Energy-absorbing metal-ceramic composite particle stacking and preparation method thereof

Abstract

The present invention relates to an energy-absorbing metal-ceramic composite particle stack and a preparation method thereof, wherein the composite particle stack comprises superelastic ceramic particles Ce x Zr 1‑x O2 and metal particles M, the composition expression is: y%M@(100‑y)%Ce x Zr 1‑x O2; wherein the particle size of the superelastic ceramic particles is 1-10 μm; the metal particles M are one of Cu, Al, Ti, Ni or an alloy, and have a particle size of 0.5-5 μm; in the composition expression, x is the atomic molar ratio, 0.14≤x≤0.18; y is the mass ratio, 5≤y≤45. The metal-ceramic composite particle stack is composed of superelastic ceramic particles and metal particles that are dispersed in a solvent, dried, and stacked and pre-pressed. The metal-ceramic composite particle stack provided by the present invention has excellent compressive strength, energy dissipation density and cyclic stability, and the preparation process is energy-saving and time-saving, and has broad applications in damping, shock absorption, energy absorption and other fields.

Description

Technical Field

[0001] The present invention relates to the technical field of composite particle stacking and energy dissipation, and specifically to a metal-ceramic composite particle stacking and a preparation method thereof. The stacking has excellent energy dissipation density and cyclic stability, and the preparation process is energy-saving and time-saving, and has broad applications in damping, shock absorption, energy absorption and other fields. Background Art

[0002] Superelastic ceramics are smart materials that undergo a reversible martensitic phase transformation in response to temperature and / or stress. They have broad applications in areas such as shape memory, robotics, and microelectromechanical systems (MEMS). However, these polycrystalline superelastic ceramics are limited by intrinsic grain boundary brittleness and significant phase transformation-induced lattice strain (~5-10%, far exceeding the elastic limit of approximately 1%), which restricts their large-scale applications (Nature 322, 234-236, 1986).

[0003] In the past decade, researchers have improved the macroscopic brittleness of this type of ceramics to a certain extent through miniaturization (Science 341, 1505-1508, 2013), lattice engineering (Nature 610, 491-495, 2022), configuration (Sci. Adv. 4, eaas8925, 2018), and composite (Nat. Commun. 14, 7103, 2023). For example, Yu Hang et al. proposed a strategy for superelastic ceramic particle stacking (Acta Mater. 132, 455-466, 2017; Acta Mater. 168, 362-375, 2019). Combining in-situ neutron diffraction experiments with simulations, they revealed the phase transition mechanism and energy dissipation principle of superelastic ceramic particle stacking, and achieved good cyclic stability and energy dissipation density. This type of superelastic particle stacking not only converts external kinetic energy into internal energy through friction between particles, but also achieves high energy dissipation and reuse through stress-induced reversible phase transitions within the particles. Furthermore, in this type of superelastic ceramic particle stacking, the brittle fracture of the particles further releases strain energy, resulting in an even more superior superelastic effect.

[0004] However, the aforementioned superelastic ceramic particle stacking also has problems such as insufficient stress transmission, a threshold value for phase transition variables, and low energy dissipation density. In view of this, the present invention is proposed. Summary of the Invention

[0005] In response to the "size-brittleness" contradiction of superelastic ceramics and the problems of low phase change threshold and energy dissipation density in the stacking of superelastic ceramic particles, the first purpose of the present invention is to provide an energy-absorbing metal-ceramic composite particle stacking that can induce a higher level of reversible phase change of superelastic ceramics, with high compressive strength, energy dissipation density and good cyclic stability.

[0006] The second purpose of the present invention is to provide a preparation method for energy-absorbing metal-ceramic composite particle stacking. This method, while ensuring the integrity of the three-dimensional network force chain and the monomer performance of the superelastic ceramic, fills the three-dimensional network pores of the ceramic with metal to fully transfer stress and deformation, and has the advantages of energy-saving and time-saving preparation process and high output.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] The present invention provides an energy-absorbing metal-ceramic composite particle stacking, wherein the composite particle stacking includes superelastic ceramic particles Ce x Zr 1-x O2 and metal particles M, the composition expression is: y%M@(100-y)%Ce x Zr 1-x O2;

[0009] The superelastic ceramic has a particle size of 1-10 μm and serves as a structural framework and energy dissipation device.

