CN115871249A - Carbon fiber metal composite material structure and preparation method thereof - Google Patents
Carbon fiber metal composite material structure and preparation method thereof Download PDFInfo
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- CN115871249A CN115871249A CN202211657444.3A CN202211657444A CN115871249A CN 115871249 A CN115871249 A CN 115871249A CN 202211657444 A CN202211657444 A CN 202211657444A CN 115871249 A CN115871249 A CN 115871249A
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- carbon fiber
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 206
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 206
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 239000002905 metal composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 167
- 239000002184 metal Substances 0.000 claims abstract description 167
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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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
- C22C47/08—Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
- C22C47/12—Infiltration or casting under mechanical pressure
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
- C21D1/28—Normalising
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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
- C22C47/02—Pretreatment of the 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
- C22C49/08—Iron group 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
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
- C23C8/22—Carburising of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/44—Carburising
- C23C8/46—Carburising of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
- C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
- C23C8/64—Carburising
- C23C8/66—Carburising of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F17/00—Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/004—Dispersions; Precipitations
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
The invention belongs to the technical field of carbon fiber composite materials, and particularly relates to a preparation method of a carbon fiber metal composite material. A preparation method of a carbon fiber metal composite material comprises the following steps: compounding carbon fiber raw material tows with a metal piece to obtain a raw material tow complex; the compounding comprises winding compounding or filling compounding, wherein the winding compounding is to wind a metal piece on the side wall of the carbon fiber raw material tows; the filling and compounding step is to fill the carbon fiber raw material tows in the open cavity of the metal piece; and pre-oxidizing, thermally treating and carbonizing the raw material tow complex to obtain the carbon fiber metal composite material. The carbon fiber metal composite material prepared by the preparation method provided by the invention has the advantages of high temperature resistance, wear resistance, high strength, good toughness and the like, good bonding performance and long service life.
Description
Technical Field
The invention belongs to the technical field of carbon fiber composite materials, and particularly relates to a preparation method of a carbon fiber metal composite material.
Background
Metallic materials are the pillars of today's manufacturing industry, while carbon fiber is the most suitable material found by people today to replace metals. The carbon fiber is high-strength high-modulus fiber with carbon content of more than 90%. The carbon fiber has light weight, and the manufactured parts have small motion inertia, so that the speed is high, the precision is high, and the noise is low, which has obvious advantages on all occasions with mechanical motion.
However, carbon fiber materials have the defects of poor abrasion resistance and poor impact resistance, so that carbon fiber composite materials are produced at the same time, and composite materials obtained by compounding carbon fiber materials and matrix materials have the properties of carbon fibers and matrix materials at the same time, so that the properties of the two materials are complementary. At present, carbon fiber reinforced composite materials can be classified into carbon fiber resin composite materials, carbon fiber carbon composite materials, carbon fiber metal composite materials, carbon fiber ceramic composite materials and the like according to different matrixes.
The carbon fiber metal composite material not only has higher strength and elastic modulus, but also improves the high-temperature performance of the metal. Namely, the high-temperature strength and modulus are high, and the dimensional stability is good at high temperature, so that the service temperature of the part is increased. Meanwhile, the composite material has better machining performance and connection performance, and the problems that the carbon fiber resin composite material is easy to age and the like are solved. Has been used for structural parts in the aspects of satellite and aerospace. However, the carbon fiber and the metal are not firmly bonded due to poor wettability of the carbon fiber to the metal interface.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a carbon fiber metal composite material, and the carbon fiber metal composite material prepared by the preparation method provided by the invention has the properties of high temperature resistance, wear resistance, high strength, good toughness and the like, good bonding performance and long service life.
In order to solve the technical problem, the invention provides a preparation method of a carbon fiber metal composite material, which comprises the following steps:
compounding carbon fiber raw material tows with a metal piece to obtain a raw material tow complex; the compounding comprises winding compounding or filling compounding, wherein the winding compounding is to wind a metal piece on the side wall of the carbon fiber raw material tows; the filling and compounding step is to fill the carbon fiber raw material tows in the open cavity of the metal piece;
carrying out pre-oxidation treatment on the raw material tow complex to obtain a pre-oxidized part;
carrying out heat treatment on the pre-oxidized part to obtain a heat-treated part; the heat treatment comprises a first heat treatment or a second heat treatment;
the first heat treatment includes: carbonizing the raw material tow complex under a first temperature condition in a protective gas to obtain a carbon fiber complex; performing first forging and pressing on the carbon fiber composite under the condition of a second temperature, wherein the second temperature is higher than the first temperature, and the second temperature is higher than the liquidus temperature of the metal profile body;
the second heat treatment includes: carrying out second forging and pressing molding on the raw material filament bundle complex under the condition of a third temperature in protective gas, wherein graphitization occurs in the forging and pressing molding, and the third temperature is higher than the liquidus temperature of the metal profiled body;
in the invention, the first forging and pressing forming and the second forging and pressing forming are both ' extrusion stress cooling forming ', concretely, in the stress extrusion process, the carbon fiber raw material tows ' subjected to pre-oxidation treatment keep a solid state, a metal melt obtained by melting metal penetrates into gaps of the carbon fiber raw material tows ' when the carbon fiber raw material tows ' in the solid state bear extrusion, and a heat treatment piece is obtained after cooling, wherein the heat treatment piece comprises carbon fibers, metal penetrating among the carbon fibers and a metal surface formed on part of the surface of the carbon fibers; the first forging and pressing forming and the second forging and pressing forming are made of non-metal materials.
And performing carburizing treatment on the heat-treated piece to obtain the carbon fiber metal composite material.
Preferably, the metal piece comprises an arc-shaped metal profile body or an I-shaped metal profile body;
the arc-shaped metal irregular body and the carbon fiber raw material tows are compounded into a winding compound;
the I-shaped metal irregular body and the carbon fiber raw material tows are compounded into filling composite.
Preferably, the carburizing process comprises a liquid carburizing process or a gas carburizing process.
Preferably, the carburizing treatment results in a carburized part; the carburization treatment also comprises the following steps: and (3) bonding the carbon fiber, the metal and the metal surface in the carburized part by using a high-temperature adhesive to obtain the carbon fiber metal composite material, wherein the high-temperature adhesive comprises copper oxide or aluminum dihydrogen phosphate.
Preferably, the high-temperature adhesive also comprises copper oxide or aluminum dihydrogen phosphate added with molybdenum disulfide and/or aluminum hydroxide ash.
Preferably, the bonding is performed to obtain a bonded piece, wherein the bonded piece comprises carbon fibers, metal infiltrated among the carbon fibers and a metal surface formed on the surface of the carbon fibers; after the bonding, the method further comprises the following steps: welding a plurality of adhesive pieces by taking a metal surface as a welding surface to obtain the carbon fiber metal composite material; and when welding, pressing the non-welding surface of the bonding piece.
