CN109318547A - A kind of MAX phase ceramics-layered metal composite material, preparation method and purposes - Google Patents

A kind of MAX phase ceramics-layered metal composite material, preparation method and purposes Download PDF

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CN109318547A
CN109318547A CN201811069484.XA CN201811069484A CN109318547A CN 109318547 A CN109318547 A CN 109318547A CN 201811069484 A CN201811069484 A CN 201811069484A CN 109318547 A CN109318547 A CN 109318547A
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max
composite material
phase ceramics
ceramics
max phase
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CN109318547B (en
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王钰
司鹏超
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
    • B23K35/0272—Rods, electrodes, wires with more than one layer of coating or sheathing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3033—Ni as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/18—Handling of layers or the laminate
    • B32B38/1808—Handling of layers or the laminate characterised by the laying up of the layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L5/00—Current collectors for power supply lines of electrically-propelled vehicles
    • B60L5/18—Current collectors for power supply lines of electrically-propelled vehicles using bow-type collectors in contact with trolley wire
    • B60L5/20—Details of contact bow
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0414—Layered armour containing ceramic material
    • F41H5/0421—Ceramic layers in combination with metal layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/544—Torsion strength; Torsion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/548—Creep
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2571/00—Protective equipment
    • B32B2571/02—Protective equipment defensive, e.g. armour plates, anti-ballistic clothing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/10—Trains

Abstract

The present invention relates to a kind of MAX phase ceramics-layered metal composite material, preparation method and purposes, MAX phase ceramics-the layered metal composite material includes n-layer superpositing unit, each superpositing unit includes metal foil layer and the MAX phase ceramics layer that is attached on metal foil layer, n >=2.MAX phase ceramics-the layered metal composite material is with Ti2AlC powder and metal foil are raw material, and the metal foil coated with MAX ceramic phase particle, which is superimposed, is made basic products, are then heat-treated basic products pressurization to get MAX phase ceramics-layered metal composite material is arrived.MAX phase ceramics-the layered metal composite material is used for apparatus of transport field, power transmission and transformation field or military project Material Field.

Description

A kind of MAX phase ceramics-layered metal composite material, preparation method and purposes
Technical field
The invention belongs to field of compound material, and in particular to a kind of MAX phase ceramics-layered metal composite material and its preparation Method and purposes, the MAX phase ceramics-layered metal composite material are used for apparatus of transport Material Field, power transmission and transformation field or army Work Material Field.
Background technique
MAX phase ceramics are the common names of a kind of ternary layered ceramic, and M is transition elements, and A is certain in III or IV main group Element, X are C or N.The existing covalent bond of atom combination of all MAX phase ceramics compounds, ionic bond have metallic bond again, because And have the property of metal and ceramics concurrently, such as the thermally conductive of metalloid, electric conductivity, thermal shock resistance and machinability, similar ceramics Inoxidizability, wearability, self-lubrication, corrosion resistance and heat-resisting quantity.Therefore, valence is applied with important in many fields Value.
Metal has the excellent performances such as conductive, thermally conductive, corrosion-resistant and ductile, therefore is widely used in electric power electricity The fields such as son, machine-building.But the intensity of metal is low, hardness is low, poor heat resistance and wears no resistance, and limits its use condition And the service life.In order to improve the mechanical property of metal under the premise of excessively not sacrificing electric conductivity and thermal conductivity, many people were once It attempts MAX phase ceramics and metal composite to achieve the purpose that enhance metallicity.
CN103085395A discloses a kind of Cu-Ti2The preparation method of AlC functionally graded material, the method preparation The composite material that functionally gradient material (FGM) side is pure Cu or main component is Cu, the other side are pure Ti2AlC or main component are Ti2AlC Composite material, the intermediate number of plies be 1~4 layer, with thickness direction, Cu and Ti2The content of AlC changes in gradient, and with performance It gradually changes.The material is by with Cu and Ti2AlC powder is raw material, after evenly mixing layer-by-layer distribution, under certain atmosphere It being prepared using hot pressed sintering, sintering temperature is 800~1000 DEG C, and heating rate is 8~20 DEG C/min, and pressure is 20~40MPa, Heat preservation 0.5~3 hour.The functionally gradient material (FGM) has for meeting the particular surroundings that different contact surfaces have different service performances Significance, but being only applicable to particular surroundings can not large-scale use.
