CN110125179A - Graphene composition metal and preparation method thereof - Google Patents
Graphene composition metal and preparation method thereof Download PDFInfo
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- CN110125179A CN110125179A CN201810133543.9A CN201810133543A CN110125179A CN 110125179 A CN110125179 A CN 110125179A CN 201810133543 A CN201810133543 A CN 201810133543A CN 110125179 A CN110125179 A CN 110125179A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B47/00—Auxiliary arrangements, devices or methods in connection with rolling of multi-layer sheets of metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B47/00—Auxiliary arrangements, devices or methods in connection with rolling of multi-layer sheets of metal
- B21B47/02—Auxiliary arrangements, devices or methods in connection with rolling of multi-layer sheets of metal for folding sheets before rolling
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
- B21B2001/383—Cladded or coated products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
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Abstract
The present invention provides a kind of graphene composition metal and preparation method thereof, wherein the preparation method includes: to provide multiple metal plates；Graphene is applied to the metal sheet surface；Metal plate is overlapped, how hardened component is formed；First passage hot rolling is imposed to the how hardened component；By the structural member cutting after the first passage hot rolling；The structural member of cutting is superimposed, and forms laminated construction part；Second passage hot rolling is imposed to the laminated construction part；With the process for continuing to repeat n times cutting, superposition, hot rolling, N is the integer more than or equal to zero.Graphene composition metal provided by the invention maintains the impact flexibility and excellent strong plasticity of metal.
Description
Technical field
The present invention relates to a kind of alloys and preparation method thereof for entering metal inside using graphene as the second phase material, especially
It is related to a kind of alloy preparation method of Roll-bonding.
Background technique
With the progress of global industry, the demand of high-intensitive nonferrous materials grows stronger day by day；In terms of energy saving
From the point of view of, Industrial Metal lightweight is a trend；From the point of view of saving metallic mineral resources, the huge carbon materials of reserves on the earth are utilized
Material is come to enhance non-ferrous metal will be a quantum jump.Since aluminium, copper, magnesium, nickel etc. are not that (materialogy is fixed for carbide former
Justice), carbon atom solid solubility in these elements is very low, and traditional carbon material can not be separately as reinforcing material.The increasing of these metals
Strong is usually to obtain compound between high duty metal by 1) alloying, this causes machine-shaping process to add multiple tracks heat treatment
Process, the consumed resources such as metal, rare earth are huge, reinforcing effect close to the upper limit and technological difficulty it is increasing, product is comprehensive
Closing performance constraints (such as plasticity, thermally conductive, electric conductivity decline etc. while intensity rising) causes application environment restricted；2) additional
Hard particles or fiber, such as carbon fiber and carbon nano tube enhanced aluminium base alloy have obtained great development and application in recent years, but
Melting and casting difficulty or powder metallurgy cost are very big always, while being limited to material property and structural requirement, can only do certain multiple
Composite product and technique application.Such as fibre reinforced aluminium alloy racket.The disadvantage is that: 1, it can only once be cast into
Type, subsequent no longer extruding etc. plastic processings；2, material anisotropy is obvious, corresponding carbon fiber axle to material tension do not resist but
It cuts.If carbon fiber is not axially parallel along club when casting, which sharply declines.
Graphene be one kind by carbon atom with sp2The hexangle type of hybridized orbit composition is in honeycomb lattice, only one carbon is former
The two-dimensional material of sub- thickness.Theoretically possess Young's modulus (1TPa), high breaking strength (125GPa), super-high heat-conductive coefficient
(5000W·m-1·K-1) and electron mobility (200000cm2v-1·s-1), it is the material for being currently known maximum intensity.If
Carbon can be added in these four non-ferrous metals in the form of graphene is enhanced, and will realize stronger lighter alloy, less expensive
Social cost.But according to the above-mentioned strict notion of graphene, graphene is single layer two-dimension nano materials, obtains such material
Expect that cost is excessively high, and it is difficult to ensure that purity.Changzhou No.6 Element Material Technology Co., Ltd. passes through different graphene systems
The adjustment of standby technique and technological parameter, the graphene of available controllable different number of plies ranges, graphene in the disclosure
Concept is the graphene single-layer or multi-layer of above-mentioned strict notion.In addition, Changzhou No.6 Element Material Technology Co., Ltd. is logical
Cross different preparation processes, the graphene of available controllable different reducing degrees, the graphene of as above-mentioned strict notion
Upper to have different degrees of oxygen atom and hydrogen atom, this is also allowed in the patent application document of the disclosure.
