron particles;

[0085] A NiTi alloy with an atomic ratio of Ni:53.7 and Ti:46.3 is melted at high temperature to obtain a NiTi alloy melt; the alloy melt is atomized by a high-purity Ar gas through an atomization method to obtain a NiTi alloy powder, and powder particles with an average particle size of 6.5 μm are screened out, and the powder is aged at 450°C for 30 minutes and quenched.

[0086] (4) 0.5wt% NiTiPt@CNT, 0.025g / ml NiTi spherical particles and 0.03g / ml SA solution were fully mixed, and the porous CuAlMn skeleton cuboid was put into the solution. NiTiPt@CNT+NiTi+SA aerogel was generated in the pores of CuAlMn alloy by freeze drying at -60℃ for 24h;

[0087] (5) Add the porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material obtained in step (4) into the prepared epoxy solution. The epoxy solution is prepared as follows: E51:MeTHPa:669:DMP-30 = 100:85:30:3. The polymer is infiltrated into the voids in the framework-aerogel by vacuum infiltration. Subsequently, through a curing process of 60°C for 5 h + 130°C for 6 h + 240°C for 2 h, a porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) / polymer composite material is obtained.

[0088] After testing, the loss factor of the composite material at room temperature (25 degrees Celsius, the same below) reaches 0.052, the storage modulus is 3675 MPa, the compressive strength at room temperature is 75.3 MPa, and the density is 2.26 g / cm 3 . In the temperature range of 100 - 150 degrees Celsius, the loss factor of the material is greater than 0.41, its peak loss factor is 0.7921, and the storage modulus is higher than 1521 MPa.

[0089] Figure 2 It is the appearance diagram of the multi-scale shape memory alloy / aerogel / polymer damping composite material in Example 1, indicating that the overall surface of the sample is flat and smooth, without macroscopic defects and bubbles.

[0090] Figure 3 It is the TEM photo and EDS result of NiTiPt@CNT in Example 1, indicating that NiTiPt particles are successfully loaded on the surface of CNT, and the average diameter is 5 nm.

[0091] Figure 4 It is the tissue morphology of the porous CuAlMn framework before and after infiltrating the polymer in Example 1, indicating that the aerogel has a layered structure with a thickness of 2 μm, and NiTi spherical particles are embedded on the surface. After infiltrating epoxy, the epoxy is tightly combined with the aerogel and the CuAlMn framework, without peeling and defects.

[0092] Example 2

[0093] The preparation method of the multi-scale shape memory alloy / aerogel / polymer damping composite material in this example specifically includes the following steps:

[0094] (1) Prepare a porous CuAlMn alloy framework;

[0095] 1.1) Melt the Cu-11.9Al-2.5Mn alloy at high temperature to obtain an alloy melt; and atomize the melt by passing high-purity Ar gas to obtain CuAlMn alloy powder, and screen out powder particles with a particle size less than 60 μm;

[0096] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0097] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0098] (2) Preparation of NiTiPt@CNT by solution impregnation method;

[0099] 2.1) Prepare 50 ml of a mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinite (ratio 2:1:1) and hydrochloric acid, with a total metal particle concentration of 0.04 M and a hydrochloric acid concentration of 0.01 M. Add 250 mg of CNT to the mixed solution, and obtain a uniform mixture of Ni, Ti, Pt metal salts / CNTs through ultrasonic stirring and vacuum drying.

[0100] 2.2) The uniform mixture of Ni, Ti, Pt metal salts / CNTs in step 2.1) was placed in a H2 / Ar atmosphere at 300°C for 1 hour, taken out and repeatedly rinsed with deionized water and dried again, and then the powder was kept at 900°C for 2 hours, and then quenched with liquid nitrogen to obtain NiTiPt@CNT.

[0101] (3) preparing NiTi ball micron particles;

[0102] A NiTi alloy with an atomic ratio of Ni:53.7 and Ti:46.3 is melted at high temperature to obtain a NiTi alloy melt; the alloy melt is atomized by a high-purity Ar gas through an atomization method to obtain a NiTi alloy powder, and powder particles with an average particle size of 6.5 μm are screened out, and the powder is aged at 450°C for 30 minutes and quenched.