CN101028749B discloses one kind (Cu-Al)/(Ti3C2- Cu-Al) laminar composite and preparation method thereof, institute Material is stated with Ti3C2The layer structure that-Cu-Al cermet coating and Cu-Al alloy-layer are superimposed, and Ti3C2- Cu-Al gold Belong to ceramic layer and Cu-Al alloy-layer is by Ti3AlC2Chemical reaction occurs with Cu and is formed in situ.The material be with Ti3AlC2Powder and Cu powder are raw material, are cold-pressed layered green body after being successively alternately laid with, then green body are placed in high temperature furnace, in argon Under gas shielded, furnace temperature is risen to 1100~1200 DEG C, is cooled down after keeping the temperature 15~60min to get laminar composite is arrived.The material Expect that there is good wear-resisting and impact resistance load ability, but its tensile strength properties is bad.
CN102206771A discloses a kind of pantograph slide composite material and preparation method thereof, the composite material be by Made from copper powder and ceramic particle, wherein ceramic grain surface has chemical plating copper layer.Surface is had to the pottery of chemical plating copper layer Porcelain particle and copper powder mix to obtain mixed material, then by mixed material through hot-pressing sintering technique or hot pressed sintering and hot extrusion knot After closing process.Prepared composite inner Ti3AlC2Ceramic particle is evenly distributed, but its tensile strength properties It is bad.
So this field needs to develop a kind of novel MAX phase ceramics-metallic composite, good stretch by force is made it have The advantages that degree, compressive strength, ductility, electric conductivity and thermal conductivity, and it is suitable for industrialized production.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of MAX phase ceramics-layered metal is compound Material, the MAX phase ceramics-layered metal composite material includes n-layer superpositing unit, and each superpositing unit includes metal Layers of foil and the MAX phase ceramics layer being attached on the metal foil layer, n >=2, such as 5,10,30,50,100,200,500 Deng.
The present invention is mutually compound using MAX phase ceramics and metal foil, and MAX phase ceramics layer and metal foil interval are arranged.Metal The excellent electric conductivity of the composite material, mechanical ductility and tensile strength are assigned, MAX phase ceramics material is coated on metal foil layer It after material, is overlapped, the alternately laminated arrangement of hard phase (aragonite piece) and soft phase (organic matter) that can be obtained similar to shell is formed " brick-mud " composite construction, assigns the higher intensity of the composite material and toughness, relative to answering for reinforced phase even dispersion distribution Condensation material, the structure have higher mechanical strength.
It is superimposed further, since composite material is spaced apart from each other for metal foil with MAX phase ceramics, so that it has along bedding angle Continuous metal layer exist, perpendicular slice direction have continuous N AX phase ceramics layer barrier, so composite material have it is each to (along level Direction and perpendicular to bedding angle) anisotropic tensile strength, compressive strength, ductility and electric conductivity etc..
The structure of MAX phase ceramics-layered metal composite material of the present invention has multiple layer metal layers of foil and multilayer MAX phase Ceramic layer, and the metal foil layer and MAX phase ceramics layer are arranged alternately, and form metal foil layer-MAX phase ceramics layer-metal foil layer- MAX phase ceramics layer-metal foil layer-MAX phase ceramics layer-... layer structure material.In MAX phase ceramics-of the present invention In layered metal composite material, the metal foil layer-MAX phase ceramics layer is a superpositing unit.
The thickness of n of the present invention is not specifically limited, and those skilled in the art can carry out n according to desired thickness Selection.
Preferably, n >=10 of the present invention, preferably n >=20, further preferred n >=50, most preferably 50≤n≤100.
Preferably, metal foil of the present invention includes copper foil and/or nickel foil.
Preferably, in each superpositing unit, the volume contents of MAX phase ceramics is 5%~30%, such as 5%, 10%, 15%, 22%, 25%, 28%, 30% etc..
The volume content of MAX phase ceramics is too small, and enough reinforcing effects are not achieved, and volume content is excessive, and composite material is crisp Property increase, electric conductivity degradation.
Preferably, in each superpositing unit, MAX phase ceramics layer is with a thickness of 2~16 μm, such as 2 μm, 5 μm, 7 μm, 10 μm, 13 μm, 15 μm, 16 μm etc..
When MAX phase ceramics thickness degree is less than 2 μm, it is easy in the follow-up heat treatment process because of surrounding metal atom for this layer It spreads and destroys, when MAX phase ceramics thickness degree is greater than 16 μm, internal bond is weak layer by layer for MAX phase ceramics.
Preferably, in each superpositing unit, metal foil layer is with a thickness of 9~80 μm, such as 9 μm, 15 μm, 27 μm, 30 μ M, 43 μm, 55 μm, 67 μm, 80 μm etc..
