CN102329976A - Preparation method of graphene reinforced metal-matrix composite - Google Patents
Preparation method of graphene reinforced metal-matrix composite Download PDFInfo
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Abstract
The invention discloses a preparation method of a graphene reinforced metal-matrix composite, which comprises the following steps of: firstly, dispersing the graphene oxide on the surface of the flaky metal powder; and then obtaining the graphene/metal composite powder through the reducing treatment; and at last, carrying out densification treatment by adopting a powder metallurgic technology to obtain the compact graphene reinforced metal-matrix composite. The flaky metal powder has the plane two-dimensional form, is inclined to the directional piling to form a laminated structure, and is helpful for inducing the graphene orientation distribution and giving play to the reinforcing effect. The preparation method disclosed by the invention is simple and feasible, is capable of regulating the graphene content and is suitable for preparing the massive composite.
Description
Technical field
What the present invention relates to is material of a kind of technical field of composite materials and preparation method thereof, specifically is the preparation method that a kind of Graphene strengthens metal-base composites.
Background technology
Graphene is to come to light in recent years and a kind of novel two dimensional surface carbonaceous nano material of synthetic, has impayable high electron mobility (~ 200000 cm
2/ Vs), thermal conductivity (~ 5000 W/mK), Young's modulus (1100 GPa) and breaking tenacity (125GPa), show excellent conduction, heat conduction and mechanical characteristic.Compare with carbon nanotube; Graphene has similar physical properties, bigger specific surface area and lower production cost; Be electronic material of future generation so Graphene not only is expected, and be expected to replace carbon nanotube to become optimal filler or enhancing body in the following matrix material.Therefore, research and development are march toward important directions of practical application of Graphene based on the nano composite material of Graphene.Early, obtained the Graphene/polymkeric substance of bigger progress with starting and compared with Graphene/ceramic composite, the research that strengthens metal-base composites relevant for Graphene is also less.At present, the research that Graphene is strengthened metal-base composites mainly concentrates on functional noble metal nano particles such as Pt, Au, Ag is dispersed on the graphene film, so that grapheme modified and improve its Electronic Performance.On the other hand; Graphene is joined in the common metal materials such as Al, Cu, duraluminum; The structure-function integration matrix material of functional performances such as expection can obtain high-strength light, has both conduction, heat conduction, wear-resisting, vibration damping has huge potential application foreground.Yet the R&D work of this type material but is hampered by the difficulty of technology of preparing.Because the nature difference between Graphene and the metallic substance is maximum, the neither hydrophilic also oleophylic not of Graphene in addition, reactive behavior is not high, makes it is carried out difficulty of modification ratio, thereby causes Graphene and metal matrix material compound relatively more difficult yet.
Through the prior art literature search is found; USP (application number 20100092723) " NANO-SCALED GRAPHENE PLATE-REINFORCED COMPOSITE MATERIALS AND METHOD OF PRODUCING SAME " (nano-scale graphene film reinforced composite and preparation method thereof); At first prepare the mixture of forming, be fluidised form by nano-scale graphene film and body material; Obtain fento and be woven into precast body through extruding then, obtain final matrix material through solidifying again.This method it is said various body materials such as being applicable to organism, polymkeric substance, metal, pottery, glass, and can regulate and control the orientation of graphene film through arranging of fiber, thereby makes its performance maximum effect.Obviously, have bigger limitation when this method is used for metal matrix material: Graphene/metal fento extrude and the braiding process all quite complicated, inefficiency, the Graphene that is not suitable for the preparation bulk strengthens metal-base composites; If added too much organism or polymkeric substance for the ease of extruding, also can give the final performance deleterious impact of matrix material.
Summary of the invention
The objective of the invention is to deficiency, a kind of preparation method who strengthens metal-base composites based on the Graphene of PM technique is provided to prior art.The present invention adopts flaky metal powder as body material, utilizes its planar form effectively to regulate and control the homodisperse and the distribution of orientations of graphene film.