[0103] (4) 1.0wt% NiTiPt@CNT, 0.025g / ml NiTi spherical particles and 0.03g / ml SA solution were fully mixed, and the porous CuAlMn skeleton cuboid was put into the solution. NiTiPt@CNT+NiTi+SA aerogel was generated in the pores of CuAlMn alloy by freeze drying at -60℃ for 24h;

[0104] (5) The porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material obtained in step (4) was added to the prepared epoxy solution, the epoxy solution was prepared in the following manner: E51:MeTHPa:669:DMP-30=100:85:30:3, and the polymer was infiltrated into the voids in the skeleton-aerogel by vacuum infiltration. Subsequently, a porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) / polymer composite material was obtained by a curing process at 60°C for 5h+130°C for 6h+240°C for 2h.

[0105] After testing, the composite material has a room temperature (25 degrees Celsius, the same below) loss factor of 0.048, a storage modulus of 3841 MPa, a room temperature compressive strength of 54.4 MPa, and a density of 2.32 g / cm 3 In the temperature range of 100-150 degrees Celsius, the material loss factor is greater than 0.39, its peak loss factor is 0.7715, and the storage modulus is higher than 1610MPa.

[0106] Example 3

[0107] The preparation method of the multi-scale memory alloy / aerogel / polymer damping composite material of this embodiment includes the following steps:

[0108] (1) preparing a porous CuAlMn alloy skeleton;

[0109] 1.1) melting a Cu-11.9Al-2.5Mn alloy at a high temperature to obtain an alloy melt; atomizing the melt by atomizing high-purity Ar gas to obtain a CuAlMn alloy powder, and screening out powder particles with a particle size of less than 60 μm;

[0110] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0111] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0112] (2) Preparation of NiTiPt@CNT by solution impregnation method;

[0113] 2.1) Prepare 50 ml of a mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinite (ratio 2:1:1) and hydrochloric acid, with a total metal particle concentration of 0.04 M and a hydrochloric acid concentration of 0.01 M. Add 250 mg of CNT to the mixed solution, and obtain a uniform mixture of Ni, Ti, Pt metal salts / CNTs through ultrasonic stirring and vacuum drying.

[0114] 2.2) The uniform mixture of Ni, Ti, Pt metal salts / CNTs in step 2.1) was placed in a H2 / Ar atmosphere at 300°C for 1 hour, taken out and repeatedly rinsed with deionized water and dried again, and then the powder was kept at 900°C for 2 hours, and then quenched with liquid nitrogen to obtain NiTiPt@CNT.

[0115] (3) preparing NiTi ball micron particles;

[0116] A NiTi alloy with an atomic ratio of Ni:53.7 and Ti:46.3 is melted at high temperature to obtain a NiTi alloy melt; the alloy melt is atomized by a high-purity Ar gas through an atomization method to obtain a NiTi alloy powder, and powder particles with an average particle size of 6.5 μm are screened out, and the powder is aged at 450°C for 30 minutes and quenched.

[0117] (4) 0.5wt% NiTiPt@CNT, 0.05g / ml NiTi spherical particles and 0.03g / ml SA solution were fully mixed, and the porous CuAlMn skeleton cuboid was put into the solution. NiTiPt@CNT+NiTi+SA aerogel was generated in the pores of CuAlMn alloy by freeze drying at -60℃ for 24h;

[0118] (5) The porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material obtained in step (4) was added to the prepared epoxy solution, the epoxy solution was prepared in the following manner: E51:MeTHPa:669:DMP-30=100:85:30:3, and the polymer was infiltrated into the voids in the skeleton-aerogel by vacuum infiltration. Subsequently, a porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) / polymer composite material was obtained by a curing process at 60°C for 5h+130°C for 6h+240°C for 2h.

[0119] After testing, the composite material has a room temperature (25 degrees Celsius, the same below) loss factor of 0.045, a storage modulus of 3841 MPa, a room temperature compressive strength of 77.3 MPa, and a density of 2.47 g / cm 3The material loss factor is greater than 0.29 in the temperature range of 100-150 degrees Celsius, its peak loss factor is 0.5514, and the storage modulus is higher than 1874MPa.