So far, graphene is added in the non-ferrous metals such as aluminium, copper there is no obtain metal industry approve at
Fruit.Most of is that PM technique route does graphene-aluminium composite material, i.e., by the metal powders such as aluminium powder and graphene powder
Stirring and adsorbing in high speed ball milling mixing/liquid, the type of being then pressed into, which reburns, becomes integral blocks material.It is reported that intensity improve 30~
120MPa etc., but because without reporting distributed intelligence of the graphene inside multiple material, and the working hardening in such technique
Or refined crystalline strengthening etc. can also reach same index；The same period has been reported that the ball milling of powder metallurgy mixes powder process and has aluminium carbide generation,
Aluminium carbide can generate methane and aluminium oxide with the water reaction in air in subsequent technical process, i.e., graphene is in powder metallurgy mistake
It will be largely lost in journey；The microcosmic condition of powder theoretically when high speed ball milling can also promote carbon-reactive aluminum, so to being at present
Only, powder metallurgy alkene aluminium alloy does not have the report of the application of any authority.And it because graphene is two-dimensional film structure, is easy
Distortion, thickness is nano material, and length and width are micrometer structures, and the super tensile strength by graphene carrys out reinforced metal, to metal
Dislocation motion, the stopping effect of crack extesion and the second traditional phase hard particles will have significantly different, this completely new reinforcing
Mechanism has particular/special requirement to the form of the graphene inside alloy, position, distribution and two-phase interface；Powder metallurgy is difficult to take into account
These aspects, the graphene enhancing acieral that can which make industry approval leave a question open.Powder metallurgy preparation
Graphene enhancing acieral has the disadvantage that 1) powder adsorption gas cannot completely eliminate in technique later, produces
There is porosity one in product performance assessment criteria, the tensile strength of product is limited, cannot prepare the big part of industry；2) powder metallurgical technique
Process is more, and the production cycle is long；3) graphene-aluminium composite material reported at present does not obtain industrial neck still in the exploratory stage
The approval in domain；4) aluminium powder is rocket fuel, is regulated item.
The technology contents listed in the prior art only represent the technology that inventor is grasped, and are not considered naturally
It is the prior art and is used to evaluate novelty and creativeness of the invention.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide the graphene composition metals that a kind of hot rolling combines；
It is a further object of the present invention to provide the preparation methods of above-mentioned graphene composition metal.
The purpose of the present invention is achieved by the following technical scheme:
In one aspect of the invention, a kind of preparation method of graphene composition metal is provided, comprising:
Multiple metal plates are provided；
Graphene is applied to the metal sheet surface；
Metal plate is overlapped, how hardened component is formed；
First passage hot rolling is imposed to the how hardened component；
By the structural member cutting after the first passage hot rolling；
The structural member of cutting is superimposed, and forms laminated construction part；
Second passage hot rolling is imposed to the laminated construction part；With
Continue the process for repeating n times cutting, superposition, hot rolling, N is the integer more than or equal to zero.
According to an aspect of the present invention, the piece spacing for repeating n times graphene film into metal is≤80 microns,
Preferably, the number of repetition N meets following equation:
When the number for providing multiple metal plates is 2, N >=log2 H+ 3, wherein H is the thickness of the original metal plate, single
Position is mm；
When the number for providing multiple metal plates is 3, N >=log3 H+ 1, wherein H is the thickness of the original metal plate, single
Position is mm；
When the number for providing multiple metal plates is m, N >=logm H, wherein H is the thickness of the original metal plate, unit
For mm；M is the integer more than or equal to 4.