When metal foil layer thickness is less than 9 μm, the easily-deformable breakage in follow-up heat treatment process, it is difficult to maintain continuous shape State when metal foil layer thickness is greater than 80 μm, folds and the subsequent techniques such as cutting is difficult.
Preferably, MAX phase ceramics of the present invention include 312 phase MAX phase ceramics, 211 phase MAX phase ceramics and 413 phase MAX In phase ceramics any one or at least two combination.
Preferably, the 312 phase MAX phase ceramics include Ti3AlC2、Ti3SiC2And Ti3SnC2In any one or at least Two kinds of combination.
Preferably, the 211 phase MAX phase ceramics include Ti2AlC、Ti2AlN、Nb2AlC、Ti2AlN0.5C0.5、Cr2AlC、 Ti2SnC and Nb2In SnC any one or at least two combination.
Preferably, the 413 phase MAX phase ceramics include Ti4AlC3And/or Nb4AlC3。
The second object of the present invention is to provide a kind of preparation method of MAX phase ceramics-layered metal composite material, the system Preparation Method the following steps are included:
(1) on metal foil by the coating of MAX ceramic phase particle suspension；
(2) it is coated with the metal foil superposition of MAX ceramic phase particle, and removes point in MAX ceramic phase particle suspension Powder obtains basic products；
(3) basic products are pressurizeed and is heat-treated, MAX phase ceramics-layered metal composite material is made.
The present invention prepares multilayer materials in such a way that MAX phase ceramics are superimposed with metal foil interval, between layers Orderly aligned (is metal layer-MAX phase ceramics layer-metal layer-MAX phase ceramics layer-metal layer-MAX phase ceramics layer-... Layer structure material), MAX phase ceramics thickness degree differs very little in MAX phase ceramics-each superpositing unit of layered metal composite material (such as thickness deviation≤5 μm).MAX phase ceramics-layered metal composite material of preparation has good uniformity and order, Preparation method has the advantages that simple and easy and operation link temperature is low etc..
Preferably, step (1) the MAX ceramic phase particle suspension concentration of the present invention is 5wt%~20wt%, such as 5wt%, 7wt%, 10wt%, 12wt%, 15wt%, 20wt% etc..
MAX ceramic phase particle suspension concentration is excessively high, be easy to cause coating thickness uneven, and concentration is too low, be easy to cause The distribution of MAX ceramic phase particle is discontinuous, or coating step is caused to repeat, and operating cost improves.
Preferably, the dispersing agent in the MAX ceramic phase particle suspension include PVA aqueous solution, PMMA methyl phenyl ethers anisole solution, One of polyethylene glycol and hexamethylene or at least two combination.
The present invention is not specifically limited the concentration of the dispersing agent of MAX ceramic phase particle suspension, if can satisfy by MAX ceramic phase particle stable suspersion can realize the present invention.
Preferably, the metal foil thickness be 6~400 μm, such as 6 μm, 20 μm, 40 μm, 80 μm, 100 μm, 150 μm, 200 μm, 300 μm, 400 μm etc..
Preferably, the MAX ceramic phase particle partial size is more than 200 mesh, such as 210 mesh, 270 mesh, 300 mesh, 350 mesh Deng.
Preferably, the coating method is spraying, brushing, spin coating, any one in Best-Effort request.
Preferably, MAX ceramic phase particle suspension coating with a thickness of 4~16 μm, such as 4 μm, 6 μm, 8 μm, 10 μ M, 12 μm, 14 μm, 16 μm etc..
Preferably, stacked system described in step (2) of the present invention includes folding or being laminated.
Preferably, the mode of the superposition is to fold, and each superposition of MAX phase ceramics-layered metal composite material is single In member, MAX phase ceramics layer average thickness is 4~16 μm, such as 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm etc..
Preferably, the mode of the superposition is stacking, and each superposition of MAX phase ceramics-layered metal composite material is single In member, MAX phase ceramics layer average thickness is 2~8 μm, such as 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm etc..
The folding means to be coated with the metal foils of MAX phase ceramics according to identical ceramic layer and ceramic layer to mutually rolling over Folded, metal foil layer carries out the mode mutually folded with metal foil layer.
The stacking means that the metal foil for being coated with MAX phase ceramics is opposite with metal foil layer according to ceramic layer, by certain The mode that direction is layering carries out.
Preferably, the method for removing the dispersing agent in MAX ceramic phase particle suspension is heating evaporation.
Preferably, step (3) the of the present invention pressurization heat treatment includes hot pressed sintering, (SPS is burnt discharge plasma sintering Knot), any one in hot rolling.