[0120] Example 4

[0121] The preparation method of the multi-scale memory alloy / aerogel / polymer damping composite material of this embodiment includes the following steps:

[0122] (1) preparing a porous CuAlMn alloy skeleton;

[0123] 1.1) melting a Cu-11.9Al-2.5Mn alloy at a high temperature to obtain an alloy melt; atomizing the melt by atomizing high-purity Ar gas to obtain a CuAlMn alloy powder, and screening out powder particles with a particle size of less than 60 μm;

[0124] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0125] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0126] (2) Preparation of NiTiPt@CNT by solution impregnation method;

[0127] 2.1) Prepare 50 ml of a mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinite (ratio 2:1:1) and hydrochloric acid, with a total metal particle concentration of 0.04 M and a hydrochloric acid concentration of 0.01 M. Add 250 mg of CNT to the mixed solution, and obtain a uniform mixture of Ni, Ti, Pt metal salts / CNTs through ultrasonic stirring and vacuum drying.

[0128] 2.2) The uniform mixture of Ni, Ti, Pt metal salts / CNTs in step 2.1) was placed in a H2 / Ar atmosphere at 300°C for 1 hour, taken out and repeatedly rinsed with deionized water and dried again, and then the powder was kept at 900°C for 2 hours, and then quenched with liquid nitrogen to obtain NiTiPt@CNT.

[0129] (3) preparing NiTi ball micron particles;

[0130] The NiTi alloy with an atomic ratio of Ni: 53.7; Ti: 46.3 is melted at high temperature to obtain a NiTi alloy melt; and the alloy melt is atomized by high-purity Ar gas through an atomization method to obtain NiTi alloy powder, and powder particles with an average particle size of 6.5 μm are screened out, and aged and heat-insulated at 450 °C for 30 minutes and then quenched.

[0131] (4) 0.5 wt% of NiTiPt@CNT, 0.025 g / ml of NiTi spherical particles and 0.05 g / ml of SA solution are fully mixed, and the porous CuAlMn framework cuboid is put into the solution. By freeze-drying at -60 °C for 24 h, NiTiPt@CNT+NiTi+SA aerogel is generated in the pores of the CuAlMn alloy;

[0132] (5) The porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material obtained in step (4) is added to the prepared epoxy solution. The epoxy solution is prepared in the following way: E51:MeTHPa:669:DMP-30 = 100:85:30:3, and the polymer is infiltrated into the voids in the framework-aerogel through vacuum infiltration. Subsequently, through a curing process of 60 °C for 5 h + 130 °C for 6 h + 240 °C for 2 h, a porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) / polymer composite material is obtained.

[0133] After testing, the loss factor of the composite material at room temperature (25 degrees Celsius, the same below) reaches 0.061, the storage modulus is 3841 MPa, the compressive strength at room temperature is 58.5 MPa, and the density is 2.15 g / cm 3 . In the temperature range of 100 - 150 degrees Celsius, the loss factor of the material is greater than 0.31, its peak loss factor is 0.5513, and the storage modulus is higher than 1647 MPa.

[0134] Example 5

[0135] The preparation method of the multi-scale memory alloy / aerogel / polymer damping composite material of this example specifically includes the following steps:

[0136] (1) Prepare a porous CuAlMn alloy framework;

[0137] 1.1) The Cu-11.9Al-2.5Mn alloy is melted at high temperature to obtain an alloy melt; and the melt is atomized by high-purity Ar gas through an atomization method to obtain CuAlMn alloy powder, and powder particles with a particle size less than 60 μm are screened out;

[0138] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0139] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0140] (2) Preparation of NiTiPt@CNT by solution impregnation method;

[0141] 2.1) Prepare 50 ml of a mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinite (ratio 2:1:1) and hydrochloric acid, with a total metal particle concentration of 0.04 M and a hydrochloric acid concentration of 0.01 M. Add 250 mg of CNT to the mixed solution, and obtain a uniform mixture of Ni, Ti, Pt metal salts / CNTs through ultrasonic stirring and vacuum drying.

[0142] 2.2) The uniform mixture of Ni, Ti, Pt metal salts / CNTs in step 2.1) was placed in a H2 / Ar atmosphere at 300°C for 1 hour, taken out and repeatedly rinsed with deionized water and dried again, and then the powder was kept at 900°C for 2 hours, and then quenched with liquid nitrogen to obtain NiTiPt@CNT.

[0143] (3) preparing NiTi ball micron particles;

[0144] A NiTi alloy with an atomic ratio of Ni:53.7 and Ti:46.3 is melted at high temperature to obtain a NiTi alloy melt; the alloy melt is atomized by a high-purity Ar gas through an atomization method to obtain a NiTi alloy powder, and powder particles with an average particle size of 6.5 μm are screened out, and the powder is aged at 450°C for 30 minutes and quenched.

