Cage-mesh metal composite material with ultra-wide temperature range and low expansion as well as preparation and application of cage-mesh metal composite material

Abstract

The invention belongs to the technical field of new materials, and particularly relates to a low-expansion cage-mesh metal composite material with an ultra-wide temperature range and preparation and application thereof.The preparation method comprises the steps that a Co phase is introduced into Re-Fe binary cage-mesh metal, the low-expansion temperature range of the Re-Fe binary cage-mesh metal is effectively widened, then alpha-Fe is introduced, and the low-expansion temperature range of the Re-Fe binary cage-mesh metal is expanded; a double-phase structure of a Re-Fe-Co matrix and alpha-(Fe / Co) is constructed, Re-Fe-Co shows negative thermal expansion, alpha-(Fe, Co) shows positive thermal expansion, the thermal expansion behavior is regulated and controlled by controlling the Fe content to regulate and control the proportion of the two phases, and the ultra-wide-temperature-range low-expansion cage-mesh metal composite material is obtained. According to the prepared ultra-wide-temperature-range low-expansion cage-mesh metal composite material, a soft / hard heterostructure is constructed, the synthesis steps are simple and easy to implement, and the ultra-wide-temperature-range low-expansion performance and the mechanical strength are remarkably improved through a two-step method.

Description

Technical Field

[0001] The present invention belongs to the technical field of new materials, and particularly relates to a kagome metal composite material with ultra-wide temperature range and low expansion, and its preparation and application. Background Art

[0002] In the fields of high-temperature precision instruments, aerospace, etc., the dimensional stability of components is directly related to the performance and lifespan of equipment. Therefore, there is an urgent need to develop low-expansion materials that can maintain their dimensions unchanged in extreme high-temperature environments. However, the existing types of low-expansion materials are limited, especially those that can maintain low-expansion characteristics in high-temperature environments are scarce.

[0003] Although ceramic materials have certain high-temperature resistance, their insufficient mechanical properties and limitations in thermal and electrical conductivity make it difficult for them to meet the requirements of high-temperature precision applications. Although metal materials perform excellently in thermal and electrical conductivity, intermetallic compounds with high-temperature low-expansion properties have inherent brittleness, and their low-expansion temperature range is often relatively low, making it difficult to be applied in high-temperature environments.

[0004] To solve the above problems, the design of composite materials is an effective strategy. Traditional composite materials are prepared by solid-phase sintering. However, this method often leads to limited improvement in mechanical properties, and the mismatch of the thermal expansion coefficients of the two materials is likely to cause thermal cracks, thereby resulting in material failure. Therefore, how to scientifically design and prepare composite materials that can maintain low-expansion characteristics in high-temperature environments and have excellent mechanical properties at the same time is a research hotspot and difficulty in the current field of materials science. Summary of the Invention

[0005] The present invention discloses a kagome metal composite material with ultra-wide temperature range and low expansion, and its preparation and application, so as to solve any of the above and other potential problems in the prior art.

[0006] To solve the above technical problems, the technical solution of the present invention is: a kagome metal composite material with ultra-wide temperature range and low expansion, and the chemical formula of the kagome metal composite material with ultra-wide temperature range and low expansion is Re 2 Fe 11 Co 6 Fe x , where 0 < x ≤ 50, Re is a rare earth element, and the kagome metal composite material with ultra-wide temperature range and low expansion has a Re-Fe-Co phase and an α-(Fe,Co) phase.

[0007] Furthermore, the Re-Fe-Co phase is a hard matrix phase, showing strong magnetism, and the Curie temperature is as high as 800K. The α-(Fe,Co) phase is a plastic second phase, which improves the strength of the matrix phase through chemical compounding.

[0008] Furthermore, the Re-Fe-Co phase is hexagonal crystal system with the space group of P6 3 / mmc; the α-(Fe,Co) phase is cubic crystal system with the space group of Im-3m.

[0009] Furthermore, the chemical formula of the ultra-wide temperature range low-expansion kagome metal composite is Lu 2 Fe 11 Co 6 Fe 9 and the Lu 2 Fe 11 Co 6 Fe 9 shows low-expansion characteristics in the temperature range of 110~800K, and the linear expansion coefficient α l is 0.98×10 -6 , and the compressive strength reaches 1110 Mpa.

