Aluminum-based composite material and preparation method thereof

Abstract

The invention relates to an aluminum-based composite material and a preparation method thereof.The preparation raw materials of the aluminum-based composite material comprise anti-perovskite Mn3XN powder, and X is any one or a combination of at least two of Cu, Zn, Ga, Ge or Sn; the average particle size of the anti-perovskite Mn3XN powder ranges from 25 nm to 35 nm; the aluminum-based composite material can further comprise 10 vol%-25 vol% of a core reinforcing phase and 0-8 vol% of an auxiliary reinforcing phase. The anti-perovskite Mn3XN powder with the average particle size of 25-35 nm is used, so that an intragranular reinforced structure can be formed, the thermal expansion coefficient of the aluminum-based composite material is further reduced, and meanwhile, higher conductivity is kept.

Description

Technical Field

[0001] This invention belongs to the field of advanced metal-based materials technology, and relates to an aluminum-based composite material and its preparation method. Background Technology

[0002] The widespread application of aluminum-based composite materials in the field of thermal management benefits from their excellent comprehensive performance, but their coefficient of thermal expansion (CTE) has become a bottleneck restricting their development. This coefficient of thermal expansion is not compatible with the key supporting materials in thermal management systems such as semiconductors and ceramics. During temperature cycling, thermal stress is easily generated, which can lead to problems such as interface cracking and structural failure, seriously affecting the reliability and service life of the device.

[0003] To address the aforementioned issues, the mainstream solution in existing technologies is to add ceramic-based negative thermal expansion materials to the aluminum matrix to adjust the overall thermal expansion performance. Commonly used materials include ZrW2O8 and ZrO2. However, this approach has three significant drawbacks: First, conductivity is severely compromised. Most ceramic materials are insulators, and their addition significantly reduces the original excellent conductivity of the aluminum matrix, failing to meet the needs of scenarios requiring both thermal management and conductivity. Second, interfacial bonding performance is poor. The wettability between ceramics and metallic aluminum is inherently insufficient, easily leading to voids or weak bonding layers at the interface after molding, resulting in a decrease in the mechanical and thermal conductivity of the composite material. Third, process stability is limited. Taking ZrW2O8 as a typical example, it undergoes a phase transformation decomposition at approximately 777°C, directly compressing the temperature window for the sintering process of aluminum-based composite materials, increasing the difficulty and cost of preparation.

[0004] Therefore, there is a need to provide an aluminum-based composite material with excellent comprehensive performance and its preparation method. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an aluminum-based composite material and its preparation method. This aluminum-based composite material can form an "intracrystalline" reinforcing structure by using anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm, thereby further reducing the coefficient of thermal expansion of the aluminum-based composite material while maintaining higher electrical conductivity.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides an aluminum-based composite material, wherein the raw material for preparing the aluminum-based composite material includes anti-perovskite Mn3XN powder, wherein X is any one or a combination of at least two of Cu, Zn, Ga, Ge or Sn;

[0008] The average particle size of the anti-perovskite Mn3XN powder is 25nm~35nm.

[0009] Anti-perovskite Mn3XN powder is a type of metallic material with negative thermal expansion. It exhibits significant negative thermal expansion characteristics over a wide temperature range of up to 100K near room temperature and also possesses metallic conductivity (resistivity of approximately 10). -5 With its high thermal conductivity (approximately 5 W / (m·K)) and excellent thermal conductivity (Ω·cm), this material is an ideal reinforcement for low-expansion, high-conductivity aluminum-based composites. This invention utilizes anti-perovskite Mn3XN powder with an average particle size of 25 nm to 35 nm, which increases the surface atomic ratio at the nanoscale, enhancing the negative thermal expansion effect. It also enables the anti-perovskite Mn3XN powder to form large-area coherent / semi-coherent interfaces. This not only exerts a negative expansion effect but also pins grain boundaries, suppressing thermal vibrations of the aluminum lattice. Therefore, by using anti-perovskite Mn3XN powder with an average particle size of 25 nm to 35 nm, this invention enables the formation of an "intragranular" reinforcement structure, further reducing the coefficient of thermal expansion of the aluminum-based composite while maintaining higher electrical conductivity.

[0010] The average particle size of the anti-perovskite Mn3XN powder is 25nm~35nm, for example, it can be 25nm, 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm or 35nm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0011] If the average particle size of the anti-perovskite Mn3XN powder is too large, its nano-effect will be significantly attenuated, resulting in a substantial reduction in the atomic ratio on the particle surface. This weakens the negative thermal expansion effect and greatly diminishes its ability to regulate the thermal expansion coefficient of the aluminum matrix, making it difficult to achieve the low expansion target. Furthermore, the contact area between large particles and the aluminum matrix will be limited, preventing the formation of a large-area coherent / semi-coherent interface. Insufficient interfacial wettability and bonding strength will easily lead to voids or weak layers at the interface, resulting in a decrease in the mechanical stability, thermal conductivity, and electrical conductivity of the composite material. At the same time, the pinning effect of large particles on the grain boundaries of the aluminum matrix is ​​weak, failing to effectively suppress the thermal vibration of the aluminum lattice. The dual CTE reduction mechanism is difficult to take effect, and large particles are prone to agglomeration or uneven distribution in the aluminum matrix, further exacerbating the volatility of the composite material's properties.

