A negative thermal expansion particle reinforced la-based amorphous composite material and a preparation method thereof

Abstract

The application provides a kind of negative thermal expansion particle reinforced La-based amorphous composite material and preparation method, belongs to the technical field of composite materials, different negative thermal expansion phases are separated by La-based amorphous alloy, the negative thermal expansion phase is ceramic reinforcing phase or metal reinforcing phase, the La-based amorphous alloy is La-Al-Cu, La-Al-Co, La-Al-Ni, La-Al-(Cu, Ni) or La-Al-(Cu, Ag)-(Ni, Co) system.By adjusting the volume fraction of the reinforcing body to reduce the thermal expansion coefficient of the amorphous alloy while retaining certain high strength, wear resistance and other characteristics of the amorphous alloy, it can adapt to the low expansion even zero expansion application environment that cannot be achieved before.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a negative thermal expansion particle-reinforced La-based amorphous composite material and its preparation method. Background Technology

[0002] Amorphous alloys, also known as "metallic glasses," are solid alloys formed when the atoms of a liquid alloy do not have enough time to arrange themselves in an orderly manner during rapid cooling. Their structure is characterized by long-range disorder and short-range order, lacking the grains, grain boundaries, and dislocations found in crystalline alloys. Due to their unique structure, amorphous alloys exhibit excellent properties in magnetism, electricity, mechanics, and corrosion resistance, making them promising for applications in aerospace and other fields.

[0003] The pursuit of high standards and precision is especially important in industrial manufacturing, particularly for high-tech industries. However, most materials exhibit thermal expansion and contraction, meaning their volume increases with temperature and decreases with temperature. This inherent property of materials can reduce structural stability and reliability, weakening or even destroying their functional properties. For example, when a spacecraft is flying at high altitudes, it is exposed to sunlight, resulting in a significant temperature difference between its sun-exposed and shaded sides. The thermal stress generated by the mismatch in the coefficients of thermal expansion between components can cause functional failure or even render the components unusable.

[0004] Based on the above issues, La-based amorphous low-expansion composite materials, while retaining the advantages of amorphous materials such as high strength and wear resistance, also possess the characteristic of low expansion, making them suitable for environments requiring low-expansion devices. For composite materials, the reinforcement and matrix can be balanced by leveraging their respective advantages and disadvantages to improve the overall performance of the composite material. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a negative thermal expansion particle-reinforced La-based amorphous composite material and its preparation method. By controlling the volume fraction of the reinforcement, the thermal expansion coefficient of the amorphous alloy is reduced while retaining its high strength and wear resistance, enabling it to adapt to previously unattainable low-expansion or even zero-expansion application environments.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] This invention provides a negative thermal expansion particle-reinforced La-based amorphous composite material, wherein the La-based amorphous alloy separates different negative thermal expansion phases, the negative thermal expansion phases being ceramic reinforcement phases or metal reinforcement phases, and the La-based amorphous alloy being a La-Al-Cu, La-Al-Co, La-Al-Ni, La-Al-(Cu,Ni) or La-Al-(Cu,Ag)-(Ni,Co) system.

[0008] Further, the ceramic reinforcement phase is ZrW2O8, Cu2P2O7, Cu2V2O 7、 Mn3Zn 1-x Sn x N or Mn3Zn 1-x Ge x N, wherein 0<x<1, and the average size of the ceramic reinforcement phase is 50-500μm.

[0009] Further, the volume fraction of the ceramic reinforcement phase accounts for 20-70% of the total volume.

[0010] Further, the metal reinforcement phase is (Hf 1-x Nb x )Fe2, (Hf 1-x Ti x )Fe2, (Zr 1-x Nb x )Fe2, La(Fe 1-x (Co 1-y Si y ) x ) 13 and La(Fe 1-x Si x ) 13 , wherein 0<x<1, 0<y<1, and the average size of the metal reinforcement phase is 10-400μm.

[0011] Further, when the metal reinforcement phase is Zr 0.72 Nb 0.28 Fe2, the volume fraction of the Zr 0.72 Nb 0.28 Fe2 reinforcement phase accounts for 15-70% of the total volume.

[0012] The present invention provides a preparation method of the above negative thermal expansion particle reinforced La-based amorphous composite material, comprising the following steps: weighing negative thermal expansion particles according to a volume ratio, placing the particles into a mold and vibrating to compact; arranging a La-based amorphous alloy directly above the mold, and performing vacuum heating infiltration; after heat preservation is completed, carrying out pressure-holding treatment; and quenching to obtain the negative thermal expansion particle reinforced La-based amorphous composite material.

[0013] Further, the negative thermal expansion particles are ceramic particles, and the average size of the ceramic particles is 50-500μm.

[0014] Further, the vacuum heating infiltration process is as follows: the vacuum degree is not higher than 0.1Pa, the heating rate is 30-60°C / min, and the first heating temperature is T m -T m +100, wherein T m is the melting point of the La-based amorphous alloy, and the heat preservation time is 15-70min.

[0015] Furthermore, the pressurized heat preservation process is as follows: inert gas is used to pressurize to 0.3-1.5 MPa, and the second heating temperature is T. m -T m Hold at +100°C for 10-100 minutes.

[0016] Furthermore, the negative thermal expansion particles are metal particles with an average size of 10-400 μm.

[0017] Furthermore, the vacuum heating impregnation process is as follows: the vacuum degree is not higher than 0.1 Pa, the heating rate is 35-55℃ / min, and the first heating temperature is T. m -T m +80, where T m The melting point of the La-based amorphous alloy is given, and the holding time is 10-60 minutes.

[0018] Furthermore, the pressurized heat preservation process is as follows: inert gas is used to pressurize to 0.5-1.5 MPa, and the second heating temperature is T. m -T m Keep warm and pressurized at +80°C for 30-90 minutes.

[0019] The beneficial effects of the technical solutions provided by the embodiments of the present invention include:

[0020] (1) This invention adds a negative thermal expansion reinforcing phase to the La-based amorphous alloy matrix. By controlling the volume fraction of the reinforcing phase, the thermal expansion coefficient of the amorphous alloy is reduced while retaining the high strength and wear resistance of the amorphous alloy. This allows it to adapt to application environments with low expansion or even zero expansion that were previously unattainable. The composite material prepared by this invention has a density of over 99%, and high hardness and strength. When a metal reinforcing phase is used, its compressive strength is 550-710 MPa; when a ceramic reinforcing phase is used, its compressive strength is 450-550 MPa.