Preferably, the temperature of the pressurization heat treatment is 850~1050 DEG C, such as 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, 1050 DEG C etc..
Preferably, it is described pressurization heat treatment pressure be 20~200MPa, such as 20MPa, 40MPa, 80MPa, 100MPa, 120MPa, 150MPa, 180MPa, 200MPa etc..
Preferably, it is described pressurization heat treatment time be 15~120min, such as 15min, 40min, 50min, 60min, 70min, 80min, 100min, 120min etc..
Pressurization heat treatment can make that interfacial reaction occurs between metal layer and MAX phase ceramics layer, enhance boundary strength, and Densify composite material.
As optimal technical scheme, a kind of preparation method of MAX phase ceramics-layered metal composite material of the present invention, Include the following steps:
(1) the MAX ceramic phase particle by partial size more than 200 mesh is added in dispersion PMMA methyl phenyl ethers anisole solution, and concentration is made For the suspension of 5wt%~20wt%, and it is coated in the metal foil of 6~400 μ m-thicks using spraying method, coating thickness 4 ~16 μm；
(2) it is coated with the metal foil superposition of MAX ceramic phase particle, and heating evaporation removes MAX ceramic phase particle and suspends Dispersing agent in liquid, obtains basic products；
(3) pressurize basic products 15~120min of heat treatment at 850~1050 DEG C of temperature and 20~200MPa pressure, system Obtain MAX phase ceramics-layered metal composite material.
The three of the object of the invention are to provide a kind of MAX phase ceramics-layered metal composite material as described in the first purpose Purposes, the composite material are used for apparatus of transport field, power transmission and transformation field or military project Material Field.
Preferably, the composite material is for the high-speed train pantograph slide plate in apparatus of transport field.
Preferably, the composite material is for the transformer conducting wire or power transmission line in power transmission and transformation field.
Preferably, the composite material is for the spot-wedling electrode in field of material processing.
Preferably, the composite material is for the armoured equipment in military project Material Field.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention uses metal foil to greatly enhance as the substrate of the MAX phase ceramics-layered metal composite material The mechanical strength of the composite material (tensile strength, compressive strength etc.).
(2) present invention is mutually compound using MAX phase ceramics and metal foil, and the composite material had both had metal foil is excellent to lead Electrically, mechanical ductility and tensile strength, and the intensity and toughness excellent with MAX phase ceramics.
(3) MAX phase ceramics-layered metal composite material prepared by the present invention, metal foil are spaced apart from each other with MAX phase ceramics Superposition so that its along bedding angle with the presence of continuous metal layer, there are AX layers of continuous N barrier in perpendicular slice direction, so compound Material has each tensile strength, compressive strength and the electric conductivity etc. anisotropic to (along bedding angle and perpendicular to bedding angle), institute It states composite material and is parallel to bedding angle tensile strength and reach 300MPa or more, compression strength reaches 660MPa or more, perpendicular layers Face direction compression strength reaches 820MPa or more.
(4) MAX phase ceramics layer average thickness differs very in MAX phase ceramics-each superpositing unit of layered metal composite material Small (such as thickness deviation≤5 μm).MAX phase ceramics-layered metal composite material of preparation is with good uniformity and orderly Property, preparation method have the advantages that simple and easy and operation link temperature is low etc..
Detailed description of the invention
Fig. 1 gives MAX phase ceramics-layered metal composite material optical morphology figure that embodiment 1 obtains；
Fig. 2 gives MAX phase ceramics-layered metal composite material electronics shape appearance figure that embodiment 1 obtains；
Fig. 3 gives MAX phase ceramics-layered metal composite material optical morphology figure that embodiment 7 obtains；
Fig. 4 gives MAX phase ceramics-layered metal composite material electronics shape appearance figure that embodiment 7 obtains；
Fig. 5 gives MAX phase ceramics-layered metal composite material optical morphology figure that embodiment 9 obtains；
Fig. 6 gives MAX phase ceramics-layered metal composite material electronics shape appearance figure that embodiment 9 obtains.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of preparation method of MAX phase ceramics-layered metal composite material includes the following steps:
(1) Ti of 400 meshes was taken2AlC powder is dissolved in PMMA solution and the MAX phase ceramics that concentration is 10wt% is made Grain suspension, by MAX ceramic phase particle suspension spray on the copper foil of 18 μ m-thicks, the coating of MAX ceramic phase particle suspension With a thickness of 10 μm, the copper foil coated with MAX ceramic phase particle is obtained；
(2) copper foil for being coated with MAX ceramic phase particle is laminated into 20 layers of superpositing unit, and the structure of stacking is placed in heat In compression mould, heating evaporation removes PMMA solution, obtains basic products；
(3) basic products are pressurizeed and is heat-treated, be warming up to 1000 DEG C and the 25MPa that pressurizes, heat-insulation pressure keeping 30min is finally obtained Ti in MAX phase ceramics-copper laminar composite material2AlC volume content is that 20%, MAX phase ceramics layer average thickness is 5 μm, preparation Obtained MAX phase ceramics-copper laminar composite material pattern is as depicted in figs. 1 and 2, and metal foil layer and MAX phase ceramics layer are alternately set It sets, forms metal foil layer-MAX phase ceramics layer-metal foil layer-MAX phase ceramics layer-metal foil layer-MAX phase ceramics layer-... Layer structure material, the structure have good uniformity and order.