[0012] If the average particle size of the anti-perovskite Mn3XN powder is too small, the surface energy of the nanoparticles will increase sharply, and the thermodynamic stability will deteriorate. During powder storage, transportation, or composite material preparation, agglomeration will easily occur, forming agglomerates with a size much larger than the original particle size. This not only loses the advantages of the nano-effect but also forms macroscopic defects in the aluminum matrix, seriously affecting the uniformity of material properties. If the particles are too small, the surface activity will be too high, and they will easily react chemically with the aluminum matrix, leading to the degradation of the powder's core properties such as negative thermal expansion and metallic conductivity. The preparation and dispersion process of ultrafine powder is difficult and costly, and excessive ultrafine particles may disrupt the continuity of the aluminum matrix, increase the interfacial resistance, and lead to a decrease in the conductivity of the composite material, which is not conducive to industrial applications.

[0013] In some embodiments, the aluminum matrix composite material comprises 10 vol% to 25 vol% of a core reinforcing phase by volume percentage, for example, 10 vol%, 12 vol%, 15 vol%, 18 vol%, 20 vol%, 21 vol%, 24 vol%, or 25 vol%, but is not limited to the listed values; other unlisted values ​​within the range are also applicable.

[0014] The core reinforcing phase is derived from the anti-perovskite Mn3XN powder.

[0015] In some embodiments, the aluminum-based composite material further includes, by volume percentage, less than 8 vol% of an auxiliary reinforcing phase, such as 0.1 vol%, 0.5 vol%, 1 vol%, 2 vol%, 3 vol%, 4 vol%, 5 vol%, 6 vol%, 7 vol%, or 8 vol%, but not limited to the listed values; other unlisted values ​​within the range are also applicable.

[0016] In some embodiments, the auxiliary reinforcing phase comprises a carbon material; the carbon material includes graphene nanoparticles and / or carbon nanotubes.

[0017] Secondly, the present invention provides a method for preparing an aluminum-based composite material, the method comprising the following steps:

[0018] (1) Provide anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm;

[0019] (2) Mix aluminum powder with the anti-perovskite Mn3XN powder to obtain a mixture;

[0020] (3) The mixture is sintered and plastically processed, and then aged to obtain the aluminum-based composite material described in the first aspect.

[0021] The resulting aluminum-based composite material comprises an aluminum matrix obtained from aluminum powder and a core reinforcing phase obtained from anti-perovskite Mn3XN powder. In a preferred embodiment, the aluminum-based composite material comprises 10 vol% to 25 vol% of the core reinforcing phase by volume percentage.

[0022] In some embodiments, obtaining the mixture further includes mixing aluminum powder, carbon material and the anti-perovskite Mn3XN powder to obtain the mixture.

[0023] The resulting aluminum-based composite material further includes an auxiliary reinforcing phase derived from carbon materials, including graphene nanoparticles and / or carbon nanotubes. In a preferred embodiment, the aluminum-based composite material comprises less than 8 vol% of the auxiliary reinforcing phase by volume.

[0024] In some embodiments, the preparation method of the anti-perovskite Mn3XN powder includes: ball milling and mixing manganese powder, metal X powder and nitrogen source to obtain micron-sized Mn3XN compound; wet ball milling the micron-sized Mn3XN compound to obtain the anti-perovskite Mn3XN powder;

[0025] The material of the metal X powder includes any one or at least two combinations of Cu, Zn, Ga, Ge or Sn. Typical but non-limiting combinations include Cu and Zn, Ga and Ge, Ga and Sn, Cu, Zn and Ge, or Cu, Zn, Ga, Ge and Sn.

[0026] In some embodiments, the nitrogen source includes a gaseous nitrogen source and / or a solid nitrogen source;

[0027] The gaseous nitrogen source includes a mixture of argon and ammonia;

[0028] The solid nitrogen source includes boron nitride nanopowder.

[0029] In some embodiments, the volume percentage of ammonia in the mixture is 10% to 50%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0030] This invention uses ball milling to mix powder particles, which are then continuously torn apart by mechanical force to create fresh surfaces. These surfaces react with nitrogen provided by a nitrogen source, and micron-sized Mn3XN compounds are directly synthesized through solid-phase diffusion.

[0031] In some embodiments, the mass ratio of balls to material in the ball milling mixture is 10:1 to 20:1, for example, it can be 10:1, 12:1, 15:1, 16:1, 18:1 or 20:1, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0032] In some embodiments, the ball milling speed is 400 rpm to 500 rpm, for example, 400 rpm, 410 rpm, 420 rpm, 430 rpm, 440 rpm, 450 rpm, 460 rpm, 470 rpm, 480 rpm, 490 rpm or 500 rpm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0033] In some embodiments, the ball milling mixing time is 20h to 60h, for example, it can be 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h or 60h, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0034] This invention enables the production of anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm through wet ball milling.

