CN114606453A - Novel metal-based composite material and preparation method and application thereof - Google Patents

Novel metal-based composite material and preparation method and application thereof Download PDF

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CN114606453A
CN114606453A CN202210244630.8A CN202210244630A CN114606453A CN 114606453 A CN114606453 A CN 114606453A CN 202210244630 A CN202210244630 A CN 202210244630A CN 114606453 A CN114606453 A CN 114606453A
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metal matrix
fibers
matrix composite
composite material
fiber
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周小兵
蒋龙飞
单旭
黄庆
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Ningbo Hangzhou Bay New Materials Research Institute
Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Hangzhou Bay New Materials Research Institute
Ningbo Institute of Material Technology and Engineering of CAS
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Priority to PCT/CN2023/080631 priority patent/WO2023174159A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/04—Light metals
    • C22C49/06—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/10—Refractory metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/10—Refractory metals
    • C22C49/11—Titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments

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Abstract

The invention discloses a novel metal-based composite material, and a preparation method and application thereof. The metal matrix composite includes a metal matrix and a reinforcing phase, the reinforcing phase including selected fibers and a rare earth boro-carbon compound material, the rare earth boro-carbon compound material being RExByCzAnd RE is at least one of Sc, Y and lanthanoid. The invention takes the rare earth boron-carbon compound particles and the selected fibers as the reinforcing phase of the metal matrix composite material together, because RExByCzThe ceramic has unique layered structure and excellent mechanical property, and has high oxidation resistance and high temperature stability, and the addition of the selected fiber is favorable to raising the strength of metal material, so that the reinforcing phase can improve obviously various performance of metal-base composite material.

Description

Novel metal-based composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of fiber and ceramic particle reinforced metal matrix composite materials, in particular to a novel fiber and ceramic particle reinforced metal matrix composite material and a preparation method and application thereof, and especially relates to a fiber and novel RExByCzA metal matrix composite material with synergistically enhanced ceramic particles and a preparation method thereof.
Background
The traditional single ceramic material has the advantages of high strength, high hardness, good corrosion resistance, wear resistance and the like, but the toughness is poor, so the processing difficulty is high and the application field is limited. The metal or alloy material with different properties has excellent mechanical properties, high ductility, good toughness and high strength, but correspondingly, the wear resistance, corrosion resistance and high temperature resistance are poor. In comparison, the ceramic reinforced metal matrix composite material which combines the advantages of the ceramic reinforced metal matrix composite material and the metal reinforced metal matrix composite material has the advantages of high temperature resistance of the ceramic and good toughness of the metal, low density, high specific strength, high specific rigidity, high specific modulus, high temperature resistance, wear resistance and the like, shows incomparable excellent performance of a single ceramic or metal material, and has good application prospect in the fields of structural members or functional members such as aerospace materials, automobile manufacturing, electromagnetic shielding, neutron absorption and shielding, electronic packaging, precision instruments and the like.
At present, the focus of research on ceramic reinforced metal matrix composite materials is mostly on the preparation, microstructure and final product performance of the composite materials, the selection of the composition of a ceramic reinforced phase and a metal matrix is started, the performance of the materials is gradually enhanced by continuously trying to change the size of fibers and particles and the proportion of the composition, and meanwhile, various preparation methods are selected and various fine adjustments are performed on the preparation path to control the properties of the products.
So far, copper base, iron base, aluminum base and the like are taken as representatives of metal base, carbon fiber, silicon carbide fiber and the like are selected on the fiber, a plurality of choices are available on ceramic particle reinforced phase, the choices of the types, the sizes of the particles, the content proportion and the like can cause great influence on the final performance of the composite material, the currently available common ceramic particles comprise oxide ceramic, carbide ceramic, nitride ceramic and the like, and Al is taken as a representative2O3Ceramics, B4C ceramics, SiC ceramics, and the like.
Conventional particle reinforcement methods have many disadvantages, and one of the common preparation methods is a powder metallurgy method, and a method of mixing a reinforcing phase ceramic powder and a matrix metal powder, sufficiently compacting the mixture, and then burning the compacted mixture to obtain a final product. The powder metallurgy process is simple, but the product prepared by the method has poor strength, particularly low tensile strength and poor toughness under impact load, so that the service performance of the product is reduced, and the service life of the product is shortened.
