High-entropy alloy / photocurable resin composite micro-nano lattice and preparation method thereof

Abstract

This invention discloses a high-entropy alloy / photocurable resin composite micro / nano lattice and its preparation method. The micro / nano lattice is composed of multiple layers of resin micro / nano lattice material uniformly coated inside and outside with a high-entropy alloy film. This invention utilizes additive manufacturing technology to prepare micro / nano lattices with topological characteristics. Combined with magnetron sputtering technology, by adjusting the magnetron sputtering parameters and performing two sputtering operations, a high-entropy alloy micro / nano composite lattice with a size spanning two orders of magnitude, a fracture strength of 36.8 MPa, and a compressive plasticity of 59.8% was obtained. Optical characterization and mechanical testing show that the high-entropy micro / nano composite lattices prepared under different magnetron sputtering parameters exhibit different film coating states and mechanical properties. The high-entropy alloy micro / nano composite lattices prepared under single sputtering and low-power sputtering still exhibit resin characteristics, while the high-entropy alloy micro / nano composite lattices prepared under two sputtering operations and higher power perfectly combine the plasticity of resin and the strength of high-entropy alloy.

Description

Technical Field

[0001] This invention belongs to the field of metamaterials technology, specifically relating to a method for depositing high-entropy alloys on micron-scale complex lattice structures. Background Technology

[0002] Micro / nanolattices are the strongest metamaterials available, extremely lightweight, composed of 50%-99% air, yet possessing a strength comparable to steel. The extremely small volume of individual members thus statistically eliminates material defects, allowing the underlying materials of micro / nanolattices to achieve mechanical strength comparable to that of ideal crystals.

[0003] The properties of micro / nano lattices are influenced not only by structural design and size effects, but also by the constituent materials. Existing research has combined amorphous and ceramic materials with micro / nano lattices to prepare composite metamaterials; however, achieving a balance between strength and plasticity is often challenging. High-entropy alloys are novel alloys containing five or more elements, each with a content between 5% and 35% (mole fraction). Reported high-entropy alloys possess numerous superior properties, such as high strength / hardness, high wear resistance, high fracture toughness, excellent low-temperature performance and structural stability, good corrosion resistance, and oxidation resistance. High-entropy alloy thin films are low-dimensional (typically within tens of micrometers in thickness) high-entropy alloy materials, i.e., multi-component, high-mixed-entropy alloy thin films. In recent years, it has been found that high-entropy alloy thin films exhibit similar excellent properties to bulk materials, and even outperform bulk materials in some aspects, making them a potential toughening material for micro / nano lattices.

[0004] Fabricating micro / nano composite lattices remains a challenge. Previous attempts have involved combining the original structure with materials such as ceramics, metals, and pyrolytic carbon using techniques like atomic layer deposition, magnetron sputtering, electrolytic deposition, and high-temperature pyrolysis to obtain the final micro / nano composite lattice. However, no one has yet explored a fabrication method applicable to all structures or clarified the impact of different fabrication parameters on the combination of the original structure and the toughening material. Summary of the Invention

[0005] The purpose of this invention is to provide a toughening process for photocurable resin micro / nano lattices.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A high-entropy alloy / photocurable resin composite micro / nano lattice with a unique topological structure and deformation mode, and its preparation method thereof, wherein the composite micro / nano lattice consists of multiple layers coated with high-entropy alloy thin films (CoCrFeNiTi). 0.1 It consists of resin micro-nano lattice materials uniformly coated inside and out, and is prepared by photopolymerization and magnetron sputtering, through the following steps:

[0008] Step 1: Design a support model for a micro / nano lattice structure and extend the model into a multilayer structure;

[0009] Step 2: 3D print the above multilayer structure to obtain resin micro / nano lattice material;

[0010] Step 3: Using resin micro-nano lattice material as a substrate, fix it on an inverted tray, use high-entropy alloy as a target, and perform two magnetron sputtering operations to uniformly coat all surfaces of the substrate to form the composite micro-nano lattice.

[0011] Preferably, in step 1, the micro / nano lattice structure includes any one of the following: a six-element three-cap triangular prism (6M-TTP), a three-dimensional octahedron, a tetrahedron, and a pyramidal.

[0012] Preferably, in step 1, a support model is designed based on the micro / nano lattice structure, and the model is extended into a three-layer structure.

[0013] Preferably, in step 2, the printing material is a photopolymer resin, and the minimum printing layer thickness is 0.025 mm.