The present invention realizes through following technical scheme:
The present invention is earlier with flaky metal powder adsorption and oxidation Graphene from graphene oxide solution; Obtain graphene oxide/composite metal powder; Handle through reduction again and obtain Graphene/composite metal powder, adopt powder metallurgical technique to prepare closely knit bulk matrix material more at last.Flaky metal powder tends to " orientation is piled up " and forms rhythmo structure, helps inducing the Graphene distribution of orientations and brings into play reinforced effects.Therefore, the present invention is simple and easy to do, has the mass-producing application potential.
The present invention includes following steps:
(1) graphene oxide is joined in water or the organic solvent preparation graphene oxide solution;
(2) flaky metal powder is joined in the graphene oxide solution, lasting stirring makes graphene oxide by the flaky metal powder surface adsorption, washs then, drying, promptly obtains graphene oxide/composite metal powder;
(3) under inertia or reducing atmosphere, graphene oxide/composite metal powder is reduced processing, promptly obtain Graphene/composite metal powder;
(4) adopt powder metallurgical technique, Graphene/composite metal powder is carried out densification, promptly obtain closely knit Graphene and strengthen metal-base composites.
Described flaky metal powder is the one to multiple kind in aluminium, copper, magnesium, titanium, iron and the powdered alloy thereof, and available melt gets rid of any means preparations such as band, casting, ball milling, and radius-thickness ratio is greater than 10, and thickness is between 200nm-5 μ m, and the sheet footpath is between 5-500um.
Described graphene oxide and Graphene have the single or multiple lift graphite-structure, and thickness is less than 20nm.
The present invention adopts graphite oxide as starting raw material; Be because oxy radicals such as a large amount of carboxyls, hydroxyl, epoxy group(ing) are contained on its surface; In methyl alcohol, ethanol, acetone, water equal solvent, be easy to disperse; Obtain described graphene oxide solution; And can not add or add one or more of tensio-active agents such as sodium lauryl sulphate, X 2073, cetyl trimethylammonium bromide, Triton, chitosan, β-cyclodextrin, LUTARALDEHYDE or biliary salts, further promotes oxidn Graphene homodisperse.In said graphene oxide solution, the concentration of graphene oxide is usually within the scope of 0.1-10 mg/mL.
In the inventive method, can preferably, in the scope of 0.1-5wt%, regulate the quality percentage composition of Graphene in the prepared matrix material arbitrarily easily through the concentration of controlled oxidation Graphene solution and the thickness and the specific surface area of flaky metal powder.
In the inventive method; Said flaky metal powder passes through polymer surface modification in advance; Promptly coat the one layer of polymeric film on the flaky metal powder surface in advance,, promote absorption graphene oxide so that improve the affinity of its surface for solvent and graphene oxide.Method of modifying is said polymkeric substance to be joined in water or the organic solvent preparation polymers soln; Said polymkeric substance can be chosen any one kind of them at Z 150PH, polyoxyethylene glycol, Vinylpyrrolidone polymer, polyacrylonitrile, ROHM, SEPIGEL 305, polymeric amide, YSR 3286, TKK 021; The mass percent concentration of described polymers soln is 0.2-5%.Then flaky metal powder is joined and continue stirring until the surface in the solution of said polymkeric substance and form polymeric film, wash then, drying., when heat, be easy to removed built in nanometer scale in the surface coated polymeric film controllable thickness of metal-powder by pyrolysis.
Because the transmission that the oxy radical on graphene oxide surface and defective can hinder electronics,, need reduce processing to graphene oxide/composite metal powder for conduction and the heat conductivility that improves final matrix material.When heat, graphene oxide can be reduced by reactive metal or reducing atmosphere, thereby obtains Graphene/composite metal powder.Reduction reaction for the promotes oxidn Graphene; Can also in the surface coated polymeric film of metal-powder, introduce a certain amount of organic reducing agent, for example quadrol, Hydrazine Hydrate 80, glucose, sucrose, SANMALT-S, dextrin, vitamins C, oxalic acid, propanedioic acid, Hydrocerol A, oxysuccinic acid, tartrate and tartrate etc.The reduction treatment temperature is lower than the fusing point of said flaky metal powder.