Disclosure of Invention
The invention mainly aims to provide a novel metal-based composite material, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a novel metal matrix composite material which comprises a metal matrix and a reinforcing phase, wherein the reinforcing phase comprises selected fibers and a rare earth boron carbon compound material, and the rare earth boron carbon compound material is RExByCzThe ceramic particles are characterized in that RE is one or a combination of more than two of Sc, Y and lanthanoid, the lanthanoid comprises La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x is 1-10, Y is 1-20, and z is 1-20.
In some embodiments, the rare earth borocarbide material is a medium-high entropy rare earth borocarbide compound, and the medium-high entropy ceramic material has a chemical formula of RExByCzWherein RE is any three or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and x, Y and z are selected from any one of 1:1:1, 1:2:1 and 1:2: 2.
Wherein when x, y and z are 1:2:2, the medium-high entropy ceramic material has a chemical general formula of RE1B2C2Wherein
Figure BDA0003544619290000021
REi＝Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu，xiIs REiThe molar constant of the component in RE is 3-17.
In some embodiments, the selected fibers include any one or a combination of two or more of carbon fibers, silicon nitride fibers, silica carbon fibers, alumina fibers, quartz fibers, mullite fibers, basalt fibers, silicate fibers, aluminate fibers.
The embodiment of the invention also provides a preparation method of the novel metal matrix composite material, which comprises the following steps:
will select the fiber, RExByCzUniformly mixing the ceramic particles with a metal or alloy material to obtain a mixture;
heat treating the mixture to obtain the fiber and RExByCzNovel metal matrix composites synergistically reinforced with ceramic particles.
The embodiment of the invention also provides application of the novel metal-based composite material in the fields of aerospace, nuclear energy, electromagnetic shielding, neutron absorption or shielding, radiology, electronic packaging, precision instruments and the like.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes the rare earth boron-carbon compound particles and the selected fibers as the reinforcing phase of the metal matrix composite material together, because RExByCzThe ceramic has a unique nano-layered structure so that the ceramic has good mechanical properties, and the addition of the selected fiber is more beneficial to improving the strength, so that the selected fiber and RE are usedxByCzThe ceramic particles are used as the reinforcing phase together, so that various properties of the metal matrix composite material can be obviously improved, the reinforcing phase in the form has higher strength, the high temperature resistance, the oxidation resistance, the corrosion resistance and the wear resistance are greatly improved, the service life of the material is greatly prolonged, and finally the fiber and RE prepared by the methodxByCzThe novel metal-based composite material cooperatively enhanced by ceramic particles can be applied in the fields of aerospace, nuclear energy, electromagnetic shielding, neutron absorption or shielding, radiology, electronic packaging, precision instruments and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of a novel metal matrix composite in an exemplary embodiment of the invention;
FIG. 2 shows a reinforcing phase prepared in example 1 of the present invention asCarbon fiber and YB2C2A schematic of the structure of the particulate aluminum metal matrix composite;
FIG. 3 shows that the reinforcing phase prepared in example 8 of the present invention has (Y)0.2La0.2Ce0.2Sm0.2Ho0.2)B2C2Quartz fiber and (La) of interfacial layer0.2Pm0.2Sm0.2Dy0.2Lu0.2)B2C2A schematic of the structure of the particulate aluminum metal matrix composite;
Detailed Description
In view of the defects of the prior art, the inventor of the present invention, during long-term research and extensive practice, has surprisingly found that rare earth boron carbon compound particles and selected types of fibers can be adopted to act synergistically to serve as a reinforcing phase of a metal matrix composite material. Based on the unexpected findings, the inventors of the present invention have proposed the technical solution of the present invention, and the technical solution, the implementation process and the principle thereof will be further explained as follows.
In one aspect of the present invention, a novel metal matrix composite is provided, as shown in fig. 1, comprising a metal matrix and a reinforcing phase comprising selected fibers and a rare earth borocarbide material, wherein the rare earth borocarbide material is RExByCzThe ceramic particles are characterized in that RE is one or a combination of more than two of Sc, Y and lanthanoid, the lanthanoid comprises La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x is 1-10, Y is 1-20, and z is 1-20.