Embodiment 2
The difference from embodiment 1 is that in step (1) MAX ceramic phase particle suspension coat with a thickness of 4 μm, finally Obtain Ti in MAX phase ceramics-copper laminar composite material2AlC volume content is 10%, MAX phase ceramics layer with a thickness of 2 μm.
Embodiment 3
The difference from embodiment 1 is that in step (1) MAX ceramic phase particle suspension coat with a thickness of 16 μm, finally Obtain Ti in MAX phase ceramics-copper laminar composite material2AlC volume content is 30%, MAX phase ceramics layer with a thickness of 8 μm.
Embodiment 4
The difference from embodiment 1 is that in step (1) MAX ceramic phase particle suspension coat with a thickness of 3 μm, finally Obtain Ti in MAX phase ceramics-copper laminar composite material2AlC volume content is 5%, MAX phase ceramics layer with a thickness of 1.5 μm.
Embodiment 5
The difference from embodiment 1 is that in step (1) MAX ceramic phase particle suspension coat with a thickness of 20 μm, finally Obtain Ti in MAX phase ceramics-copper laminar composite material2AlC volume content is that 35%, MAX phase ceramics layer average thickness is 10 μm.
Embodiment 6
The difference from embodiment 1 is that in step (1) copper foil with a thickness of 6 μm, finally obtain MAX phase ceramics-copper laminar Copper foil layer with a thickness of 6 μm in composite material.
Embodiment 7
The difference from embodiment 1 is that in step (1) copper foil with a thickness of 400 μm, finally obtain MAX phase ceramics-layers of copper In shape composite material copper foil layer with a thickness of 400 μm, MAX phase ceramics-copper laminar composite material pattern such as Fig. 3 for being prepared and Shown in Fig. 4, metal foil layer and MAX phase ceramics layer are arranged alternately, and form metal foil layer-MAX phase ceramics layer-metal foil layer-MAX phase Ceramic layer-metal foil layer-MAX phase ceramics layer-... layer structure material, the structure is with good uniformity and orderly Property.
Embodiment 8
The difference from embodiment 1 is that copper foil is replaced with nickel foil.
Embodiment 9
A kind of preparation method of MAX phase ceramics-layered metal composite material includes the following steps:
(1) 600 mesh Ti are taken2AlN powder is dissolved in PMMA solution and the MAX ceramic phase particle suspension that concentration is 5wt% is made Liquid, by MAX ceramic phase particle suspension spray on the copper foil of 18 μ m-thicks, MAX ceramic phase particle suspension coating with a thickness of 10 μm, obtain the copper foil coated with MAX ceramic phase particle；
(2) copper foil for being coated with MAX ceramic phase particle is laminated into 10 layers of superpositing unit, is placed in hot pressing die, adds Thermal evaporation removes PMMA solution, obtains basic products；
(3) basic products are pressurizeed and is heat-treated, be warming up to 850 DEG C and the 200MPa that pressurizes, heat-insulation pressure keeping 15min is finally obtained MAX phase ceramics-copper laminar composite material pattern it is as shown in Figure 5 and Figure 6, metal foil layer and MAX phase ceramics layer are arranged alternately, shape At metal foil layer-MAX phase ceramics layer-metal foil layer-MAX phase ceramics layer-metal foil layer-MAX phase ceramics layer-... stratiform knot Structure material, the structure have good uniformity and order.