To gained Graphene/composite metal powder, cold pressing earlier or isostatic cool pressing obtains powder compact, and then carry out thermal distortions processing such as hot pressing, hot isostatic pressing, hot extrusion, hot rolling, can obtain closely knit Graphene and strengthen metal-base composites.In the method for the invention, reduction is handled and the densification temperature all should be lower than the fusing point of said metal-powder, but is higher than the pyrolysis temperature of polymkeric substance.
As everyone knows, each item performance of Graphene all is anisotropic.In the method in the present invention; Receive the constraint of flaky metal powder and rhythmo structure and induce; Graphene is along the stack direction distribution of orientations in powder is colded pressing base; Deformation processing such as follow-up hot extrusion and hot rolling can further be strengthened the distribution of orientations of Graphene, thereby bring into play the strengthening effect to mechanical property and electrical and thermal conductivity performance substantially.Therefore, the invention provides a kind of metal-base composites preparation method of simple and easy to do, the height-oriented distribution of Graphene, the gained matrix material is high-strength light not only, also has both functional performances such as conduction, heat conduction, wear-resisting, vibration damping.
Compared with prior art, the present invention has the following advantages: (1) adopts flaky metal powder as starting raw material, helps evenly adsorbing Graphene and impels its height-oriented combination; (2) further; Selection is carried out surface-treated to flaky metal powder; Improve the affinity of its surface, thereby be easy to homodisperse and therefrom even adsorption and oxidation Graphene in graphene oxide solution, obtain homodisperse Graphene/composite metal powder for solvent and graphene oxide; (3) in the surface coated polymeric film controllable thickness of metal-powder built in nanometer scale, so contained amount of polymers is few in Graphene/composite metal powder, is convenient to remove through pyrolysis; (4) be employed in inertia or reducing atmosphere graphene oxide/composite metal powder is reduced processing, combine, simply be easy to obtain Graphene/composite metal powder with thermal process in the whole technological process; (5) Graphene content can be regulated and control through flaky metal powder thickness and graphene oxide strength of solution, the preferably adjustment arbitrarily in the scope of 0.1-5% of its quality percentage composition.
Description of drawings
Fig. 1 is an embodiment of the invention schematic flow sheet;
Fig. 2 is the DSC curve (a) and thermogravimetric TG curve (b) figure of graphene oxide in the embodiment of the invention/aluminium composite powder;
Fig. 3 is the Raman spectrum of powder in the embodiment of the invention; Wherein: (a) Raman spectrum of graphite oxide powder; (b) Raman spectrum of 0.3wt% graphene oxide/aluminium composite powder; (c) Raman spectrum of the Graphene/aluminium composite powder after 0.3wt% graphene oxide/aluminium composite powder thermal reduction;
Fig. 4 be the aluminium powder (a) of dry grinding 1h in the embodiment of the invention and inhale graphene oxide after the SEM image of (b).
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Table 1 provides is the formulation parameter of polymers soln and Graphene solution among each embodiment, and abides by technical process shown in Figure 1 and implement.
The formulation parameter of polymers soln and Graphene solution among table 1. embodiment
annotates: PVA is a Z 150PH, and PVP is a Vinylpyrrolidone polymer.