In some embodiments, the rare earth borocarbide material includes REBC phase ceramic particles, REB2C-phase ceramic particles, REB2C2Any one or a combination of two or more of the phase ceramic particles.
In some embodiments, the rare earth borocarbide material is a medium-high entropy rare earth borocarbide compound, and the medium-high entropy ceramic material has a general chemical formula of RExByCzWherein RE is Sc, Y, La, Ce, Pr, Nd,Any three or more of Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in combination, wherein x, y and z are selected from any one of 1:1:1, 1:2:1 and 1:2: 2.
Further, when x, y and z are 1:2:2, the medium-high entropy ceramic material has a chemical general formula of RE1B2C2Wherein
Figure BDA0003544619290000041
REi＝Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu，xiIs REiThe molar constant of the component in RE is 3-17.
The rare earth element boron carbide RE adopted by the inventionxByCzHas a nano-layered structure, and mainly comprises REBC phase and REB phase2Phase C, REB2C2RE is one or the combination of two or more of Sc and Y and lanthanide elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like, has good mechanical, thermal and electrical properties, can form a layer of boron oxide, rare earth oxide and/or rare earth borate protective film on the surface after high-temperature oxidation, and has excellent oxidation resistance in different temperature zones, so that the metal-based composite material taking rare earth element boron carbide as a reinforcing phase can simultaneously have good mechanical properties and excellent high-temperature resistance and oxidation resistance, and can be widely used in special environments such as aerospace, nuclear energy and the like.
In some embodiments, the selected fibers include any one or a combination of two or more of carbon fibers, silicon nitride fibers, silica carbon fibers, alumina fibers, quartz fibers, mullite fibers, basalt fibers, silicate fibers, aluminate fibers, and the like, but are not limited thereto.
In some embodiments, the rare earth boro-carbon material (i.e., RE)xByCzCeramic particles) comprising REBC phase ceramic particles, REB2C-phase ceramic particles, REB2C2Phase ceramic particles, and the like. The invention makes the rare earth boron carbonCompound material (i.e. RE)xByCzCeramic particles) as a reinforcing phase for the ceramic particles, the reinforcing phase comprising both fibres and RExByCzCompared with the traditional particle reinforced metal matrix composite material, the ceramic particles have the advantages that the strength of the reinforcing phase in the form is higher under the impact load, the wear resistance is better, and the service life of the material is greatly prolonged.
Further, the RExByCzThe ceramic particles can also be coated on the surface of the fiber in the form of a coating, and the thickness of the coating is 10 nm-100 μm, preferably 50 nm-2 μm. The RExByCzThe ceramic particles have both metal bonds and covalent bonds, and the interface wettability of the fibers and a metal matrix can be improved on the surfaces of the fibers, so that the interface bonding strength of the composite material is improved, and the mechanical property of the composite material is improved.
The rare earth element boron carbide RE of the reinforcing phase adopted by the inventionxByCzHas a nano-layered structure, and is a three-dimensional space nano-layered three-dimensional structure formed by alternately stacking grids consisting of B-C eight-membered rings and four-membered rings and grids consisting of rare earth element atoms. The rare earth boron carbon compound ceramic has good oxidation resistance, excellent high temperature resistance, oxidation resistance, corrosion resistance, ablation resistance, wear resistance and good chemical stability, so compared with the traditional ceramic reinforcing phase, the rare earth boron carbon compound ceramic reinforcing phase can bring more characteristics to the metal matrix composite.
In some embodiments, the material of the metal matrix includes metal or alloy materials including most metal materials, preferably metal materials or alloys thereof including at least any one or more of Al, Ti, Zr, W, Fe, Cu, Ni, Mg, etc., but not limited thereto.
In some embodiments, the composite material is a metal or alloy matrix, with the selected fibers and RExByCzThe ceramic particles cooperate as a reinforcing phase.
In some embodiments, the RExByCzGrains of ceramic particlesThe diameter is 10nm to 100 μm, preferably 50nm to 20 μm.