[0010] The metal particles M are at least one of Cu, Al, Ti, Ni metal powder or alloy powder thereof, with a particle size of 0.5-5 μm, in the form of discontinuous particles, and have the functions of being deformable and filling pores;

[0011] In the composition expression, x is the atomic molar ratio, 0.14≤x≤0.18; y is the mass ratio, 5≤y≤45, that is, the mass content of the metal particles M is 5-45%.

[0012] As a preferred solution, in the composition expression, 5≤y≤25, that is, the mass content of the metal particles M is 5-25%.

[0013] As a preferred solution, the superelastic ceramic particles Ce x Zr 1-x The particle size ratio of O2 to the metal particles M is 2-5:1.

[0014] As a preferred solution, the metal particles M are at least one of Cu, Ti, Ni metal powder or alloy powder thereof; when the metal particles M are Cu, Ti, or Ni, the improvement of the energy dissipation density may be more obvious.

[0015] As a preferred solution, the compressive strength of the composite particle stack is above 0.6 GPa, more preferably above 0.8 GPa.

[0016] As a preferred solution, after 50 cycles of the composite particles stacking, the energy dissipation density is 1.8 J / cm 3 More than 2.5 J / cm 3 above.

[0017] As a preferred solution, when the metal particles M are Cu, in the composition expression, 5≤y≤25, the superelastic ceramic particles Ce x Zr 1-x When the particle size ratio of O2 to metal particles M is 2-5:1, the energy dissipation density of the prepared metal-ceramic composite particles can reach 2.5 J / cm after 50 cycles. 3 above;

[0018] When the metal particles M are Al, in the composition expression, 5≤y≤15, the superelastic ceramic particles Ce x Zr 1-x When the particle size ratio of O2 to metal particles M is 2-5:1, the energy dissipation density of the prepared metal-ceramic composite particles can reach 2.6 J / cm after 50 cycles. 3 above;

[0019] When the metal particles M are Ni, in the composition expression, 5≤y≤20, the superelastic ceramic particles Ce x Zr 1-x When the particle size ratio of O2 to metal particles M is 2-5:1, the energy dissipation density of the prepared metal-ceramic composite particles can reach 3.1 J / cm after 50 cycles. 3 The present invention also provides a method for preparing a stack of energy-absorbing metal-ceramic composite particles, comprising the following steps:

[0020] A1. Solvent dispersion: weigh superelastic ceramic particles Ce x Zr 1-x O2 and metal particles M are added to a sufficient amount of solvent and mixed thoroughly for 6-18 hours;

[0021] A2. Drying: Place the mixed slurry obtained in step A1 in a ventilated environment at 50-100° C. and dry for 6-12 hours to obtain metal-ceramic composite particles;

[0022] A3. Stacking pre-pressing: The metal-ceramic composite particles are placed in a mold and pre-pressed at 100-200 MPa to obtain a stack of metal-ceramic composite particles.

[0023] As a preferred embodiment, in step A1, the solvent is one of ethanol, propanol, isopropanol, acetone, butanone, or a mixture of several of them.

[0024] As a preferred solution, in step A1, the rotation speed used during the mixing does not exceed 150 rpm.

[0025] As a preferred solution, in step A1, a ball mill or a powder mixer is used for mixing.

[0026] In the energy-absorbing metal-ceramic composite particle stacking described in the present invention, the superelastic ceramic assumes the main structural skeleton and energy dissipation functions; by regulating a reasonable metal content, the pores can be effectively filled in the structural skeleton of the superelastic ceramic, and synergistically deformed during the loading process to achieve additional energy dissipation. It should be noted that too high a metal content can easily destroy the Hertzian contact between the superelastic ceramic particles, resulting in a reduction in the amount of phase transition. When the particle size of the superelastic ceramic is too small, it is easy to cause the critical stress of the phase transition to be too large, which is not conducive to phase transition; when the particle size is too large, the superelastic ceramic mainly exists in the form of polycrystalline, resulting in a specific surface area that is too small, which is not conducive to sufficient contact with the metal.