[0021] (2) The increased density increases the thermal conductivity of the material after pressure and heat preservation treatment, and the molten metal melt structure can be transformed into an amorphous structure through quenching process. Finally, the present invention places the La-based amorphous alloy directly above the mold. During the melting process of the amorphous alloy, amorphous particles are mixed in the melt and flow into the gap between the negative thermal expansion particles together with the melt. The molten La-based metal enters the smaller gap between the negative thermal expansion particles, while the amorphous particles fill the larger gap between the negative thermal expansion particles. The above mechanism is combined with the quenching process to synergistically prepare a negative thermal expansion particle-reinforced La-based amorphous composite material. The gas pressure infiltration process is used to pull the melt in the extremely small gap between the negative thermal expansion particles by capillary action, which ensures that the La-based amorphous alloy matrix completely isolates the negative thermal expansion particles and does not cause the negative thermal expansion particles to agglomerate. For ceramic particles, the presence of pores reduces thermal conductivity. This invention utilizes a gas pressure infiltration process to allow the melt to enter the pores within the ceramic particles, increasing thermal conductivity. Combined with a quenching process, negative thermal expansion particle-reinforced La-based amorphous composite materials can be prepared.

[0022] (3) The volume fraction of the metal-reinforced phase / La-based amorphous composite material reinforcement prepared by the present invention reaches 10-70%, and the volume fraction of the ceramic-reinforced phase / La-based amorphous composite material reinforcement reaches 20-70%. The coefficient of thermal expansion can be adjusted by adjusting the volume fraction of the reinforcement. Moreover, the preparation process is simple and flexible, and the equipment investment is low. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 Zr prepared in Example 1 of this invention 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Scanning electron microscope images of amorphous composite materials;

[0025] Figure 2 Zr prepared in Example 1 of this invention 0.72 Nb 0.28 Fe2 / La 65 Al14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Linear expansion curves of amorphous composite materials, 1 represents La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloy, 2 is Zr 0.72 Nb 0.28 Fe2,3 is Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite materials;

[0026] Figure 3 Zr prepared in Example 1 of this invention 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 XRD pattern of amorphous composite material, where 1 in a represents La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloy, 2 is Zr 0.72 Nb 0.28 Fe2,3 is Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite material; b is a magnified view of part 3.

[0027] Figure 4 Zr prepared in Example 1 of this invention 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Line scan image at the interface of amorphous composite materials;

[0028] Figure 5 Cu2P2O7 / La prepared in Example 6 of this invention 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Scanning electron microscope images of amorphous composite materials;

[0029] Figure 6 Cu2P2O7 / La prepared in Example 6 of this invention 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Linear expansion curves of amorphous composite materials, 1 represents La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloy, 2 is Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite material, 3 is Cu2P2O7;

[0030] Figure 7 Cu2P2O7 / La prepared in Example 6 of this invention 65 Al 14 (Cu 5 / 6 Ag 1 / 6 )11 (Ni 1 / 2 Co 1 / 2 ) 10 XRD pattern of amorphous composite material, where 1 in a represents La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloy, 2 is Cu2P2O7 / La 65 Al 14 (Cu 5 / 6Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite material, 3 is Cu2P2O7; b is a magnified view of 2.

[0031] Figure 8 Cu2P2O7 / La prepared in Example 6 of this invention 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Line scan image at the interface of amorphous composite materials. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0033] This invention discloses a negative thermal expansion particle-reinforced La-based amorphous composite material, wherein the La-based amorphous alloy separates different negative thermal expansion phases, the negative thermal expansion phases being ceramic reinforcement phases or metal reinforcement phases, and the La-based amorphous alloy being a La-Al-Cu, La-Al-Co, La-Al-Ni, La-Al-(Cu,Ni) or La-Al-(Cu,Ag)-(Ni,Co) system.

[0034] This invention reduces the coefficient of thermal expansion of amorphous alloys by adding a negative thermal expansion reinforcing phase to a La-based amorphous alloy matrix and adjusting the volume fraction of the reinforcing phase, while retaining the high strength and wear resistance of amorphous alloys. This allows the alloys to adapt to application environments with low or even zero expansion that were previously unattainable.

[0035] It should be noted that La-based alloys are prone to form an amorphous matrix through quenching, and the metal negative thermal expansion reinforcing phase has high thermal conductivity. Not all La-based alloys can be combined with metal particles through the gas pressure infiltration process to produce composites with an amorphous structure. When the alloy system proposed in the present invention is combined with metal particles, on one hand, amorphization of the La-based alloy can be achieved, and on the other hand, tight bonding between the La-based amorphous alloy and the metal reinforcing phase is ensured. Secondly, the ceramic reinforcing phase has low thermal conductivity. Not all La-based alloys can be combined with ceramic particles through the gas pressure infiltration process to produce composites with an amorphous structure. When the alloy system proposed in the present invention is combined with ceramics, on one hand, amorphization of the La-based alloy can be achieved, and on the other hand, tight bonding between the La-based amorphous alloy and the ceramic reinforcing phase is ensured.

[0036] Pores in the same ceramic reinforcing phase are filled with the La-based amorphous alloy. Ceramic particles have low density, and large particles have pores inside. If the sintering process in the prior art is used to sinter and mold ceramic particles and La-based alloy, the ceramic particles are easily crushed during the pressing and molding stage. Moreover, in order to prevent the reaction between the La-based alloy and the reinforcing particles, the heating temperature and holding time will not allow the molten metal to enter the pores of the reinforcing phase. In the present invention, the method of gas pressure infiltration is adopted to fill the pores of ceramic particles with molten La-based alloy, which improves the density of the composite material, thereby indirectly improving the thermal conductivity of the composite material, increasing the possibility of preparing an amorphous matrix, and eliminates the pressing on ceramic particles, further improving the thermal conductivity.

[0037] The ceramic reinforcing phase is ZrW2O8, Cu2P2O7, Cu2V2O 7、 Mn3Zn 1-x Sn x N or Mn3Zn 1-x Ge x N, where 0 < x < 1, and the average size of the ceramic reinforcing phase is 50-500 μm. Since ceramic particles have low density and large particles have pores inside, the size of the ceramic reinforcing phase proposed in the present invention can reach 500 μm. This improves the efficiency of preparing ceramic particles.

[0038] The volume fraction of the ceramic reinforcing phase accounts for 20-70% of the total volume. Within this range, the composite material can have low expansion performance, and the coefficient of linear expansion is less than 10×10 -6 K -1 .

[0039] The volume fraction of the ceramic reinforcing phase accounts for 50-70% of the total volume. Within this range, the composite material can have near-zero expansion performance, and the coefficient of linear expansion is less than 2×10 -6 K -1 .

[0040] Said metal reinforcing phase is (Hf 1-x Nb x )Fe₂, (Hf 1-x Ti x )Fe₂, (Zr 1-x Nb x )Fe₂, La(Fe 1-x (Co 1-y Si y ) x ) 13 and La(Fe 1-x Si x ) 13 wherein 0<x<1, 0<y<1, and the average size of the metal reinforcing phase is 10-400μm. An excessively large average size of the metal reinforcing phase will deteriorate the mechanical properties of the La-based amorphous matrix; while an excessively small average size will cause agglomeration among particles, resulting in poor performance uniformity of the prepared composite material.