Preferably, the winding composite is equal-interval composite winding, and the interval distance between two circles of circular arc-shaped metal irregular bodies wound adjacently is the diameter of the carbon fiber raw material tows.
Preferably, the temperature of the pre-oxidation treatment is 200 to 400 ℃.
Preferably, the depth of the i-shaped opening of the i-shaped metal profile body is as follows: the sum of the tensile force born by the filled carbon fibers of the I-shaped opening and the tensile force born by the combined contact surface of the carbon fibers and the metal special-shaped body is not less than the tensile force generated by the carbon fibers with the same thickness as the I-shaped opening in the length direction.
Preferably, the welding is performed to obtain a welding part, and the rolling and leveling treatment is performed to the welding part in sequence to obtain the carbon fiber metal composite material.
The invention provides a preparation method of a carbon fiber metal composite material, which comprises the following steps: compounding a carbon fiber raw material tow with a metal piece to obtain a raw material tow complex; the compounding comprises winding compounding or filling compounding, wherein the winding compounding is to wind a metal piece on the side wall of the carbon fiber raw material tows; the filling and compounding step is to fill the carbon fiber raw material tows in the open cavity of the metal piece; carrying out pre-oxidation treatment on the raw material tow complex to obtain a pre-oxidized part; carrying out heat treatment on the pre-oxidized part to obtain a heat-treated part; the heat treatment comprises a first heat treatment or a second heat treatment; the first heat treatment includes: carbonizing the raw material tow complex under a first temperature condition in a protective gas to obtain a carbon fiber complex; performing first forging and pressing on the carbon fiber composite under the condition of a second temperature, wherein the second temperature is higher than the first temperature, and the second temperature is higher than the liquidus temperature of the metal profile body; the second heat treatment includes: carrying out second forging and pressing molding on the raw material filament bundle complex under the condition of a third temperature in protective gas, wherein graphitization occurs in the forging and pressing molding, and the third temperature is higher than the liquidus temperature of the metal profiled body; and carrying out carburizing treatment on the heat-treated piece to obtain the carbon fiber metal composite material. The preparation method provided by the invention can be used for in-situ self-growing the carbon fiber reinforced phase in the metal matrix: the method comprises the steps of firstly compounding carbon fiber raw material tows with metal pieces, then carrying out in-situ carbonization or graphitization on the raw material tows through pre-oxidation treatment, heat treatment and carburization treatment to obtain carbon fiber reinforced phases and forming the carbon fiber reinforced phases with a metal matrix, wherein compared with the case that the carbon fiber reinforced phases are compounded with the metal matrix in an additional mode, the carbon fiber reinforced phases and the matrix are in a non-coherent orientation relationship, so that a certain gap exists between the carbon fiber reinforced phases and the matrix, and the interface bonding is weak. The carbon fiber and the metal in the in-situ grown carbon fiber metal composite material belong to coherent or semi-coherent interface combination, so the interface combination force can be obviously improved, and the mechanical problem of weaker interface combination of the carbon fiber metal composite material can be solved from the source.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of a metal strip having a circular arc-shaped cross-section;
FIG. 2 is a cross-sectional view of a metal strip having a circular arc-shaped cross-section;
FIG. 3 is a schematic view of a metal strip having an I-shaped cross-section;
FIG. 4 is a cross-sectional view of a metal strip having an I-shaped cross-section;
FIG. 5 is a schematic view of a carbon fiber raw material tow combined with a metal strip having a circular arc-shaped cross section;
FIG. 6 is a schematic view of a carbon fiber feedstock tow being composited with a metal strip having an I-shaped cross-section;
FIG. 7 is a schematic view of a carbon fiber metal composite;
fig. 8 is a schematic view of a carbon fiber metal composite.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The invention provides a preparation method of a carbon fiber metal composite material, which comprises the following steps:
compounding carbon fiber raw material tows with a metal piece to obtain a raw material tow complex; the compounding comprises winding compounding or filling compounding, wherein the winding compounding is to wind a metal piece on the side wall of the carbon fiber raw material tows; the filling and compounding step is to fill the carbon fiber raw material tows in the open cavity of the metal piece;
carrying out pre-oxidation treatment on the raw material tow complex to obtain a pre-oxidized part;
carrying out heat treatment on the pre-oxidized part to obtain a heat-treated part; the heat treatment comprises a first heat treatment or a second heat treatment;
the first heat treatment includes: carbonizing the raw material tow complex under a first temperature condition in a protective gas to obtain a carbon fiber complex; performing first forging and pressing forming on the carbon fiber composite under the condition of a second temperature, wherein the second temperature is higher than the first temperature, and the second temperature is higher than the liquidus temperature of the metal profile body;
the second heat treatment includes: carrying out second forging and pressing molding on the raw material filament bundle complex under the condition of a third temperature in protective gas, wherein graphitization occurs in the forging and pressing molding, and the third temperature is higher than the liquidus temperature of the metal profiled body;
and carrying out carburizing treatment on the heat-treated piece to obtain the carbon fiber metal composite material.
Compounding carbon fiber raw material tows and a metal piece to obtain a raw material tow complex; the compounding comprises winding compounding or filling compounding, wherein the winding compounding is to wind a metal piece on the side wall of the carbon fiber raw material tows; and the filling compounding is to fill the carbon fiber raw material tows in the open cavity of the metal piece.
In the present invention, the carbon fiber raw material tow is preferably a tow formed of one or more of viscose fiber, polyacrylonitrile fiber and pitch fiber.
In a specific embodiment of the invention, the viscose has the chemical formula (C) 6 H 10 O 5 ) n 。
In a specific embodiment of the present invention, the polyacrylonitrile fiber has a chemical formula of (C) 3 H 3 N) n 。
In a particular embodiment of the invention, the carbon content of the viscose fibres is preferably 45wt%.
In a specific embodiment of the present invention, the carbon content of the polyacrylonitrile fiber is preferably 68wt%.
In a specific embodiment of the invention, the carbon content of the pitch fibers is preferably 95wt%.
In the present invention, the carbon fiber yield of the viscose fiber is preferably 21 to 35wt%.
In the present invention, the carbon fiber yield of the polyacrylonitrile fiber is preferably 40 to 55wt%.
In the present invention, the carbon fiber yield of the pitch fiber is preferably 82 to 90wt%.
In the present invention, before the compounding, the present invention preferably further comprises washing, sizing and drying the carbon fiber raw material filaments in sequence. The invention has no special requirements for the specific implementation processes of cleaning, sizing and drying.
In the present invention, the metal member is preferably a metal profile body.
In the present invention, the metal member preferably includes a circular arc-shaped metal profile body or an i-shaped metal profile body;
in the invention, the circular arc-shaped metal special-shaped body and the carbon fiber raw material tows are compounded, preferably wound and compounded.
In the invention, the I-shaped metal special-shaped body and the carbon fiber raw material tows are compounded, preferably filled and compounded.