According to an aspect of the present invention, the multiple plate thickness is suitable.
According to an aspect of the present invention, it is described graphene is applied to the metal plate before, in advance to the metal
The surface of plate is handled；Preferably, the surface treatment uses one or more of grinding, alkali cleaning, pickling, scouring, into
Preferably, the surface treatment makes Metal Surface Roughness Ra10 ± 6 μm to one step.
According to an aspect of the present invention, the execution method for applying graphene in the metal sheet surface are as follows: by stone
Black alkene slurry is coated to the metal sheet surface and dries, it is preferable that after being coated to the graphene slurry drying of metal sheet surface
Surface density≤0.8mg/cm of graphene in coating2；Preferably, the graphene slurry is that graphene divides in easy volatile solvent
Slurry is obtained after dissipating.
According to an aspect of the present invention, the execution method for applying graphene in the metal sheet surface are as follows: use stone
Black alkene-tungsten chromic salts electroplate liquid mixing prepares graphene composite plating solution, Brush Plating graphene to the metal sheet surface simultaneously
Cleaning, drying；Preferably, the face of graphene is close in coating after the graphene composite plating solution that brush is plated to metal sheet surface is dried
Degree≤0.8mg/cm2。
According to an aspect of the present invention, if rolling temperature is below the metal plate recrystallization temperature, to structural member
Diffusion annealing is first carried out after hot rolling to cut off again；Preferably, the annealing temperature of the diffusion annealing is 0.4Tm ± 0.1Tm, wherein Tm
For the fusing point of metal plate.
According to an aspect of the present invention, the structural member of the cutting before superposition, the metal sheet surface between lamination
Apply graphene；Preferably, the application graphene number C≤N+1；
Preferably, the metal sheet surface between the lamination applies graphene and executes as follows:
To the graphene coated slurry of metal sheet surface or Brush Plating graphene, drying in lamination station, it is coated to gold
Belong to after the graphene slurry drying of plate surface or brush is plated to after the graphene composite plating solution drying of metal sheet surface in coating
Surface density≤0.8mg/cm of graphene2；
Preferably, first the metal sheet surface for the graphene of being applied is surface-treated before applying graphene.
According to an aspect of the present invention, in the structural member cutting to after hot rolling, according to of the metal plate of offer
Identical number of segment is cut off in number selection, and each segment length is equal.
According to an aspect of the present invention, the hot rolling more than the recrystallization temperature of the metal plate, the metal plate again
It is rolled below crystallization temperature or the recrystallization temperature of the metal plate, is preferably carried out more than the recrystallization temperature of the metal plate
Rolling；
Preferably, when the number for providing multiple metal plates is 2, the hot rolling volume under pressure is 40-70%, preferably
50%；When the number for providing multiple metal plates is 3, the hot rolling volume under pressure is 50-80%, and preferably 66.6%；Offer is provided
When the number of multiple metal plates is 4, the hot rolling volume under pressure is 60-90%, and preferably 75%；As of the multiple metal plates of offer
When number is 5, the hot rolling volume under pressure is 70-95%, and preferably 80%；When the number for providing multiple metal plates is 6 or more, institute
It states hot rolling volume under pressure and is all larger than 75%, preferably 83.3%, guarantee after hot rolling plate thickness close to single-layer metal plate thickness before non-hot rolling.
According to an aspect of the present invention, the metal plate is aluminium sheet, magnesium plate, nickel plate, copper sheet or aluminium alloy plate.
In another aspect of this invention, a kind of graphene composition metal, including graphene, metal are provided, the ink alkene is multiple
The amount of institute's containing graphene is 0.5 ‰ -3wt%, preferably 3wt ‰ in alloy category.