[0027] In the preparation method of the energy-absorbing metal-ceramic composite particle stack, by further regulating the particle size ratio of the superelastic ceramic to the metal, the superelastic ceramic can be effectively prevented from being wrapped by the metal particles, ensuring direct and effective contact between the ceramic particles to form a connected three-dimensional skeleton; further selecting solvent dispersion and low ball milling speed can eliminate the influence of mechanical stress on the superelastic ceramic to the greatest extent, while avoiding the breakage of the superelastic ceramic during the ball milling process.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The preparation method adopted by the present invention ensures the structural integrity of the three-dimensional ceramic network stacking and the reversible phase change ability of the ceramic monomer, and realizes the uniform filling of metal particles in the gaps of the ceramic stacking. It can fully transfer stress through the metal gap filling, which is conducive to fully inducing the reversible phase change of the superelastic ceramic.

[0030] 2. The composite particle stacking prepared by the present invention can induce a higher level of reversible phase transition of superelastic ceramics, with high compressive strength, high energy dissipation density and good cyclic stability.

[0031] 3. The preparation method adopted by the present invention alleviates the bottleneck problem of the phase transition variable threshold of superelastic ceramics. It has a wide range of applications, saves energy and time, and has a reliable and efficient process, which is conducive to the realization of large-scale preparation and large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Other features, objects and advantages of the present invention will become more apparent upon reading the detailed description of non-limiting embodiments with reference to the following drawings:

[0033] Figure 1 1. A physical diagram (left) and a structural diagram (right) of a sleeve die for stacking pre-pressing according to an embodiment of the present invention;

[0034] Figure 2 This is a scanning electron microscope image of the energy-absorbing metal ceramic composite particle stacking prepared according to Example 1 of the present invention. The nominal composition of the composite particle stacking is 5% Cu@95% Ce 0.16 Zr 0.84 O2;

[0035] Figure 3 This is an X-ray diffraction pattern of the energy-absorbing metal-ceramic composite particle stacking prepared according to Example 1 of the present invention. The horizontal axis is the 2θ angle and the vertical axis is the diffraction intensity. The nominal composition of the composite particle stacking is 5% Cu@95% Ce. 0.16 Zr 0.84 O2;

[0036] Figure 4 This is the X-ray diffraction pattern of the energy-absorbing metal ceramic composite particle stack prepared according to Example 1 of the present invention after 50 cycles of loading. The horizontal axis is the 2θ angle and the vertical axis is the diffraction intensity. The nominal composition of the composite particle stack is 5% Cu@95% Ce 0.16 Zr 0.84 O2;

[0037] Figure 5 The force versus displacement diagram of the energy-absorbing metal ceramic composite particle stack prepared according to Example 1 of the present invention is shown in FIG. 1 , where the horizontal axis is the uniaxial force applied to the mold and the vertical axis is the corrected particle stack displacement. The nominal composition of the composite particle stack is 5% Cu@95% Ce. 0.16 Zr 0.84 O2;

[0038] Figure 6 The graph shows the relationship between the energy dissipation density of the energy-absorbing metal ceramic composite particle stack prepared according to Example 1 of the present invention and the number of cycles. The horizontal axis is the number of cycles and the vertical axis is the energy dissipation density. The nominal composition of the composite particle stack is 5% Cu@95% Ce. 0.16 Zr 0.84 O2, compared with the particle accumulation Ce in Comparative Example 1 0.16 Zr 0.84 O2 contrasts. DETAILED DESCRIPTION

[0039] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those skilled in the art, several variations and improvements can be made without departing from the scope of the present invention. These all fall within the scope of protection of the present invention.