In the present invention, the material of the metal profile is preferably an alloy profile.
The type of the alloy profile body depends on the application field of the added workpiece.
In the present invention, the method for forming the metal profile body preferably includes die forging, forming or hot melt spray forming.
In the present invention, the alloy composition of the alloy profile body preferably comprises microalloying elements capable of forming carbides.
In the invention, the microalloying elements capable of forming carbides in the alloy profile body comprise one or more of B, cr, zr and Ti.
In the present invention, the metal profile body comprises a circular arc shaped metal profile body, as shown in fig. 1.
In the present invention, the cross section of the circular arc shaped metal profile body is circular arc shaped as shown in fig. 2.
In the present invention, the metal profile body includes an i-shaped metal profile body, as shown in fig. 3.
In the present invention, the cross section of the i-shaped metal profile body is i-shaped, as shown in fig. 4.
In the invention, the method for compounding the arc-shaped metal profile body comprises the following steps: and uniformly winding the metal profile body on the side wall of the carbon fiber raw material tows, as shown in fig. 5.
In the invention, the winding composite is equal-interval composite winding, and the interval distance between two circles of circular arc-shaped metal special-shaped bodies wound adjacently is the diameter of the carbon fiber raw material tows, as shown in fig. 5.
In the present invention, R in fig. 5 is R, when winding and compounding are adopted, the radius of the carbon fiber raw material tow is R, and the diameter is 2R.
The invention can achieve the best state of light weight and high strength of the carbon fiber metal composite structure through the winding mode shown in figure 5.
In the invention, the method for compounding the I-shaped metal profile body comprises the following steps: and filling the carbon fiber raw material tows in the I-shaped opening of the metal profiled body, as shown in fig. 6.
The present invention has no particular requirement on the specific embodiment of the filling.
In the present invention, the depth of the i-shaped opening of the i-shaped metal profile body is preferably: the sum of the tensile force born by the filled carbon fiber of the I-shaped opening and the tensile force born by the combined contact surface of the carbon fiber and the metal profile body is not less than the tensile force generated by the carbon fiber with the same thickness as the I-shaped opening in the length direction.
After the raw material filament bundle compound is obtained, the raw material filament bundle compound is subjected to pre-oxidation treatment to obtain a pre-oxidized part.
In the present invention, the heat-retention temperature of the heat-stabilization treatment is preferably 200 to 400 ℃, more preferably 250 to 350 ℃.
In the invention, the pre-oxidation treatment converts linear molecular chains of Polyacrylonitrile (PAN) carbon fiber precursors into pre-oxidized fibers with heat-resistant ladder structures; in a high-temperature carbonization environment under the protection of inert gas, PAN does not melt and burn, maintains the fiber form, and further turns into carbon fibers with a disordered-layer graphite structure.
In the present invention, the pre-oxidation treatment prevents the linear molecular chains of the raw filaments from thermally breaking at high temperatures and converting into resin carbon rather than fibrous carbon having only a certain strength, and the carbonization yield is extremely low.
In the invention, in the thermal environment of the pre-oxidation treatment, the high-orientation PAN protofilament is physically shrunk and increased in conformation so as to be in a thermodynamically stable state. To prevent free shrinkage, the fibers are loose and pulverized, without strength. Draw with tension to prevent disorientation. Chemical reactions occur which necessarily produce chemical shrinkage, and tension is applied to control the degree of shrinkage. The draft is throughout the pre-oxidation process.
In the invention, various chemical reactions occur in the pre-oxidation treatment process, the main reactions are cyclization, oxidation and dehydrogenation, and the three reactions are exothermic reactions to instantly remove and take away the exothermic heat. Preventing heat accumulation and overheating inside the fibers, causing thermal fusion between the monofilaments.
In the invention, the functional group containing non-metal atoms such as O, F, N and the like is preferably introduced to the surface of the carbon fiber raw material wire through pre-oxidation treatment, on one hand, the purpose of improving the bonding strength of the carbon fiber and a metal interface is achieved by utilizing the high-temperature sintering molding of the carbon fiber metal composite material at the later stage and forming a metal-O-C covalent bond at the carbon fiber phase-alloy interface, on the other hand, the conductivity of the carbon fiber reinforced phase-metal interface is improved through the formation of the C-O, C-N, C-F and other covalent bonds, and the improvement of the electric conductivity and the thermal conductivity of the carbon fiber metal composite material is realized.
After a pre-oxidized part is obtained, carrying out heat treatment on the pre-oxidized part to obtain a heat-treated part; the heat treatment comprises a first heat treatment or a second heat treatment; the first heat treatment includes: carbonizing the raw material tow complex under a first temperature condition in a protective gas to obtain a carbon fiber complex; performing first forging and pressing on the carbon fiber composite under the condition of a second temperature, wherein the second temperature is higher than the first temperature, and the second temperature is higher than the liquidus temperature of the metal profile body; the second heat treatment includes: and carrying out second forging and pressing forming on the raw material filament bundle complex under a third temperature condition in protective gas, wherein graphitization occurs in the forging and pressing forming, and the third temperature is higher than the liquidus temperature of the metal profile body.
In the present invention, in the first heat treatment, the first temperature is preferably 400 to 1400 ℃, and more preferably 450 to 1350 ℃.
In the present invention, the second temperature is preferably 1300 to 1500 ℃, more preferably 1350 to 1450 ℃.
In the present invention, in the second heat treatment, the third temperature is preferably not less than 1800 ℃, and more preferably 1800 to 2000 ℃.
In the present invention, the protective gas is preferably an inert gas, more preferably argon.
The present invention has no particular requirement for the heating means used to bring the raw tow composite to the first, second or third temperature.
As an embodiment of the invention, the invention uses a temperature sensor and PLC control to ensure that the carbon fiber and the metal profile body have the optimal temperature for carrying out the combination reaction, and the heat preservation time is up to the time for the carbon fiber and the metal profile body to be fully combined.
As a specific embodiment of the invention, the invention adopts laser to melt a metal profile body on carbon fiber into a molten state, then uses laser (focusing) pulse to be vertical to the surface of the alloy carbon fiber, impacts the molten metal alloy to enable the impacted metal melt to enter pores between the carbon fiber and the carbon fiber, the laser (focusing) pulse point regularly changes the laser (focusing) pulse position to prevent the carbon fiber and the metal melt from being combined unevenly and regularly, and the laser (focusing) pulse point sets the distance and the changing time of the laser (focusing) pulse point entering the carbon fiber according to the material element components and the element component content of the metal profile body and the temperature of the molten state to enable the laser (focusing) pulse point to reach the optimal state.
The invention preferably modifies the contact interface between the carbon fiber and the metal profile body by covalent bonds.
The invention preferably can improve the interface wettability between the carbon fiber reinforced phase and the alloy matrix through the covalent bond modification, improve the interface bonding force of the carbon fiber metal composite material, and realize the regulation and control of the interface conductivity of the carbon fiber metal composite material.