According to an aspect of the present invention, above-mentioned graphene composition metal, is prepared according to the method described above.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the preparation method flow chart of graphene composition metal according to an embodiment of the invention；
Fig. 2 is metal plate/graphene middle according to one embodiment of present invention/metal plate structure part disassemblying structure signal
Figure；
Fig. 3 is the schematic diagram of metal plate/graphene/metal plate structure part middle according to one embodiment of present invention；
Fig. 4 be according to one embodiment of present invention in the first passage course of hot rolling schematic diagram；
Fig. 5 be according to one embodiment of present invention in the clad metal sheet schematic diagram that is formed after the first passage hot rolling；
Fig. 6 be according to one embodiment of present invention in clad metal sheet cutting additive process signal after the first passage hot rolling
Figure；
Fig. 7 be according to one embodiment of present invention in shape after clad metal sheet cutting additive process after the first passage hot rolling
At structural member schematic diagram；
Fig. 8 be according to one embodiment of present invention in the second passage course of hot rolling schematic diagram；
Fig. 9 be according to one embodiment of present invention in the clad metal sheet signal that is formed after the second passage course of hot rolling
Figure；
Figure 10 be according to one embodiment of present invention in the clad metal sheet signal that is formed after third passage course of hot rolling
Figure；
Figure 11 be according to one embodiment of present invention in the clad metal sheet signal that is formed after the 5th passage course of hot rolling
Figure；
Wherein, 1- metal plate, 2- graphene.
Specific embodiment
Hereinafter, certain exemplary embodiments are simply just described.As one skilled in the art will recognize that
Like that, without departing from the spirit or scope of the present invention, the various different modes such as increase, deletion, modification can be passed through
Modify described embodiment.Therefore, attached drawing and description are considered essentially illustrative rather than restrictive.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
In the first embodiment of the present invention, the side that a kind of Roll-bonding prepares graphene composition metal is provided
Method.As shown in Figure 1, the preparation method 100 of the graphene composition metal of first embodiment of the invention includes:
101: multiple metal plates are provided；
102: graphene is applied to the metal sheet surface；
103: overlapping metal plate forms how hardened component；
104: the first passage hot rolling is imposed to the how hardened component；
105: the structural member after the first passage hot rolling is cut off；
106: the structural member superposition of cutting forms laminated construction part；
107: the second passage hot rolling is imposed to the laminated construction part；With
108: continuing the process for repeating n times cutting, superposition, hot rolling, N is the integer more than or equal to zero.
According to a preferred embodiment of the present invention, in step 108, the n times that repeat are into graphene composition metal
Piece spacing≤80 micron of graphene film.
According to a preferred embodiment of the present invention, in step 108, the number of repetition N meets following equation:
When the number for providing multiple metal plates is 2, N >=log2 H+ 3, wherein H is the thickness of the original metal plate, single
Position is mm；
When the number for providing multiple metal plates is 3, N >=log3 H+ 1, wherein H is the thickness of the original metal plate, single
Position is mm；
When the number for providing multiple metal plates is m, N >=logm H, wherein H is the thickness of the original metal plate, unit
For mm；M is the integer more than or equal to 4.
Mentioned here spacing includes the piece spacing of graphene film in either direction.In general, in level side
It is micron order to the spacing between adjacent two panels graphene, in vertical direction, the distance between adjacent two panels graphene is also micro-
Meter level.In the present invention, the length and width of the graphene film used are micron orders；Graphene in finally obtained graphene composition metal
The distance between piece and piece are micron orders, at this point, graphene dispersion degree is high and uniform.The thickness H of original metal plate is millimeter
Grade (thickness h of graphene is small negligible), thickness of the H from original metal plate, and micron order before are not related, and H determines
Rolling total degree is determined, H is bigger, and rolling total degree is more.Such as when two plate pack rolling, H is 2mm, rolls total degree at least 6；H is
4mm rolls total degree at least 7, meets above-mentioned formula.
According to a preferred embodiment of the present invention, in step 101, as shown in Fig. 2, 2 metal plates 1 are provided, it is described
Metal plate can be that aluminium sheet, copper sheet, magnesium plate, nickel plate or aluminium alloy plate etc. select aluminium according to a preferred embodiment of the present invention
Plate or copper sheet are as metal plate.