[0145] (4) 0.5wt% NiTiPt@CNT, 0.025g / ml NiTi spherical particles and 0.03g / ml SA solution were fully mixed, and the porous CuAlMn skeleton cuboid was put into the solution. NiTiPt@CNT+NiTi+SA aerogel was generated in the pores of CuAlMn alloy by freeze drying at -60℃ for 24h;

[0146] (5) The porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material obtained in step (4) was added to the prepared epoxy solution, wherein the epoxy solution was prepared in the following manner: E51:MeTHPa:669:DMP-30=100:85:30:3, and the polymer was infiltrated into the voids in the skeleton-aerogel by vacuum infiltration. Subsequently, a porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) / polymer composite material was obtained by a curing process of 60°C for 5h+130°C for 6h+200°C for 2h.

[0147] After testing, the composite material has a room temperature (25 degrees Celsius, the same below) loss factor of 0.062, a storage modulus of 3995 MPa, a room temperature compressive strength of 65.4 MPa, and a density of 2.37 g / cm 3 In the temperature range of 100-150 degrees Celsius, the material loss factor is greater than 0.29, its peak loss factor is 0.5203, and the storage modulus is higher than 1518MPa.

[0148] Comparative Example 1

[0149] Compared with Example 1, this comparative example uses CNT to replace NiTiPt@CNT.

[0150] (1) preparing a porous CuAlMn alloy skeleton;

[0151] 1.1) melting a Cu-11.9Al-2.5Mn alloy at a high temperature to obtain an alloy melt; atomizing the melt by atomizing high-purity Ar gas to obtain a CuAlMn alloy powder, and screening out powder particles with a particle size of less than 60 μm;

[0152] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0153] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0154] (2) preparing NiTi ball micron particles;

[0155] The NiTi alloy with an atomic ratio of Ni: 53.7; Ti: 46.3 is melted at high temperature to obtain a NiTi alloy melt; and the alloy melt is atomized by high-purity Ar gas through an atomization method to obtain NiTi alloy powder, and powder particles with an average particle size of 6.5 μm are screened out, and aged and insulated at 450 °C for 30 minutes and then quenched.

[0156] (3) 0.5 wt% of CNT, 0.025 g / ml of NiTi spherical particles and 0.03 g / ml of SA solution are fully mixed, and the porous CuAlMn framework cuboid is put into the solution. By freeze-drying at -60 °C for 24 h, CNT+NiTi+SA aerogel is generated in the pores of the CuAlMn alloy;

[0157] (4) The porous CuAlMn / (CNT+NiTi+SA aerogel) material obtained in step (3) is added to the prepared epoxy solution. The epoxy solution is prepared in the following way: E51:MeTHPa:669:DMP-30 = 100:85:30:3. The polymer is infiltrated into the voids in the framework-aerogel through vacuum infiltration. Subsequently, through a curing process of 60 °C for 5 h + 130 °C for 6 h + 240 °C for 2 h, a porous CuAlMn / (CNT+NiTi+SA aerogel) / polymer composite material is obtained.

[0158] After testing, the loss factor of the composite material at room temperature (25 °C, the same below) is 0.034, the storage modulus is 2784 MPa, and the compressive strength at room temperature is 55.7 MPa. In the temperature range of 100 - 150 °C, the loss factor of the material is greater than 0.18, its peak loss factor is 0.3433, and the storage modulus is higher than 1437 MPa.

[0159] Figure 5 For Comparative Example 1, the microstructures of the porous CuAlMn framework before and after infiltrating the polymer, epoxy and aerogel are tightly combined, without shedding or defects.

[0160] Comparative Example 2

[0161] Compared with Example 1, this comparative example does not add NiTiPt@CNT, NiTi spherical micron particles and aerogel, and is a porous CuAlMn / polymer composite material.

[0162] (1) Prepare a porous CuAlMn alloy framework;

[0163] 1.1) The Cu-11.9Al-2.5Mn alloy is melted at high temperature to obtain an alloy melt; and the melt is atomized by high-purity Ar gas through an atomization method to obtain CuAlMn alloy powder, and powder particles with a particle size less than 60 μm are screened out;

[0164] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0165] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0166] (2) The porous CuAlMn skeleton obtained in step (1) was added to the prepared epoxy solution, wherein the epoxy solution was prepared in the ratio of E51: MeTHPa: 669: DMP-30 = 100: 85: 30: 3, and the polymer was infiltrated into the voids in the skeleton-aerogel by vacuum infiltration. Subsequently, a porous CuAlMn / polymer composite material was obtained by a curing process at 60°C for 5h + 130°C for 6h + 240°C for 2h.