Embodiment 10
A kind of preparation method of MAX phase ceramics-layered metal composite material includes the following steps:
(1) 200 mesh Ti are taken2AlN powder is dissolved in PMMA solution and the MAX ceramic phase particle suspension that concentration is 25wt% is made Liquid, by MAX ceramic phase particle suspension spray on the copper foil of 18 μ m-thicks, MAX ceramic phase particle suspension coating with a thickness of 10 μm, obtain the copper foil coated with MAX ceramic phase particle；
(2) copper foil for being coated with MAX ceramic phase particle is laminated into 50 layers of superpositing unit, is placed in hot pressing die, adds Thermal evaporation removes PMMA solution, obtains basic products；
(3) basic products are pressurizeed and is heat-treated, be warming up to 1050 DEG C and the 20MPa that pressurizes, heat-insulation pressure keeping 120min, evaporation removes PMMA solution finally obtains MAX phase ceramics-copper laminar composite material.
Embodiment 11
A kind of preparation method of MAX phase ceramics-layered metal composite material includes the following steps:
(1) Ti of 400 meshes was taken2AlC powder is dissolved in PMMA solution and the MAX phase ceramics that concentration is 10wt% is made Grain suspension, by MAX ceramic phase particle suspension spray on the copper foil of 18 μ m-thicks, the coating of MAX ceramic phase particle suspension With a thickness of 16 μm, the copper foil coated with MAX ceramic phase particle is obtained；
(2) copper foil for being coated with MAX ceramic phase particle is folded into 20 layers of superpositing unit, is placed in hot pressing die, adds Thermal evaporation removes PMMA solution, obtains basic products；
(3) basic products are pressurizeed and is heat-treated, be warming up to 1000 DEG C and the 25MPa that pressurizes, heat-insulation pressure keeping 30min is finally obtained MAX phase ceramics layer is in MAX phase ceramics-copper laminar composite material with a thickness of 16 μm.
Embodiment 12
A kind of preparation method of MAX phase ceramics-layered metal composite material includes the following steps:
(1) Ti of 400 meshes was taken2AlC powder is dissolved in PMMA solution and the MAX phase ceramics that concentration is 10wt% is made Grain suspension, by MAX ceramic phase particle suspension spray on the copper foil of 18 μ m-thicks, the coating of MAX ceramic phase particle suspension With a thickness of 4 μm, the copper foil coated with MAX ceramic phase particle is obtained；
(2) the copper foil folding for being coated with MAX ceramic phase particle is placed in hot pressing die, and it is molten that heating evaporation removes PMMA Liquid obtains basic products；
(3) basic products are pressurizeed and is heat-treated, be warming up to 1000 DEG C and the 25MPa that pressurizes, heat-insulation pressure keeping 30min is finally obtained MAX phase ceramics layer is in MAX phase ceramics-copper laminar composite material with a thickness of 4 μm.
Comparative example 1
It is comparative example with embodiment 1 in CN102260803B, preparation method includes the following steps:
(1) Ti that purity is 98.5% is weighed20.74 gram of AlC powder, 159 grams of Cu powder that purity is 99.9%；
(2) ingredient of step (1) is mixed, 110 milliliters of dehydrated alcohols and 320 grams of agate balls is added, ball mill mixing 2 is small When, it grinds, sieve with 100 mesh sieve with 60 DEG C of drying, by the mixed raw material of drying；
(3) by the mixed raw material of step (2) under 140MPa pressure, cold pressing is in strip green body；
(4) bar shaped green body prepared by step (3) is put into the graphite jig in high temperature furnace, under protection of argon gas, with 40 DEG C/rate of min is warming up to 1100 DEG C, keeps the temperature 20min, furnace temperature is down to 60 DEG C to get to this hair with the rate of 10 DEG C/min Bright nano TiC0.5Particle in-situ Reinforced Cu (Al) composite material.
Comparative example 2
It is comparative example with embodiment 1 in CN101028749B, preparation method includes the following steps:
By Ti3AlC2The mold that it is 50mm into diameter that powder and Cu powder are uniformly spread layer by layer, applies the pressure of 120MPa, is made 3 Layer Ti3AlC2The Ti of powder, 2 layers of Cu powder3AlC2-Cu-Ti3AlC2-Cu-Ti3AlC2Stratiform green body；This stratiform green body is packed into graphite Crucible is put into high temperature sintering furnace, under protection of argon gas, furnace temperature is risen to 1150 DEG C with the heating rate of 30 DEG C/min, heat preservation It cools down after 30min to get to 3 layers of Ti3C2The laminar composite of-Cu-Al cermet, 2 layers of Cu-Al alloy.
Performance test:
The MAX being prepared phase ceramics-layered metal composite material is performed the following performance tests:
(1) tensile strength at room temperature
Think carefully that CMT4105 type electronic universal tester is tested using Shenzhen, stretches the parallel segment length 18mm of sample, it is horizontal Sectional area 1.7mm × 3mm calculates the tensile strength of each sample according to calculating formula as defined in GB/T228-2002.Every kind of material Material is surveyed three times respectively, and final tensile strength takes the average value of test result three times.