According to a preferred embodiment of the present invention, the multiple plate thickness is suitable.
In a step 102, according to a preferred embodiment of the present invention, graphene is applied to metal sheet surface.According to
A preferred embodiment of the present invention, the execution method that graphene is applied to metal sheet surface are as follows: by graphene slurry
It sprays to the metal sheet surface and dries；Preferably, stone in coating is coated to after the graphene slurry drying of metal sheet surface
Surface density≤0.8mg/cm of black alkene2.Wherein the graphene slurry is to be starched after graphene disperses in easy volatile solvent
Material.Wherein the easy volatile solvent can be ethyl alcohol, acetone, water etc..
According to a preferred embodiment of the present invention, the execution method that graphene is applied to metal sheet surface are as follows:
Graphene composite plating solution, Brush Plating graphene to the metal plate table are prepared with graphene-tungsten chromic salts electroplate liquid mixing
Face and cleaning, drying；Preferably, it is coated to the face of graphene in coating after the graphene composite plating solution drying of metal sheet surface
Density≤0.8mg/cm2。
Research obtains, above two in the process of metal sheet surface setting graphene executing, and is coated to metal plate table
After graphene slurry or graphene the composite plating solution drying in face in coating graphene surface density≤0.8mg/cm2.If face
Density is excessive, can not be by two plate soldering, and surface density is too small, and the graphene content in gained alkene alloy material is small.It is sent out through the present invention
Bright people gos deep into comparative study repeatedly, controls surface density≤0.8mg/cm2If the high alkene of graphene content closes in order to obtain
Golden material, can control surface density is 0.6mg/cm2、0.7mg/cm2Deng the value close to the upper limit.These embodiments and modifications thereof, all
Within the scope of the invention.
Fig. 2 is the dismantling schematic diagram for overlapping metal plate, and Fig. 3 is overlapping metal plate schematic diagram, forms how hardened component, example
Such as: metal plate/graphene/metal plate structural member (these metal plates-graphene-structured part can also be carried out end riveting or
Metal seals are fixed, and the metal plate-graphene-metal plate composite construction (the meat clip Mo or sandwich) being superimposed is easy to slide
It is dynamic, can be fixed with riveting and strip of paper used for sealing, become an integral material after rolling and these additives are removed again).According to industrial
Size needed for graphene composite metal product of the present invention, such as with a thickness of H+1/2h (thickness that h is the graphene applied), then
It is the metal plates that L, thickness are H with regard to selection length.Such as: when two metal plate pack rolling, two pieces of 2mm thick sheet metals (apply graphene
Thickness h can be ignored substantially), 4mm is stacked, pushing 50% is exactly pressure for thickness 2mm, and length becomes one piece of original twice
Plank, stacks after being truncated in the middle or original 4mm is thick and length, no longer cutting superposition after last passes, this
When, enhance non-ferrous metal board with a thickness of 2mm.When three pieces of metal plate pack rolling, three pieces of 2mm thick sheet metals (substantially may be used by graphene thickness
To ignore), 6mm is stacked, pushing 2/3 is exactly pressure for thickness 2mm, and length becomes one piece of plank of original three times, is truncated into
Stacked after isometric three sections or original 6mm after and length, no longer cutting superposition after last passes, at this point,
Enhance non-ferrous metal board with a thickness of 2mm.
According to a preferred embodiment of the present invention, it is described graphene is applied to the metal plate before, in advance to institute
The surface for stating metal plate is handled；Preferably, the surface treatment is using one or more in grinding, alkali cleaning, pickling, scouring
It is a, it is further preferred that the surface treatment makes Metal Surface Roughness Ra10 ± 6 μm.Metal sheet surface is handled
Main purpose be degreasing and rust removal, remove oxidation of impurities skin, adjust the roughness of metal sheet surface, make graphene and metal plate table
Face better contacts with.