[0035] In some embodiments, the dispersion medium for the wet ball milling is ethanol.

[0036] In some embodiments, the grinding media of the wet ball milling includes zirconia microspheres with an average particle size of 0.1 mm to 0.3 mm, such as 0.1 mm, 0.2 mm or 0.3 mm, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0037] In some embodiments, the rotational speed of the wet ball mill is 800 rpm to 1200 rpm, for example, 800 rpm, 900 rpm, 1000 rpm, 1100 rpm or 1200 rpm.

[0038] In some embodiments, the wet ball milling process is followed by vacuum drying; wherein the vacuum drying temperature can be 55°C to 65°C, and the vacuum degree can be ≤10. -2 Pa, the time can be ≥24h.

[0039] In some embodiments, the method for obtaining the mixture includes mixing in an argon atmosphere using a three-dimensional mixer; for example, the mixing time can be 4h to 6h, and the rotation speed can be 45rpm to 55rpm. Under the above conditions, the agglomeration of nanoparticles caused by high-speed shear can be avoided.

[0040] In some embodiments, the sintering method includes performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain an SPS blank.

[0041] In some embodiments, the temperature of the SPS is 520°C to 580°C, for example, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C or 580°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0042] In some embodiments, the pressure of the SPS is 50MPa to 70MPa, for example, it can be 50MPa, 55MPa, 60MPa, 65MPa or 70MPa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0043] In some embodiments, the holding time of SPS is 2 min to 5 min, for example, it can be 2 min, 3 min, 4 min or 5 min, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0044] The anti-perovskite structure can be maintained during the heat preservation time of the SPS used in this invention.

[0045] In some embodiments, plastic processing includes: hot extrusion of the SPS billet, followed by multiple cold drawing passes to obtain wires or bars; and intermediate annealing when the deformation in each pass reaches 50%.

[0046] The temperature of hot extrusion can be 400℃~500℃, for example, 400℃, 420℃, 440℃, 450℃, 480℃, 490℃ or 500℃, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0047] The intermediate annealing temperature can be 290℃~310℃, and the time can be 28min~32min.

[0048] In some embodiments, the total deformation during plastic processing is 90% or more, for example, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97% or 98%, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0049] In some embodiments, the preparation method further includes a cryogenic treatment between plastic processing and aging treatment.

[0050] In some embodiments, the cryogenic treatment is performed at a temperature below -196°C for a duration of more than 1 hour.

[0051] This invention eliminates processing stress and stabilizes the properties of the resulting aluminum-based composite material through aging treatment.

[0052] In some embodiments, the aging treatment temperature is 150°C to 250°C, for example, 150°C, 160°C, 180°C, 200°C, 210°C, 240°C or 250°C, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0053] In some embodiments, the aging process takes 1 to 4 hours, for example, 1 hour, 2 hours, 3 hours or 4 hours, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0054] In some embodiments, the preparation method further includes depositing a copper layer on the surface of the aluminum-based composite material, or electroplating a Cu / Ag bilayer, to further reduce contact resistance.

[0055] As one of the preferred technical solutions of the preparation method provided by the present invention, the preparation method includes the following steps:

[0056] (1) Ball milling of manganese powder, metal X powder and nitrogen source to obtain micron-sized Mn3XN compound; wet ball milling of the micron-sized Mn3XN compound and vacuum drying to obtain anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm;

[0057] The nitrogen source includes a gaseous nitrogen source and / or a solid nitrogen source;

[0058] The ball milling process involves mixing balls in a mass ratio of 10:1 to 20:1, rotating at a speed of 400 rpm to 500 rpm, and for a time of 20 h to 60 h.

[0059] The dispersion medium for the wet ball milling is ethanol, the grinding medium is zirconium oxide microspheres with an average particle size of 0.1 mm to 0.3 mm, and the rotation speed is 800 rpm to 1200 rpm.

[0060] The vacuum drying temperature is 55℃~65℃, and the vacuum degree is ≤10. -2 Pa, time ≥24h;

[0061] (2) In an argon atmosphere, aluminum powder and the anti-perovskite Mn3XN powder are mixed using a three-dimensional mixer to obtain a mixture;

[0062] The mixing time is 4h~6h, and the rotation speed is 45rpm~55rpm;

[0063] (3) The mixture is sintered and plastically processed, and then aged to obtain an aluminum-based composite material; the aluminum-based composite material comprises 10 vol% to 25 vol% of core reinforcing phase by volume percentage.

[0064] The sintering method includes: performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain SPS billet; the heating rate of SPS is ≥150℃ / min, the temperature is 520℃~580℃, the pressure is 50MPa~70MPa, and the holding time is 2min~5min.

[0065] Plastic processing includes: hot extrusion of SPS billet at a temperature of 400℃~500℃, followed by multiple cold drawing passes to obtain wire or bar stock, with a total deformation of more than 90%; intermediate annealing is performed when the deformation of each pass reaches 50%.