[0040] The metal matrix powders used in the following examples are all commercially available with a purity higher than 99.9% (mass percentage). 0.135 Zr 0.865 O2, Ce 0.14 Zr 0.86 O2, Ce 0.16 Zr 0.84 O2, Ce 0.18 Zr 0.82 O2) are prepared by the conventional method described in the US20190039959A1 patent: according to the ratio of elements in the superelastic ceramic particles, zirconium oxide and oxide nanoparticles doped with the element Ce are weighed accordingly, uniformly dispersed, and then gel-injected and sintered. Finally, the superelastic ceramic particles of the required particle size are screened.

[0041] The compressive stress and energy dissipation performance of the energy-absorbing metal-ceramic composite particle stacks in all embodiments and comparative examples were tested using the test method in GB / T 11106-2022. The specific test method for energy dissipation density is as follows: a "load-unload-reload" cyclic loading experiment is performed at a set stress amplitude to obtain the original force-displacement curve; after deducting the background correction curve, the energy dissipation density of each cycle is extracted based on the integrated area of ​​the curve. In all embodiments, the austenite content of the composite particle stacks in the prepared state and after loading is higher than 85% (mass percentage).

[0042] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0043] Example 1

[0044] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (5% Cu@95% Ce 0.16 Zr 0.84 O2), the specific steps of its preparation are as follows:

[0045] 1) Solvent dispersion: weigh 9.5 g Ce 0.16 Zr 0.84O2 superelastic ceramic particles (particle size of 2 μm) and 0.5 g of pure copper particles (particle size of 1 μm) were added to 50 ml of ethanol and thoroughly mixed using a ball mill at 150 rpm for 12 hours.

[0046] 2) Drying: The mixed slurry obtained in step 1) is placed in a ventilated environment at 50° C. and dried for 8 hours to obtain metal-ceramic composite particles.

[0047] 3) Stacking pre-pressing: The metal-ceramic composite particles are Figure 1 The sleeve mold shown is preloaded with 200MPa for pre-compression to obtain a metal-ceramic composite particle accumulation. The sleeve mold is homemade and the material used is commercially available C300 alloy steel. It is pre-wired and then subjected to solution treatment at 830°C for 1 hour, quenching, and aging at 480°C for 12 hours to obtain the final sleeve mold. The sleeve mold includes a push rod, a pad 1, a sleeve, a pad 2 and a base arranged in sequence from top to bottom; the sleeve is a hollow structure, and the lower end of the push rod and the pad can be sleeved on the hollow part of the sleeve (the dimensions of each component are well matched, see the specific dimensions for details). Figure 1 During pre-pressing, the metal-ceramic composite particles are loaded into the hollow part of the hollow cylindrical sleeve. Pads 1 and 2 act as a seal for the particles. Then, an external pressure device applies pressure to the upper end of the circular push rod, transferring the load through the pads and pressing the particles downward into the hollow part of the hollow cylindrical sleeve, thereby achieving pre-pressing of the metal-ceramic composite particles.

[0048] 4) Material characterization: Scanning electron microscopy (SEM) was used to characterize the metal-ceramic composite particles with a 5% Cu@95% Ce 0.16 Zr 0.84 O2, such as Figure 2 As shown, fine metal Cu powder is dispersed in the superelastic ceramic Ce 0.16 Zr 0.84 O2 pores. X-ray diffraction (XRD) calibration of the phase composition of the prepared composite particles, such as Figure 3 As shown, the austenite content is 97%. Further, the composite particles are piled in a sleeve mold and a cyclic loading experiment is carried out with a stress amplitude of 1GPa. The phase measurement of the composite particles after 50 cycles of loading is carried out, and the austenite content is 86%, as shown in FIG. Figure 4 The corrected force and displacement curves are shown in Figure 5 As shown in the figure, the relationship between energy dissipation density and cycle number is as follows: Figure 6 As shown. After the 10th cycle, the energy dissipation density is basically stable. After 50 cycles, the energy dissipation density is ~3.6J / cm 3 Finally, the metal-ceramic composite particles (5% Cu@95% Ce 0.16 Zr0.84 The composition and properties of O2 are listed in Table 1.