According to a preferred embodiment of the present invention, at step 104, as shown in figure 4, being imposed to the how hardened component
First passage hot rolling, in this embodiment, the first passage hot rolling carry out under the conditions of 300-600 DEG C.In the present embodiment,
Volume under pressure uses 50%, obtains with a thickness of H+1/2h, 1 times of length elongation (2L) of graphene clad metal sheet (as shown in Figure 5).
According to a preferred embodiment of the present invention, the heat bundle can be more than the recrystallization temperature of the metal plate, the gold
Belong to the recrystallization temperature of plate or the recrystallization temperature of the metal plate or less to be rolled, preferably in the recrystallization temperature of the metal plate
It is rolled above.
According to a preferred embodiment of the present invention, when the number for providing multiple metal plates is 2, the hot rolling volume under pressure
It is 40-70%, preferably 50%；When the number for providing multiple metal plates is 3, the hot rolling volume under pressure is 50-80%, excellent
Select 66.6%；When the number for providing multiple metal plates is 4, the hot rolling volume under pressure is 60-90%, and preferably 75%；When mentioning
When number for multiple metal plates is 5, the hot rolling volume under pressure is 70-95%, and preferably 80%；When the multiple metal plates of offer
When number is 6 or more, the hot rolling volume under pressure is all larger than 75%, preferably 83.3%, guarantees after hot rolling plate thickness close to non-hot rolling
Preceding single-layer metal plate thickness.
According to a preferred embodiment of the present invention, right if rolling temperature is below the metal plate recrystallization temperature
Diffusion annealing is first carried out after structural member hot rolling to cut off again；Preferably, the annealing temperature of the diffusion annealing is 0.4Tm ± 0.1Tm,
Wherein Tm is the fusing point of metal plate, and the national standard that can consult the alloy designations obtains.In general, above-mentioned hot-rolled temperature is in metal
More than plate recrystallization temperature, then without annealing；If above-mentioned hot-rolled temperature is lower than the metal plate recrystallization temperature, in order to more preferable
Effect, in step 105 first carry out diffusion annealing carry out Cutting process again.
According to a preferred embodiment of the present invention, in step 106, as shown in fig. 6, the structural member of the cutting is superimposed it
Before, the metal sheet surface between lamination applies graphene；Laminated construction part is formed after superposition, as shown in Figure 7.
According to a preferred embodiment of the present invention, the number C≤N+1 for applying graphene, wherein N is to continue to repeat
Number.
According to a preferred embodiment of the present invention, can not have to before last time pack rolling folded in the structural member of cutting
In addition apply graphene in metal sheet surface before, be more advantageous to graphene in this way and divide in the graphene composition metal being prepared
Cloth is more uniform.
According to a preferred embodiment of the present invention, the metal surface between the lamination applies graphene according to such as lower section
Method executes:
To the graphene coated slurry in metal surface or Brush Plating graphene composite plating solution for being in lamination station, dry,
It is applied to surface density≤0.8mg/cm of graphene in coating after the graphene drying of metal sheet surface2。
According to a preferred embodiment of the present invention, first to the metal plate for the graphene of being applied before applying graphene
Surface is surface-treated.One or more of grinding, alkali cleaning, pickling or scouring, main mesh can be used in the surface treatment
Be degreasing and rust removal, remove oxidation of impurities skin, adjust the roughness of metal sheet surface, make graphene slurry and metal sheet surface more
It contacts well；It is highly preferred that the surface treatment makes Metal Surface Roughness Ra10 ± 6 μm.
According to a preferred embodiment of the present invention, in the structural member cutting step to after hot rolling, according to offer
Identical number of segment is cut off in the number selection of metal plate, and each segment length is equal.Such as when providing 2 metal plates, by the knot after hot rolling
Component is cut to 2 sections；When providing 3 metal plates, the structural member after hot rolling is cut to 3 sections, etc..
According to a preferred embodiment of the present invention, in step 107, as shown in figure 8, carrying out the to the laminated construction part
Two passage hot rollings, the structural member after obtaining the second passage hot rolling, as shown in Figure 9.It is to be carried out to laminated construction part as shown in Figure 10
After third passage hot rolling, obtained structural member.It is after carrying out the hot rolling of third passage to laminated construction part, to obtain as shown in figure 11
Structural member.