[0066] The intermediate annealing temperature is 290℃~310℃, and the time is 28min~32min;

[0067] The aging treatment is performed at a temperature of 150℃ to 250℃ for a time of 1 hour to 4 hours.

[0068] As a second preferred embodiment of the preparation method provided by the present invention, the preparation method includes the following steps:

[0069] (1) Ball milling of manganese powder, metal X powder and nitrogen source to obtain micron-sized Mn3XN compound; wet ball milling of the micron-sized Mn3XN compound and vacuum drying to obtain anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm;

[0070] The nitrogen source includes a gaseous nitrogen source and / or a solid nitrogen source;

[0071] The ball milling process involves mixing balls in a mass ratio of 10:1 to 20:1, rotating at a speed of 400 rpm to 500 rpm, and for a time of 20 h to 60 h.

[0072] The dispersion medium for the wet ball milling is ethanol, the grinding medium is zirconium oxide microspheres with an average particle size of 0.1 mm to 0.3 mm, and the rotation speed is 800 rpm to 1200 rpm.

[0073] The vacuum drying temperature is 55℃~65℃, and the vacuum degree is ≤10. -2 Pa, time ≥24h;

[0074] (2) In an argon atmosphere, aluminum powder, carbon material and the anti-perovskite Mn3XN powder are mixed using a three-dimensional mixer to obtain a mixture;

[0075] The mixing time is 4h~6h, and the rotation speed is 45rpm~55rpm;

[0076] The carbon material includes graphene nanoparticles and / or carbon nanotubes;

[0077] (3) The mixture is sintered and plastically processed, and then aged to obtain an aluminum-based composite material; by volume percentage, the aluminum-based composite material includes 10 vol% to 25 vol% of core reinforcing phase and less than 8 vol% of auxiliary reinforcing phase;

[0078] The sintering method includes: performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain SPS billet; the heating rate of SPS is ≥150℃ / min, the temperature is 520℃~580℃, the pressure is 50MPa~70MPa, and the holding time is 2min~5min.

[0079] Plastic processing includes: hot extrusion of SPS billet at a temperature of 400℃~500℃, followed by multiple cold drawing passes to obtain wire or bar stock, with a total deformation of more than 90%; intermediate annealing is performed when the deformation of each pass reaches 50%.

[0080] The intermediate annealing temperature is 290℃~310℃, and the time is 28min~32min;

[0081] The aging treatment is performed at a temperature of 150℃ to 250℃ for a time of 1 hour to 4 hours.

[0082] As a third preferred embodiment of the preparation method provided by the present invention, the preparation method includes the following steps:

[0083] (1) Ball milling of manganese powder, metal X powder and nitrogen source to obtain micron-sized Mn3XN compound; wet ball milling of the micron-sized Mn3XN compound and vacuum drying to obtain anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm;

[0084] The nitrogen source includes a gaseous nitrogen source and / or a solid nitrogen source;

[0085] The ball milling process involves mixing balls in a mass ratio of 10:1 to 20:1, rotating at a speed of 400 rpm to 500 rpm, and for a time of 20 h to 60 h.

[0086] The dispersion medium for the wet ball milling is ethanol, the grinding medium is zirconium oxide microspheres with an average particle size of 0.1 mm to 0.3 mm, and the rotation speed is 800 rpm to 1200 rpm.

[0087] The vacuum drying temperature is 55℃~65℃, and the vacuum degree is ≤10. -2Pa, time ≥24h;

[0088] (2) In an argon atmosphere, aluminum powder and the anti-perovskite Mn3XN powder are mixed using a three-dimensional mixer to obtain a mixture;

[0089] The mixing time is 4h~6h, and the rotation speed is 45rpm~55rpm;

[0090] (3) The mixture is sintered and plastically processed, and then subjected to cryogenic treatment and aging treatment to obtain an aluminum-based composite material; the aluminum-based composite material comprises 10 vol% to 25 vol% of core reinforcing phase by volume percentage.

[0091] The sintering method includes: performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain SPS billet; the heating rate of SPS is ≥150℃ / min, the temperature is 520℃~580℃, the pressure is 50MPa~70MPa, and the holding time is 2min~5min.

[0092] Plastic processing includes: hot extrusion of SPS billet at a temperature of 400℃~500℃, followed by multiple cold drawing passes to obtain wire or bar stock, with a total deformation of more than 90%; intermediate annealing is performed when the deformation of each pass reaches 50%.

[0093] The intermediate annealing temperature is 290℃~310℃, and the time is 28min~32min;

[0094] The cryogenic treatment is performed at a temperature below -196°C for a duration of more than 1 hour.

[0095] The aging treatment is performed at a temperature of 150℃ to 250℃ for a time of 1 hour to 4 hours.