[0167] After testing, the composite material has a room temperature (25 degrees Celsius, the same below) loss factor of 0.029, a storage modulus of 2519MPa, and a room temperature compression strength of 51.9MPa. In the temperature range of 100-150 degrees Celsius, the material loss factor is greater than 0.15, its peak loss factor is 0.2722, and the storage modulus is 1366MPa.

[0168] Comparative Example 3

[0169] Compared with Example 1, this comparative example uses Ni@CNT instead of NiTiPt@CNT.

[0170] (1) preparing a porous CuAlMn alloy skeleton;

[0171] 1.1) melting a Cu-11.9Al-2.5Mn alloy at a high temperature to obtain an alloy melt; atomizing the melt by atomizing high-purity Ar gas to obtain a CuAlMn alloy powder, and screening out powder particles with a particle size of less than 60 μm;

[0172] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0173] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0174] (2) Preparation of Ni@CNT by solution impregnation method;

[0175] 2.1) Prepare 50 ml of a mixed solution of nickel nitrate and hydrochloric acid, with a total metal particle concentration of 0.04 M and a hydrochloric acid concentration of 0.01 M. Add 250 mg of CNT to the mixed solution, and obtain a uniform mixture of Ni, Ti, Pt metal salts / CNTs through ultrasonic stirring and vacuum drying.

[0176] 2.2) The uniform mixture of Ni, Ti, Pt metal salts / CNTs in step 2.1) was placed in a H2 / Ar atmosphere at 300°C for 1 hour, taken out and repeatedly rinsed with deionized water and dried again, and then the powder was kept at 900°C for 2 hours, and then quenched with liquid nitrogen to obtain Ni@CNTs.

[0177] (3) preparing NiTi ball micron particles;

[0178] A NiTi alloy with an atomic ratio of Ni:53.7 and Ti:46.3 is melted at high temperature to obtain a NiTi alloy melt; the alloy melt is atomized by a high-purity Ar gas through an atomization method to obtain a NiTi alloy powder, and powder particles with an average particle size of 6.5 μm are screened out, and the powder is aged at 450°C for 30 minutes and quenched.

[0179] (4) 0.5wt% Ni@CNT, 0.025g / ml NiTi spherical particles and 0.03g / ml SA solution were fully mixed, and the porous CuAlMn skeleton cuboid was put into the solution. Ni@CNT+NiTi+SA aerogel was generated in the pores of CuAlMn alloy by freeze drying at -60℃ for 24h;

[0180] (5) The porous CuAlMn / (Ni@CNT+NiTi+SA aerogel) material obtained in step (4) was added to the prepared epoxy solution, the epoxy solution was prepared in the following manner: E51:MeTHPa:669:DMP-30=100:85:30:3, and the polymer was infiltrated into the voids in the skeleton-aerogel by vacuum infiltration. Subsequently, a porous CuAlMn / (Ni@CNT+NiTi+SA aerogel) / polymer composite material was obtained by a curing process at 60°C for 5h+130°C for 6h+240°C for 2h.

[0181] After testing, the room temperature loss factor of the composite material reached 0.038, the storage modulus was 2873MPa, the compression strength at room temperature was 52.2MPa, and the density was 2.28g / cm 3 In the temperature range of 100-150 degrees Celsius, the material loss factor is greater than 0.25, its peak loss factor is 0.4823, and the storage modulus is higher than 1498MPa.

[0182] Comparative Example 4

[0183] Compared with Example 1, in this comparative example, no aerogel is formed, and NiTiPt@CNT and NiTi ball micron particles are directly mixed into the epoxy solution.

[0184] (1) preparing a porous CuAlMn alloy skeleton;

[0185] 1.1) melting a Cu-11.9Al-2.5Mn alloy at a high temperature to obtain an alloy melt; atomizing the melt by atomizing high-purity Ar gas to obtain a CuAlMn alloy powder, and screening out powder particles with a particle size of less than 60 μm;

[0186] 1.2) NaCl particles with a size of 1 to 1.5 mm were fully mixed with CuAlMn alloy powder at a mass ratio of 0.872:1, and sintered at 750°C in a vacuum press, with the vacuum degree controlled at 10 -3 Pa, the pressure was set to 30-35 MPa, and the temperature was kept for 2.5 h to obtain a composite initial hot pressed embryo of the mixed powder.