In some embodiments, RE in the novel metal matrix compositesxByCzThe volume fraction of the ceramic particles is 0.01 to 95%, preferably 0.1 to 30%, and more preferably 1 to 15%.
In some embodiments, the novel metal matrix composite has a volume fraction of selected fibers in the range of 0.1 to 95%, preferably 1 to 30%, more preferably 5 to 15%.
As another aspect of the technical solution of the present invention, it also relates to a method for preparing a novel metal matrix composite, comprising:
will select the fiber, RExByCzUniformly mixing the ceramic particles with a metal or alloy material to obtain a mixture;
heat treating the mixture to obtain the fiber and RExByCzThe novel metal-based composite material with synergistically enhanced ceramic particles can overcome the defects of nonuniform dispersion, weak interface bonding and the like caused by the enhancement of the single ceramic particles, and simultaneously, the axial tensile strength of the fiber is high, and RE (rare earth) isxByCzThe ceramic particles can be pinned at the interface of the fiber and the metal matrix, and the strength of the composite material is further improved.
In some embodiments, the preparation method specifically comprises the following steps:
(1) the selected fiber, RExByCzUniformly mixing the powder and the metal powder;
(2) and carrying out heat treatment on the uniformly mixed powder to prepare the metal matrix composite material with the synergistic enhancement of the fibers and the particles.
Further, the preparation method further comprises the following steps: firstly, preprocessing the selected fibers to obtain a fiber preform; thereafter subjecting the fiber preform, RExByCzCeramic particles, metal or alloy materials are mixed uniformly.
In some more preferred embodiments, the preparation method may include the steps of:
(1) pretreating the selected fibers to remove surface impurities and obtain a fiber preform;
(2) combining the treated fiber preform with RExByCzGrinding the ceramic powder and the metal or alloy powder to a proper size;
(3) and carrying out heat treatment on the powder to prepare the novel metal-based composite material with the synergistic enhancement of the fibers and the particles.
In some embodiments, the RExByCzThe preparation method of the ceramic particles may specifically include:
taking more than one rare earth element-containing material (rare earth simple substance or rare earth element-containing compound), boron simple substance or boron-containing compound, carbon simple substance or carbon-containing compound, according to target phase RExByCzMixing the elements in proportion, and obtaining RE by a molten salt method or a solid phase reaction method at 600-2000 ℃ under the conditions of certain temperature and atmosphere protection or vacuumxByCzCeramic particles.
Wherein, the material containing rare earth elements comprises one or the combination of two or more of rare earth element simple substance, hydride, oxide, carbide or boride of rare earth elements, and the like.
Wherein the boron-containing material comprises one or a combination of two or more of boron carbide, boron oxide, boric acid, borane, carborane, and the like.
Wherein, the carbon-containing material comprises one or the combination of two or more of carbon simple substance, phenolic resin, glucose and starch.
Wherein the molar mass ratio of the rare earth element-containing material to the boron-containing material to the carbon-containing material is 1-10: 1-10: 1 to 10.
In some embodiments, the heat treatment method includes at least any one of a powder metallurgy method, a mechanical alloying method, a hot press sintering method, a discharge plasma sintering method, and an extrusion casting method, but is not limited thereto.
In some embodiments, the temperature of the heat treatment is 100 to 2200 ℃ and the time is 0.1 to 10 hours.
In another aspect, the embodiment of the present invention further provides that any one of the above-mentioned novel metal-matrix composite materials can be applied in the fields of aerospace, nuclear energy, electromagnetic shielding, neutron absorption or shielding, radiology, electronic packaging, precision instruments, and the like.