[0096] As a fourth preferred embodiment of the preparation method provided by the present invention, the preparation method includes the following steps:

[0097] (1) Ball milling of manganese powder, metal X powder and nitrogen source to obtain micron-sized Mn3XN compound; wet ball milling of the micron-sized Mn3XN compound and vacuum drying to obtain anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm;

[0098] The nitrogen source includes a gaseous nitrogen source and / or a solid nitrogen source;

[0099] The ball milling process involves mixing balls in a mass ratio of 10:1 to 20:1, rotating at a speed of 400 rpm to 500 rpm, and for a time of 20 h to 60 h.

[0100] The dispersion medium for the wet ball milling is ethanol, the grinding medium is zirconium oxide microspheres with an average particle size of 0.1 mm to 0.3 mm, and the rotation speed is 800 rpm to 1200 rpm.

[0101] The vacuum drying temperature is 55℃~65℃, and the vacuum degree is ≤10. -2 Pa, time ≥24h;

[0102] (2) In an argon atmosphere, aluminum powder, carbon material and the anti-perovskite Mn3XN powder are mixed using a three-dimensional mixer to obtain a mixture;

[0103] The mixing time is 4h~6h, and the rotation speed is 45rpm~55rpm;

[0104] The carbon material includes graphene nanoparticles and / or carbon nanotubes;

[0105] (3) The mixture is sintered and plastically processed, and then subjected to cryogenic treatment and aging treatment to obtain an aluminum-based composite material; by volume percentage, the aluminum-based composite material includes 10 vol% to 25 vol% of core reinforcing phase and less than 8 vol% of auxiliary reinforcing phase;

[0106] The sintering method includes: performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain SPS billet; the heating rate of SPS is ≥150℃ / min, the temperature is 520℃~580℃, the pressure is 50MPa~70MPa, and the holding time is 2min~5min.

[0107] Plastic processing includes: hot extrusion of SPS billet at a temperature of 400℃~500℃, followed by multiple cold drawing passes to obtain wire or bar stock, with a total deformation of more than 90%; intermediate annealing is performed when the deformation of each pass reaches 50%.

[0108] The intermediate annealing temperature is 290℃~310℃, and the time is 28min~32min;

[0109] The cryogenic treatment is performed at a temperature below -196°C for a duration of more than 1 hour.

[0110] The aging treatment is performed at a temperature of 150℃ to 250℃ for a time of 1 hour to 4 hours.

[0111] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0112] Compared with the prior art, the present invention has the following beneficial effects:

[0113] Anti-perovskite Mn3XN powder is a type of metallic material with negative thermal expansion. It exhibits significant negative thermal expansion characteristics over a wide temperature range of up to 100K near room temperature and also possesses metallic conductivity (resistivity of approximately 10). -5 With its high thermal conductivity (approximately 5 W / (m·K)) and excellent thermal conductivity (Ω·cm), this invention makes it an ideal reinforcement for low-expansion, high-conductivity aluminum-based composites. The invention utilizes anti-perovskite Mn3XN powder with an average particle size of 25 nm to 35 nm, which increases the surface atomic ratio at the nanoscale, enhancing the negative thermal expansion effect. It also enables the anti-perovskite Mn3XN powder to form large-area coherent / semi-coherent interfaces. This not only exerts a negative expansion effect but also pins grain boundaries, suppressing thermal vibrations of the aluminum lattice. Therefore, by using anti-perovskite Mn3XN powder with an average particle size of 25 nm to 35 nm, this invention enables the formation of an "intracrystalline" reinforcement structure, further reducing the coefficient of thermal expansion of the aluminum-based composite while maintaining higher electrical conductivity. Detailed Implementation

[0114] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0115] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0116] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0117] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0118] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0119] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0120] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0121] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0122] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0123] In this invention, "optional" means that something is optional, that is, it refers to any one of the two parallel solutions of "having" or "not having". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0124] In this invention, "room temperature" generally refers to 4℃~35℃, and can refer to 20℃±5℃. In some embodiments of this invention, room temperature refers to 20℃~30℃.

[0125] Example 1

[0126] This embodiment provides an aluminum-based composite material comprising 20 vol% of a core reinforcing phase, 3 vol% of an auxiliary reinforcing phase, and the remainder being an aluminum matrix; wherein the core reinforcing phase is derived from anti-perovskite Mn3GaN powder, and the auxiliary reinforcing phase is derived from graphene.

[0127] In this embodiment, the preparation method of the aluminum-based composite material includes the following steps:

[0128] (1) Ball milling mixed manganese powder, metallic Ga powder and nitrogen source to obtain micron-sized Mn3GaN compound; wet ball milling of the micron-sized Mn3GaN compound and vacuum drying to obtain anti-perovskite Mn3GaN powder with an average particle size of 30nm;

[0129] The nitrogen source is a gaseous nitrogen source, comprising a mixture of argon and ammonia, wherein the volume percentage of ammonia is 30%.

[0130] The ball milling process involves mixing balls and materials at a mass ratio of 15:1, rotating at 450 rpm, and for 40 hours.

[0131] The dispersion medium for the wet ball milling is ethanol, the grinding medium is zirconium oxide microspheres with an average particle size of 0.2 mm, and the rotation speed is 1000 rpm.