[0041] When said (Zr 1-x Nb x )Fe₂ is Zr 0.72 Nb 0.28 Fe₂, the volume fraction of the Zr 0.72 Nb 0.28 Fe₂ reinforcing phase accounts for 15-70% of the total volume. Within this range, the composite material can have low expansion performance, with a coefficient of linear expansion less than 10×10 -6 K -1 .

[0042] For convenience of description, the present invention separately describes the preparation methods of La-based amorphous materials with metal reinforcing phases and ceramic reinforcing phases.

[0043] Since ZrW₂O₈, Cu₂P₂O₇, Cu₂V₂O₇, Mn₃Zn 1-x Sn x N or Mn₃Zn 1-x Ge x N, wherein 0<x<1, belong to the same type of ceramic material, Cu₂P₂O₇ is taken as an example for description for convenience; the La-based amorphous alloy selects La y Al 14 (Cu 5 / 6 Ag 1 / 6 ) 76-y (Ni 1 / 2 Co 1 / 2 ) 10 wherein y=65; the metal reinforcing phase is Zr 0.72 Nb 0.28Fe2+, as a negatively expanding phase, has a thermal expansion coefficient of -2.01 × 10⁻⁶. -6 K -1 Zr 0.72 Nb 0.28 When Fe2 is combined with the base metal, it can compensate for the large thermal expansion coefficient of the base metal.

[0044] The present invention also provides the above-mentioned ceramic particle-reinforced La-based amorphous composite material, taking Cu2P2O7 / La-based amorphous composite material as an example, including the following steps:

[0045] S1. Weigh out Cu2P2O7 particles according to the volume ratio and place them into the mold, then tap them to compact.

[0046] The preparation method of Cu2P2O7 particles in this embodiment of the invention is as follows: CuO powder and NH4H2PO4 are mixed and ball-milled. The resulting mixture is placed in an alumina crucible and kept at 250℃~300℃ for 5~10 hours to fully remove ammonia and water. The resulting precursor powder is then ground and annealed at 700~1100℃ for 8~12 hours. The Cu2P2O7 particles prepared by this method are not easily decomposed at high temperatures for short periods, thus avoiding loss or significant weakening of their negative expansion properties. When combined with La-based amorphous gas pressure infiltration composites, the interfacial reaction is small and the thermal expansion is effectively reduced.

[0047] To prevent smaller particles from depositing at the bottom of the mold during compaction, which would result in uneven distribution of the reinforcing phase in the composite material, and to ensure that the molten metal can quickly penetrate the gaps and pores between Cu2P2O7 particles during gas pressure infiltration, the Cu2P2O7 particles are divided into three grades according to their average particle size: Grade I particles have a particle size larger than the average particle size, Grade III particles have a particle size less than one-third of the average particle size, and Grade II particles fall in between. The Grade I and Grade II particles are mixed evenly and then placed in the mold for compaction. Subsequently, the Grade III particles are spread evenly on the surface. The Grade III particles, along with the molten metal, enter the gaps between the Grade I and Grade II particles after compaction, resulting in a uniform distribution of the reinforcing phase, high shape stability, and consistent mechanical properties in the prepared sample.

[0048] It should be noted that the method of mixing primary, secondary, and tertiary particle sizes in this invention differs significantly from directly mixing tertiary particle sizes. The main difference lies in the mixing process. After separating the primary and secondary particle sizes, they can be added to the mold simultaneously in a certain proportion, or added alternately multiple times, to improve the uniformity of the mixture. However, directly mixing the primary and secondary particle sizes results in secondary particles tending to deposit at the bottom of the mold, while primary particles tend to deposit at the top.

[0049] Preferably, the vibration acceleration of the present invention does not exceed 10g, and the amplitude is 0-5mm.

[0050] S2. Place the La-based amorphous alloy directly above the mold and perform vacuum heating impregnation.

[0051] The vacuum heating impregnation process is as follows: the vacuum degree is not higher than 0.1 Pa, the heating rate is 30-60℃ / min, and the first heating temperature is T. m -T m +100, where T m The melting point of the La-based amorphous alloy is given, and the holding time is 15-70 minutes.

[0052] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0053] The pressurized heat preservation process is as follows: inert gas is used to pressurize to 0.3-1.5 MPa, and the second heating temperature is T. m -T m Hold at +100°C for 10-100 minutes.

[0054] S4. Quenching yields a low-expansion composite material of Cu2P2O7-reinforced La-based amorphous alloy.

[0055] The quenching cooling rate is at least 1.1v. c v c The minimum cooling rate for the La-based amorphous alloy to form an amorphous structure.

[0056] This invention prepares a low-expansion composite material of Cu2P2O7-reinforced La-based amorphous alloy using a gas pressure infiltration process. First, the preparation process and compaction process of the Cu2P2O7 particles are precisely controlled to ensure that the subsequently molten La-based amorphous alloy is infiltrated through gaps. Furthermore, as the melt flows, the tertiary particles are transported to the compacted primary and secondary mixture, improving the shape stability and uniformity of the composite material's mechanical properties. Second, the gas pressure infiltration method prevents the pores within the same Cu2P2O7 particle from being crushed, allowing the melt to more easily penetrate these pores, thus increasing the density of the composite material. The composite material prepared by this invention achieves a density of over 99%, along with high hardness and strength. Third, the increased density enhances the... The thermal conductivity of the material after pressure insulation treatment can be transformed into an amorphous structure through quenching. Finally, the present invention places the La-based amorphous alloy directly above the mold. During the melting process, the amorphous alloy contains amorphous particles, which flow into the gaps between Cu2P2O7 particles along with the melt. The molten La-based metal enters the pores inside the Cu2P2O7 particles and the smaller gaps between the Cu2P2O7 particles, while the amorphous particles fill the larger gaps between the Cu2P2O7 particles. The above mechanism, combined with the quenching process, synergistically prepares a low-expansion composite material of Cu2P2O7 reinforced La-based amorphous alloy.

[0057] The present invention also provides the above-mentioned metal particle-reinforced La-based amorphous composite material, with (Zr) 1-x Nb x Taking Fe2 / La-based amorphous composite materials as an example, the following steps are included:

[0058] In the embodiments of the present invention, (Zr) 1-x Nb x Fe2 particles are produced by high-temperature melting of Zr, Nb, and Fe metals in an electric arc furnace. At high temperatures, their composition does not easily change, thus reducing or eliminating their negative thermal expansion properties. When combined with La-based amorphous materials through pressure infiltration, the interfacial reaction is minimal, effectively reducing their thermal expansion.

[0059] The (Zr) 1-x Nb x The average size of Fe2 particles is 10–400 μm.