Embodiment 1
Graphene oxide is added in the deionized water, and ultra-sonic dispersion made the graphene oxide homodisperse in 2 hours, added deionized water then and regulated graphene oxide concentration, obtained the graphene oxide ethanolic soln of 1.0mg/mL;
Under 98 ℃ of water bath with thermostatic control heating conditions, Z 150PH is dissolved in the deionized water, mechanical stirring is to dissolving fully, is cooled to add deionized water after the room temperature and regulate polyvinyl alcohol concentration, obtains the polyvinyl alcohol water solution of 3wt%;
Get the 100g aluminium powder, and take by weighing the Triple Pressed Stearic Acid of 1g, join the 1h that dry grinds in the stirring ball mill jointly, obtain the flake aluminum that thickness is 2 μ m, and put into the box-type furnace temperature and be 400 ℃ and carry out pyrolysis, remove Triple Pressed Stearic Acid, obtain required flake aluminum.Because metallic aluminium is very active; Easily with various material generation chemical reactions; So carry out DTA with adding certain graphite oxide in the flake aluminum and mixed powder being cold-pressed into block, investigate the thermostability between aluminium powder and the graphite oxide, confirmed before the aluminium fusing; Do not react between aluminium powder and the graphene oxide, the DSC curve and the thermogravimetric curve of test are seen Fig. 2.
Get the flake aluminum of 100g, join in the polyvinyl alcohol water solution of 3wt% of 1L, mechanical stirring 0.5 hour is filtered repeatedly with deionized water wash then, can obtain the aluminium powder of surperficial coating polyvinyl alcohol;
The Z 150PH of getting 100g coats aluminium powder and adds respectively and stir in the water of 1L and be the graphite oxide aqueous solution of 1.0mg/mL to the concentration that wherein adds 300mL constantly; Mechanical stirring to the aqueous solution becomes limpid by pale brown look; Show that graphene oxide is all by the PVA (PVOH) FILM absorption on aluminium powder surface; After filtering repeatedly with deionized water wash; Under 40 ℃, carry out vacuum-drying 12 hours,, remove Z 150PH organic composition wherein then 400 ℃ of following vacuum pyrolysiss 2 hours; Promptly obtaining massfraction is graphene oxide/aluminium composite powder of 0.3wt%, in chamber type electric resistance furnace, is rapidly heated under the argon shield to carry out thermal reduction to 500 ℃ and handle and to obtain Graphene/aluminium composite powder.In this process; Adopt Raman spectrum test graphene oxide whether successfully to join in the aluminium powder situation that is reduced to Graphene with graphene oxide; Confirm in the aluminium powder of the adding that graphene oxide is successful and through on certain degree, being reduced to Graphene after the thermal reduction, the Raman spectrum curve is seen Fig. 3.With Graphene after the thermal reduction of surface sweeping electronic microscope photos the distribution situation on sheet aluminium flake surface and with the aluminium flake surface ratio of the graphene oxide of absorption not, confirm Graphene the aluminium powder surface arrangement very evenly, its surface sweeping sem image is seen Fig. 4;
Earlier above Graphene/aluminium composite powder is cold-pressed into base, carries out hot extrusion after 2 hours 440 ℃ of following vacuum strippings then, extrusion ratio is 20:1, obtains closely knit Graphene/aluminum composite.The material that obtains is carried out mechanical property, and (room temperature, strain rate are 5 * 10
﹣ 4s
﹣ 1, AUTOGRAPH AG-I 50KN), (room temperature, TCT416) and the performance test of damping capacity (room temperature, frequency are 0.2Hz, 20.0 Hz, DMA TAQ800), test result is seen table 2 to heat conductivility.