[0132] The vacuum drying temperature is 60°C and the vacuum degree is 10. -2 Pa, the time is 24 hours;

[0133] (2) In an argon atmosphere, aluminum powder, graphene and the anti-perovskite Mn3GaN powder are mixed using a three-dimensional mixer to obtain a mixture;

[0134] The mixing time was 5 hours and the rotation speed was 50 rpm.

[0135] (3) The mixture is sintered and plastically processed, and then subjected to cryogenic treatment and aging treatment to obtain an aluminum-based composite material; by volume percentage, the aluminum-based composite material includes 20 vol% of the core reinforcing phase and 3 vol% of the auxiliary reinforcing phase;

[0136] The sintering method includes: performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain SPS billet; the heating rate of SPS is 150℃ / min, the temperature is 550℃, the pressure is 60MPa, and the holding time is 4min.

[0137] Plastic processing includes: hot extrusion of SPS billet at 450℃ to obtain φ8mm bar stock, followed by multiple cold drawing passes to obtain φ2mm wire stock; intermediate annealing is performed when the deformation amount in each pass reaches 50%;

[0138] The intermediate annealing temperature is 300℃ and the time is 30 minutes;

[0139] The cryogenic treatment was carried out in liquid nitrogen at a temperature of -196°C for 1 hour.

[0140] The aging treatment was performed at a temperature of 200°C for 2 hours.

[0141] Example 2

[0142] This embodiment provides an aluminum-based composite material comprising 20 vol% of a core reinforcing phase, 3 vol% of an auxiliary reinforcing phase, and the remainder being an aluminum matrix; wherein the core reinforcing phase is derived from anti-perovskite Mn3GaN powder, and the auxiliary reinforcing phase is derived from graphene.

[0143] In this embodiment, the preparation method of the aluminum-based composite material includes the following steps:

[0144] (1) Ball milling mixed manganese powder, metallic Ga powder and nitrogen source to obtain micron-sized Mn3GaN compound; wet ball milling of the micron-sized Mn3GaN compound and vacuum drying to obtain anti-perovskite Mn3GaN powder with an average particle size of 30nm;

[0145] The nitrogen source is a gaseous nitrogen source, comprising a mixture of argon and ammonia, wherein the volume percentage of ammonia is 10%.

[0146] The ball milling process involves mixing balls and materials at a mass ratio of 10:1, rotating at 400 rpm, and for 60 hours.

[0147] The dispersion medium for the wet ball milling is ethanol, the grinding medium is zirconium oxide microspheres with an average particle size of 0.1 mm, and the rotation speed is 800 rpm.

[0148] The vacuum drying temperature is 55°C, and the vacuum degree is 10. -2 Pa, the time is 24 hours;

[0149] (2) In an argon atmosphere, aluminum powder, graphene and the anti-perovskite Mn3GaN powder are mixed using a three-dimensional mixer to obtain a mixture;

[0150] The mixing time was 4 hours and the rotation speed was 55 rpm.

[0151] (3) The mixture is sintered and plastically processed, and then subjected to cryogenic treatment and aging treatment to obtain an aluminum-based composite material; by volume percentage, the aluminum-based composite material includes 20 vol% of the core reinforcing phase and 3 vol% of the auxiliary reinforcing phase;

[0152] The sintering method includes: performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain SPS billet; the heating rate of SPS is 150℃ / min, the temperature is 520℃, the pressure is 50MPa, and the holding time is 5min.

[0153] Plastic processing includes: hot extrusion of SPS billet at 400℃ to obtain φ8mm bar stock, followed by multiple cold drawing passes to obtain φ2mm wire stock; intermediate annealing is performed when the deformation amount in each pass reaches 50%;

[0154] The intermediate annealing temperature was 290℃ and the time was 32 minutes;

[0155] The cryogenic treatment was carried out in liquid nitrogen at a temperature of -196°C for 1 hour.

[0156] The aging treatment was performed at a temperature of 150°C for 4 hours.

[0157] Example 3

[0158] This embodiment provides an aluminum-based composite material comprising 20 vol% of a core reinforcing phase, 3 vol% of an auxiliary reinforcing phase, and the remainder being an aluminum matrix; wherein the core reinforcing phase is derived from anti-perovskite Mn3GaN powder, and the auxiliary reinforcing phase is derived from graphene.

[0159] In this embodiment, the preparation method of the aluminum-based composite material includes the following steps:

[0160] (1) Ball milling mixed manganese powder, metallic Ga powder and nitrogen source to obtain micron-sized Mn3GaN compound; wet ball milling of the micron-sized Mn3GaN compound and vacuum drying to obtain anti-perovskite Mn3GaN powder with an average particle size of 30nm;

[0161] The nitrogen source is a gaseous nitrogen source, comprising a mixture of argon and ammonia, wherein the volume percentage of ammonia is 50%.

[0162] The ball milling process involves mixing balls in a ball-to-material mass ratio of 20:1, rotating at 500 rpm, and for 20 hours.