[0060] To prevent smaller particles from depositing at the bottom of the mold during compaction, which would result in uneven distribution of the reinforcing phase in the composite material, and to ensure rapid penetration of the molten metal into (Zr) during pressure infiltration. 1-x Nb x The gaps between Fe2 particles, the (Zr) 1-x Nb xFe2 particles are classified into three grades according to their average particle size: Grade I particles have a particle size larger than the average particle size, Grade III particles have a particle size less than one-third of the average particle size, and Grade II particles fall in between. The Grade I and Grade II particles are mixed evenly and then compacted in a mold. Subsequently, Grade III particles are spread evenly on the surface. The Grade III particles, along with the molten metal, enter the gaps between the compacted Grade I and Grade II particles, resulting in a uniform distribution of the reinforcing phase in the prepared sample, high shape stability, and uniform mechanical properties. It should be noted that the compaction in this invention refers to increasing the density between particles through vibration, not applying external force to the particles through tamping, which could cause cracks or breakage.

[0061] Preferably, the vibration acceleration of the present invention does not exceed 10g, and the amplitude is 0-5mm.

[0062] It should be noted that the method of mixing the primary, secondary, and tertiary particle sizes in this invention differs significantly from directly mixing the tertiary particle sizes. The main difference lies in the mixing process. After separating the primary and secondary particle sizes, they can be added to the mold simultaneously in a certain proportion, or added alternately multiple times, to improve the uniformity of the mixture. However, directly mixing the primary and secondary particle sizes results in the secondary particles tending to deposit at the bottom of the mold, while the primary particles tend to deposit at the top.

[0063] S2. Place the La-based amorphous alloy directly above the mold and perform vacuum heating impregnation.

[0064] The vacuum heating impregnation process is as follows: the vacuum degree is not higher than 0.1 Pa, the heating rate is 35-55℃ / min, and the first heating temperature is T. m -T m +80, where T m The melting point of the La-based amorphous alloy is given, and the holding time is 10-60 minutes.

[0065] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0066] The pressurized heat preservation process is as follows: inert gas is used to pressurize to 0.5-1.5 MPa, and the second heating temperature is T. m -T m Keep warm and pressurized at +80°C for 30-90 minutes.

[0067] S4. Quenching, to obtain (Zr 1-x Nb x Fe2 / La-based amorphous composite materials.

[0068] The quenching cooling rate is at least 1.1v. c v cThe minimum cooling rate for the formation of an amorphous structure in the La-based amorphous alloy can be determined experimentally based on different alloy materials.

[0069] This invention prepares (Zr) through a gas pressure impregnation process. 1-x Nb x Fe2+ ​​reinforced La-based amorphous composite material. (Zr 1- x Nb x Fe2+ ​​has a high melting point, typically above 1000℃. In subsequent gas pressure infiltration processes, (Zr...) 1-x Nb x The interfacial reaction between Fe2+ and La-based amorphous alloys is small. Firstly, regarding (Zr...) 1-x Nb x The preparation process and compaction process of Fe2 particles are specified to ensure that the subsequently melted La-based amorphous alloy is infiltrated through gaps. Furthermore, as the melt flows, the tertiary particles are transported to the compacted primary and secondary mixture, ensuring the uniformity of the composite material's expansion and mechanical properties. Secondly, the use of a pneumatic infiltration method improves the density of the composite material; the composite material prepared by this invention achieves a density of over 99%, with high hardness and strength. Thirdly, the increased density enhances the thermal conductivity of the material after pressure and heat treatment, enabling the molten metal to transform into an amorphous structure through quenching. Finally, this invention places the La-based amorphous alloy directly above the mold. During the melting process, amorphous particles are embedded in the melt and flow into (Zr) 1-x Nb x The gaps between Fe2 particles allow molten La-based metal to enter (Zr) 1-x Nb x The Fe2+ particles have small gaps between them, while amorphous particles fill the gaps between them. 1-x Nb x The relatively large gaps between Fe2 particles, combined with the above mechanism and the quenching process, synergistically produce (Zr) 1-x Nb x Fe2+ ​​reinforced La-based amorphous composite material; using a pneumatic impregnation process, in (Zr) 1-x Nb x Within the extremely small gaps between Fe2 particles, capillary action pulls the melt, ensuring the La-based amorphous alloy matrix's adhesion to (Zr) 1-x Nb x Fe2 particles are completely isolated, and (Zr) will not appear. 1-x Nb x The problem of Fe2 aggregation.

[0070] It should be noted that the inert gas used in this invention is a gas that will not react with the alloy in the technical solution. Ar gas is preferred, but other gases that meet the above conditions are also acceptable.

[0071] To better illustrate the embodiments of the present invention, the present invention will be further described in detail below through specific examples.

[0072] Example 1

[0073] This invention provides a Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Methods for preparing amorphous composite materials include:

[0074] S1. Weigh Zr according to the volume ratio 0.72 Nb 0.28 Fe2 granules were placed in the mold and compacted. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In composite materials with an amorphous alloy matrix, the volume fraction of the reinforcing agent is 65% with the addition of Zr. 0.72 Nb 0.28 Fe2 particles, the prepared Zr 0.72 Nb 0.28 The average particle size of Fe2 is 100 μm. The particles are graded according to size, and Zr particles larger than 100 μm are separated into primary grades. 0.72 Nb 0.28 Fe2 particles, and tertiary Zr particles with a diameter of less than 30 μm 0.72 Nb 0.28 Fe2 particles, primary and secondary Zr 0.72 Nb 0.28 The Fe2 particles were mixed evenly and compacted by vibration, and then coated with a three-stage Zr coating. 0.72 Nb 0.28 Fe2 particles.

[0075] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11(Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 50℃ / min, and the measured melting temperature is 500℃. Therefore, the first heating temperature is set to 500℃, and the holding time is 60min.

[0076] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0077] The pressurized heat preservation process is as follows: pressurize to 0.6 MPa with inert gas, heat at a second temperature of 500°C, and maintain the temperature and pressure for 90 minutes.

[0078] S4. Quenching yields Zr. 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite materials. This invention utilizes water quenching.

[0079] Prepared Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The microstructure of composite materials, such as Figure 1 As shown, gray represents Zr. 0.72 Nb 0.28 Fe2+ ​​reinforced phase, white is La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In an amorphous alloy matrix, La can be observed. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloy matrix filled with Zr0.72 Nb 0.28 The gaps between the Fe2 reinforcing phases can effectively suppress the thermal expansion of the matrix and improve the overall performance of the composite material. 0.72 Nb 0.28 The Fe2+ reinforcing phase has a size of 100 μm and is uniformly distributed in the amorphous matrix. Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material is well bonded and the reinforcement does not agglomerate, thanks to the excellent properties of air pressure infiltration.

[0080] For La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloys, Zr 0.72 Nb 0.28 Fe2 and Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 XRD tests were performed on amorphous composite materials, such as... Figure 2 As shown, the prepared Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material is in the temperature range of 233K to 323K, with a thermal expansion coefficient as low as 2×10⁻⁶. -6 K -1 It belongs to near-zero expansion composite materials.