In the present invention, the covalent bond modification preferably regulates the bonding atomic species and content of the carbon fiber and the metal element.
In the present invention, the metal profile body preferably includes one or more of B, cr, zr, and Ti, which are capable of improving the wettability between the metal matrix and the carbon fiber reinforced phase, and the B, cr, zr, and Ti react with the carbon fiber reinforced phase at the interface of the carbon fiber and the metal to form carbide, and the thickness of the carbide is preferably controlled by adjusting the contents of the above elements.
The invention can obviously improve the mechanical property of the carbon fiber alloy composite material by alloying the metal matrix, and has the same advantages of improving the heat-conducting property.
The invention preferably relates to a preparation method of the in-situ self-generated reinforcing phase in the alloy matrix.
The invention preferably adopts interface covalent bond modification and surface alloying of a reinforcing phase to further improve the interface bonding force of the carbon fiber and the metal matrix.
The invention preferably adopts a preparation method of in-situ grown carbon fiber reinforced phase, not only can utilize the metal matrix as a catalyst to simplify the preparation process, but also can solve the problem of weaker interface bonding between the carbon fiber reinforced phase and the alloy matrix from the source. Compared with the non-coherent orientation relation between the externally-added carbon fiber reinforced phase and the metal matrix, the in-situ grown carbon fiber metal composite material belongs to coherent or semi-coherent interface bonding, so the interface bonding force can be remarkably improved.
In the invention, the interface structure of the carbon fiber reinforced phase and the metal matrix is preferably realized by interface covalent bond modification, surface alloying of the carbon fiber reinforced phase, alloying of an alloy matrix, interface reaction and in-situ growth of the carbon fiber reinforced phase.
After the heat treatment piece is obtained, the heat treatment piece is subjected to carburizing treatment to obtain the carbon fiber metal composite material.
In the present invention, the heat treatment member preferably includes carbon fibers, a metal infiltrated between the carbon fibers, and a metal face formed on a surface of a part of the carbon fibers.
In the present invention, the carbon concentration in the carburizing treatment is preferably 0.8 to 1.5%, preferably 0.8 to 1.2, and more preferably 0.9 to 1.0%.
In the present invention, the temperature for maintaining the temperature of the carburizing treatment is preferably 900 to 950 ℃, and more preferably 920 to 940 ℃.
In the present invention, the carburizing treatment preferably further includes an energizer, and the energizer is particularly preferably BaCO 3 In the present invention, the BaCO is 3 The mass amount of (A) is not less than 4%, preferably 4-7%. In the present invention, the energizer is preferably calculated on the mass of the active carburizing medium.
In the present invention, the liquid carburizing process preferably includes the steps of:
and putting the heat-treated workpiece into an active carburizing medium for liquid carburizing.
In the present invention, a specific embodiment of the liquid carburization is preferably: the heat treatment piece is placed in an active carburizing medium, heated to a single-phase austenite area of 900-950 ℃, and after the heat preservation is carried out for enough time, activated carbon atoms decomposed from the carburizing medium are infiltrated into a metal surface layer, so that high carbon on the surface layer is obtained, and then quenching and low-temperature tempering are carried out, so that the surface layer of the workpiece has high hardness and wear resistance, and the central part of the workpiece still maintains the toughness and plasticity of alloy steel.
In the present invention, for machine parts working under conditions of alternating load, impact load, large contact stress and severe wear, such as gears, piston pins, camshafts, etc., the surface of the workpiece is required to have high wear resistance, fatigue strength and bending strength, while the core has sufficient strength and toughness to satisfy the performance requirements by carburizing heat treatment.
In the present invention, after the infiltration treatment, the carburized workpiece is subjected to post-treatment to obtain the carburized workpiece.
In the present invention, the post-treatment preferably comprises: sequentially quenching and tempering. In the present invention, the firing is preferably performed by lowering the temperature of the workpiece from the carburizing temperature to the quenching temperature.
In the invention, the workpiece is taken out from the carburizing furnace to be directly quenched and then tempered so as to obtain the hardness and metallographic structure process characteristics required by the surface.
In the present invention, the quenching temperature is preferably 800 to 850 ℃.
In the present invention, the quenching at the above temperature is performed to reduce the quenching distortion and reduce the amount of retained austenite on the surface by precipitation of carbide.
In the present invention, the active carburizing medium is specifically preferably one or more of kerosene, benzene, alcohol, acetone, silicon carbide, and 603 carburizing agent.
In the present invention, the gas carburizing is preferably: a carburizing process for preparing high-carbon surface layer includes loading the workpiece to be heat treated in a closed carburizing furnace, introducing gaseous carburizing agent, decomposing out active carbon atoms at high temp and infiltrating it to workpiece surface.
In the present invention, the gaseous carburizing agent preferably includes methane and/or ethane.
In the present invention, the carburizing treatment also includes 3 basic processes, as well as other chemical heat treatments. Decomposition, adsorption and diffusion are carried out in sequence. In the present invention, the decomposition into decomposition of the carburizing medium produces activated carbon atoms. The adsorption is that activated carbon atoms are dissolved in surface austenite after being absorbed by the surface of the metal, so that the carbon content in the austenite is increased. The diffusion is that the carbon content on the surface is increased, so that the concentration difference with the carbon content in the core occurs, and the carbon on the surface is diffused inwards.
In the present invention, the diffusion rate of carbon in the metal depends mainly on the temperature, and is related to the difference in the concentration of the diffused element in the workpiece between the inside and outside and the content of the alloying element in the steel. After carburizing and quenching, the surface of the workpiece generates compressive internal stress, which is beneficial to improving the fatigue strength of the workpiece.
In the present invention, when the carburization is preferably performed at 800 to 850 ℃, the structure and performance characteristics of the carburized part are as follows: the quenching deformation of the workpiece can be reduced, the residual austenite amount in the carburized layer can be slightly reduced, the surface hardness is slightly improved, and the austenite grains are not changed. The reason is that: the surface layer of the steel receives the most various loads (abrasion, fatigue, mechanical load and chemical corrosion), and the elements such as carbon and the like are infiltrated to achieve high surface hardness, high wear resistance, high fatigue strength and high corrosion resistance. In order to prevent austenite grains from coarsening in the carburizing process, a proper amount of titanium is added into steel, and when the content of titanium exceeds 0.032%, titanium nitride is precipitated during smelting and solidification of carburized steel. The size of the titanium nitride reaches the micron order, which does not play a role in stopping the growth of austenite grains, but rather becomes micro-cracks and crack propagation due to the sharp angle effect of the cubic grains and the discontinuity of the matrix structure, and seriously damages the toughness and plasticity of the metal. The titanium content is reduced to 0.02-0.032%, the function of controlling the growth of austenite grains can be effectively realized, and the formation of harmful titanium nitride grains can be avoided.