[0163] The dispersion medium for the wet ball milling is ethanol, the grinding medium is zirconium oxide microspheres with an average particle size of 0.3 mm, and the rotation speed is 1200 rpm.

[0164] The vacuum drying temperature is 65°C and the vacuum degree is 10. -2 Pa, the time is 24 hours;

[0165] (2) In an argon atmosphere, aluminum powder, graphene and the anti-perovskite Mn3GaN powder are mixed using a three-dimensional mixer to obtain a mixture;

[0166] The mixing time was 6 hours and the rotation speed was 45 rpm.

[0167] (3) The mixture is sintered and plastically processed, and then subjected to cryogenic treatment and aging treatment to obtain an aluminum-based composite material; by volume percentage, the aluminum-based composite material includes 20 vol% of the core reinforcing phase and 3 vol% of the auxiliary reinforcing phase;

[0168] The sintering method includes: performing spark plasma sintering (SPS) under vacuum or inert atmosphere conditions to obtain SPS billet; the heating rate of SPS is 150℃ / min, the temperature is 580℃, the pressure is 70MPa, and the holding time is 2min.

[0169] Plastic processing includes: hot extrusion of SPS billet at 500℃ to obtain φ8mm bar stock, followed by multiple cold drawing passes to obtain φ2mm wire stock; intermediate annealing is performed when the deformation amount in each pass reaches 50%;

[0170] The intermediate annealing temperature is 310℃ and the time is 28 minutes;

[0171] The cryogenic treatment was carried out in liquid nitrogen at a temperature of -196°C for 1 hour.

[0172] The aging treatment was performed at a temperature of 250°C for 1 hour.

[0173] The coefficient of thermal expansion, electrical conductivity, and tensile strength of the aluminum-based composite materials provided in Examples 1 to 3 were tested, and the results are shown in Table 1. The coefficient of thermal expansion was tested using a thermomechanical analyzer in a nitrogen atmosphere at a temperature range of 25℃ to 150℃; the electrical conductivity was tested using an eddy current conductivity meter according to IACS standards; and the tensile strength was tested using a universal testing machine at a tensile rate of 2 mm / min.

[0174] Table 1

[0175]

[0176] Example 4

[0177] This embodiment provides an aluminum-based composite material, which is the same as that in Example 1 except that, by volume percentage, the aluminum-based composite material includes 15 vol% of the core reinforcing phase.

[0178] Example 5

[0179] This embodiment provides an aluminum-based composite material, which is the same as that in Example 1 except that, by volume percentage, the aluminum-based composite material includes 10 vol% of the core reinforcing phase.

[0180] Example 6

[0181] This embodiment provides an aluminum-based composite material, which is the same as that in Example 1 except that, by volume percentage, the aluminum-based composite material includes 25 vol% of the core reinforcing phase.

[0182] The coefficient of thermal expansion, electrical conductivity and tensile strength of the aluminum-based composite materials provided in Examples 1 to 3 were tested, and the results are shown in Table 2.

[0183] Table 2

[0184]

[0185] Example 7

[0186] This embodiment provides an aluminum-based composite material, which is the same as in Example 1 except that, by volume percentage, the aluminum-based composite material includes 1 vol% of an auxiliary reinforcing phase (graphene).

[0187] Example 8

[0188] This embodiment provides an aluminum-based composite material, which is the same as in Example 1 except that, by volume percentage, the aluminum-based composite material includes 5 vol% of an auxiliary reinforcing phase (graphene).

[0189] Example 9

[0190] This embodiment provides an aluminum-based composite material, which is the same as in Example 1 except that, by volume percentage, the aluminum-based composite material includes 8 vol% of an auxiliary reinforcing phase (graphene).

[0191] The coefficient of thermal expansion, electrical conductivity and tensile strength of the aluminum-based composite materials provided in Examples 7 to 9 were tested, and the results are shown in Table 3.

[0192] Table 3

[0193]

[0194] Example 10

[0195] This embodiment provides an aluminum-based composite material. Except for changing the wet ball milling time to make the average particle size of the anti-perovskite Mn3GaN powder 25nm, everything else is the same as in Example 1.

[0196] Example 11

[0197] This embodiment provides an aluminum-based composite material. Except for changing the wet ball milling time to make the average particle size of the anti-perovskite Mn3GaN powder 35nm, everything else is the same as in Example 1.

[0198] Comparative Example 1

[0199] This comparative example provides an aluminum-based composite material, which is the same as in Example 1 except that the wet ball milling time is changed to make the average particle size of the anti-perovskite Mn3GaN powder 15nm.

[0200] Comparative Example 2

[0201] This comparative example provides an aluminum-based composite material, which is the same as in Example 1 except that the wet ball milling time is changed to make the average particle size of the anti-perovskite Mn3GaN powder 45nm.

[0202] To verify the advantages of the 25nm~35nm particle size range of the present invention, powders with excessively small (15nm) and excessively large (45nm) particle sizes were selected for comparison. The coefficient of thermal expansion, electrical conductivity and tensile strength of the aluminum-based composite materials provided in Examples 10~11 and Comparative Examples 1~2 were tested, and the results are shown in Table 4.