[0010] Furthermore, the chemical formula of the ultra-wide temperature range low-expansion kagome metal composite is Y 2 Fe 11 Co 6 Fe 9 and the Y 2 Fe 11 Co 6 Fe 9 shows low-expansion characteristics in the temperature range of 110~800K, and the linear expansion coefficient α l <3×10 -6 , and the compressive strength <1110 Mpa.

[0011] Furthermore, the chemical formula of the ultra-wide temperature range low-expansion kagome metal composite is Tb 2 Fe 11 Co 6 Fe 9 and the Tb 2 Fe 11 Co 6 Fe 9 shows low-expansion characteristics in the temperature range of 110~800K, and the linear expansion coefficient α l is less than 3×10 -6 , and the compressive strength <1110 Mpa.

[0012] The chemical formula of the ultra-wide temperature range low-expansion kagome metal composite is Lu 2 Fe 11 Co 6 Fe 15 and the Lu 2 Fe 11 Co 6 Fe 15 has strong anisotropic characteristics.

[0013] Another object of the present invention is to provide a method for preparing the above-mentioned ultra-wide temperature range low-expansion kagome metal composite material, and the method specifically comprises the following steps: S1) Prepare corresponding raw materials according to Re-Fe-Co ternary kagome metal and α-(Fe,Co) phase; S2) Mix the raw materials prepared in S1); S3) Uniformly melt the raw materials mixed in S2) through an electric arc furnace; S4) Anneal the uniformly melted sample under a protective atmosphere; S5) After the annealing is completed, an ultra-wide temperature range low-expansion kagome metal composite material is obtained.

[0014] The above-mentioned ultra-wide temperature range low-expansion kagome metal composite material exhibits low-expansion characteristics in the temperature range of 110~800K, and the linear expansion coefficient α l <3×10 -6 , and the compressive strength ≤ 1110 Mpa Furthermore, the purities of the Re-Fe-Co ternary kagome metal raw material and the α-Fe raw material in S1) are both > 99.9%.

[0015] Furthermore, the specific annealing process in S4) is: annealing at a temperature of 1100 °C for at least 72 h; the protective atmosphere is an inert gas.

[0016] An above-mentioned ultra-wide temperature range low-expansion kagome metal composite material is applied in the fields of optical instruments, microelectronic devices, and high-precision instruments in aerospace.

[0017] The technical effect of the present invention: Due to the adoption of the above technical solution, the present invention provides an ultra-wide temperature range low-expansion kagome metal composite material and a preparation method thereof. First, an appropriate amount of Co is introduced into the Re-Fe binary kagome metal (Re refers to rare earth elements) to prepare a Re-Fe-Co ternary precursor compound. Subsequently, α-Fe is introduced to form a Re-Fe-Co ternary kagome metal composite material, constructing a soft / hard heterogeneous structure. The synthesis steps are simple and easy to implement, and the significant improvement of the ultra-wide temperature range low-expansion performance and mechanical strength is achieved through a two-step method.

[0018] On the one hand, the present invention provides a method for preparing an ultra-wide temperature range low-expansion kagome metal composite material. In the Re-Fe binary kagome metal, a Co phase is introduced to effectively broaden its low-expansion temperature range. Then, α-Fe is introduced to construct a dual-phase structure of Re-Fe-Co matrix and α-(Fe / Co). Among them, Re-Fe-Co exhibits negative thermal expansion, and α-(Fe,Co) exhibits positive thermal expansion. By controlling the Fe content to regulate the proportion of the two phases, the thermal expansion behavior is regulated to obtain an ultra-wide temperature range low-expansion kagome metal composite material.

[0019] The ultra-wide temperature range low-expansion kagome metal composite material prepared by the present invention has excellent dimensional stability, high precision, and long service life. Its remarkable feature is that its shape and size are not affected by temperature changes, achieving a constant length / volume within a specific temperature range, that is, the zero thermal expansion property.

[0020] The ultra-wide temperature range low-expansion kagome metal composite material provided by the present invention has the characteristics of high strength in the high-temperature range, and its shape and size remain stable when the temperature changes. Compared with intermetallic compounds, this material broadens the working temperature range and eliminates its intrinsic brittleness. At the same time, compared with ceramic materials, this material exhibits better thermal and electrical conductivity, and the raw material cost is lower, providing the possibility for practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0022] Figure 1 is the low-expansion composite material of the present invention. When Re = Lu, Lu 2 Fe 11 Co 6 Fe 9 X-ray diffraction structure refinement pattern of the dual-phase powder at 300K; Figure 2 is the crystal structure diagram of the Re-Fe-Co phase and α-(Fe,Co) phase of the present invention; Figure 3 is the backscattered electron diffraction microstructural diagram of the Re-Fe-Co phase and α-(Fe,Co) phase of the present invention; Figure 4 is Re of the present invention 2 Fe 11 Co 6 Fe x(Re = Lu, x = 9, 15, 25, and 50) and the linear thermal expansion diagram of the α-Fe phase line; Figure 5 is Lu described in the present invention 2 Fe 11 Co 6 Fe 9 Engineering stress-strain curves at 300K and diagrams of processed and formed samples. Detailed implementation manners