[0049] Example 2

[0050] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (25% Cu@75% Ce 0.16 Zr 0.84 The specific preparation steps are basically the same as those in Example 1, except that:

[0051] In step 1) of this embodiment, 7.5 g of Ce was weighed. 0.16 Zr 0.84 O2 superelastic ceramic particles (particle size 2μm) and 2.5g pure copper particles (particle size 1μm). The energy dissipation density of the 50th cycle is ~3.0J / cm 3 Finally, the metal-ceramic composite particles (25% Cu@75% Ce 0.16 Zr 0.84 The composition and properties of O2 are listed in Table 1.

[0052] Example 3

[0053] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (15% Cu@85% Ce 0.14 Zr 0.86 The specific preparation steps are basically the same as those in Example 1, except that:

[0054] In step 1) of this embodiment, 8.5 g of Ce was weighed. 0.14 Zr 0.86 O2 superelastic ceramic particles (particle size 10μm) and 1.5g pure copper particles (particle size 5μm). The energy dissipation density of the 50th cycle is ~2.5J / cm 3 Finally, the metal-ceramic composite particles (15% Cu@85% Ce 0.14 Zr 0.86 The composition and properties of O2 are listed in Table 1.

[0055] Example 4

[0056] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (45% Cu@55% Ce 0.18 Zr 0.82 The specific preparation steps are basically the same as those in Example 1, except that:

[0057] In step 1) of this embodiment, 5.5 g of Ce was weighed. 0.18 Zr 0.82O2 superelastic ceramic particles (particle size 7μm) and 4.5g pure copper particles (particle size 2μm). The energy dissipation density of the 50th cycle is ~2.4J / cm 3 Finally, the metal-ceramic composite particles (45% Cu@55% Ce 0.18 Zr 0.82 The composition and properties of O2 are listed in Table 1.

[0058] Example 5

[0059] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (5% Al@95% Ce 0.14 Zr 0.86 O2), the specific steps of its preparation are as follows:

[0060] 1) Solvent dispersion: weigh 9.5 g Ce 0.14 Zr 0.86 O2 superelastic ceramic particles (particle size of 5 μm) and 0.5 g of pure aluminum particles (particle size of 1 μm) were added to 75 ml of propanol and thoroughly mixed using a ball mill at 100 rpm for 8 hours.

[0061] 2) Drying: The mixed slurry obtained in step 1) is placed in a ventilated environment at 80° C. and dried for 12 hours to obtain metal-ceramic composite particles.

[0062] 3) Stacking pre-pressing: The metal-ceramic composite particles are Figure 1 The sleeve mold shown is preloaded with 100 MPa for pre-compression to obtain a metal-ceramic composite particle stack.

[0063] 4) Material Characterization: The composite particles were stacked in a sleeve mold and subjected to cyclic loading at a stress amplitude of 1 GPa. After the 10th cycle, the energy dissipation density was essentially stable. The energy dissipation density at the 50th cycle was ~2.8 J / cm 3 Finally, the metal-ceramic composite particles (5% Al@95% Ce 0.14 Zr 0.86 The composition and properties of O2 are listed in Table 1.

[0064] Example 6

[0065] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (15% Al@85% Ce 0.16 Zr 0.84 The specific preparation steps are basically the same as those in Example 5, except that:

[0066] In step 1) of this embodiment, 8.5 g of Ce was weighed. 0.16 Zr 0.84O2 superelastic ceramic particles (particle size 2μm) and 1.5g pure aluminum particles (particle size 1μm). The energy dissipation density of the 50th cycle is ~2.6J / cm 3 Finally, the metal-ceramic composite particles (15% Al@85% Ce 0.16 Zr 0.84 The composition and properties of O2 are listed in Table 1.