According to a preferred embodiment of the present invention, when the number of the metal plate of offer is two, if after hot rolling
Apply graphene in metal sheet surface before structural member cutting overlapping, the thickness of the graphene applied between lamination every time is
H, the metal plate provided with a thickness of H, then after carrying out the n-th passage hot rolling, structural member with a thickness of H+n/2h.In multi-pass
Hot rolling after, graphene is dispersed in metal, realizes the combination of graphene and metal, obtains graphene of the invention
Composition metal.
The present invention is directed to the film characteristics of graphene, borrows the Roll-bonding principle in metal nanosizing field, carries out
Graphene enhancing metal alloy is prepared after improvement, guarantees that graphene is not destroyed in preparation process, solid-state of the graphene in metal
Dispersed in rheology, while cold welding occurs for graphene and metal alloy, finally obtains real alkene alloy (keeping metallic character)
New material and can large-scale pipeline production new process.
The present invention provides a kind of graphene composition metal of new existence form, graphene uniform is distributed in the alloy,
Quantity is enough, and the amount of institute's containing graphene is 0.5 ‰ -3wt% in the ink alkene composition metal, such as: 0.5wt ‰, 1wt ‰,
1.5wt ‰, 2wt ‰, 2.5wt ‰, 3wt ‰, 5wt ‰, 7wt ‰, 9wt ‰, 1wt%, 1.5wt%, 2wt%, 2.5wt%,
3wt%, etc.；Alkene is tightly engaged with metal (such as aluminium) interface；There is no loose and hole.Therefore, graphene provided by the invention
Composition metal maintains the impact flexibility and excellent strong plasticity of metal.In addition, present invention process difficulty is low, technological parameter is easy control
System can be directly amplified and be prepared for large-scale workpiece, and safety, high production efficiency.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (13)
1. a kind of preparation method of graphene composition metal, comprising:
Multiple metal plates are provided；
Graphene is applied to the metal sheet surface；
Metal plate is overlapped, how hardened component is formed；
First passage hot rolling is imposed to the how hardened component；
By the structural member cutting after the first passage hot rolling；
The structural member of cutting is superimposed, and forms laminated construction part；
Second passage hot rolling is imposed to the laminated construction part；With
Continue the process for repeating n times cutting, superposition, hot rolling, N is the integer more than or equal to zero.
2. the preparation method of graphene composition metal according to claim 1, which is characterized in that the n times that repeat are to metal
The piece spacing of middle graphene film is≤80 microns,
Preferably, the number of repetition N meets following equation:
When the number for providing multiple metal plates is 2, N >=log2 H+ 3, wherein H is the thickness of the original metal plate, and unit is
mm；
When the number for providing multiple metal plates is 3, N >=log3 H+ 1, wherein H is the thickness of the original metal plate, and unit is
mm；
When the number for providing multiple metal plates is m, N >=logm H, wherein H is the thickness of the original metal plate, and unit is
mm；M is the integer more than or equal to 4.
3. the preparation method of graphene composition metal according to claim 1, which is characterized in that the multiple hickness of metal plate
Degree is suitable.
4. the preparation method of graphene composition metal according to claim 1, which is characterized in that described to apply graphene
To before the metal plate, the surface of the metal plate is handled in advance；Preferably, the surface treatment using grinding,
One or more of alkali cleaning, pickling, scouring, it is further preferred that the surface treatment makes Metal Surface Roughness Ra10
±6μm。
5. the preparation method of graphene composition metal according to claim 1, which is characterized in that described in the metal plate table
The execution method of face application graphene are as follows: graphene slurry is coated to the metal sheet surface and is dried, it is preferable that is coated to
After the graphene slurry drying of metal sheet surface in coating graphene surface density≤0.8mg/cm2；Preferably, the graphene
Slurry is to obtain slurry after graphene disperses in easy volatile solvent.