[0187] 1.3) Unloading the hot press pressure, and raising the embryo temperature to 950°C, completely removing the NaCl particles by evaporation, and obtaining a porous skeleton of CuAlMn alloy with a diameter of 25 mm, a porosity of 80%, and a pore size of 1.5 mm. The obtained skeleton is cut into a 20*5*3 mm cuboid by a wire cutting machine.

[0188] (2) Preparation of NiTiPt@CNT by solution impregnation method;

[0189] 2.1) Prepare a 50 ml mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinate (in a ratio of 2:1:1), and hydrochloric acid. The total metal particle concentration is 0.04 M, and the hydrochloric acid concentration is 0.01 M. Add 250 mg of CNT to the mixed solution, and after ultrasonic stirring and vacuum drying, a uniform mixture of Ni, Ti, Pt metal salts / CNT is obtained.

[0190] 2.2) Place the uniform mixture of Ni, Ti, Pt metal salts / CNT in step 2.1) in a H2 / Ar atmosphere at 300 °C for 1 h. After taking it out, rinse it repeatedly with deionized water and dry it again. Then, keep the powder at 900 °C for 2 h, and subsequently quench it with liquid nitrogen to obtain NiTiPt@CNT.

[0191] (3) Prepare NiTi spherical micro-particles;

[0192] Melt the NiTi alloy at high temperature with an atomic ratio of Ni: 53.7; Ti: 46.3 to obtain a NiTi alloy melt; and atomize the alloy melt by passing high-purity Ar gas to obtain NiTi alloy powder. Screen out powder particles with an average particle size of 6.5 μm, and age and keep them at 450 °C for 30 minutes and then quench.

[0193] (4) Add 0.5 wt% of NiTiPt@CNT and 0.025 g / ml of NiTi spherical particles to the prepared epoxy solution and mix evenly. The epoxy solution is prepared as follows: E51: MeTHPa: 669: DMP-30 = 100: 85: 30: 3. Put the porous CuAlMn framework cuboid into the solution, and infiltrate the polymer into the voids in the framework-aerogel through vacuum infiltration. Subsequently, through a curing process of 60 °C for 5 h + 130 °C for 6 h + 240 °C for 2 h, a porous CuAlMn / (NiTiPt@CNT + NiTi + polymer) composite material is obtained.

[0194] After testing, the room temperature loss factor of the composite material reaches 0.021, the storage modulus is 2138 MPa, the compressive strength at room temperature is 41.9 MPa, and the density is 2.67 g / cm 3 . In the temperature range of 100 - 150 °C, the loss factor of the material is greater than 0.20, its peak loss factor is 0.3314, and the storage modulus is higher than 1513 MPa.

[0195] Comparative Example 5

[0196] Compared with Example 1, this comparative example does not add NiTi spherical micro-particles.

[0197] (1) Prepare a porous CuAlMn alloy framework;

[0198] 1.1) The Cu-11.9Al-2.5Mn alloy is melted at high temperature to obtain an alloy melt; and the melt is atomized by passing high-purity Ar gas through an atomization method to obtain CuAlMn alloy powder, and powder particles with a particle size less than 60 μm are screened out;

[0199] 1.2) NaCl particles with a size of 1 - 1.5 mm are fully mixed with the CuAlMn alloy powder at a mass ratio of 0.872:1, and vacuum high-temperature sintering is carried out at 750 °C by a hot press. The vacuum degree is controlled below 10-3 Pa, the pressure is set at 30 - 35 MPa, and the temperature is kept for 2.5 h to obtain a composite initial hot-pressed blank of the mixed powder.

[0200] 1.3) The pressure of the hot press is unloaded, and the temperature of the initial blank is raised to 950 °C to completely remove the NaCl particles by evaporation, obtaining a porous skeleton of the CuAlMn alloy with a diameter of 25 mm, a porosity of 80% for the porous alloy skeleton, and a pore diameter of 1.5 mm. The obtained skeleton is cut into a cuboid of 20*5*3 mm by a wire cutting machine.