In summary, the rare earth boron carbide compound particles and the selected fibers are used together as the reinforcing phase of the metal matrix composite material in the invention, because RExByCzThe ceramic has a unique nano-layered structure and good mechanical properties, the defects of non-uniform dispersion, weak interface bonding and the like caused by single ceramic particle reinforcement can be overcome by adding the selected fiber, and simultaneously, the axial tensile strength of the fiber is high, and RE (rare earth) is highxByCzThe ceramic particles can be pinned at the interface of the fiber and the metal matrix, and the strength of the composite material is further improved. The obtained metal-based composite material can be applied to the fields of aerospace, nuclear energy, electromagnetic shielding, neutron absorption or shielding, radiology, electronic packaging, precision instruments and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are explained in further detail below with reference to the accompanying drawings and several preferred embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
In this embodiment, the metal matrix composite material is an aluminum metal matrix composite material reinforced by carbon fiber, and the ceramic particle reinforcement is YB2C2The preparation method comprises the following specific steps:
(1) grinding the pretreated carbon fibers, and controlling the volume fraction of the carbon fibers to be 10%; regrinding YB2C2The particle size of the particles is controlled to be 1 mu m, and the volume fraction is controlled to be 5%;
(2) adopting a high-energy ball mill to mix aluminum powder, the ground carbon fiber and YB2C2Mixing uniformly at a rotation speed of 300r/min for 5 h;
(3) preparing a final product by adopting a mechanical alloying method, and sintering the final product at the high temperature of 1000 ℃ for 5 hours to obtain a carbon fiber and YB as reinforcing phases2C2The particulate aluminum metal matrix composite is schematically shown in figure 2, and the composite has a tensile strength of 237 MPa.
Example 2
In the embodiment, the metal-based composite material is a titanium metal-based composite material toughened by carbon fibers, and the ceramic particle reinforcement is HoB2C, the preparation method comprises the following specific steps:
(1) grinding the pretreated carbon fibers, and controlling the volume fraction of the carbon fibers to be 30%; regrinding YB2C2The particle size is controlled to be 2 mu m, and the volume fraction is controlled to be 1%;
(2) adopting a high-energy ball mill to mix titanium powder with the ground carbon fiber and HoB2C, uniformly mixing, wherein the rotating speed is 400r/min and the mixing lasts for 4 hours;
(3) preparing a final product by adopting a mechanical alloying method, and sintering at 1500 ℃ for 3h to obtain a product with reinforcing phases of carbon fiber and HoB2The schematic structure of the titanium metal matrix composite material of the C particles is similar to that of the example 1.
Example 3
In this embodiment, the metal-based composite material is a silicon nitride fiber toughened zirconium metal-based composite material, and the ceramic particle reinforcement is DyB2C2The preparation method comprises the following specific steps:
(1) grinding the pretreated silicon nitride fiber, and controlling the volume fraction of the silicon nitride fiber to be 15%; regrind DyB2C2Particles, the particle size is controlled to be 0.5 mu m, and the volume fraction is controlled to be 5 percent;
(2) adopting a high-energy ball mill to mix zirconium powder, the silicon nitride fiber and DyB2C2Mixing uniformly at a rotation speed of 500r/min for 4 h;
(3) preparing final product by spark plasma sintering method, sintering at 2000 deg.C for 2 hr to obtain reinforcing phase of silicon nitride fiber and DyB2C2Particulate zirconium metalThe schematic structure of the matrix composite is similar to that of example 1.
Example 4
In this embodiment, the metal matrix composite material is an aluminum metal matrix composite material toughened by carbon fibers, and the ceramic particle reinforcement is (Y)0.2Nd0.2Sm0.2Eu0.2Er0.2)B2C2The particles are prepared by the following steps:
(1) grinding the pretreated carbon fibers, and controlling the volume fraction of the carbon fibers to be 10%; regrinding (Y)0.2Nd0.2Sm0.2Eu0.2Er0.2)B2C2The particle size is controlled to be 2 mu m, and the volume fraction is controlled to be 5 percent;
(2) aluminum powder and the above-mentioned carbon fibers and (Y) are ground by a ball mill0.2Nd0.2Sm0.2Eu0.2Er0.2)B2C2Uniformly mixing the particles, wherein the rotating speed is 100r/min and lasts for 5 hours;
(3) preparing final product by hot-pressing sintering method, sintering at 2200 deg.C for 0.1 hr to obtain reinforcing phase of carbon fiber and (Y)0.2Nd0.2Sm0.2Eu0.2Er0.2)B2C2The particulate aluminum metal matrix composite is similar in structure to example 1.