In the present invention, the carburizing process has the following common drawbacks:
first, the cause and harm of too high carbon concentration: if the carburization is heated sharply, the temperature is too high, or if a new carburizing agent is used in the case of solid carburization, or if a strong carburizing agent is used too much, the carburization concentration is too high. With too high carbon concentration, massive coarse carbides or network carbides appear on the surface of the workpiece. The toughness of the carburized layer is drastically reduced by the generation of such a hard and brittle structure. High-carbon martensite is formed during quenching, and grinding cracks are easy to appear during grinding; the prevention method comprises the following steps: (1) the steel cannot be heated rapidly, and proper heating temperature is needed, so that the crystal grains of the steel are not well grown. If the grains are coarse during carburizing, the grains should be refined by normalizing or quenching twice after carburizing. (2) The furnace temperature uniformity is strictly controlled, and the fluctuation cannot be too large. (3) When solid is carburized, the carburizing agent needs to be used in a new and old proportion. The accelerant agent is preferably 4-7% BaCO 3 Without using Na 2 CO 3 Used as an energizer. The carbon concentration is too low.
Second, a large temperature fluctuation or too little of the permeation enhancer may cause insufficient carbon concentration at the surface. In the present invention, when the carbon concentration is insufficient, the parts are easily worn; the method for preventing comprises the following steps: (1) the carburizing temperature is generally 920-940 ℃, and the low carburizing temperature can cause the low carbon concentration and prolong the carburizing time; too high a carburizing temperature causes coarsening of crystal grains. (2) Osmosis promoter (BaCO) 3 ) Should not be used in an amount less than 4%. The carburized surface is partially carbon-depleted.
Thirdly, when solid carburization is carried out, charcoal particles are too large or impurities such as stones are mixed in, or the permeation promoter and the charcoal are mixed unevenly, or workpieces are contacted with each other, so that local carbon is not available or carbon is poor. Contamination of the workpiece surface can also cause carbon depletion; the method for preventing comprises the following steps: (1) the solid carburizing agent is prepared according to a certain proportion and is stirred evenly. (2) The charged workpieces are careful not to have contact. The solid is carburized by tamping the carburizer without allowing the carburize to collapse and contact the workpiece. (3) And removing the dirt on the surface. The carburized concentration is more rapidly transitioned.
Fourth, the abrupt transition of the carburized concentration is that the change of the carbon concentration between the surface and the center is increased, and the transition is not uniform from high to low but abrupt. The reason for this defect is that the carburizing agent has a strong action (e.g. newly prepared charcoal, the addition of old carburizing agent is very small), and the presence of alloy elements such as Cr, mn, mo, etc. in the steel promotes the formation of carbides strongly, resulting in high surface concentration, low center concentration and no transition layer. The defect causes considerable internal stress on the surface and the inside, and cracks or peeling phenomena are generated in the quenching process or the grinding process; the method for preventing comprises the following steps: the carburizing agent is prepared according to the specified proportion between new and old carburizing agents, so that the carburizing is eased. By BaCO 3 It is preferable as an energizer because of Na 2 CO 3 It is relatively sharp. Tempering and cracking are generated during grinding.
In the present invention, the carburizing results in carbon steel, which is characterized by:
(1) The carbon content of the carburized steel is generally in the range of 0.15-0.25%, for heavy-load cementite, the carbon content can be increased to 0.25-0.30%, the most used is 15 and 20 steel, and the surface hardness of the carburized and heat-treated carburized steel can reach 56-62 HRC. But because the hardenability is lower, the quenching device is only suitable for small parts with low core strength requirement, small stress and abrasion resistance, such as shaft sleeves, chains and the like.
(2) The alloy elements in the carburizing steel have the functions of improving hardenability, refining grains, strengthening solid solution and influencing the carbon content, the thickness and the structure of a carburized layer. The alloying elements commonly added to carburized steel are manganese, chromium, nickel, molybdenum, tungsten, vanadium, boron, etc. Low alloy carburized steel such as 20Cr, 20Cr2MnVB, 20Mn 2 TiB, etc. has higher permeability and core strength than carbon carburized steel, and may be used in making carburized parts in common machinery, such as gear, piston pin, etc. in automobile and tractor. Alloy carburized steel such as 20Cr2Ni4, 18Cr2N4W, 15Si3MoWV and the like is mainly used for manufacturing parts with large sections, heavy load bearing and complex stress, such as gears, shafts and the like of aeroengines, due to high hardenability and high strength and toughness.
In the present invention, the carburizing temperature of the solid carburizing, the liquid carburizing or the gas carburizing is preferably 900 to 950 ℃, the surface layer carbon content is preferably 0.8 to 1.2%, and the carburized layer depth is preferably 0.5 to 2.0mm.
In the present invention, the quenching and tempering heat treatment after carburization-carburized workpieces should actually be regarded as a composite material having a greatly different surface to center content. Carburization can only change the carbon content of the surface of the workpiece, while the final strengthening of the surface and the core of the workpiece can only be realized by proper heat treatment. And quenching and low-temperature tempering are required for the carburized workpiece. The purpose of quenching is to form high carbon martensite or high carbon martensite and fine grained carbide structure on the surface.
In the present invention, the low temperature tempering temperature is preferably 150 to 200 ℃.
In the present invention, before the carburizing treatment, it is preferable to subject the heat-treated material to a normalizing pretreatment.
In the invention, the pretreatment normalizing before carburizing aims at improving the original structure of the material, reducing the banding, eliminating the Widmannstatten structure, thinning the surface roughness and eliminating the unreasonable flow line state of the material.
In the present invention, the heat-retaining temperature of the normalizing treatment is preferably 860 to 980 ℃.
In the present invention, the hardness of the workpiece after the heat-treated member after the normalization treatment is air-cooled to room temperature is preferably 179 to 217HBS.
In the invention, the hardness of the workpiece needing mechanical processing after the carburization treatment is not higher than 30HRC.
In the present invention, for carburized and quenched parts having thin-walled grooves, the thin-walled grooves cannot be machined prior to carburization.
In the present invention, the galvanization method must be used to prevent carburization.
In the present invention, the carburizing treatment obtains a carburized piece; the present invention preferably further comprises, after the carburizing treatment: and (3) bonding the carbon fiber, the metal and the metal surface in the carburized part by using a high-temperature adhesive to obtain the carbon fiber metal composite material, wherein the high-temperature adhesive comprises copper oxide or aluminum dihydrogen phosphate.
In the present invention, the high temperature binder preferably further comprises copper oxide or aluminum dihydrogen phosphate with molybdenum disulfide and/or aluminum hydroxide ash.
In the invention, the aluminum hydroxide ash can improve the high-temperature resistance of the high-temperature adhesive.
In the present invention, the molybdenum disulfide can improve the friction resistance and hardness of the high temperature adhesive.