[0014] Preferably, in step 3, a composite micro / nano lattice is prepared by magnetron sputtering, wherein the high-entropy alloy target material is composed of CoCrFeNiTi. 0.1 The target material has a diameter of 5.08cm and a thickness of 8mm.

[0015] Preferably, in step 3, after sealing the sputtering chamber, a vacuum of 4×10⁻⁶ is drawn. -4 Pa, then argon gas is introduced at a flow rate of 20 sccm; the sputtering power is controlled at 10W~500W, the target-substrate distance is 0°~60°, and the sputtering pressure is 0.1Pa~2Pa.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. This invention employs a magnetron sputtering fabrication process. Compared to the cumbersome micro / nano lattice toughening processes such as atomic layer deposition and electrolytic deposition, this physical method is simple, low-cost, and technically stable. It does not involve any flammable or explosive hazardous materials and is suitable for practical industrial production.

[0018] 2. For micro-nano lattices of different scales and structures, this method can achieve uniform coating of inner and outer rod diameters by adjusting the magnetron sputtering parameters. Compared with the limitation of atomic layer deposition and electrolytic deposition, which can only be applied to specific toughening materials, this invention has universal applicability to all micro-nano lattices and the preparation of micro-nano composite materials from micro-nano lattice toughening materials.

[0019] 3. This invention can control the thickness and uniformity of high-entropy thin films by adjusting the magnetron sputtering parameters, thereby controlling the properties of composite metamaterials to obtain the desired micro-nano composite lattice. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the hexa-element three-cap triangular prism structure (a), the expanded resin micro / nano lattice after printing, and the magnetron sputtering principle described in this invention.

[0021] Figure 2 These are optical micrographs (a, b) of the high-entropy alloy / photocurable resin micro / nano composite lattice and scanning electron microscope images (c, d) of the support fracture surface described in this invention.

[0022] Figure 3 These are the compressive stress-strain curves of the single-sided / double-sided sputtered micro / nano composite lattice and the resin micro / nano lattice described in this invention.

[0023] Figure 4 These are the compressive stress-strain curves of the micro / nano composite lattice obtained under sputtering powers of 10W, 100W, and 500W, respectively, as described in this invention.

[0024] Figure 5 These are the compressive stress-strain curves of the micro / nano composite lattice obtained under sputtering pressures of 0.1 Pa, 0.5 Pa, and 2 Pa, respectively, as described in this invention.

[0025] Figure 6 These are the compressive stress-strain curves of the micro-nano composite lattice obtained at target-substrate distances of 5 cm, 10 cm, and 15 cm, respectively, as described in this invention. Detailed Implementation

[0026] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. The examples given below are not intended to limit the scope of the invention.

[0027] This invention utilizes magnetron sputtering technology to prepare high-entropy alloy micro / nano lattice composite metamaterials with topological structures. On one hand, magnetron sputtering is currently the most mature physical deposition technology, and its stable and inexpensive toughening method facilitates the rapid preparation of composite micro / nano lattices for practical applications. On the other hand, magnetron sputtering allows for the adjustment of multiple parameters such as power, gas pressure, target-substrate distance, and temperature to match micro / nano lattice designs with different structures, thus identifying the most suitable process parameters. The following steps are used to prepare high-entropy alloy micro / nano lattice composite metamaterials with topological structures.

[0028] The present invention discloses a high-entropy alloy micro / nano composite lattice with a topological structure. The magnetron sputtering method achieves composite micro / nano lattices with various properties by adjusting parameters [sputtering power (10W~500W), target-substrate distance (angle: 0°~60°), sputtering pressure (0.1Pa~2Pa)].

[0029] Comparative Example 1

[0030] A high-entropy alloy / photocurable resin micro / nano composite lattice with a topological structure is described. Taking the 6M-TTP three-layer one-unit micro / nano lattice as an example, a high-entropy alloy (CoCrFeNiTi) is selected to coat one side of it.

[0031] Step 1: Design a support model for the micro / nano lattice structure and extend the support model into a multilayer structure. The support model of the micro / nano lattice structure is a three-layer, one-unit 6M-TTP structure, which is composed of three 6M-TTP stacked one on top of the other. This support model constitutes a close-packed structure with a topological structure.