[0201] (2) NiTiPt@CNT is prepared by the solution impregnation method;

[0202] 2.1) A 50 ml mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinate (in a ratio of 2:1:1) and hydrochloric acid is prepared, with a total metal particle concentration of 0.04 M and a hydrochloric acid concentration of 0.01 M. 250 mg of CNT is added to the mixed solution, and after ultrasonic stirring and vacuum drying, a uniform mixture of Ni, Ti, Pt metal salts / CNT is obtained.

[0203] 2.2) The uniform mixture of Ni, Ti, Pt metal salts / CNT in step 2.1) is placed in a H2 / Ar atmosphere at 300 °C and kept for 1 h. After taking out and repeatedly rinsing with deionized water and drying again, the powder is kept at 900 °C for 2 h, and then quenched with liquid nitrogen to obtain NiTiPt@CNT.

[0204] (3) 0.5 wt% of NiTiPt@CNT is fully mixed with a 0.03 g / ml SA solution, and the porous CuAlMn skeleton cuboid is put into the solution. By freeze-drying at -60 °C for 24 h, a NiTiPt@CNT+SA aerogel is formed in the pores of the CuAlMn alloy;

[0205] (4) The porous CuAlMn / (NiTiPt@CNT + SA aerogel) material obtained in step (3) was added to the prepared epoxy solution. The epoxy solution was prepared in the following ratio: E51:MeTHPa:669:DMP - 30 = 100:85:30:3. The polymer was infiltrated into the voids in the framework - aerogel by vacuum infiltration. Subsequently, through a curing process of 60 °C for 5 h + 130 °C for 6 h + 240 °C for 2 h, a porous CuAlMn / (NiTiPt@CNT + SA aerogel) / polymer composite material was obtained.

[0206] After testing, the loss factor of the composite material at room temperature (25 degrees Celsius, the same below) reached 0.052, the storage modulus was 2517 MPa, the compressive strength at room temperature was 47.7 MPa, and the density was 2.07 g / cm3. In the temperature range of 100 - 150 degrees Celsius, the loss factor of the material was greater than 0.29, its peak loss factor was 0.4618, and the storage modulus was higher than 1450 MPa.

[0207] Compared with Example 1, in Example 2, the content of NiTiPt@CNT was increased. The loss factor of the material decreased slightly, the strength decreased, but the storage modulus increased. This is because after the content of NiTiPt@CNT increased to a certain threshold, CNTs would agglomerate, and the agglomerated spheres changed the contact conditions between NiTiPt@CNT and the SA aerogel, thus reducing the damping performance of the material. Compared with Example 1, in Example 3, the content of NiTi spherical particles increased. The loss factor of the material decreased slightly, but the storage modulus and strength increased. The NiTi spherical particles provided micron - sized interfaces for the material, increasing the strength of the epoxy, thus enhancing the final storage modulus and strength of the material. However, because NiTi has a certain density, increasing the content of NiTi increased the difficulty of dispersing NiTi particles, so the loss factor of the material decreased. Compared with Example 1, in Example 4, the content of SA increased. The strength of the material decreased, the peak loss factor decreased, but the loss factor at room temperature increased. The increase in the content of SA increased the thickness of the SA aerogel, reduced the specific surface area of the SA aerogel, and decreased the infiltration amount of the epoxy, thus reducing the peak damping performance of the material. At the same time, the viscosity of the SA + CNT + NiTi solution also increased, increasing the difficulty of uniform dispersion of the material, so the strength of the material decreased. Compared with Example 1, in Example 5, the highest curing temperature decreased. The strength of the material decreased, the peak damping decreased, but the loss factor and storage modulus at room temperature increased. Changing the curing temperature of the epoxy polymer led to incomplete curing of the epoxy, so the cross - linking density decreased, thus reducing the peak damping of the material. At the same time, the free volume of the epoxy increased, thereby reducing the strength at room temperature and increasing the loss factor at room temperature.

[0208] It can be seen from the comparison between Example 1 and Comparative Example 1 that, compared with pure CNT, the damping performance and strength are significantly improved by using NiTiPt@CNT. It can be seen from the comparison between Example 1 and Comparative Example 2 that, compared with the porous CuAlMn / polymer composite material, the damping performance and strength of the porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) / polymer composite material are significantly improved. It can be seen from the comparison between Example 1 and Comparative Example 3 that, when Ni@CNT is used to replace NiTiPt@CNT, the damping performance and strength decrease. It can be seen from the comparison between Example 1 and Comparative Example 4 that, without forming an aerogel and directly mixing NiTiPt@CNT and NiTi spherical micron particles into the epoxy solution, the damping performance and strength decrease significantly. Compared with Comparative Example 5, when the NiTi spherical micron particles are not embedded on the aerogel, the damping performance and strength of the obtained composite material both decrease.