The comparative example 1
Under 98 ℃ of water bath with thermostatic control heating conditions, Z 150PH is dissolved in the deionized water, mechanical stirring is to dissolving fully, is cooled to add deionized water after the room temperature and regulate polyvinyl alcohol concentration, obtains the polyvinyl alcohol water solution of 3wt%;
Get the 100g aluminium powder, and take by weighing the Triple Pressed Stearic Acid of 1g, join the 1h that dry grinds in the stirring ball mill jointly, obtain the flake aluminum that thickness is 2 μ m, and put into the box-type furnace temperature and be 400 ℃ and carry out pyrolysis, remove Triple Pressed Stearic Acid, obtain testing required flake aluminum;
Get the flake aluminum of 100g, join in the polyvinyl alcohol water solution of 3wt% of 1L, mechanical stirring 0.5 hour is filtered repeatedly with deionized water wash then, can obtain the aluminium powder of surperficial coating polyvinyl alcohol;
The Z 150PH of getting 100g coats aluminium powder and adds respectively and stir in the water of 1L and constantly to the deionized water that wherein adds 300mL; Mechanical stirring 30min; Under 40 ℃, carry out vacuum-drying 12 hours,, remove Z 150PH organic composition wherein then 400 ℃ of following vacuum pyrolysiss 2 hours; In chamber type electric resistance furnace, be rapidly heated to 500 ℃ under the argon shield, obtain the powder of the fine aluminium under needed and embodiment 1 same process;
Earlier above-mentioned powder is cold-pressed into base, carries out hot extrusion after 2 hours 440 ℃ of following vacuum strippings then, extrusion ratio is 20:1, obtains closely knit material.The material that obtains is carried out mechanical property, and (room temperature, strain rate are 5 * 10
﹣ 4s
﹣ 1, AUTOGRAPH AG-I 50KN), (room temperature, TCT416) and the performance test of damping capacity (room temperature, frequency are 0.2Hz, 20.0 Hz, DMA TAQ800), test result is seen table 2 to heat conductivility.
The result that the result who obtains and embodiment 1 are obtained compares, thereby the adding of explanation Graphene makes prepared material show the mechanical characteristic and the functional performance of the excellence of Graphene, the performance that outstanding Graphene enhanced metal-base composites is excellent more.
Table 2. embodiment 1 compares with comparing embodiment 1 performance
Embodiment 2
Graphene oxide is added in the ethanol and adds a spot of chitosan, and ultra-sonic dispersion made the graphene oxide homodisperse in 2 hours, added ethanol then and regulated Graphene concentration, obtained the graphene oxide ethanolic soln of 2.0mg/mL;
Vinylpyrrolidone polymer is dissolved in the ethanol and to wherein adding a spot of Hydrazine Hydrate 80, and mechanical stirring is to dissolving fully, is cooled to add ethanol after the room temperature and regulate Vinylpyrrolidone polymer concentration, obtains the Vinylpyrrolidone polymer ethanolic soln of 5wt%;
Getting quality is 6061 Al alloy powders of 100g, adds the Triple Pressed Stearic Acid of 1g, and joining the thickness of dry grinding in the stirring ball mill is the plate of sheet 6061 duraluminums of 1 μ m, and in 400 ℃ of chamber type electric resistance furnaces in the argon gas atmosphere pyrolysis remove Triple Pressed Stearic Acid;
Join respectively in the Vinylpyrrolidone polymer ethanolic soln of 5wt% of 1L, magnetic agitation 0.5 hour is filtered repeatedly with washing with alcohol then, can obtain the flaky aluminum powdered alloy that Vinylpyrrolidone polymer evenly coats;
Above Vinylpyrrolidone polymer is coated 6061 Al alloy powders to join in the graphene oxide ethanolic soln of 2.0mg/mL of 1000ml; Magnetic agitation to ethanolic soln becomes limpid by pale brown look; Show that Graphene is all by the Vinylpyrrolidone polymer thin film adsorbs on 6061 plates surface; After filtering repeatedly with washing with alcohol, under 40 ℃, carry out vacuum-drying 12 hours, then vacuum pyrolysis 2 hours in 400 ℃, argon gas atmosphere; Remove Vinylpyrrolidone polymer organic composition wherein; Promptly obtain graphene oxide/6061 composite powders, in the mixed atmosphere of argon gas and hydrogen, be rapidly heated and carry out thermal reduction to 500 ℃ and handle and to obtain Graphene/6061 composite powders, wherein the mass percent of Graphene is about 2wt%;
Earlier above Graphene/6061 composite powders are cold-pressed into base, 550 ℃ of following vacuum hotpressings 3 hours, obtain closely knit Graphene/6061 matrix materials then.