Example 5
In this embodiment, the metal matrix composite material is an aluminum metal matrix composite material toughened by aluminum oxide fibers, and the ceramic particle reinforcement is ErB2C2And GdB2C, the preparation method comprises the following specific steps:
(1) grinding the pretreated alumina fiber, and controlling the volume fraction of the alumina fiber to be 50%; regrinding ErB2C2And GdB2C, particles with the particle size controlled between 1 μm and 2 μm and the volume fraction controlled between 10% and 5%;
(2) aluminum powder, the grinded alumina fiber and ErB are processed by a high-energy ball mill2C2And GdB2C, uniformly mixing the particles, wherein the rotating speed is 300r/min and lasts for 7 hours;
(3) by using a devicePreparing a final product by an electric plasma sintering method, and obtaining the reinforcing phase of alumina fiber and ErB after sintering for 10 hours at the high temperature of 100 DEG C2C2/GdB2The schematic structure of the C particle aluminum metal matrix composite was similar to that of example 1.
Example 6
In the embodiment, the metal-based composite material is a copper metal-based composite material toughened by silica carbon fiber, and the ceramic particle reinforcement is (La)0.2Ce0.2Nd0.2Dy0.2Yb0.2)B2C2The preparation method comprises the following specific steps:
(1) grinding the pretreated silica carbon fiber, and controlling the volume fraction of the silica carbon fiber to be 5%; regrinding (La)0.2Ce0.2Nd0.2Dy0.2Yb0.2)B2C2Particles, the particle size is controlled to be 500nm, and the volume fraction is controlled to be 30%;
(2) copper powder and the above-mentioned silica carbon fibers and (La) were mixed by a ball mill0.2Ce0.2Nd0.2Dy0.2Yb0.2)B2C2Uniformly mixing the particles, and keeping the rotation speed at 150r/min for 6 hours;
(3) preparing a final product by adopting a mechanical alloying method, and sintering at the high temperature of 1200 ℃ for 6 hours to obtain a product with reinforcing phases of silicon-oxygen carbon fiber and (La)0.2Ce0.2Nd0.2Dy0.2Yb0.2)B2C2The schematic structural diagram of the particulate titanium metal matrix composite is similar to that of example 1.
Example 7
In this embodiment, the metal matrix composite material is an iron metal matrix composite material toughened by carbon fiber, and the ceramic particle reinforcement is (Pr)0.2Pm0.2Nd0.2Ho0.2Er0.2)B2C2The preparation method comprises the following specific steps:
(1) grinding the pretreated carbon fibers, and controlling the volume fraction of the carbon fibers to be 20%; regrinding (Pr)0.2Pm0.2Nd0.2Ho0.2Er0.2)B2C2Granules, particle size controlAt 2 μm, the volume fraction is controlled to be 5%;
(2) mixing iron powder and the above-mentioned carbon fibers and (Pr) by ball mill0.2Pm0.2Nd0.2Ho0.2Er0.2)B2C2Uniformly mixing the particles, wherein the rotating speed is 300r/min and the time lasts for 4 hours;
(3) preparing the final product by adopting a spark plasma sintering method, and sintering at the high temperature of 500 ℃ for 8h to obtain the carbon fiber and (Pr) as the reinforcing phase0.2Pm0.2Nd0.2Ho0.2Er0.2)B2C2The schematic structural diagram of the iron metal matrix composite of the particles is similar to that of example 1.
Example 8
In this embodiment, the metal matrix composite material is an aluminum metal matrix composite material toughened by quartz fibers, and the fiber interface layer is (Y)0.2La0.2Ce0.2Sm0.2Ho0.2)B2C2The ceramic particle reinforcement is (La)0.2Pm0.2Sm0.2Dy0.2Lu0.2)B2C2The preparation method comprises the following specific steps:
(1) preparation on the pretreated surface of the quartz fiber by chemical coprecipitation (Y)0.2La0.2Ce0.2Sm0.2Ho0.2)B2C2An interfacial layer having a thickness of about 5 μm;
(2) grinding the quartz fiber with the interface layer, and controlling the volume fraction of the quartz fiber to be 5%; regrinding ErB2C, controlling the particle size to be 2 mu m and the volume fraction to be 30%;
(3) aluminum powder, the ground quartz fiber and (Y) are mixed by a ball mill0.2La0.2Ce0.2Sm0.2Ho0.2)B2C2Uniformly mixing the particles, wherein the rotating speed is 100r/min and the time lasts for 7 hours;
(4) preparing a final product by adopting a hot-pressing sintering method, and sintering at the high temperature of 800 ℃ for 6 hours to obtain a reinforced phase with a (Y)0.2La0.2Ce0.2Sm0.2Ho0.2)B2C2Interfacial layerQuartz fiber of (La) and (La)0.2Pm0.2Sm0.2Dy0.2Lu0.2)B2C2Particulate aluminum metal matrix composite material, as shown in figure 2.