[0209] The above are only the preferred embodiments of the present invention and do not impose any form of limitation on the present invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention shall fall within the scope of protection of the technical solution of the present invention.

Claims

1. A multi-scale memory alloy / aerogel / polymer damping composite material, characterized in that: It includes: Porous CuAlMn memory alloy skeleton; A NiTiPt@CNT+NiTi+SA aerogel is formed by freeze drying in the pores of a porous CuAlMn memory alloy skeleton; in the NiTiPt@CNT+NiTi+SA aerogel, a porous network composed of SA aerogel sheets wraps NiTiPt@CNT therein, and NiTi ball particles are embedded on the surface of the SA aerogel; wherein NiTiPt@CNT is a carbon nanotube with NiTiPt nano alloy particles loaded on the surface; And the polymer filled in the gap between the porous CuAlMn memory alloy skeleton and the NiTiPt@CNT+NiTi+SA aerogel.

2. The multi-scale memory alloy / aerogel / polymer damping composite material according to claim 1, characterized in that: The NiTiPt nano alloy particles loaded on the surface of the NiTiPt@CNT have a particle size of 5-10 nm, wherein the atomic percentages of Ni, Ti and Pt are 20%-20.7%, 11.9%-12.2% and 67.1-68.1% respectively.

3. A method for preparing the multi-scale memory alloy / aerogel / polymer damping composite material according to claim 1 or 2, characterized in that: The following steps are involved: The NiTiPt@CNT and NiTi ball particles are mixed with a sodium alginate solution to obtain a mixed solution, and then a porous CuAlMn memory alloy skeleton is placed in the mixed solution, and NiTiPt@CNT+NiTi+SA aerogel is generated in the pores of the CuAlMn alloy by freeze drying to obtain a porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material; The porous CuAlMn / (NiTiPt@CNT+NiTi+SA aerogel) material is added to the resin solution, the polymer is infiltrated into the voids of the material by vacuum infiltration, and then cured to obtain the multi-scale memory alloy / aerogel / polymer damping composite material.

4. The preparation method according to claim 3, characterized in that: The preparation method of the NiTiPt@CNT comprises: A mixed solution of nickel nitrate, titanium sulfate, potassium chloroplatinite and hydrochloric acid is prepared to obtain a metal salt solution acidified by hydrochloric acid, the metal salt solution acidified by hydrochloric acid is mixed with carbon nanotubes, and a uniform mixture of Ni, Ti, Pt metal salt / CNT is obtained by ultrasonic stirring and drying; A uniform mixture of Ni, Ti, Pt metal salts / CNTs is placed in a reducing atmosphere and kept at 250-300°C, then washed with water and dried, and the obtained powder is kept at 850-950°C again, and then quenched to obtain NiTiPt@CNTs.

5. The preparation method according to claim 4, characterized in that: The total metal particle concentration in the metal salt solution acidified with hydrochloric acid is 0.03-0.05M, wherein the molar ratio of nickel nitrate, titanium sulfate and potassium chloroplatinite is (1.5-2.5):(0.8-1.2):

1.

6. The preparation method according to claim 4, characterized in that: The concentration of carbon nanotubes in the solution after the metal salt solution acidified with hydrochloric acid is mixed with carbon nanotubes is 3-6 mg / mL.

7. The preparation method according to any one of claims 3 to 6, characterized in that: The atomic ratio of Ni to Ti in the NiTi spherical particles is (50-55): (45-50).

8. The preparation method according to any one of claims 3 to 6, characterized in that: In the mixed solution obtained by mixing the NiTiPt@CNT, NiTi spherical particles and sodium alginate solution, the NiTiPt@CNT concentration is 0.5-1wt%, the NiTi spherical particles concentration is 0.025-0.05g / mL, and the sodium alginate concentration is 0.03-0.05g / mL.

9. The preparation method according to any one of claims 3 to 6, characterized in that: The polymer is an epoxy resin.

10. The preparation method according to claim 9, characterized in that: The curing process is: first keep warm at 55-65°C for 4-6 hours, then keep warm at 120-140°C for 5-7 hours, and then keep warm at 200-240°C for 1-3 hours.

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