Embodiment 3
Graphene oxide is added in the deionized water and adds a spot of sodium lauryl sulphate, and ultra-sonic dispersion made the Graphene homodisperse in 2 hours, added deionized water then and regulated graphene oxide concentration, obtained the graphite oxide aqueous solution of 5.0mg/mL;
Under 98 ℃ of water bath with thermostatic control heating conditions; Be dissolved in the deionized water Z 150PH and to wherein adding a spot of quadrol; Mechanical stirring is to dissolving fully, is cooled to add deionized water after the room temperature and regulate polyvinyl alcohol concentration, obtains the polyvinyl alcohol water solution of 0.2wt%;
Get the copper powder of 200g, add the pure water of 200mL, join that wet-milling obtains the slip that thickness is the flake copper of 500nm in the planetary ball mill, carry out the suction filtration drying then, obtain that sheet is thick to be the copper powder of 500nm;
Get copper powder 100g, join in the polyvinyl alcohol water solution of 0.2wt% of 1L, magnetic agitation 0.5 hour is filtered repeatedly with deionized water wash then, can obtain the flake copper of surperficial coating polyvinyl alcohol;
The flake copper that above Z 150PH is coated joins respectively in the graphite oxide aqueous solution of 5.0mg/mL of 600mL; Magnetic agitation to the aqueous solution becomes limpid by pale brown look; Show that graphene oxide is all by the PVA (PVOH) FILM absorption on copper powder surface; After filtering repeatedly with deionized water wash, under 40 ℃, carry out vacuum-drying 12 hours, then 400 ℃ of following vacuum pyrolysiss 2 hours; Remove Z 150PH organic composition wherein; Promptly obtain graphene oxide/copper composite powder, in the mixed atmosphere of argon gas and hydrogen, be rapidly heated and carry out thermal reduction to 500 ℃ and handle and to obtain Graphene/copper composite powder, wherein the mass percent of Graphene is about 3.0wt%;
Earlier above composite powder is cold-pressed into base, 550 ℃ of following vacuum hotpressings 3 hours, obtains closely knit Graphene/carbon/carbon-copper composite material then.
Embodiment 4
Graphene oxide is added in the ethanol and adds a spot of Triton and chitosan, and ultra-sonic dispersion made the Graphene homodisperse in 2 hours, added ethanol then and regulated graphene oxide concentration, obtained the graphite oxide ethanolic soln of 0.1mg/mL;
Under 98 ℃ of water bath with thermostatic control heating conditions; Be dissolved in the ethanol Vinylpyrrolidone polymer and to wherein adding a spot of Hydrazine Hydrate 80; Mechanical stirring is to dissolving fully, is cooled to add ethanol after the room temperature and regulate polyvinyl alcohol concentration, obtains the Vinylpyrrolidone polymer ethanolic soln of 5wt%;
Get the copper powder of 100g, add the pure water of 200mL, join that wet-milling obtains the slip that thickness is the flake copper of 5 μ m in the planetary ball mill, carry out the suction filtration drying then, obtaining sheet thick is the copper powder of 5 μ m; Get the niobium powder of 100g, add the pure water of 200mL, join that wet-milling obtains the slip that thickness is the sheet niobium powder of 5 μ m in the planetary ball mill, carry out the suction filtration drying then, obtaining sheet thick is the niobium powder of 5 μ m.