[0023] For a better understanding of the technical solution of the present invention, the embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0024] It should be clear that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0025] The terms used in the embodiments of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. The singular forms "a", "the", and "said" used in the embodiments of the present invention and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0026] The present invention provides a super-wide temperature range low-expansion kagome metal composite material, and the chemical formula of the super-wide temperature range low-expansion kagome metal composite material is Re 2 Fe 11 Co 6 Fe x , where 0 < X ≤ 50, R is a rare earth element, and the super-wide temperature range low-expansion kagome metal composite material includes Lu 2 Fe 11 Co 6 Fe 9 , and the Lu 2 Fe 11 Co 6 Fe 9 exhibits low-expansion characteristics in the temperature range of 110 - 800K, and the linear expansion coefficient α l is 0.98 × 10 -6 .

[0027] The preparation method introduces a Co phase into the Re-Fe binary kagome metal, effectively broadening its low-expansion temperature range. Subsequently, α-Fe is introduced to construct a dual-phase structure of Re-Fe-Co matrix and α-(Fe / Co), where Re-Fe-Co exhibits negative thermal expansion and α-(Fe,Co) exhibits positive thermal expansion. The thermal expansion behavior is regulated by controlling the Fe content to adjust the ratio of the two phases, obtaining a low-expansion kagome metal composite material with an ultra-wide temperature range.

[0028] The preparation method includes the following steps: S1): Prepare the corresponding raw materials for the Re-Fe-Co and α-(Fe,Co) phases. The purity of the raw materials is >99.9%. The Re-Fe-Co phase is a hexagonal crystal system with a space group of P6 3 / mmc, and the α-(Fe,Co) phase is a cubic crystal system with a space group of Im-3m.

[0029] S2): Mix the raw materials prepared in S1). S3): Melting the mixed raw materials evenly by an arc furnace. S4): Place the evenly melted sample under a protective atmosphere and anneal it at 1100 °C for at least 72 h. S5): After the annealing is completed, an ultra-wide temperature range low-expansion kagome metal composite material is obtained.

[0030] The protective atmosphere is an inert atmosphere.

[0031] Example 1: Prepare the low-expansion kagome metal composite material block with the composition of Lu 2 Fe 11 Co 6 Fe 9 of the present invention by arc furnace melting method respectively: The specific operation is carried out according to the following steps: Weigh 8 g of Lu, Fe, and Co raw materials with a molar ratio of 2:20:6 respectively. Mix the raw materials in an arc furnace, evacuate the furnace body (vacuum degree < 2×10 -3 Pa), and then repeatedly melt for 4 times under the protection of inert gas Ar, 2 min each time. Place the obtained sample under an inert atmosphere and anneal it at a temperature of 1100 °C for 72 h. The X-ray diffraction results show that the obtained product is Lu 2 (Fe,Co) 17 and α-(Fe,Co) composite phase without other impurities.

[0032] Example 2: Prepare the low-expansion kagome metal composite material with the composition of Y 2 Fe 11 Co 6Fe 9 The ultra-wide temperature range low-expansion kagome metal composite blocks were synthesized by the arc furnace melting method respectively: The specific operation is carried out according to the following steps: Weigh 8 g of raw materials of Y, Fe, and Co with a molar ratio of 2:20:6 respectively. Mix the raw materials in an arc furnace, and evacuate the furnace body (vacuum degree < 2×10 -3 Pa), and then repeatedly melt for 4 times under the protection of inert gas Ar, 2 minutes each time. Place the obtained sample in an inert atmosphere, anneal at a temperature of 1100 °C for 75 h. The X-ray diffraction results show that the obtained product is Y 2 (Fe, Co) 17 and α-(Fe, Co) composite phases, without other impurities.