[0067] Example 7

[0068] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (5% Al@95% Ce 0.14 Zr 0.86 The specific preparation steps are basically the same as those in Example 5, except that:

[0069] In step 1) of this embodiment, 9.5 g of Ce was weighed. 0.14 Zr 0.86 O2 superelastic ceramic particles (particle size 7 μm) and 0.5 g pure aluminum particles (particle size 1 μm). The energy dissipation density of the 50th cycle is ~2.0 J / cm 3 Finally, the metal-ceramic composite particles (5% Al@95% Ce 0.14 Zr 0.86 The composition and properties of O2 are listed in Table 1.

[0070] Example 8

[0071] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (5% Al@95% Ce 0.14 Zr 0.86 The specific preparation steps are basically the same as those in Example 5, except that:

[0072] In step 1) of this embodiment, 9.5 g of Ce was weighed. 0.14 Zr 0.86 O2 superelastic ceramic particles (particle size 1 μm) and 0.5 g pure aluminum particles (particle size 1 μm). The energy dissipation density of the 50th cycle is ~1.8 J / cm 3 Finally, the metal-ceramic composite particles (5% Al@95% Ce 0.14 Zr 0.86 The composition and properties of O2 are listed in Table 1.

[0073] Example 9

[0074] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (20% Ni@80% Ce 0.14 Zr 0.86 O2), the specific steps of its preparation are as follows:

[0075] 1) Solvent dispersion: weigh 8.0 g Ce 0.14 Zr 0.86 O2 superelastic ceramic particles (particle size of 2 μm) and 2.0 g of pure nickel particles (particle size of 0.5 μm) were added to 50 ml of ethanol and thoroughly mixed using a ball mill at 100 rpm for 12 hours.

[0076] 2) Drying: The mixed slurry obtained in step 1) was placed in a ventilated environment at 50° C. and dried for 12 hours to obtain metal-ceramic composite particles.

[0077] 3) Stacking pre-pressing: The metal-ceramic composite particles are Figure 1 The sleeve mold shown is preloaded with 200 MPa for pre-compression to obtain a metal-ceramic composite particle stack.

[0078] 4) Material Characterization: The composite particles were stacked in a sleeve mold and subjected to cyclic loading at a stress amplitude of 1 GPa. After the 10th cycle, the energy dissipation density was essentially stable. The energy dissipation density at the 50th cycle was ~3.8 J / cm 3 Finally, the metal-ceramic composite particles (20% Ni@80% Ce 0.14 Zr 0.86 The composition and properties of O2 are listed in Table 1.

[0079] Example 10

[0080] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (5% Ni@95% Ce 0.16 Zr 0.84 The specific preparation steps are basically the same as those in Example 9, except that:

[0081] In step 1) of this embodiment, 9.5 g of Ce was weighed. 0.16 Zr 0.84 O2 superelastic ceramic particles (particle size 2 μm) and 0.5 g pure nickel particles (particle size 1 μm). The energy dissipation density of the 50th cycle is ~3.1 J / cm 3 Finally, the metal-ceramic composite particles (5% Ni@95% Ce 0.16 Zr 0.84 The composition and properties of O2 are listed in Table 1.

[0082] Example 11

[0083] This embodiment provides an energy-absorbing metal-ceramic composite particle stack (5% Ti@95% Ce 0.16 Zr 0.84The specific preparation steps are basically the same as those in Example 1, except that:

[0084] In step 1) of this embodiment, 9.5 g of Ce was weighed. 0.16 Zr 0.84 O2 superelastic ceramic particles (particle size 3 μm) and 0.5 g pure titanium particles (particle size 1 μm). The energy dissipation density of the 50th cycle is ~2.9 J / cm 3 Finally, the metal-ceramic composite particles (5% Ti@95% Ce 0.16 Zr 0.84 The composition and properties of O2 are listed in Table 1.

[0085] Comparative Example 1

[0086] This comparative example provides a ceramic particle stacking (Ce 0.16 Zr 0.84 O2), the specific preparation steps are basically the same as those in Example 1, except that pure copper particles are not added in this comparative example. The relationship between the energy dissipation density and the number of cycles is shown in Figure 2. Figure 6 The components and properties of the superelastic ceramic particle stack are listed in Table 1.