Get flake copper 50g and niobium powder 50g; Join simultaneously in the Vinylpyrrolidone polymer ethanolic soln of 0.2wt% of 1L; Magnetic agitation 0.5 hour is filtered repeatedly with washing with alcohol then, can obtain the surface and coat the flake copper of Vinylpyrrolidone polymer and the mixed powder of sheet niobium powder;
The plate of above Vinylpyrrolidone polymer coating is joined the graphite oxide ethanolic soln of the 0.1mg/mL of 1000ml respectively; Magnetic agitation to solution becomes limpid by pale brown look; Show that graphene oxide is all by the Vinylpyrrolidone polymer thin film adsorbs on copper powder surface; After spending washing with alcohol and filtering repeatedly, under 40 ℃, carry out vacuum-drying 12 hours, then 400 ℃ of following vacuum pyrolysiss 2 hours; Remove Vinylpyrrolidone polymer organic composition wherein; Promptly obtain graphene oxide/copper niobium composite powder, in the mixed atmosphere of argon gas and hydrogen, be rapidly heated and carry out thermal reduction to 500 ℃ and handle and to obtain Graphene/copper niobium composite powder, wherein the mass percent of Graphene is about 0.1wt%;
Earlier above composite powder is cold-pressed into base, 550 ℃ of following vacuum hotpressings 3 hours, obtains closely knit matrix material then.
Embodiment 5
Graphene oxide is added in the deionized water and adds a spot of X 2073, and ultra-sonic dispersion made the Graphene homodisperse in 2 hours, added deionized water then and regulated graphene oxide concentration, obtained the graphite oxide aqueous solution of 10.0mg/mL;
Under 98 ℃ of water bath with thermostatic control heating conditions; Be dissolved in the deionized water Z 150PH and to wherein adding a spot of sucrose and oxalic acid; Mechanical stirring is to dissolving fully, is cooled to add deionized water after the room temperature and regulate polyvinyl alcohol concentration, obtains the polyvinyl alcohol water solution of 3wt%;
Get the aluminium powder of 200g, add the pure water of 200mL, join that wet-milling obtains the slip that thickness is the flake aluminum of 200nm in the planetary ball mill, carry out the suction filtration drying then, obtain that sheet is thick to be the flake aluminum of 200nm;
Get flake aluminum 100g, join in the polyvinyl alcohol water solution of 3wt% of 1L, magnetic agitation 0.5 hour is filtered repeatedly with deionized water wash then, can obtain the flake aluminum of surperficial coating polyvinyl alcohol;
The flake aluminum that above Z 150PH is coated joins respectively in the graphite oxide aqueous solution of 10.0mg/mL of 500ml; Magnetic agitation to the aqueous solution becomes limpid by pale brown look; Show that graphene oxide is all by the PVA (PVOH) FILM absorption on aluminium powder surface; After filtering repeatedly with deionized water wash, under 40 ℃, carry out vacuum-drying 12 hours, then 400 ℃ of following vacuum pyrolysiss 2 hours; Remove Z 150PH organic composition wherein; Promptly obtain graphene oxide/aluminium composite powder, in the mixed atmosphere of argon gas and hydrogen, be rapidly heated and carry out thermal reduction to 500 ℃ and handle and to obtain Graphene/aluminium composite powder, wherein the mass percent of Graphene is about 5.0wt%;
Earlier above composite powder is cold-pressed into base, 550 ℃ of following vacuum hotpressings 3 hours, obtains closely knit Graphene/aluminum composite then.
The present invention can simply be easy to obtain Graphene and strengthen metal composite, and the gained matrix material is high-strength light not only, also has both functional performances such as conduction, heat conduction, wear-resisting, vibration damping, is suitable for preparing the bulk matrix material.
More than be the preferred embodiments of the present invention, certainly, enforcement of the present invention is not limited to the foregoing description, such as the configuration of graphene oxide solution, can also be other combination etc., and the prescription of final matrix material designs according to actual needs.Do not have the operation of special instruction among the present invention, can directly adopt technique means commonly used in the prior art to realize.
Although content of the present invention has been done detailed introduction through above-mentioned preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be conspicuous.Therefore, protection scope of the present invention should be limited appended claim.
Claims (10)
1. a Graphene strengthens the preparation method of metal-base composites; It is characterized in that; At first graphene oxide is dispersed in the surface of flaky metal powder; Handle through reduction then and obtain Graphene/composite metal powder, adopt powder metallurgical technique to carry out densification at last again, obtain closely knit Graphene and strengthen metal-base composites.