6. the preparation method of graphene composition metal according to claim 1, which is characterized in that described in the metal plate table
The execution method of face application graphene are as follows: prepare graphene composite plating solution with graphene-tungsten chromic salts electroplate liquid mixing, electricity
Brush plating graphene is to the metal sheet surface and dries；Preferably, brush is plated to the graphene composite plating solution of metal sheet surface
After drying in coating graphene surface density≤0.8mg/cm2。
7. the preparation method of graphene composition metal according to claim 1, which is characterized in that if rolling temperature is described
When below metal plate recrystallization temperature, cut off again to diffusion annealing is first carried out after structural member hot rolling；Preferably, the diffusion annealing
Annealing temperature be 0.4Tm ± 0.1Tm, wherein Tm be metal plate fusing point.
8. the preparation method of the graphene composition metal described in any one of according to claim 1, which is characterized in that
Before superposition, the metal sheet surface between lamination applies graphene to the structural member of the cutting；Preferably, the application
Graphene number C≤N+1；
Preferably, the metal sheet surface between the lamination applies graphene and executes as follows:
To the graphene coated slurry of metal sheet surface or Brush Plating graphene composite plating solution, drying in lamination station, apply
Be layed onto metal sheet surface graphene slurry drying after or brush be plated to metal sheet surface graphene composite plating solution drying after
Surface density≤0.8mg/cm of graphene in coating2；
Preferably, first the metal sheet surface for the graphene of being applied is surface-treated before applying graphene.
9. the preparation method of graphene composition metal according to claim 1, which is characterized in that the knot to after hot rolling
In cutting of members, identical number of segment is cut off according to the selection of the number of the metal plate of offer, each segment length is equal.
10. the preparation method of graphene composition metal according to claim 1, which is characterized in that the hot rolling is in the gold
Belong to the recrystallization temperature of the recrystallization temperature of plate or more, the recrystallization temperature of the metal plate or the metal plate or less to be rolled,
It is preferred that being rolled more than the recrystallization temperature of the metal plate；
Preferably, when the number for providing multiple metal plates is 2, the hot rolling volume under pressure is 40-70%, and preferably 50%；When
When the number for providing multiple metal plates is 3, the hot rolling volume under pressure is 50-80%, and preferably 66.6%；When the multiple metals of offer
When the number of plate is 4, the hot rolling volume under pressure is 60-90%, and preferably 75%；When the number for providing multiple metal plates is 5,
The hot rolling volume under pressure is 70-95%, and preferably 80%；When the number for providing multiple metal plates is 6 or more, under the hot rolling
Pressure amount is all larger than 75%, preferably 83.3%.
11. the preparation method of graphene composition metal according to claim 1 to 10, which is characterized in that described
Metal plate is aluminium sheet, magnesium plate, nickel plate, copper sheet or aluminium alloy plate.
12. a kind of graphene composition metal, including graphene, metal, the amount of institute's containing graphene is in the ink alkene composition metal
0.5 ‰ -3wt%, preferably 3wt ‰.
13. graphene composition metal according to claim 12 is prepared according to any one of claim 1-11 the method
It forms.
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| CN111926206A (en) * | 2020-08-25 | 2020-11-13 | 哈尔滨工业大学 | Preparation method of high-toughness graphene reinforced aluminum-based composite material |
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| CN111203443A (en) * | 2020-01-14 | 2020-05-29 | 河北科技大学 | Preparation method of high-strength Zr-based alloy composite material |
| CN111229833A (en) * | 2020-02-08 | 2020-06-05 | 西北工业大学太仓长三角研究院 | Method for preparing laminated metal composite material by multilayer-cumulative pack rolling |
| CN111229833B (en) * | 2020-02-08 | 2022-05-10 | 西北工业大学太仓长三角研究院 | Method for preparing laminated metal composite material by multilayer-cumulative pack rolling |
| CN111627728A (en) * | 2020-07-20 | 2020-09-04 | 南昌航空大学 | MnO doped with graphene2Preparation method of carbon cloth-based flexible composite electrode |
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