Example 9
In the embodiment, the metal-based composite material is a titanium metal-based composite material toughened by silicon carbide fibers, and the fiber interface layer is (Nd)1/6En1/6Ho1/6Dy1/6Y1/6Yb1/6)B2C2The ceramic particle reinforcement is (Pm)0.2Y0.2Eu0.2Yb0.2Ce0.2)B2C2. The preparation method comprises the following specific steps:
(1) preparation of (Nd) on the surface of pretreated silicon carbide fiber by adopting precursor conversion method1/6En1/6Ho1/6Dy1/6Y1/ 6Yb1/6)B2C2An interfacial layer having a thickness of about 500 nm;
(2) grinding the silicon carbide fiber with the interface layer, and controlling the volume fraction of the silicon carbide fiber to be 5%; regrinding (Pm)0.2Y0.2Eu0.2Yb0.2Ce0.2)B2C2Particles, the particle size is controlled to be 1 mu m, and the volume fraction is controlled to be 40%;
(3) aluminum powder, the silicon carbide fiber and (Pm) are ground by a ball mill0.2Y0.2Eu0.2Yb0.2Ce0.2)B2C2Uniformly mixing the particles, wherein the rotating speed is 300r/min and lasts for 6 hours;
(4) preparing a final product by adopting a mechanical alloying method, and obtaining a reinforced phase with a (Nd) phase after sintering for 5 hours at a high temperature of 1000 DEG C1/6En1/6Ho1/6Dy1/6Y1/6Yb1/6)B2C2Silicon carbide fiber sum (Pm) of interface layer0.2Y0.2Eu0.2Yb0.2Ce0.2)B2C2The schematic structural representation of the particulate titanium metal matrix composite was similar to that of example 8.
Example 10
In this embodiment, the metal matrix composite material is an iron metal matrix composite material toughened by carbon fiber, and the fiber interface layer is (Er)0.25Gd0.25Ho0.25Tm0.25)B2C2The ceramic particle reinforcement is (Y)0.25La0.25Lu0.25Er0.25)B2C2. The preparation method comprises the following specific steps:
(1) preparing (Er) on the surface of the pretreated carbon fiber by adopting a physical vapor deposition method0.25Gd0.25Ho0.25Tm0.25)B2C2An interfacial layer having a thickness of about 10 μm;
(2) grinding the carbon fiber with the interface layer, and controlling the volume fraction of the carbon fiber to be 25%; regrinding (Y)0.25La0.25Lu0.25Er0.25)B2C2Particles, the particle size is controlled to be 5 mu m, and the volume fraction is controlled to be 15 percent;
(3) mixing iron powder and the above-mentioned carbon fibers and (Y) by means of a ball mill0.25La0.25Lu0.25Er0.25)B2C2Uniformly mixing the particles, wherein the rotating speed is 250r/min and the time lasts for 4 hours;
(4) preparing a final product by a spark plasma sintering method, and sintering at 1600 ℃ for 4 hours to obtain an enhanced phase (Er)0.25Gd0.25Ho0.25Tm0.25)B2C2Carbon fiber of interface layer and (Y)0.25La0.25Lu0.25Er0.25)B2C2The schematic structural diagram of the iron metal matrix composite of the particles is similar to that of example 8.
Comparative example 1
The comparative example differs from example 1 only in that: the reinforcement is YB2C2The interface strength of the obtained composite material was 105 MPa.
Comparative example 2
The comparative example differs from example 1 only in that: the reinforcement is carbon fiber, and the interface strength of the obtained composite material is 179 MPa.