(2) compression strength at room temperature
Think carefully that CMT4105 type electronic universal tester is tested using Shenzhen, test sample is diameter 4mm, height 7mm Cylindrical body, loading speed 0.25mm/min, according to calculating formula as defined in GB/T 7314-2005 calculate compression strength.Every kind Material is surveyed three times, and final compression strength takes the average value of test result three times.
(3) electric conductivity at room temperature
It is tested using Agilent 433B milliohmmeter, sample is having a size of 3mm × 3mm × 36mm.After measuring resistance value, according to Formula ρ=RS/L calculates resistivity.Every kind of material is surveyed three times, and final resistivity takes the average value of test result three times.
The performance test results are (a representative is parallel to bedding angle, and b is represented perpendicular to bedding angle) as shown in table 1:
Table 1
It can be seen from Table 1 that MAX phase ceramics-layered metal composite material material that embodiment 1-12 is provided, is parallel to The compressive yield strength of bedding angle is apparently higher than perpendicular to bedding angle, and the compression strength for being parallel to bedding angle is obviously low In perpendicular to bedding angle, thus it is speculated that when being due to being parallel to bedding angle on-load pressure, the high MAX phase ceramics layer of modulus directly by Power, when perpendicular to bedding angle on-load pressure, MAX phase ceramics layer and the common stress of the lower metal foil layer of modulus, therefore it is parallel There is bigger compressive yield strength relative to perpendicular to bedding angle in bedding angle；When further increasing the pressure of load, Since the two-phase interface binding force for being parallel to bedding angle is relatively weak, under the action of outer plus-pressure, two-phase combination interface is disconnected It splits, when perpendicular to bedding angle on-load pressure, is equivalent to and densification compacting is carried out to MAX phase ceramics layer and metal foil layer, therefore The maximum compressive strength of bedding angle is parallel to lower than perpendicular slice direction；At the same time, have due to being parallel to bedding angle Continuous metal layers exist, and electric conductivity is significantly better than the perpendicular slice direction of MAX phase ceramics layer and metal foil layer interleaved.
It can be seen from Table 1 that embodiment 4, relative to embodiment 1, tensile strength and anti-yield strength are lower, it may be possible to Since the high MAX phase ceramics layer volume content of modulus is smaller；Electric conductivity is higher, it may be possible to since the layers of copper volume of good conductivity contains It measures larger.For embodiment 5 relative to embodiment 1, compressive yield strength and compression strength are higher, it may be possible to due to the high MAX of modulus Phase ceramics layer volume content is larger；Tensile strength is lower, it may be possible to and since MAX phase ceramics layer volume content is larger, brittleness is larger, So tensile property is lower；Electric conductivity is lower, it may be possible to since layers of copper volume content with good conductivity is smaller, so electric conductivity It is lower.
It can be seen from Table 1 that 1 tensile property of comparative example and compressive property are lower, it may be possible to due to using Ti2AlC powder It is that raw material is uniformly mixed with Cu powder, so that reinforced phase is what even dispersion was distributed, while being prepared in the composite material of preparation Composite material is single layer structure, so mechanical performance is lower.
For comparative example 2 compared to embodiment 1, tensile property and resistance to compression are relatively low, it may be possible to due to using Cu powder for copper source, Cu powder is lower relative to copper foil mechanical performance, so the composite material machinery performance of preparation is lower.
One column of compression strength is without specific data in composite material prepared by embodiment 2,4,7 and 12, because preparation is compound Material plasticity is good, and final flatten will not be cracked, so compression strength is not present in the composite material of preparation.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention, But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention Within protection scope and the open scope.

Claims (10)

1. a kind of MAX phase ceramics-layered metal composite material, which is characterized in that the composite material includes n-layer superpositing unit, Each superpositing unit includes metal foil layer and the MAX phase ceramics layer that is attached on the metal foil layer, n >=2.
2. composite material as described in claim 1, which is characterized in that n >=10, preferably n >=20, further preferred n >= 50, most preferably 50≤n≤100.
3. composite material as claimed in claim 1 or 2, which is characterized in that the metal foil includes copper foil and/or nickel foil；
Preferably, in each superpositing unit, the volume content of MAX phase ceramics is 5%~30%；
Preferably, in each superpositing unit, MAX phase ceramics layer average thickness is 2~16 μm；
Preferably, in each superpositing unit, metal foil layer is with a thickness of 9~80 μm.