[0081] like Figure 3 As shown in Figure a, the diffuse scattering peaks exhibited by XRD indicate that the amorphous material has excellent formation ability after infiltration. Figure 3As shown in b, the local XRD magnification of the composite material shows that the amorphous peaks are well preserved and no crystallization characteristic peaks are observed. The XRD peaks of the reinforcement are also well preserved. From the XRD pattern, it can be seen that there are almost no impurity peaks other than the two phases, which also indicates that the interfacial reaction is minimal.

[0082] like Figure 4 As shown, the atomic diffusion trend at the interface indicates that Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite materials exhibit minimal interfacial reactions, thanks to the short gas pressure infiltration process and minimal interfacial reaction time, resulting in almost no impurity phase formation.

[0083] The compressive strength was measured to be 690 MPa.

[0084] Example 2

[0085] This invention provides a Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Methods for preparing amorphous composite materials include:

[0086] S1. Weigh Zr according to the volume ratio 0.72 Nb 0.28 Fe2 granules were placed in the mold and compacted. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In composite materials with an amorphous alloy matrix, the volume fraction of the reinforcing agent is 15% with the addition of Zr. 0.72 Nb 0.28 Fe2 particles, the prepared Zr 0.72 Nb 0.28 The average particle size of Fe2 is 10 μm. Based on particle size, Zr particles larger than 10 μm were separated into primary grades. 0.72 Nb 0.28Fe2 particles, and tertiary Zr particles with a diameter of less than 3 μm 0.72 Nb 0.28 Fe2 particles, primary and secondary Zr 0.72 Nb 0.28 The Fe2 particles were mixed evenly and compacted by vibration, and then coated with a three-stage Zr coating. 0.72 Nb 0.28 Fe2 particles.

[0087] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.09 Pa, heating rate is 35℃ / min, first heating temperature is set to 550℃, and holding time is 10min.

[0088] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0089] The pressurization and heat preservation process is as follows: pressurize to 1.0 MPa with inert gas, heat at a second temperature of 550°C, and maintain the temperature and pressure for 30 minutes.

[0090] S4. Quenching yields Zr. 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite materials. This invention utilizes water quenching.

[0091] Prepared Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In the microstructure of composite materials, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni1 / 2 Co 1 / 2 ) 10 Matrix filled with Zr 0.72 Nb 0.28 In the gaps between the Fe2-reinforced phases, the Zr 0.72 Nb 0.28 The average size of the Fe2+ reinforced phase is 10 μm, and the reinforcement is uniformly distributed in the amorphous matrix. Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material is well bonded, and the reinforcement does not agglomerate.

[0092] Prepared Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 233K to 323K, with a coefficient as low as 8×10⁻⁶. -6 K -1 It belongs to low-expansion composite materials.

[0093] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0094] Interfacial reactions are minimal, with almost no impurity phase formation. The compressive strength was measured to be 600 MPa.

[0095] Example 3

[0096] This invention provides a Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co1 / 2 ) 10 Methods for preparing amorphous composite materials include:

[0097] S1. Weigh Zr according to the volume ratio 0.72 Nb 0.28 Fe2 granules were placed in the mold and compacted. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In composite materials with an amorphous alloy matrix, 50% Zr is added as reinforcement. 0.72 Nb 0.28 Fe2 particles, the prepared Zr 0.72 Nb 0.28 The average particle size of Fe2 is 400 μm. Based on particle size, the particles are graded, and Zr particles larger than 400 μm are separated into primary grades. 0.72 Nb 0.28 Fe2 particles, and tertiary Zr particles with a diameter of less than 130 μm 0.72 Nb 0.28 Fe2 particles, primary and secondary Zr 0.72 Nb 0.28 The Fe2 particles were mixed evenly and compacted by vibration, and then coated with a three-stage Zr coating. 0.72 Nb 0.28 Fe2 particles.

[0098] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 50℃ / min, first heating temperature is set to 580℃, and holding time is 30min.

[0099] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0100] The pressurization and heat preservation process is as follows: pressurize to 1.5 MPa with inert gas, heat at a second temperature of 520°C, and maintain the temperature and pressure for 60 minutes.

[0101] S4. Quenching yields Zr. 0.72 Nb 0.28 Fe2 enhances La65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite materials. This invention utilizes water quenching.

[0102] Prepared Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In the microstructure of composite materials, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Matrix filled with Zr 0.72 Nb 0.28 In the gaps between the Fe2-reinforced phases, the Zr 0.72 Nb 0.28 The Fe2+ reinforcing phase has a size of 400 μm and is uniformly distributed in the amorphous matrix. Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material is well bonded, and the reinforcement does not agglomerate.

[0103] Prepared Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 233K to 323K, with a coefficient as low as 4.5×10⁻⁶. -6 K -1 It belongs to low-expansion composite materials.

[0104] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0105] Interfacial reactions were minimal, with almost no impurity phase formation. The compressive strength was measured to be 650 MPa.

[0106] Example 4

[0107] This invention provides a Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Methods for preparing amorphous composite materials include:

[0108] S1. Weigh Zr according to the volume ratio 0.72 Nb 0.28 Fe2 granules were placed in the mold and compacted. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In composite materials with an amorphous alloy matrix, the volume fraction of the reinforcing agent is 15% with the addition of Zr. 0.72 Nb 0.28 Fe2 particles, the prepared Zr 0.72 Nb 0.28 The average particle size of Fe2 is 10 μm. Based on particle size, Zr particles larger than 10 μm were separated into primary grades. 0.72 Nb 0.28 Fe2 particles, and tertiary Zr particles with a diameter of less than 3 μm 0.72 Nb 0.28 Fe2 particles, primary and secondary Zr 0.72 Nb 0.28 The Fe2 particles were mixed evenly and compacted by vibration, and then coated with a three-stage Zr coating. 0.72 Nb 0.28 Fe2 particles.

[0109] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.09 Pa, heating rate is 35℃ / min, first heating temperature is set to 550℃, and holding time is 10min.

[0110] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0111] The pressurization and heat preservation process is as follows: pressurize to 1.0 MPa with inert gas, heat at a second temperature of 550°C, and maintain the temperature and pressure for 30 minutes.

[0112] S4. Quenching yields Zr. 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous composite materials. This invention utilizes water quenching.

[0113] Prepared Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In the microstructure of composite materials, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Matrix filled with Zr 0.72 Nb 0.28 In the gaps between the Fe2-reinforced phases, the Zr 0.72 Nb 0.28 The average size of the Fe2+ reinforced phase is 10 μm, and the reinforcement is uniformly distributed in the amorphous matrix. Zr 0.72 Nb0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material is well bonded, and the reinforcement does not agglomerate.

[0114] Prepared Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 233K to 323K, with a coefficient as low as 10×10⁻⁶. -6 K -1 It belongs to low-expansion composite materials.

[0115] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0116] Interfacial reactions were minimal, with almost no impurity phase formation. The compressive strength was measured to be 550 MPa.