In the present invention, when the high temperature adhesive preferably includes copper oxide, aluminum hydroxide ash and molybdenum disulfide, the high temperature resistant inorganic adhesive is a high temperature resistant inorganic nanocomposite binder formed of copper oxide, aluminum hydroxide ash and molybdenum disulfide.
In the invention, the high-temperature adhesive is preferably a suspension dispersion system with a neutral pH value, has strong binding power and no corrosion to a carbon fiber alloy matrix, can keep good binding performance and corrosion resistance at high temperature, and has long service life.
In the present invention, the bonding results in a bonded member comprising carbon fibers, a metal infiltrated between the carbon fibers, and a metal face formed on a surface of a portion of the carbon fibers.
In the present invention, the method for preparing the carbon fiber metal composite material preferably further comprises: welding a plurality of adhesive pieces by taking a metal surface as a welding surface to obtain the carbon fiber metal composite material; and when welding, pressing the non-welding surface of the bonding piece.
In the present invention, it is preferable that the adhesive material is subjected to a pretreatment before the welding, and in the present invention, the pretreatment preferably includes: and rolling, cleaning the welding surface and leveling the welding surface at the joint after aligning the bonding pieces according to the welding surface. The invention preferably increases the flatness of the bonding piece by rolling, thereby improving the flatness of the welding surface. The invention has no special requirements for the specific implementation process of the cleaning. In the present invention, the alignment and leveling of the bonding surface is preferably performed using X-rays or infrared rays.
In a specific embodiment of the invention, the invention uses X-ray or infrared to align the adhesive piece along the metal plane and the metal plane (or the metal end face and the metal end face); according to the contact point and line of welding, the metal surfaces of the plates (sheets) of two-layer adhesive member or multi-layer adhesive member are electrified to generate electric arc, and the contact surfaces, lines and points which are closely connected are welded together under the action of the electric arc, so that the carbon fiber metal composite material formed by the carbon fiber and the metal special-shaped body has the characteristics of light weight and high strength.
In the invention, the welding is preferably argon arc welding, tungsten gas arc welding, plasma arc welding, resistance welding, high frequency welding, electron beam welding, laser welding, brazing, ultrasonic welding or a solid phase welding method using indirect heat energy as an energy source.
In the invention, the argon arc welding is preferably implemented as follows: after the adhesion piece plate (sheet) is flattened, proper pressure is applied to the non-argon arc welding surface of the plate (sheet) to prevent the plate (sheet) from deforming (stress is eliminated by forging and pressing and deformation is changed) due to the contact surface chemical reaction of carbon fibers and the alloy special-shaped strip and the stress generated by welding the alloy special-shaped strip, a pressure sensor is arranged, the pressure applied by a PLC control system to the pressure sensor is used for ensuring the welding quality, tungsten wires and metal surfaces are respectively electrified, and the electrified tungsten wires pass (slide) between every two sheets of the adhesion piece to generate electric arc welding, and when the pressure is applied, the adhesion piece is preferably two layers or more layers. The moving speed between the current, tungsten wire and the adhesive piece plate (sheet) is selected according to the material of the metal surface and the size of the section of the welding surface. The bonding pieces of the upper layer and the lower layer produce the best welding quality.
Argon gas enters and exits at the same time during argon arc welding, the gas supply direction is the same as the tungsten wire running direction, and the argon gas is conveyed in a timed and quantitative mode.
In the present invention, the resistance welding method is preferably: after the adhesive member is leveled, resistance welding is adopted according to the width, the thickness and the material of the metal surface: the plate (sheet) of the bonding piece is under the pressure action of a certain electrode (the upper and lower rollers are used as electrodes), and the metal surface which is in thermal contact with the bonding piece is melted by utilizing the resistance generated when current passes through the workpiece, so that the connection welding is realized.
In the invention, the resistance welding has short electrifying time and high productivity, and is suitable for mass production. The method is mainly used for welding thin plate assemblies with the thickness less than 3 mm.
In the present invention, the high-frequency welding can be classified into contact high-frequency welding and induction high-frequency welding according to the manner in which the high-frequency current generates heat in the workpiece. In contact high frequency welding, a high frequency current is introduced into a workpiece by mechanical contact with the workpiece. In induction high-frequency welding, a high-frequency current generates an induced current in a workpiece through the coupling action of an induction coil outside the workpiece.
In the invention, high-frequency welding is a highly specialized welding method, and special equipment is required to be equipped according to products. The productivity is high, and the welding speed can reach 30m/min.
In the invention, the electron beam welding is a method for welding by using heat energy generated when a concentrated high-speed electron beam bombards the surface of a workpiece.
In the present invention, the electron beam is generated and accelerated by an electron gun at the time of the electron beam welding. The electron beam welding used has: high vacuum electron beam welding, low vacuum electron beam welding and non-vacuum electron beam welding. Both of the first two methods are performed in a vacuum chamber. The weld preparation time (mainly the evacuation time) is long and the workpiece size is limited by the size of the vacuum chamber.
In the invention, the electron beam welding is characterized by large weld penetration, small weld width and high weld metal purity. It can be used for both precise welding of very thin materials and welding of very thick (up to 300 mm) components.
In the present invention, all metals and alloys that can be fusion welded by other welding methods can be electron beam welded. The method is mainly used for welding products requiring high quality. But also solves the problem of welding dissimilar metals, easily oxidized metals and refractory metals. But not for high volume production.
In the present invention, laser welding is welding performed using a laser beam obtained by focusing a high-power coherent monochromatic photon stream as a heat source. Such welding methods typically include continuous power laser welding and pulsed power laser welding.
In the present invention, laser welding has an advantage that it is not required to be performed in a vacuum, and has a disadvantage that the penetration force is not as strong as that of electron beam welding. The laser welding can carry out accurate energy control and realize the welding of precise micro devices. It can be used for many metals, especially for welding some metals difficult to weld and other metals.
In the invention, the heating temperature is low during soldering, carbon fiber and metal are not melted, and certain measures must be taken to remove oil stain, dust, oxidation film and the like on the surface of the workpiece to be soldered before soldering. This is an important guarantee for good wettability of the workpiece and for ensuring the quality of the joint.
In the invention, the heating temperature is lower during brazing, so the influence on the performance of the workpiece material is smaller, and the stress deformation of the weldment is smaller. However, the strength of the soldered joint is generally low and the heat resistance is poor.
In the invention, the brazing can be used for welding metal materials such as carbon steel, stainless steel, high-temperature alloy, aluminum, copper and the like, and can also be used for connecting dissimilar metals, metals and non-metals. The method is suitable for welding joints which are not subjected to large load or work at normal temperature, and is especially suitable for precise, miniature and complex multi-brazing seam weldments.