[0087] Comparative Example 2

[0088] This comparative example provides an energy-absorbing metal-ceramic composite particle stack (1% Cu@98% Ce 0.16 Zr 0.84 O2), the specific preparation steps are basically the same as those in Example 1, except that: in this comparative example, 9.9 g of Ce 0.16 Zr 0.84 O2 superelastic ceramic particles and 0.1g pure copper particles. The composition and properties of the metal-ceramic composite particles are listed in Table 1.

[0089] Comparative Example 3

[0090] This comparative example provides an energy-absorbing metal-ceramic composite particle stack (50% Cu@50% Ce 0.16 Zr 0.84 O2), the specific preparation steps are basically the same as those in Example 1, except that: in this comparative example, 5.0 g of Ce 0.16 Zr 0.84 O2 superelastic ceramic particles and 5.0 g of pure copper particles. The composition and properties of the metal-ceramic composite particles are listed in Table 1.

[0091] Comparative Example 4

[0092] This comparative example provides an energy-absorbing metal-ceramic composite particle stack (5% Cu@95% Ce 0.135 Zr 0.865 O2), the specific preparation steps are basically the same as those in Example 1, except that the ceramic particle component selected in this comparative example is Ce 0.135 Zr 0.865 O2 does not have superelasticity. The components and properties of the metal-ceramic composite particles are finally obtained and are listed in Table 1.

[0093] Comparative Example 5

[0094] This comparative example provides an energy-absorbing metal-ceramic composite particle stack (5% Cu@95% Ce 0.16 Zr 0.84 The specific preparation steps were essentially the same as those in Example 1, with the only difference being that the pure copper particles used in this comparative example had a particle size of 0.2 μm. The composition and properties of the resulting metal-ceramic composite particle stack are listed in Table 1.

[0095] Comparative Example 6

[0096] This comparative example provides an energy-absorbing metal-ceramic composite particle stack (5% Al@95% Ce 0.14 Zr 0.86 The specific preparation steps were essentially the same as those in Example 5, with the only difference being that the pure aluminum particles used in this comparative example had a particle size of 10 μm. The composition and properties of the resulting metal-ceramic composite particle stack are listed in Table 1.

[0097] Comparative Example 7

[0098] This comparative example provides an energy-absorbing metal-ceramic composite particle stack (5% Cu@95% Ce 0.16 Zr 0.84 The specific preparation steps were essentially the same as those in Example 1, except that ethanol was omitted from the solvent dispersion step in this comparative example, and dry grinding was performed. The composition and properties of the resulting metal-ceramic composite particles are listed in Table 1.

[0099] Comparative Example 8

[0100] This comparative example provides an energy-absorbing metal-ceramic composite particle stack (5% Cu@95% Ce 0.16 Zr 0.84 The specific preparation steps were essentially the same as those in Example 1, except that the ball mill speed was 300 rpm during the solvent dispersion step in this comparative example. The composition and properties of the resulting metal-ceramic composite particles are listed in Table 1.

[0101] Table 1 Composition, compressive strength and energy dissipation density of energy-absorbing metal-ceramic composite particle stacking

[0102]

[0103]

[0104] Comparing the results of Examples 1 and 2 with Comparative Examples 1, 2, and 3 in Table 1, it can be seen that adding an appropriate amount of metal (5-25%) is beneficial for transferring stress through the metal filling the gaps in the ceramic skeleton, fully inducing the reversible phase transition of the superelastic ceramic, thereby improving the energy dissipation density. However, an excessively high metal content (50%) can easily destroy the Hertzian contact between the superelastic ceramic particles, resulting in a decrease in the phase transition amount, thereby affecting the energy dissipation density.

[0105] From the comparison of the results of Example 1 and Comparative Example 4, it can be seen that the use of ceramics with superelasticity can greatly increase the energy dissipation density of the composite particle stack and make it have superelasticity.