[0117] Example 5

[0118] This invention provides a Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Methods for preparing amorphous composite materials include:

[0119] S1. Weigh Zr according to the volume ratio 0.72 Nb 0.28 Fe2 granules were placed in the mold and compacted. According to La... 65 Al 14 (Cu 5 / 6 Ag1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In composite materials with an amorphous alloy matrix, 70% of the reinforcement by volume is added with Zr. 0.72 Nb 0.28 Fe2 particles, the prepared Zr 0.72 Nb 0.28 The average particle size of Fe2 is 400 μm. Based on particle size, the particles are graded, and Zr particles larger than 400 μm are separated into primary grades. 0.72 Nb 0.28 Fe2 particles, and tertiary Zr particles with a diameter of less than 130 μm 0.72 Nb 0.28 Fe2 particles, primary and secondary Zr 0.72 Nb 0.28 The Fe2 particles were mixed evenly and compacted by vibration, and then coated with a three-stage Zr coating. 0.72 Nb 0.28 Fe2 particles.

[0120] S2. Place the La-based amorphous alloy directly above the mold and perform vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 50℃ / min, first heating temperature is set to 580℃, and holding time is 30min.

[0121] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0122] The pressurization and heat preservation process is as follows: pressurize to 1.5 MPa with inert gas, heat at a second temperature of 520°C, and maintain the temperature and pressure for 60 minutes.

[0123] S4. Quenching yields Zr. 0.72 Nb 0.28 Fe2-reinforced La-based amorphous composite material. This invention utilizes water quenching.

[0124] Prepared Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In the microstructure of composite materials, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11(Ni 1 / 2 Co 1 / 2 ) 10 Matrix filled with Zr 0.72 Nb 0.28 In the gaps between the Fe2-reinforced phases, the Zr 0.72 Nb 0.28 The Fe2+ reinforcing phase has a size of 400 μm and is uniformly distributed in the amorphous matrix. Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material is well bonded, and the reinforcement does not agglomerate.

[0125] Prepared Zr 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material has a thermal expansion coefficient in the temperature range of 233K to 323K, with a coefficient as low as 1.9×10⁻⁶. -6 K -1 It belongs to near-zero expansion composite materials.

[0126] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0127] Interfacial reactions were minimal, with almost no impurity phase formation. The compressive strength was measured to be 710 MPa.

[0128] Example 6

[0129] This invention provides a Cu2P2O7-enhanced La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10Methods for preparing low-expansion composite materials of amorphous alloys include;

[0130] S1. Weigh out Cu2P2O7 granules according to the volume ratio and place them in the mold, then tap to compact. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2Co 1 / 2 ) 10 In a low-expansion composite material with an amorphous alloy matrix, Cu2P2O7 particles were added with a reinforcement volume fraction of 55%. The average particle size of the prepared Cu2P2O7 was 200 μm. The particle size was graded according to the particle size, and primary Cu2P2O7 particles with a particle size greater than 200 μm and tertiary Cu2P2O7 particles with a particle size less than 40 μm were screened out. The primary and secondary Cu2P2O7 particles were mixed evenly and compacted, and then the tertiary Cu2P2O7 particles were covered on the surface.

[0131] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 60℃ / min, and the measured melting temperature is 450℃. Therefore, the first heating temperature is set to 500℃, and the holding time is 70min.

[0132] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0133] The pressurized heat preservation process is as follows: pressurize to 0.6 MPa with inert gas, heat at a second temperature of 500°C, and maintain the temperature and pressure for 100 minutes.

[0134] S4. Quenching yields Cu2P2O7-reinforced La. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 A low-expansion composite material of amorphous alloys. This invention utilizes water quenching.

[0135] The Cu2P2O7-enhanced Cu2P2O7 / La prepared in this embodiment 65Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The microstructure of low-expansion composite materials such as Figure 5 As shown, the gray phase is Cu2P2O7 reinforcing phase, and the white phase is La. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2Co 1 / 2 ) 10 In an amorphous alloy matrix, La can be observed. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The amorphous alloy matrix not only fills the gaps between the Cu2P2O7 reinforcing phases but also fills the pores within the same Cu2P2O7 reinforcing phase, effectively suppressing the thermal expansion of the matrix and improving the overall performance of the composite material. The Cu2P2O7 reinforcing phase has a size of 200 μm, and the reinforcement is uniformly distributed in the amorphous matrix. (Cu2P2O7 / La) 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material is well bonded and the reinforcement does not agglomerate, thanks to the excellent properties of air pressure infiltration.

[0136] like Figure 6 As shown, the prepared Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 173K to 323K, with a coefficient as low as 2×10⁻⁶. -6 K -1 It belongs to near-zero expansion composite materials.

[0137] For La respectively 65 Al 14 (Cu 5 / 6 Ag1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloys, Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 XRD analysis was performed on amorphous composite materials and Cu2P2O7. For example... Figure 7 As shown in Figure a, it can be seen that the amorphous formation is very good, and the XRD pattern shows that there are almost no impurity peaks other than the two phases. Figure 7 As shown in b, the local XRD magnification of the composite material shows obvious amorphous peaks.

[0138] like Figure 8 As shown, the atomic diffusion trend at the interface indicates that Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2Co 1 / 2 ) 10 The composite material exhibits minimal interfacial reaction, thanks to the short gas pressure infiltration process and minimal interfacial reaction time, resulting in almost no impurity phase formation.

[0139] The compressive strength was measured to be 540 MPa.

[0140] Example 7

[0141] This invention provides a Cu2P2O7-enhanced La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Methods for preparing low-expansion composite materials of amorphous alloys include;

[0142] S1. Weigh out Cu2P2O7 granules according to the volume ratio and place them in the mold, then tap to compact. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2Co 1 / 2 ) 10In a low-expansion composite material with an amorphous alloy matrix, Cu2P2O7 particles were added at a volume fraction of 50%. The average particle size of the prepared Cu2P2O7 particles was 50 μm. The particle size was graded according to the particle size, and primary Cu2P2O7 particles with a particle size greater than 50 μm and tertiary Cu2P2O7 particles with a particle size less than 15 μm were screened out. The primary and secondary Cu2P2O7 particles were mixed evenly and compacted, and then the tertiary Cu2P2O7 particles were covered on the surface.

[0143] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 60℃ / min, first heating temperature is set to 550℃, and holding time is 70min.

[0144] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0145] The pressurized heat preservation process is as follows: pressurize to 1.4 MPa with inert gas, heat at a second heating temperature of 550°C, and maintain the heat and pressure for 100 minutes.

[0146] S4. Quenching yields Cu2P2O7-reinforced La. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 A low-expansion composite material of amorphous alloys. This invention utilizes water quenching.

[0147] The Cu2P2O7-enhanced La prepared in this embodiment 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In the microstructure of low-expansion composites of amorphous alloys, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co1 / 2 ) 10 The matrix not only fills the gaps between the Cu2P2O7 reinforcing phases, but also fills the pores within the same Cu2P2O7 reinforcing phase. The size of the Cu2P2O7 reinforcing phase is 50 μm. The reinforcement is uniformly distributed in the amorphous matrix, with good bonding and no agglomeration.