[0032] Step 2: After importing the support model into the 3D printing system, the 3D printer cures the photopolymer resin based on the two-photon polymerization principle. The minimum printed layer thickness is designed to be 0.025mm. After printing, the sample is removed with tweezers and ultrasonically cleaned three times in alcohol for 10 minutes each time. After cleaning, it is placed in a 28℃ incubator to dry for 30 minutes. The dried 6M-TTP micro / nano lattice support has a diameter of 200µm and overall dimensions of 5.12mm × 5mm × 3.98mm. Figure 1 (b).

[0033] Step 3: Using the resin micro / nano lattice material obtained in Step 2 as a substrate, fix it to the tray using high-temperature resistant tape, and then insert it into the inverted tray groove to target the high-entropy alloy target (CoCrFeNiTi). 0.1 Polish and clean the sputtering surface, dry it, and then fix it on the sputtering target position, ensuring the target material is tightly attached to the target surface. Adjust the target position to a 30° angle with the ground. Turn off the equipment and evacuate the vacuum chamber. After approximately two hours, the vacuum level in the sputtering chamber should reach 4 × 10⁻⁶. -4 Pa. Open the argon valve to introduce argon gas into the sputtering chamber, and stabilize the argon gas flow rate at 20 sccm. Adjust the slide valve to make the gas pressure in the sputtering chamber about 0.6 Pa. Turn on the target power and control the sputtering power to 100 W. Turn on the rotation to make the tray groove rotate. Then adjust the slide valve to stabilize the gas pressure at 0.5 Pa. After sputtering for 30 minutes, turn off the equipment. After cooling for two hours, open the equipment and take it out to obtain a non-uniform composite micro / nano lattice.

[0034] In a non-uniform composite micro / nano lattice formed by a single magnetron sputtering operation for 30 minutes, only the side closest to the target material exhibits uniform film deposition, while the other sputtered surfaces show uneven film deposition with a gradually decreasing film thickness. The unsputtered surfaces (fixed surfaces) show only a small amount of nanoscale metal ions deposited on the surface without forming a film. Compression tests (such as...) Figure 3 It shows that its mechanical properties are superior to those of pure resin micro-nano lattices, but it still exhibits the mechanical characteristics of pure resin micro-nano lattices, that is, the elastic modulus increases slowly with increasing strain and there is no strength limit.

[0035] Example 1

[0036] A high-entropy alloy / photocurable resin micro / nano composite lattice with a topological structure is described. Taking the 6M-TTP three-layer one-unit micro / nano lattice as an example, a high-entropy alloy (CoCrFeNiTi) is selected to coat all its surfaces.

[0037] Steps 1 and 2 are the same as those in the comparative example.

[0038] Step 3: Using the resin micro / nano lattice material obtained in Step 2 as a substrate, fix one side (fixed side) of the material to the tray using high-temperature resistant tape, and then insert it into the inverted tray slot. Then, apply the high-entropy alloy target (CoCrFeNiTi) to the target. 0.1 Polish and clean the sputtering surface, dry it, and then fix it on the sputtering target position, ensuring the target material is tightly attached to the target surface. Adjust the target position to a 30° angle with the ground. Turn off the equipment and evacuate the vacuum chamber. After approximately two hours, the vacuum level in the sputtering chamber should reach 4 × 10⁻⁶. -4 Pa. Argon gas is introduced into the sputtering chamber through the argon valve, and the argon flow rate is stabilized at 20 sccm. The baffle valve is adjusted to bring the sputtering chamber pressure to approximately 0.6 Pa. The target power is turned on, and the sputtering power is controlled at 100 W. The rotation mechanism is activated, causing the tray slot to rotate. The baffle valve is then adjusted to stabilize the pressure at 0.5 Pa. After sputtering for 30 minutes, the equipment is turned off. After cooling for two hours, the equipment is opened and the substrate is removed. The substrate from the first sputtering is inverted (i.e., the fixed surface is rotated 180 degrees) and fixed to the tray using high-temperature resistant tape. The sputtering operation is repeated. Finally, a composite micro / nano lattice with uniform coating on all surfaces is obtained.