4. the composite material as described in one of claim 1-3, which is characterized in that the MAX phase ceramics include 312 phase MAX phases In ceramics, 211 phase MAX phase ceramics and 413 phase MAX phase ceramics any one or at least two combination；
Preferably, the 312 phase MAX phase ceramics include Ti3AlC2、Ti3SiC2And Ti3SnC2In any one or at least two Combination；
Preferably, the 211 phase MAX phase ceramics include Ti2AlC、Ti2AlN、Nb2AlC、Ti2AlN0.5C0.5、Cr2AlC、Ti2SnC And Nb2In SnC any one or at least two combination；
Preferably, the 413 phase MAX phase ceramics include Ti4AlC3And/or Nb4AlC3。
5. a kind of a kind of preparation method of MAX phase ceramics-layered metal composite material as described in one of claim 1-4, It is characterized in that, the preparation method includes the following steps:
(1) on metal foil by the coating of MAX ceramic phase particle suspension；
(2) it is coated with the metal foil superposition of MAX ceramic phase particle, and removes the dispersing agent in MAX ceramic phase particle suspension, Obtain basic products；
(3) basic products are pressurizeed and is heat-treated, MAX phase ceramics-layered metal composite material is made.
6. composite material and preparation method thereof as claimed in claim 5, which is characterized in that step (1) the MAX ceramic phase particle is outstanding In supernatant liquid, the concentration of MAX ceramic phase particle is 5wt%~20wt%；
Preferably, the dispersing agent in the MAX ceramic phase particle suspension includes PVA aqueous solution, PMMA methyl phenyl ethers anisole solution, poly- second In two pure and mild hexamethylenes any one or at least two combination；
Preferably, the metal foil layer is with a thickness of 6~400 μm；
Preferably, the MAX ceramic phase particle partial size is more than 200 mesh；
Preferably, the coating method includes spraying, brushing, spin coating, any one in Best-Effort request；
Preferably, MAX ceramic phase particle suspension coating with a thickness of 4~16 μm.
7. such as composite material and preparation method thereof described in claim 5 or 6, which is characterized in that the mode packet of step (2) described superposition Include folding or stacking；
Preferably, the mode of the superposition is to fold, in the MAX phase ceramics-each superpositing unit of layered metal composite material, MAX phase ceramics layer average thickness is 4~16 μm；
Preferably, the mode of the superposition is to be laminated, in the MAX phase ceramics-each superpositing unit of layered metal composite material, MAX phase ceramics layer average thickness is 2~8 μm；
Preferably, the method for removing the dispersing agent in MAX ceramic phase particle suspension is heating evaporation.
8. the composite material and preparation method thereof as described in one of claim 5-7, which is characterized in that at step (3) described pressurized heat Reason includes any one in hot pressed sintering, SPS sintering, hot rolling；
Preferably, the temperature of the pressurization heat treatment is 850~1050 DEG C；
Preferably, the pressure of the pressurization heat treatment is 20~200MPa；
Preferably, the time of the pressurization heat treatment is 15~120min.
9. a kind of preparation method of MAX phase ceramics-layered metal composite material as described in one of claim 5-8, feature It is, the preparation method includes the following steps:
(1) the MAX ceramic phase particle by partial size more than 200 mesh is added in dispersion PMMA methyl phenyl ethers anisole solution, and concentration, which is made, is The suspension of 5wt%~20wt%, and using spraying method be coated in 6~400 μ m-thicks metal foil on, coating thickness be 4~ 16μm；
(2) it is coated with the metal foil superposition of MAX ceramic phase particle, and heating evaporation removes in MAX ceramic phase particle suspension Dispersing agent, obtain basic products；
(3) pressurize basic products 15~120min of heat treatment at 850~1050 DEG C of temperature and 20~200MPa pressure, is made MAX phase ceramics-layered metal composite material.
10. a kind of purposes of MAX phase ceramics-layered metal composite material a kind of as described in one of claim 1-4, feature exist In the composite material is used for apparatus of transport field, power transmission and transformation field or military project Material Field；
Preferably, the composite material is for the high-speed train pantograph slide plate in apparatus of transport field；
Preferably, the composite material is for the transformer conducting wire or power transmission line in power transmission and transformation field；
Preferably, the composite material is for the spot-wedling electrode in field of material processing；
Preferably, the composite material is for the armoured equipment in military project Material Field.
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CN116352233A (en) * 2023-05-30 2023-06-30 中镱新材料智能制造研究院(山西)有限公司 Manufacturing method for fused accumulation additive of ejection type ceramic particle reinforced composite material
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