[0148] The prepared Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 173K to 323K, with a coefficient as low as 2×10⁻⁶. -6 K -1 It belongs to near-zero expansion composite materials.

[0149] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0150] Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material exhibits minimal interfacial reaction and almost no impurity phase formation. The compressive strength was measured to be 451 MPa.

[0151] Example 8

[0152] This invention provides a Cu2P2O7-enhanced La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Methods for preparing low-expansion composite materials of amorphous alloys include;

[0153] S1. Weigh out Cu2P2O7 granules according to the volume ratio and place them in the mold, then tap to compact. According to La... 65 Al14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2Co 1 / 2 ) 10 In a low-expansion composite material with an amorphous alloy matrix, Cu2P2O7 particles were added at a volume fraction of 70%. The average particle size of the prepared Cu2P2O7 particles was 500 μm. The particle size was graded according to the particle size, and primary Cu2P2O7 particles with a particle size greater than 500 μm and tertiary Cu2P2O7 particles with a particle size less than 150 μm were screened out. The primary and secondary Cu2P2O7 particles were mixed evenly and compacted, and then the tertiary Cu2P2O7 particles were covered on the surface.

[0154] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 30℃ / min, first heating temperature is set to 450℃, and holding time is 15min.

[0155] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0156] The pressurization and heat preservation process is as follows: pressurize to 0.3 MPa with inert gas, heat at a second temperature of 450°C, and maintain the temperature and pressure for 10 minutes.

[0157] S4. Quenching yields Cu2P2O7-reinforced La. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 A low-expansion composite material of amorphous alloys. This invention utilizes water quenching.

[0158] The Cu2P2O7-enhanced La prepared in this embodiment 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10In the microstructure of low-expansion composites of amorphous alloys, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The matrix not only fills the gaps between the Cu2P2O7 reinforcing phases, but also fills the pores within the same Cu2P2O7 reinforcing phase. The size of the Cu2P2O7 reinforcing phase is 500 μm. The reinforcement is uniformly distributed in the amorphous matrix, with good bonding and no agglomeration.

[0159] The Cu2P2O7 / La prepared in this embodiment 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 173K to 323K, with a coefficient as low as 1.5×10⁻⁶. -6 K -1 It belongs to near-zero expansion composite materials.

[0160] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0161] Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material exhibits minimal interfacial reaction and almost no impurity phase formation. The compressive strength is measured to be 450 MPa.

[0162] Example 9

[0163] This invention provides a Cu2P2O7-enhanced La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co1 / 2 ) 10 Methods for preparing low-expansion composite materials of amorphous alloys include;

[0164] S1. Weigh out Cu2P2O7 granules according to the volume ratio and place them in the mold, then tap to compact. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2Co 1 / 2 ) 10 In a low-expansion composite material with an amorphous alloy matrix, Cu2P2O7 particles were added at a volume fraction of 20%. The average particle size of the prepared Cu2P2O7 particles was 50 μm. The particle size was graded according to the particle size, and primary Cu2P2O7 particles with a particle size greater than 50 μm and tertiary Cu2P2O7 particles with a particle size less than 15 μm were screened out. The primary and secondary Cu2P2O7 particles were mixed evenly and compacted. Then, tertiary Cu2P2O7 particles were covered on the surface.

[0165] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 60℃ / min, first heating temperature is set to 550℃, and holding time is 70min.

[0166] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0167] The pressurized heat preservation process is as follows: pressurize to 1.2 MPa with inert gas, heat at a second heating temperature of 550°C, and maintain the heat and pressure for 100 minutes.

[0168] S4. Quenching yields Cu2P2O7-reinforced La. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 A low-expansion composite material of amorphous alloys. This invention utilizes water quenching.

[0169] Prepared Cu2P2O7-enhanced La 65 Al14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In the microstructure of low-expansion composites of amorphous alloys, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The matrix not only fills the gaps between the Cu2P2O7 reinforcing phases, but also fills the pores within the same Cu2P2O7 reinforcing phase. The size of the Cu2P2O7 reinforcing phase is 50 μm. The reinforcement is uniformly distributed in the amorphous matrix, with good bonding and no agglomeration.

[0170] The prepared Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 173K to 323K, with a coefficient as low as 10×10⁻⁶. -6 K -1 It belongs to low-expansion composite materials.

[0171] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0172] Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The composite material exhibits minimal interfacial reaction and almost no impurity phase formation. The compressive strength is measured to be 550 MPa.

[0173] Example 10

[0174] This invention provides a Cu2P2O7-enhanced La65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Methods for preparing low-expansion composite materials of amorphous alloys include;

[0175] S1. Weigh out Cu2P2O7 granules according to the volume ratio and place them in the mold, then tap to compact. According to La... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2Co 1 / 2 ) 10 In a low-expansion composite material with an amorphous alloy matrix, Cu2P2O7 particles were added at a volume fraction of 20%. The average particle size of the prepared Cu2P2O7 particles was 500 μm. The particle size was graded according to the particle size, and primary Cu2P2O7 particles with a particle size greater than 500 μm and tertiary Cu2P2O7 particles with a particle size less than 150 μm were screened out. The primary and secondary Cu2P2O7 particles were mixed evenly and compacted, and then the tertiary Cu2P2O7 particles were covered on the surface.

[0176] S2. La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 An amorphous alloy is placed directly above the mold and subjected to vacuum heating impregnation. The vacuum heating impregnation process is as follows: vacuum degree is 0.1 Pa, heating rate is 30℃ / min, first heating temperature is set to 450℃, and holding time is 15min.

[0177] S3. After the insulation is completed, pressure insulation treatment is carried out.

[0178] The pressurization and heat preservation process is as follows: pressurize to 0.3 MPa with inert gas, heat at a second temperature of 450°C, and maintain the temperature and pressure for 10 minutes.

[0179] S4. Quenching yields Cu2P2O7-reinforced La. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 )10 A low-expansion composite material of amorphous alloys. This invention utilizes water quenching.

[0180] Prepared Cu2P2O7-enhanced La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 In the microstructure of low-expansion composites of amorphous alloys, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The matrix not only fills the gaps between the Cu2P2O7 reinforcing phases, but also fills the pores within the same Cu2P2O7 reinforcing phase. The size of the Cu2P2O7 reinforcing phase is 500 μm. The reinforcement is uniformly distributed in the amorphous matrix, with good bonding and no agglomeration.

[0181] The prepared Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The thermal expansion coefficient of the composite material ranges from 173K to 323K, with a coefficient as low as 10×10⁻⁶. -6 K -1 It belongs to low-expansion composite materials.

[0182] Through XRD testing, La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 It is an amorphous matrix.

[0183] Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10The composite material exhibits minimal interfacial reaction and almost no impurity phase formation. The compressive strength was measured to be 548 MPa.