[0039] The micro / nano composite lattice surface and internal support film obtained by two sputtering processes, each lasting 30 minutes, exhibited a uniform metallic luster. The fracture morphology was then observed (e.g., Figure 2 The film shows a tight bond between itself and the resin skeleton, as demonstrated by compression tests (e.g.) Figure 3The results show that its mechanical properties are superior to those of a micro / nano composite lattice sputtered for 30 minutes in a single application, with a fracture strength of 20 MPa and a compressive plasticity of 55%. Its elastic modulus shows a significant increase after 20% strain. This is because before 20% strain, the deformation of the composite micro / nano lattice is mainly provided by the deformation of the equilateral tetrahedral supports extending from the sides of the triangular prisms, while after 20% strain, the deformation of the composite micro / nano lattice transforms into the deformation of a three-layer stacked triangular prism structure. (CoCrFeNiTi) 0.1 The uniform coating of high-entropy thin films provides high strength for the micro-nano composite lattice as a whole.

[0040] Example 2

[0041] A high-entropy alloy / photocurable resin micro / nano composite lattice with a topological structure is described. Taking a 6M-TTP three-layer one-unit micro / nano lattice as an example, a high-entropy alloy (CoCrFeNiTi) is selected and its entire surface is coated with a sputtering power of 10W.

[0042] Steps 1-3 are the same as in Example 1, except that the sputtering power is changed to 10W.

[0043] The micro / nano composite lattice surface sputtered with a power of 10W only showed a small amount of nano-sized thin film; the excessively low power resulted in less film bonding; compression tests (such as...) Figure 4 The composite micro-nano lattice with a sputtering power of 10W exhibits mechanical properties superior to those of pure resin micro-nano lattices. However, the composite micro-nano lattice with a sputtering power of 10W still displays the mechanical properties of pure resin micro-nano lattices, namely, the elastic modulus increases slowly with increasing strain and there is no strength limit.

[0044] Example 3

[0045] A high-entropy alloy / photocurable resin micro / nano composite lattice with a topological structure is described. Taking a 6M-TTP three-layer one-unit micro / nano lattice as an example, a high-entropy alloy (CoCrFeNiTi) is selected and its entire surface is coated with a sputtering power of 500W.

[0046] Steps 1-3 are the same as in Example 1, except that the sputtering power is changed to 500W.

[0047] Compression mechanical curves as follows Figure 4 As shown, high power causes atoms to bombard the substrate with excessively high energy during sputtering, resulting in a thicker high-entropy film with mechanical behavior more metallic. The composite micro / nano lattice with a sputtering power of 500W has a fracture strength of 26MPa and a compressive plasticity of 41%. The stress-strain curves of the 500W micro / nano composite lattice show a significant inflection point near 10% and 26.5% strain. This is because before 10% strain, the deformation of the composite micro / nano lattice is mainly provided by the deformation of the equilateral tetrahedral supports extending from the sides of the triangular prisms. After 10% strain, the deformation of the composite micro / nano lattice transforms into elastic deformation of a three-layer stacked triangular prism structure. (CoCrFeNiTi)0.1 The uniform coating of the high-entropy film provides high strength to the micro-nano composite lattice as a whole; after 26.5% strain, the composite micro-nano lattice as a whole transforms into plastic deformation; the entire deformation process is a "progressive" deformation.

[0048] Example 4

[0049] A high-entropy alloy / photocurable resin micro / nano composite lattice with a topological structure is described. Taking the 6M-TTP three-layer one-unit micro / nano lattice as an example, a high-entropy alloy (CoCrFeNiTi) is selected and its entire surface is coated under a sputtering pressure of 0.1 Pa.

[0050] Steps 1 to 3 are the same as in Example 1, except that the sputtering pressure is changed to 0.1 Pa.

[0051] The composite micro / nano lattice surface and internal support film obtained under sputtering pressure of 0.1 Pa exhibit a uniform metallic luster; compression tests (such as...) Figure 5 The results show that the fracture strength of the composite micro / nano lattice at a sputtering pressure of 0.1 Pa is 26.3 MPa, and the compressive plasticity is 54.6%. The mechanical behavior of the micro / nano composite lattice at 0.1 Pa combines the compressive behavior characteristics of both resin and metal. Its stress-strain curves show a turning point near 5% strain and 30% strain, respectively. This indicates that although the high-entropy film is uniformly coated with the micro / nano structure during low-pressure sputtering, the stress accumulation effect at the support joint causes a significant fluctuation in the stress-strain curve during compression.

[0052] Example 5

[0053] A high-entropy alloy / photocurable resin micro / nano composite lattice with a topological structure is described. Taking a 6M-TTP three-layer one-unit micro / nano lattice as an example, a high-entropy alloy (CoCrFeNiTi) is selected and its entire surface is coated under a sputtering pressure of 2Pa.