[0033] Example 3: Prepare the component described in the present invention as Tb 2 Fe 11 Co 6 Fe 9 The ultra-wide temperature range low-expansion kagome metal composite blocks were synthesized by the arc furnace melting method respectively: The specific operation is carried out according to the following steps: Weigh 8 g of raw materials of Tb, Fe, and Co with a molar ratio of 2:20:6 respectively. Mix the raw materials in an arc furnace, and evacuate the furnace body (vacuum degree < 2×10 -3 Pa), and then repeatedly melt for 4 times under the protection of inert gas Ar, 2 minutes each time. Place the obtained sample in an inert atmosphere, anneal at a temperature of 1100 °C for 80 h. The X-ray diffraction results show that the obtained product is Tb 2 (Fe, Co) 17 and α-(Fe, Co) composite phases, without other impurities.

[0034] For the ultra-wide temperature range low-expansion kagome metal composites Lu 2 Fe 11 Co 6 Fe 9 、Y 2 Fe 11 Co 6 Fe 9 、Tb 2 Fe 11 Co 6 Fe 9 obtained in Examples 1, 2, and 3, measure the linear expansion. They show low-expansion characteristics in the temperature ranges of 110~800 K, 110~800 K, and 110~800 K respectively, and the linear expansion coefficient (α l)Less than 3×10 -6 .

[0035] In the preparation method of the present invention, the Re-Fe-Co ternary kagome metal is a hard matrix phase, and the α-(Fe,Co) phase is a plastic second phase. Through a two-step method, the low-expansion temperature range can be broadened step by step and the mechanical behavior of the matrix phase can be improved, realizing high strength and low expansion performance in the high-temperature range.

[0036] Figure 1 is the ultra-wide temperature range low-expansion kagome metal composite material of the present invention. When R = Lu, Lu 2 Fe 11 Co 6 Fe 9 Powder X-ray diffraction structure refinement pattern at 300K. It can be seen from this figure that the X-ray diffraction pattern simulated based on its crystal structure is consistent with the X-ray diffraction pattern obtained experimentally, indicating the correctness of the structure model of the ultra-wide temperature range low-expansion kagome metal composite material of the present invention.

[0037] Figure 2 is the crystal structure diagram of the Re-Fe-Co phase and the α-(Fe,Co) phase of the present invention. The crystal structures of the present invention are respectively a rare earth-rich 2:17 type hexagonal phase and a cubic phase composed of Fe and a small amount of Co elements.

[0038] Figure 3 The backscattered electron diffraction micrograph of the Re-Fe-Co phase and the α-(Fe,Co) phase of the present invention shows that the Re-Fe-Co phase is the substrate phase, the α-(Fe,Co) phase is the precipitated phase, and the two phases are uniformly mixed without compositional segregation.

[0039] Figure 4 is Re of the present invention 2 Fe 11 Co 6 Fe x (Re = Lu, x = 9, 15, 25 and 50) Linear expansion diagram. From the linear expansion curve of Lu 2 Fe 11 Co 6 Fe x of the present invention, it can be seen that the thermal expansion can be regulated by controlling the doping ratio of Fe, and zero expansion characteristics are exhibited in the Lu 2 Fe 11 Co 6 Fe 9 component, and the linear expansion coefficient is 0.98×10 in the temperature range of 110 - 800K -6 .

[0040] Figure 5 is Lu of the present invention2 Fe 11 Co 6 Fe 9 The engineering stress-strain curve at 300K. It can be seen from the engineering stress-strain curve of the present invention that the above low-expansion composite material exhibits excellent mechanical property characteristics, its compressive strength reaches 1110 Mpa, and it has processability.

[0041] The above has introduced in detail a kind of low-expansion kagome metal composite material with ultra-wide temperature range, its preparation and application provided by the embodiments of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those of ordinary skill in the art, according to the idea of the present application, there will be changes in the specific implementation manners and application scopes. In summary, the content of this specification should not be construed as a limitation to the present application.

[0042] As used in the specification and claims, certain terms are used to refer to specific components. Those skilled in the art should understand that hardware manufacturers may use different terms to refer to the same component. The specification and claims do not use the difference in names as a way to distinguish components, but use the difference in functions of components as the criterion for distinction. As mentioned throughout the specification and claims, "comprising" and "including" are open-ended terms, so they should be interpreted as "comprising / including but not limited to". "Substantially" means within an acceptable error range. Those skilled in the art can solve the technical problems within a certain error range and basically achieve the technical effects. The subsequent description in the specification is the preferred implementation manner for implementing the present application, but the description is for the purpose of explaining the general principles of the present application and is not used to limit the scope of the present application. The protection scope of the present application shall be subject to what is defined by the appended claims.