[0203] Table 4

[0204]

[0205] Example 12

[0206] This embodiment provides an aluminum-based composite material, which is the same as that in Example 1 except that the Ga powder is replaced with Cu powder.

[0207] Example 13

[0208] This embodiment provides an aluminum-based composite material, which is the same as that in Embodiment 1 except that the Ga powder is replaced with Zn powder.

[0209] Example 14

[0210] This embodiment provides an aluminum-based composite material, which is the same as that in Embodiment 1 except that Ga powder is replaced with Ge powder.

[0211] Example 15

[0212] This embodiment provides an aluminum-based composite material, which is the same as that in Embodiment 1 except that the Ga powder is replaced with Sn powder.

[0213] The coefficient of thermal expansion, electrical conductivity and tensile strength of the aluminum-based composite materials provided in Examples 12 to 15 were tested, and the results are shown in Table 5.

[0214] Table 5

[0215]

[0216] In summary, anti-perovskite Mn3XN powder is a type of metallic material with negative thermal expansion. It exhibits significant negative thermal expansion characteristics over a wide temperature range of up to 100K near room temperature and also possesses metallic conductivity (resistivity of approximately 10 Ω·K). -5 With its high thermal conductivity (approximately 5 W / (m·K)) and excellent thermal conductivity (Ω·cm), this invention makes it an ideal reinforcement for low-expansion, high-conductivity aluminum-based composites. The invention utilizes anti-perovskite Mn3XN powder with an average particle size of 25 nm to 35 nm, which increases the surface atomic ratio at the nanoscale, enhancing the negative thermal expansion effect. It also enables the anti-perovskite Mn3XN powder to form large-area coherent / semi-coherent interfaces. This not only exerts a negative expansion effect but also pins grain boundaries, suppressing thermal vibrations of the aluminum lattice. Therefore, by using anti-perovskite Mn3XN powder with an average particle size of 25 nm to 35 nm, this invention enables the formation of an "intracrystalline" reinforcement structure, further reducing the coefficient of thermal expansion of the aluminum-based composite while maintaining higher electrical conductivity.

[0217] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. An aluminum-based composite material, characterized in that, The raw materials for preparing the aluminum-based composite material include anti-perovskite Mn3XN powder, wherein X is any one or a combination of at least two of Cu, Zn, Ga, Ge or Sn; The average particle size of the anti-perovskite Mn3XN powder is 25nm~35nm.

2. The aluminum-based composite material according to claim 1, characterized in that, The aluminum-based composite material comprises 10 vol% to 25 vol% of a core reinforcing phase by volume percentage; The core reinforcing phase is derived from the anti-perovskite Mn3XN powder.

3. The aluminum-based composite material according to claim 1 or 2, characterized in that, The aluminum-based composite material further includes, by volume percentage, less than 8 vol% of auxiliary reinforcing phase.

4. The aluminum-based composite material according to claim 3, characterized in that, The auxiliary reinforcing phase includes carbon materials; The carbon material includes graphene nanoparticles and / or carbon nanotubes.

5. A method for preparing an aluminum-based composite material, characterized in that, The preparation method includes the following steps: (1) Provide anti-perovskite Mn3XN powder with an average particle size of 25nm~35nm; (2) Mix aluminum powder with the anti-perovskite Mn3XN powder to obtain a mixture; (3) The mixture is sintered and plastically processed, and then aged to obtain the aluminum-based composite material according to any one of claims 1 to 4.

6. The preparation method according to claim 5, characterized in that, The mixture also includes: mixing aluminum powder, carbon material and the anti-perovskite Mn3XN powder to obtain the mixture.

7. The preparation method according to claim 5 or 6, characterized in that, The preparation method of the anti-perovskite Mn3XN powder includes: ball milling and mixing manganese powder, metal X powder and nitrogen source to obtain micron-sized Mn3XN compound; wet ball milling the micron-sized Mn3XN compound to obtain the anti-perovskite Mn3XN powder; The material of the metal X powder includes any one or a combination of at least two of Cu, Zn, Ga, Ge, or Sn.

8. The preparation method according to claim 7, characterized in that, The nitrogen source includes a gaseous nitrogen source and / or a solid nitrogen source; The gaseous nitrogen source includes a mixture of argon and ammonia; The solid nitrogen source includes boron nitride nanopowder.

9. The preparation method according to claim 7, characterized in that, The mass ratio of balls to material in the ball mill mixture is 10:1 to 20:1; And / or, the ball milling speed is 400 rpm to 500 rpm; And / or, the ball milling mixing time is 20h~60h.

10. The preparation method according to claim 7, characterized in that, The dispersion medium for the wet ball milling is ethanol; And / or, the grinding media of the wet ball milling includes zirconium oxide microspheres with an average particle size of 0.1 mm to 0.3 mm; And / or, the rotation speed of the wet ball mill is 800 rpm to 1200 rpm.

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