[0184] Comparative Example 1

[0185] Compared with Example 1, the difference is that in step S2, La is... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Amorphous alloy replaced with La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Crystal alloy.

[0186] Prepared Zr 0.72 Nb 0.28 Fe2 enhances La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The XRD of the composite material showed crystalline peaks, and its compressive strength was measured to be 401 MPa.

[0187] Based on the results of Example 1 and Comparative Example 1, it can be seen that using La-based amorphous materials in step S2 will increase the Zr content. 0.72 Nb 0.28 Fe2 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The amorphous forming ability of composite materials allows for the preparation of composite materials with excellent mechanical properties and low thermal expansion.

[0188] Comparative Example 2

[0189] Compared with Example 6, the difference is that in step S2, La is... 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co1 / 2 ) 10 Amorphous alloy replaced with La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 Crystal alloy.

[0190] Prepared Cu2P2O7 / La 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The XRD of the composite material showed crystalline peaks, and its compressive strength was measured to be 320 MPa.

[0191] Based on the results of Example 6 and Comparative Example 2, it can be seen that using La-based amorphous material in step S2 increases the Cu2P2O7 / La ratio. 65 Al 14 (Cu 5 / 6 Ag 1 / 6 ) 11 (Ni 1 / 2 Co 1 / 2 ) 10 The amorphous forming ability of composite materials allows for the preparation of composite materials with excellent mechanical properties and low thermal expansion.

[0192] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A negative thermal expansion particle-reinforced La-based amorphous composite material, characterized in that, La-based amorphous alloys separate different negative thermal expansion phases, which are ceramic reinforcing phases. The La-based amorphous alloys are La-Al-Cu, La-Al-Co, La-Al-Ni, La-Al-(Cu,Ni) or La-Al-(Cu,Ag)-(Ni,Co) systems. The volume fraction of the ceramic-reinforced phase / La-based amorphous composite reinforcement is 20%-70%; The preparation method of the negative thermal expansion particle-reinforced La-based amorphous composite material is as follows: Weigh out the negative thermal expansion particles according to the volume ratio, place them into the mold, and compact them. A La-based amorphous alloy is placed directly above the mold and then subjected to vacuum heating and impregnation. After the insulation is completed, pressure insulation treatment is carried out; Quenching yields a negative thermal expansion particle-reinforced La-based amorphous composite material. The compaction process is as follows: the negative thermal expansion particles are divided into three grades according to their average particle size. Grade 1 particles are larger than the average particle size, Grade 3 particles are smaller than one-third of the average particle size, and the particle size in between is Grade 2. The particles of Grade 1 and Grade 2 particle sizes are mixed evenly and then placed into a mold for compaction. Subsequently, the particles of Grade 3 particle size are spread evenly on the surface. The cooling rate for the quenching is at least 1.1v. c v c The minimum cooling rate required for the La-based amorphous alloy to form an amorphous structure; The negative thermal expansion particles are ceramic particles; The vacuum heating impregnation process is as follows: the vacuum degree is not higher than 0.1 Pa, the heating rate is 30℃ / min - 60℃ / min, and the first heating temperature is T. m ~T m +100℃, where T m The value is the melting point of the La-based amorphous alloy, expressed in °C, with a holding time of 15 min - 70 min.

2. The negative thermal expansion particle-reinforced La-based amorphous composite material according to claim 1, characterized in that, The ceramic reinforcing phase is ZrW2O8, Cu2P2O7, or Cu2V2O. 7、 Mn3Zn 1-x Sn x N or Mn3Zn 1-x Ge x N, 0 < x < 1, the average size of the ceramic reinforcing phase is 50 μm - 500 μm.

3. The negative thermal expansion particle-reinforced La-based amorphous composite material according to claim 1, characterized in that, The average size of the ceramic particles is 50μm-500μm.

4. The negative thermal expansion particle-reinforced La-based amorphous composite material according to claim 1, characterized in that, The pressurized heat preservation process is as follows: inert gas is used to pressurize to 0.3 MPa-1.5 MPa, and the second heating temperature is T. m ~T m Hold at +100℃ and pressure for 10 min - 100 min.

5. A negative thermal expansion particle-reinforced La-based amorphous composite material, characterized in that, La-based amorphous alloys separate different negative thermal expansion phases, which are metal reinforcement phases. The La-based amorphous alloys are La-Al-Cu, La-Al-Co, La-Al-Ni, La-Al-(Cu,Ni) or La-Al-(Cu,Ag)-(Ni,Co) systems. The volume fraction of the metal-reinforced phase / La-based amorphous composite reinforcement is 10%-70%; The preparation method of the negative thermal expansion particle-reinforced La-based amorphous composite material is as follows: Weigh out the negative thermal expansion particles according to the volume ratio, place them into the mold, and compact them. A La-based amorphous alloy is placed directly above the mold and then subjected to vacuum heating and impregnation. After the insulation is completed, pressure insulation treatment is carried out; Quenching yields a negative thermal expansion particle-reinforced La-based amorphous composite material. The compaction process is as follows: the negative thermal expansion particles are divided into three grades according to their average particle size. Grade 1 particles are larger than the average particle size, Grade 3 particles are smaller than one-third of the average particle size, and the particle size in between is Grade 2. The particles of Grade 1 and Grade 2 particle sizes are mixed evenly and then placed into a mold for compaction. Subsequently, the particles of Grade 3 particle size are spread evenly on the surface. The cooling rate for the quenching is at least 1.1v. c v c The minimum cooling rate required for the La-based amorphous alloy to form an amorphous structure; The negative thermal expansion particles are metal particles; The vacuum heating impregnation process is as follows: the vacuum degree is not higher than 0.1 Pa, the heating rate is 35℃ / min - 55℃ / min, and the first heating temperature is T. m ~T m +80℃, where T m The value is the melting point of the La-based amorphous alloy, expressed in °C, with a holding time of 10 min - 60 min.

6. The negative thermal expansion particle-reinforced La-based amorphous composite material according to claim 5, characterized in that, Said metal reinforcing phase is (Hf 1−x Nb x )Fe₂, (Hf 1−x Ti x )Fe₂, (Zr 1−x Nb x )Fe₂, La(Fe 1-x (Co 1-y Si y ) x ) 13 or La(Fe 1- x Si x ) 13 , wherein 0 < x < 1, 0 < y < 1, and the average size of the metal reinforcing phase is 10 μm - 400 μm.

7. The negative thermal expansion particle-reinforced La-based amorphous composite material according to claim 5, characterized in that, The average size of the metal particles is 10μm-400μm.

8. The negative thermal expansion particle-reinforced La-based amorphous composite material according to claim 5, characterized in that, The pressurized heat preservation process is as follows: inert gas is used to pressurize to 0.5 MPa - 1.5 MPa, and the second heating temperature is T. m ~T m Hold at +80℃ for 30-90 minutes.

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