In addition, the inventors of the present invention have also made experiments with other raw materials, process operations, and process conditions described in the present specification with reference to the above examples 1 to 10, and have obtained preferable results.
The above are only some of the preferred embodiments of the present invention, and other embodiments are possible, and the embodiments herein are only for explaining the present invention, and are not intended to limit the scope of the present invention. And all such modifications and variations are believed to be within the scope of the invention.

Claims (10)

1. A novel metal matrix composite material is characterized by comprising a metal matrix and a reinforcing phase, wherein the reinforcing phase comprises selected fibers and a rare earth borocarbide material, and the rare earth borocarbide material is RExByCzThe ceramic particles are characterized in that RE is any one or a combination of more than two of Sc, Y and lanthanide elements, the lanthanide elements comprise La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, x is 1-10, Y is 1-20, z is 1-20, and the selected fibers comprise any one or a combination of more than two of carbon fibers, silicon nitride fibers, silica carbon fibers, alumina fibers, quartz fibers, mullite fibers, basalt fibers, silicate fibers and aluminate fibers.
2. The novel metal matrix composite according to claim 1, characterized in that: the rare earth boron carbon compound material comprises REBC phase ceramic particles and REB2C-phase ceramic particles, REB2C2Any one or a combination of two or more of the phase ceramic particles.
Preferably, the rare earth boron carbon compound material is a medium-high entropy rare earth boron carbon compound, and the medium-high entropy ceramic material has a chemical general formula of RExByCzWherein RE is the combination of any three or more of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, x: Y: z is selected from any one of 1:1:1, 1:2:1 and 1:2:2, and is particularly preferable, and when x: Y: z is 1:2:2, the high-entropy ceramic material has the chemical general formula RE1B2C2Wherein
Figure FDA0003544619280000011
REi＝Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu，xiIs REiThe molar constant of the component in RE is 3-17.
3. The novel metal matrix composite according to claim 1, characterized in that: the material of the metal matrix comprises at least one or more than two alloy of Al, Ti, Zr, W, Fe, Cu, Ni and Mg.
4. The novel metal matrix composite according to claim 1, characterized in that: the RExByCzThe grain size of the ceramic particles is 10 nm-100 μm, preferably 50 nm-20 μm;
and/or, the RExByCzThe ceramic particles are coated on the surface of the selected fiber in the form of a coating, and the thickness of the coating is 10 nm-100 μm, preferably 50 nm-2 μm.
5. The novel metal matrix composite according to claim 1, characterized in that: RE in the novel metal matrix composite materialxByCzThe volume fraction of the ceramic particles is 0.01 to 95%, preferably 0.1 to 30%, and more preferably 1 to 15%.
6. The novel metal matrix composite according to claim 1, characterized in that: the volume fraction of the selected fibers in the novel metal matrix composite material is 0.1-95%, preferably 1-30%, and more preferably 5-15%.
7. The method of producing a novel metal matrix composite as claimed in any one of claims 1 to 6, comprising:
will select the fiber, RExByCzCeramic materialUniformly mixing the particles with a metal or alloy material to obtain a mixture;
heat treating the mixture to obtain the fiber and RExByCzNovel metal matrix composites synergistically reinforced with ceramic particles.
8. The method of claim 7, wherein: the heat treatment method comprises at least one of a powder metallurgy method, a mechanical alloying method, a hot pressing sintering method, a discharge plasma sintering method and an extrusion casting method;
and/or the temperature of the heat treatment is 100-2200 ℃ and the time is 0.1-10 h.
9. The method of manufacturing according to claim 7, further comprising: firstly, preprocessing the selected fibers to obtain a fiber preform; thereafter subjecting the fiber preform, RExByCzCeramic particles, metal or alloy materials are mixed uniformly.
10. Use of the novel metal matrix composite material according to any one of claims 1 to 6 in the fields of aerospace, nuclear power, electromagnetic shielding, neutron absorption or shielding, radiology, electronic packaging or precision instrumentation.
CN202210244630.8A 2022-03-14 2022-03-14 Novel metal-based composite material and preparation method and application thereof Pending CN114606453A (en)

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