In the present invention, sonic welding is a solid phase welding method using mechanical energy as an energy source. When ultrasonic welding is carried out, the welding workpiece is under lower static pressure, and the high-frequency vibration energy emitted by the sonotrode can enable the joint surface to generate strong crack friction and be heated to the welding temperature to form the combination.
In the present invention, ultrasonic welding can be used for welding between most metal materials.
In the present invention, the solid-phase welding method using indirect heat energy as an energy source is preferably: the welding is carried out in vacuum or protective atmosphere, and the surfaces of the metal and the carbon fiber are contacted and insulated at high temperature and high pressure during welding so as to reach the interatomic distance and are combined through atomic interdiffusion.
In the invention, before welding, the solid phase welding method taking indirect heat energy as energy source not only needs to clean impurities such as oxides on the surfaces of alloy and carbon fiber, but also needs to ensure the welding quality when the surface roughness is lower than a certain value.
In the invention, the solid-phase welding method taking indirect heat energy as energy hardly has harmful effect on the performance of the welded material.
In the present invention, when welding, the present invention preferably further comprises pressing the non-welding surface of the adhesive member.
During welding, the invention preferably applies pressure to the non-welding surface of the bonding piece to effectively prevent the bonding piece from generating stress deformation due to the contact surface combination reaction of the carbon fiber and the alloy special-shaped strip and the welding of the alloy special-shaped strip.
In the invention, during the pressure application, a pressure sensor is preferably adopted, and the PLC control system monitors the pressure applied by the pressure sensor in real time so as to ensure the welding quality.
In the invention, the welding part is obtained after welding, and the carbon fiber metal composite material is obtained by sequentially carrying out rolling and leveling treatment on the welding part.
In the present invention, the leveling treatment is preferably a laser leveling treatment.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Obtaining a high-temperature alloy special-shaped body by die forging forming, wherein the cross section of the high-temperature alloy special-shaped body is arc-shaped, and the high-temperature alloy special-shaped body comprises B, cr, zr and Ti elements;
decomposing, cleaning and removing surface stains from viscose fibers, polyacrylonitrile fibers and asphalt fibers, and then sizing and drying to obtain carbon fiber raw material tows;
winding the high-temperature alloy special-shaped body on the side wall of the carbon fiber raw material tows, as shown in figure 5; obtaining a raw material filament bundle complex, carbonizing the raw material filament bundle complex at 400-1400 ℃ under the protection of argon, and fully carbonizing to obtain a carbon fiber complex;
and carrying out pre-oxidation treatment on the carbon fiber composite at the temperature of 200-400 ℃ to obtain a pre-oxidized part.
Forging and pressing the pre-oxidized part at 1300-1500 ℃ to obtain a heat treatment part, wherein the heat treatment part comprises carbon fibers, metal infiltrated among the carbon fibers and a metal surface formed on the partial surface of the carbon fibers;
forging and pressing the pre-oxidized part at 1300-1500 ℃ to obtain a heat-treated part, wherein the heat-treated part comprises carbon fibers, metal infiltrated among the carbon fibers and a metal surface formed on the partial surface of the carbon fibers;
normalizing the heat-treated piece at 860-980 deg.C, liquid carburizing the heat-treated piece, putting the heat-treated piece into active carburizing medium for liquid carburizing, the active carburizing medium is coal oil, the carbon concentration of carburizing treatment is 0.8-1.0%, and BaCO is used 3 As a permeation promoter, the BaCO 3 The mass amount of the active carburizing medium is 4-7%, the heat preservation temperature of the carburizing treatment is 920-940 ℃, the temperature of the workpiece is reduced to 800-850 ℃ after the carburizing treatment, the quenching treatment is carried out, and finally the tempering treatment is carried out, wherein the depth of a carburized layer of the carburized part is 0.5-2.0 mm;
bonding carbon fibers in a carburized piece, metal infiltrated among the carbon fibers and a metal surface formed on the partial surface of the carbon fibers by using a high-temperature adhesive consisting of copper oxide, aluminum hydroxide ash and molybdenum disulfide to obtain a bonded piece;
and rolling the bonded pieces in sequence, cleaning the metal surfaces of the bonded pieces, aligning the bonded pieces according to the welding surfaces by adopting X-rays, and leveling the welding surfaces at the connection parts. The metal surface of the adhesive piece is used as a welding surface, the adhesive pieces are welded by argon arc welding, and the specific implementation is as follows: after the adhesion piece plate (sheet) is flattened, proper pressure is applied to the non-argon arc welding surface of the plate (sheet) to prevent the plate (sheet) from deforming (stress is eliminated by forging and pressing and deformation is changed) due to the contact surface chemical reaction of carbon fibers and the alloy special-shaped strip and the stress generated by welding the alloy special-shaped strip, a pressure sensor is arranged, the pressure applied by a PLC control system to the pressure sensor is used for ensuring the welding quality, tungsten wires and metal surfaces are respectively electrified, and the electrified tungsten wires pass (slide) between every two sheets of the adhesion piece to generate electric arc welding, and when the pressure is applied, the adhesion piece is preferably two layers or more layers. The current, tungsten filament and moving speed between the plates (sheets) of the bonding piece are selected according to the material of the metal surface and the size of the cross section of the welding surface. The bonding pieces of the upper layer and the lower layer produce the best welding quality. Argon gas enters and exits at the same time during argon arc welding, the argon gas is conveyed in a fixed time and a fixed quantity to obtain a welding part, and the welding part is rolled and flattened by laser to obtain the carbon fiber metal composite material, as shown in figure 7.