[0106] From the comparison of the results of Example 1 with Comparative Examples 1 and 5, it can be seen that when the metal particle size is too small (particle size less than 0.5 μm), the metal cannot effectively fill the ceramic gap and transfer the load, resulting in the energy dissipation density of the composite particle accumulation not being improved compared to Comparative Example 1 when no metal is added.

[0107] From the comparison of the results of Example 5 and Comparative Example 6, it can be seen that when the metal particle size is too large (the particle size is greater than 5 μm), the superelastic ceramic will be wrapped by the metal particles, resulting in the inability to form effective contact between the ceramic particles, destroying the three-dimensional skeleton of the superelastic ceramic, and thus causing a significant decrease in the energy dissipation density of the composite particle stack.

[0108] From the comparison of the results of Example 1 and Comparative Example 7, it can be seen that the use of solvent dispersion can eliminate the influence of mechanical stress on superelastic ceramics to the greatest extent, while dry grinding will lead to an increase in defects in ceramic particles and a partial loss of superelasticity.

[0109] From the comparison of the results of Example 1 and Comparative Example 8, it can be seen that selecting a low ball milling speed can effectively avoid the breakage of the superelastic ceramic during the ball milling process, while a high ball milling speed will lead to a decrease in energy dissipation density.

[0110] From the comparison of the results of Examples 5, 7, and 8, it can be seen that when the particle size of the superelastic ceramic particles is 1-10 μm, the particle size of the metal particles is 0.5-5 μm, and the particle size ratio of ceramic to metal is 2-5:1, the energy dissipation density of the prepared composite particle stack will be further improved.

[0111] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention, without departing from the scope of the present invention, should be within the scope of protection of the present invention.

Claims

1. An energy-absorbing metal-ceramic composite particle stack, characterized in that: The composite particle stack includes superelastic ceramic particles Ce x Zr 1-x O2 and metal particles M, the composition expression is: y%M@(100-y)%Ce x Zr 1-x O2; Wherein, the superelastic ceramic particles Ce x Zr 1-x The particle size of O2 is 1-10 μm; The metal particles M are at least one of Cu, Al, Ti, Ni metal powder or alloy powder thereof, and have a particle size of 0.5-5 μm; In the composition expression, x is the atomic molar ratio, 0.14≤x≤0.18; y is the mass ratio, 5≤y≤45; The preparation method of the energy-absorbing metal-ceramic composite particle stack comprises the following steps: A1. Solvent dispersion: weigh superelastic ceramic particles Ce x Zr 1-x O2 and metal particles M are added to a sufficient amount of solvent and mixed thoroughly for 6-18 hours; A2. Drying: Place the mixed slurry obtained in step A1 in a ventilated environment at 50-100° C. and dry for 6-12 hours to obtain metal-ceramic composite particles; A3. Stacking pre-pressing: placing the metal-ceramic composite particles in a mold and pre-pressing them at 100-200 MPa to obtain a stack of metal-ceramic composite particles; Wherein, in step A1, the rotation speed used during the mixing does not exceed 150 rpm.

2. The energy-absorbing metal-ceramic composite particle stack according to claim 1, characterized in that: In the component expression, 5≤y≤25.

3. The energy-absorbing metal-ceramic composite particle stack according to claim 1, characterized in that: The superelastic ceramic particles Ce x Zr 1-x The particle size ratio of O2 to the metal particles M is 2-5:

1.

4. The energy-absorbing metal-ceramic composite particle stack according to claim 1, characterized in that: The compressive strength of the composite particle stack is above 0.6 GPa.

5. The energy-absorbing metal-ceramic composite particle stack according to claim 1, characterized in that: After 50 cycles of the composite particle stacking, the energy dissipation density is 1.8 J / cm 3 above.

6. The energy-absorbing metal-ceramic composite particle stack according to claim 1, characterized in that: In step A1, the solvent is one or a mixture of ethanol, propanol, isopropanol, acetone, and butanone.

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