[0054] Steps 1-3 are the same as in Example 1, except that the sputtering pressure is changed to 2 Pa.

[0055] The composite micro / nano lattice surface and internal support film obtained under sputtering pressure of 2 Pa exhibit a uniform metallic luster; compression test (e.g.) Figure 5The results show that the fracture strength of the composite micro / nano lattice at a sputtering pressure of 2 Pa is 27.1 MPa, and the compressive plasticity is 54%. The stress-strain curves of the micro / nano composite lattices at 0.1 Pa and 0.5 Pa show a turning point near 5% strain and 30% strain, respectively, while the stress-strain curve of the micro / nano composite lattice at 2 Pa only shows a turning point at 3.5% strain. This indicates that although the high-entropy film is uniformly coated on the micro / nano structure during low-pressure sputtering, the stress accumulation effect at the support joint causes a significant fluctuation in the stress-strain curve during compression. In contrast, the high-entropy film is thicker at the support joint during high-pressure sputtering, making the stress accumulation at the support joint insufficient to trigger brittle fracture, thus preventing the occurrence of "progressive" deformation.

[0056] Example 6

[0057] A high-entropy alloy / photocurable resin micro / nano composite lattice with a topological structure is disclosed. Taking a 6M-TTP three-layer one-unit micro / nano lattice as an example, a high-entropy alloy (CoCrFeNiTi) is selected to coat all surfaces at a low target-substrate distance. Since the target positions are designed and fixed by the manufacturer, this invention achieves a low target-substrate distance (5cm) by adjusting the angle (0°) of the target positions.

[0058] Steps 1-3 are largely the same as in Example 1, except that the angle of the target position is changed (0°).

[0059] The composite micro / nano lattice surface and internal support film obtained at a target angle of 0° exhibit a uniform metallic luster when uniformly coated; compression test (e.g.) Figure 6 The results show that the fracture strength of the composite micro / nano lattice with a target angle of 0° is 36.8 MPa and the compressive plasticity is 55.7%. The stress-strain curve of the micro / nano composite lattice with a sputtering angle of 0° shows a turning point near 6.9% strain and 27.1% strain, exhibiting a "progressive" deformation, indicating that the effect similar to power control can be achieved by adjusting the target-substrate distance.

Claims

1. A method for preparing high-entropy alloy / photocurable resin composite micro-nano lattice, characterized in that, The composite micro / nano lattice is composed of multiple layers of resin micro / nano lattice material uniformly coated inside and outside with a high-entropy alloy film, and is prepared by photopolymerization and magnetron sputtering through the following steps: Step 1: Design a support model for the micro / nano lattice structure and extend the model into a multilayer structure, wherein the micro / nano lattice structure is a six-element three-cap triangular prism; Step 2: 3D print the above multilayer structure to obtain resin micro / nano lattice material; Step 3: Using resin micro-nano lattice material as a substrate, fix it on an inverted tray. Using high-entropy alloy as the target, perform two magnetron sputtering operations to uniformly coat all surfaces of the substrate, forming the composite micro-nano lattice. The specific process is as follows: Using resin micro-nano lattice material as a substrate, fix one side of it on the tray using high-temperature resistant tape. Use high-entropy alloy as the target and perform the first magnetron sputtering. Invert the substrate after the first sputtering and fix it on the tray again using high-temperature resistant tape. Repeat the above sputtering operation to finally obtain a composite micro-nano lattice with uniform coating on all surfaces.

2. The production method according to claim 1, wherein In step 1, a support model is designed based on the micro / nano lattice structure, and the model is extended into a three-layer structure.

3. The production method according to claim 1, wherein In step 2, the printing material is photopolymer resin, and the minimum printing layer thickness is 0.025 mm.

4. The production method according to claim 1, wherein In step 3, a composite micro / nano lattice is prepared by magnetron sputtering, wherein the high-entropy alloy target material is composed of CoCrFeNiTi. 0.1 The target material has a diameter of 5.08cm and a thickness of 8mm.

5. The production method according to claim 1, wherein In step 3, after sealing the sputtering chamber, a vacuum of 4×10⁻⁶ is drawn. - 4 Pa, then argon gas is introduced at a flow rate of 20 sccm; the sputtering power is controlled at 10W~500W, the target angle at 0°~60° and the sputtering pressure at 0.1Pa~2Pa.

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