Example 2
Obtaining a high-temperature alloy special-shaped body by die forging forming, wherein the cross section of the high-temperature alloy special-shaped body is I-shaped, and the high-temperature alloy special-shaped body comprises B, cr, zr and Ti elements;
decomposing, cleaning and removing surface stains on viscose fibers, polyacrylonitrile fibers and asphalt fibers, sizing, drying, and stabilizing at 200-400 ℃ to obtain carbon fiber raw material tows;
filling the carbon fiber raw material tows in the I-shaped openings of the metal irregular body, as shown in FIG. 6; obtaining a raw material filament bundle complex, carbonizing the raw material filament bundle complex at 400-1400 ℃ under the protection of argon, and fully carbonizing to obtain a carbon fiber complex;
forging and pressing the carbon fiber composite at 1300-1500 ℃ to obtain a heat treatment piece, wherein the heat treatment piece comprises carbon fibers, metal infiltrated among the carbon fibers and a metal surface formed on the partial surface of the carbon fibers;
normalizing the heat-treated piece at 860-980 deg.C, liquid carburizing the heat-treated piece, putting the heat-treated piece into active carburizing medium, specifically kerosene, with carbon concentration of 0.8-1.0%, and BaCO 3 As a permeation promoter, the BaCO 3 The mass amount of the active carburizing medium is 4-7%, the heat preservation temperature of the carburizing treatment is 920-940 ℃, the temperature of the workpiece is reduced to 800-850 ℃ after the carburizing treatment, the quenching treatment is carried out, and finally the tempering treatment is carried out, wherein the depth of a carburized layer of the carburized part is 0.5-2.0 mm;
bonding carbon fibers in a carburized piece, metal infiltrated among the carbon fibers and a metal surface formed on the partial surface of the carbon fibers by using a high-temperature adhesive consisting of copper oxide, aluminum hydroxide ash and molybdenum disulfide to obtain a bonded piece;
and rolling the bonded pieces in sequence, cleaning the metal surfaces of the bonded pieces, aligning the bonded pieces according to the welding surfaces by adopting X-rays, and leveling the welding surfaces at the connection parts. The metal surface of the bonding piece is used as a welding surface, a plurality of bonding pieces are welded, argon arc welding is adopted for welding, and the method comprises the following specific implementation steps: after the adhesion piece plate (sheet) is flattened, proper pressure is applied to the non-argon arc welding surface of the plate (sheet) to prevent the plate (sheet) from deforming (stress is eliminated by forging and pressing and deformation is changed) due to the contact surface chemical reaction of carbon fibers and the alloy special-shaped strip and the stress generated by welding the alloy special-shaped strip, a pressure sensor is arranged, the pressure applied by a PLC control system to the pressure sensor is used for ensuring the welding quality, tungsten wires and metal surfaces are respectively electrified, and the electrified tungsten wires pass (slide) between every two sheets of the adhesion piece to generate electric arc welding, and when the pressure is applied, the adhesion piece is preferably two layers or more layers. The current, tungsten filament and moving speed between the plates (sheets) of the bonding piece are selected according to the material of the metal surface and the size of the cross section of the welding surface. The bonding pieces of the upper layer and the lower layer produce the best welding quality. Argon gas enters and exits at the same time during argon arc welding, the argon gas is conveyed in a fixed time and a fixed quantity to obtain a welding part, and the welding part is rolled and flattened by laser to obtain the carbon fiber metal composite material, as shown in figure 8.
Example 3
The preparation method is basically the same as that of example 1, except that: the welding adopts resistance welding, and the resistance welding method comprises the following steps: after the adhesive member is leveled, resistance welding is adopted according to the width, the thickness and the material of the metal surface: the plate (sheet) of the bonding piece is under the pressure action of a certain electrode (the upper and lower rollers are used as electrodes), and the metal surface which is in thermal contact with the bonding piece is melted by utilizing the resistance generated when current passes through the workpiece, so that the connection welding is realized.
Example 4
The preparation method is basically the same as that of example 1, except that: the welding adopts laser welding.
Example 5
The preparation method is basically the same as that of example 1, except that: the welding adopts brazing welding.
Example 6
The preparation method is basically the same as that of example 1, except that: the welding adopts ultrasonic welding.
Example 7
The preparation method is basically the same as that of example 1, except that: the welding adopts a solid phase welding method taking indirect heat energy as energy, and specifically comprises the following steps: the welding is carried out in vacuum or protective atmosphere, and the surfaces of metal and carbon fiber are contacted and insulated at high temperature and high pressure during welding so as to reach the interatomic distance and are combined through atomic mutual diffusion.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (10)
1. The preparation method of the carbon fiber metal composite material is characterized by comprising the following steps of:
compounding carbon fiber raw material tows with a metal piece to obtain a raw material tow complex; the compounding comprises winding compounding or filling compounding, wherein the winding compounding is to wind a metal piece on the side wall of the carbon fiber raw material tows; the filling and compounding step is to fill the carbon fiber raw material tows in the open cavity of the metal piece;
carrying out pre-oxidation treatment on the raw material tow complex to obtain a pre-oxidized part;
carrying out heat treatment on the pre-oxidized part to obtain a heat-treated part; the heat treatment comprises a first heat treatment or a second heat treatment;
the first heat treatment includes: carbonizing the raw material tow complex under a first temperature condition in a protective gas to obtain a carbon fiber complex; performing first forging and pressing forming on the carbon fiber composite under the condition of a second temperature, wherein the second temperature is higher than the first temperature, and the second temperature is higher than the liquidus temperature of the metal profile body;
the second heat treatment includes: carrying out second forging and pressing molding on the raw material filament bundle complex under the condition of a third temperature in protective gas, wherein graphitization occurs in the forging and pressing molding, and the third temperature is higher than the liquidus temperature of the metal profiled body;
the first forging and pressing forming and the second forging and pressing forming are formed by cooling after extrusion stress;
and performing carburizing treatment on the heat-treated piece to obtain the carbon fiber metal composite material.
2. The method for preparing the carbon fiber metal composite material as claimed in claim 1, wherein the metal member comprises a circular arc shaped metal profile body or an i-shaped metal profile body;
the circular arc-shaped metal special-shaped body and the carbon fiber raw material tows are compounded in a winding way;
the I-shaped metal special-shaped body and the carbon fiber raw material tows are compounded to be filling and compounding.
3. The production method according to claim 1, wherein the carburizing treatment includes a liquid carburizing treatment, a gas carburizing treatment, or a solid carburizing treatment.
4. The production method according to claim 1, wherein the carburizing treatment results in a carburized piece; the carburization treatment also comprises the following steps: and (3) bonding the carbon fiber, the metal and the metal surface in the carburized part by using a high-temperature adhesive to obtain the carbon fiber metal composite material, wherein the high-temperature adhesive comprises copper oxide or aluminum dihydrogen phosphate.
5. The method of claim 4, wherein the high temperature binder further comprises copper oxide or aluminum dihydrogen phosphate with added molybdenum disulfide and/or aluminum hydroxide ash.
6. The production method according to claim 4, wherein the bonding results in a bonded member comprising carbon fibers, a metal infiltrated between the carbon fibers, and a metal face formed on the surface of the carbon fibers; after the bonding, the method further comprises the following steps: welding a plurality of adhesive pieces by taking a metal surface as a welding surface to obtain the carbon fiber metal composite material; and when welding, pressing the non-welding surface of the bonding piece.
7. The preparation method according to claim 2, wherein the winding composite is an equally spaced composite winding, and the spacing distance between two circles of circular arc-shaped metal profiled bodies wound adjacently is the diameter of the carbon fiber raw material tows.
8. The production method according to claim 1 or 7, wherein the temperature of the pre-oxidation treatment is 200 to 400 ℃.
9. The method according to claim 8, wherein the depth of the i-shaped opening of the i-shaped metal profile body is: the sum of the tensile force born by the filled carbon fibers of the I-shaped opening and the tensile force born by the combined contact surface of the carbon fibers and the metal special-shaped body is not less than the tensile force generated by the carbon fibers with the same thickness as the I-shaped opening in the length direction.
10. The preparation method of claim 6, wherein the welding is performed to obtain a welded part, and further comprises sequentially performing rolling and flattening treatment on the welded part to obtain the carbon fiber metal composite material.
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