2. Graphene as claimed in claim 1 strengthens the preparation method of metal-base composites, it is characterized in that, comprises following steps:
(1) graphene oxide is joined in water or the organic solvent preparation graphene oxide solution;
(2) flaky metal powder is joined in the graphene oxide solution, lasting stirring makes graphene oxide by the flaky metal powder surface adsorption, washs then, drying, obtains graphene oxide/composite metal powder;
(3) under inertia or reducing atmosphere, graphene oxide/composite metal powder is reduced processing, obtain Graphene/composite metal powder;
(4) adopt powder metallurgical technique, Graphene/composite metal powder is carried out densification, obtain closely knit Graphene and strengthen metal-base composites.
3. according to claim 1 or claim 2 Graphene strengthens the preparation method of metal-base composites, it is characterized in that described flaky metal powder passes through polymer surface modification in advance, may further comprise the steps:
(1) polymkeric substance is joined in water or the organic solvent preparation polymers soln; Described polymkeric substance is a kind of in Z 150PH, polyoxyethylene glycol, Vinylpyrrolidone polymer, polyacrylonitrile, ROHM, SEPIGEL 305, polymeric amide, YSR 3286 or the TKK 021;
(2) flaky metal powder is joined in the above-mentioned polymers soln, continue stirring until metal-powder surface and form polymeric film, wash then, drying.
4. Graphene as claimed in claim 3 strengthens the preparation method of metal-base composites, it is characterized in that the mass percent concentration of described polymers soln is 0.2-5%; In the described polymers soln, do not contain reductive agent, or contain one to multiple kind of organic reducing agent; Said reductive agent is selected from a kind of in quadrol, Hydrazine Hydrate 80, glucose, sucrose, SANMALT-S, dextrin, vitamins C, oxalic acid, propanedioic acid, Hydrocerol A, oxysuccinic acid, tartrate or the tartrates.
5. according to claim 1 or claim 2 Graphene strengthens the preparation method of metal-base composites, it is characterized in that described flaky metal powder is one or more in aluminium, copper, magnesium, titanium, iron and the powdered alloy thereof; Described flaky metal powder radius-thickness ratio is greater than 10, and thickness is between 200nm-5 μ m, and the sheet footpath is between 5-500um.
6. Graphene as claimed in claim 2 strengthens the preparation method of metal-base composites, it is characterized in that in the described graphene oxide solution, the concentration of graphene oxide is 0.1-10mg/mL; Described Graphene strengthens in the metal-base composites, and the quality percentage composition of Graphene is 0.1-5wt%.
7. strengthen the preparation method of metal-base composites like claim 2 or 6 described Graphenes; It is characterized in that; In the described graphene oxide solution; Do not contain tensio-active agent, or contain one to multiple kind of tensio-active agent, said tensio-active agent is selected from sodium lauryl sulphate, X 2073, cetyl trimethylammonium bromide, Triton, chitosan, β-cyclodextrin or LUTARALDEHYDE or the biliary salts a kind of.
8. according to claim 1 or claim 2 Graphene strengthens the preparation method of metal-base composites, it is characterized in that described graphene oxide and Graphene have the single or multiple lift graphite-structure, and thickness is less than 20nm.
9. according to claim 1 or claim 2 Graphene strengthens the preparation method of metal-base composites, it is characterized in that described reduction processing and densification temperature all are lower than the fusing point of said metal-powder, but is higher than the pyrolysis temperature of polymkeric substance; Described densification is that Graphene/composite metal powder is colded pressing by elder generation or isostatic cool pressing becomes block, below the fusing point of said flaky metal powder, carries out hot pressing, hot isostatic pressing, hot extrusion or hot rolled thermal distortion processing then.
10. a Graphene that is obtained by each said method of claim 1-9 strengthens metal-base composites, it is characterized in that described Graphene strengthens in the metal-base composites, and the quality percentage composition of Graphene is 0.1-5wt%.
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