[0043] It should also be noted that the term "including", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that a commodity or system including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or also includes elements inherent to this commodity or system. Without further limitation, the element defined by the statement "including one..." does not exclude the existence of another identical element in the commodity or system including the said element.

[0044] It should be understood that the term "and / or" used herein is only a kind of association relationship describing associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist simultaneously, and B exists alone. In addition, the character " / " herein generally represents an "or" relationship between the front and rear associated objects.

[0045] The foregoing description has shown and described several preferred embodiments of the present application. However, as previously mentioned, it should be understood that the present application is not limited to the forms disclosed herein, should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications, and environments, and can be changed within the scope of the application concept described herein through the above teachings or the techniques or knowledge in the relevant field. Any changes and variations made by those skilled in the art without departing from the spirit and scope of the present application shall fall within the protection scope of the appended claims of the present application.

Claims

1. A metal composite material with ultra-wide temperature range and low expansion, characterized in that: The chemical formula of the ultra-wide temperature range low expansion cage metal composite material is Re2Fe 11 Co6Fe x , wherein 0<x≤50, R is a rare earth element, and the ultra-wide temperature range low expansion cage metal composite material has a Re-Fe-Co phase and an α-(Fe, Co) phase.

2. The ultra-wide temperature range low expansion cage metal composite material according to claim 1, characterized in that: The Re-Fe-Co phase is a hard matrix phase, exhibiting strong magnetism, and a Curie temperature of up to 800K. The α-(Fe, Co) phase is a plastic precipitation phase, and the mechanical properties of the matrix phase are improved through chemical compounding.

3. The ultra-wide temperature range low expansion cage metal composite material according to claim 1, characterized in that: The Re-Fe-Co phase is a hexagonal crystal system with a space group of P63 / mmc; the α-(Fe, Co) phase is a cubic crystal system with a space group of Im-3m.

4. The ultra-wide temperature range low expansion cage metal composite material according to claim 1, characterized in that: The chemical formula of the ultra-wide temperature range low expansion cage metal composite material is Lu2Fe 11 Co6Fe9, Lu2Fe 11 Co6Fe9 exhibits zero expansion characteristics in the temperature range of 110~800K, and the linear expansion coefficient α l 0.98×10 -6 , the compression strength is 1110Mpa.

5. The ultra-wide temperature range low expansion cage metal composite material according to claim 1, characterized in that: The chemical formula of the ultra-wide temperature range low expansion cage metal composite material is Y2Fe 11 Co6Fe9, Y2Fe 11 Co6Fe9 exhibits low expansion characteristics in the temperature range of 110~800K, and the linear expansion coefficient is α l <3×10 -6 , compression strength <1110Mpa.

6. The ultra-wide temperature range low expansion cage metal composite material according to claim 1, characterized in that: The chemical formula of the ultra-wide temperature range low expansion cage metal composite material is Tb2Fe 11 Co6Fe9 measured linear expansion, the Tb2Fe 11 Co6Fe9 exhibits low expansion characteristics in the temperature range of 110~800K, and the linear expansion coefficient is α l <3×10 -6 , compression strength <1110Mpa.

7. A method for preparing the ultra-wide temperature range low expansion cage metal composite material according to any one of claims 1 to 6, characterized in that: The method specifically comprises the following steps: S1) preparing corresponding raw materials according to the Re-Fe-Co phase and α-(Fe, Co) phase of the ultra-wide temperature range low expansion cage metal composite material; S2) mixing the raw materials prepared in S1); S3) melting the mixed raw materials in S2) uniformly by an electric arc furnace; S4) annealing the uniformly melted sample under a protective atmosphere; S5) After annealing, an ultra-wide temperature range low expansion cage metal composite material is obtained.

8. The method according to claim 7, characterized in that The purity of the Re-Fe-Co ternary cage metal raw material and the α-Fe raw material in S1) is >99.9%.

9. The method according to claim 7, characterized in that: The specific annealing process in S4) is: annealing at a temperature of 1100° C. for at least 72 hours; the protective atmosphere is an inert gas.

10. An ultra-wide temperature range low expansion cage metal composite material as claimed in any one of claims 1 to 6, used in the fields of optical instruments, microelectronic devices, and high-precision instruments in aerospace.

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