CN114752898A - Preparation method of aluminum metal composite material with vertically grown graphene - Google Patents
Preparation method of aluminum metal composite material with vertically grown graphene Download PDFInfo
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
Abstract
The invention relates to a preparation method of an aluminum metal composite material with vertically grown graphene, which comprises the following steps: firstly, reducing and cleaning a base material, then growing a titanium layer on the surface of the base material after reduction and cleaning, then growing a graphene layer, processing the graphene layer into uniform workpieces through a later-stage powder metallurgy process, and carrying out various tests. The titanium layer is used as a connecting layer between the metal aluminum and the graphene, a foundation is provided for growth of the graphene on the aluminum, the growth of the graphene below the melting of the aluminum can be realized by adopting a plasma growth technology, the grown graphene is uniform and stable, and the vertical growth is beneficial to preparing and distributing uniformly workpieces in the later hot isostatic pressing process. The method has the advantages of high feasibility, low production cost, simple operation, improved product performance and convenient large-scale production and application.
Description
Technical Field
The invention relates to a preparation method of an aluminum metal composite material, in particular to a preparation method of the aluminum metal composite material of vertically grown graphene, which combines a graphene growth technology with a metal metallurgy technology, deeply disperses and combines with aluminum metal in the graphene forming process, and facilitates molten aluminum to flow into vertical graphene gaps in the later hot isostatic pressing process due to the vertical growth of the graphene.
Background
Aluminum and aluminum alloy have excellent performances such as low density, high strength and good ductility, but have the defects of easy deformation and poor electric and heat conduction compared with copper metal, and the reasons for the defects are that the rigidity of the aluminum alloy is insufficient and the electric and heat conduction capability is poor due to the influence of metal characteristics. In the high-end manufacturing field, light weight is inevitably developed, aluminum alloy is increasingly widely applied due to low density, high specific strength and easy processing, and aluminum alloy 'coats' are worn on airplanes, high-speed rails and the like in many times. The aluminum alloy material with high conductivity and low cost in the field of large-scale power electronics will also become the main direction of future development. However, it is difficult to further improve the electrical, thermal and mechanical properties of aluminum and aluminum alloys by conventional methods such as component addition, heat treatment and plastic deformation. The industrial industry supplements the strength by adding various materials, the aluminum lithium alloy and the aluminum ceramic alloy are development directions, and the aluminum matrix composite material formed by adding novel reinforcing phases such as carbon nano tubes and graphene is more generally seen. For example, the C919 of a domestic large airplane uses the aluminum-lithium alloy as the self weight reduction, and the proportion of the aluminum-lithium alloy in the body structure reaches 7.4 percent. Some research institutions adopt a small amount of carbon nanotubes and graphene to be uniformly dispersed in an aluminum alloy matrix, so that expensive alloy elements can be partially replaced, and the electric and heat conducting properties of the aluminum alloy can be greatly improved on the basis of keeping good processing properties of the aluminum alloy.
In recent years, carbonaceous nanomaterials have attracted attention, and particularly, graphene materials have been widely used in the fields of electronic materials and composite materials because of their excellent properties in various aspects and their mature application studies. At present, graphene is uniformly compounded on a high polymer material to obtain products with various excellent performances, aluminum is still used in a pure substance or alloy form, and the performances of electric conduction, heat conduction, strength, corrosion resistance, oxidation resistance and the like of the aluminum are greatly limited. If the novel material is formed by compounding the graphene and the aluminum, the effect of the graphene can be better reflected, the electric conduction and heat conduction performance of metal is greatly improved, the mechanical strength and the yield strength are improved, the oxidation resistance and the corrosion resistance are improved, the thinning is reduced, and the existing aluminum material is thoroughly improved. The development of the graphene-aluminum composite material is significant for changing the performance of the existing equipment and devices, saving energy and the like, and has great difficulty and great challenge. In the future, the graphene-aluminum composite material is widely applied to the field of power equipment, and the market value can reach billions or even higher.
In the prior art, hundreds of millions of enterprises invest in developing graphene aluminum alloy wire rod materials, the graphene aluminum alloy wire rods are popularized, and the graphene aluminum alloy wire rods are not applied in a large scale at present. Based on different methods, the li shiqiang team of Shanghai traffic university also takes part in many years of research and issues a plurality of achievements, but the li shiqiang team is mainly applied to laboratory preparation, has no mass production, and the produced composite material is mostly in a form of direct mixing of carbon nanotubes rather than graphene composite aluminum, for example, in patents CN103789564A and CN102534331A, the carbon nanotubes, diamond powder and aluminum powder are respectively combined in a ball milling and blending mode to produce the carbon-aluminum composite material, which can play a role in weight reduction, is poor in electrical and thermal conductivity and cannot realize the required function, and the weight reduction of the existing small amount of processed products used on a support of a lunar vehicle to replace an existing aluminum alloy component can be expected to reach 10% -30%. The group also adopts a mode of directly mixing graphene and aluminum, for example, patent CN10426400A mentions that the graphene powder and aluminum powder are directly mixed to prepare a composite material, the heat conducting property is improved, but the electric conduction and the mechanical property are deteriorated, mainly because the dispersion uniformity of the graphene in the aluminum is difficult to ensure, and a large amount of crystal boundaries and defects are generated.
Therefore, in order to realize uniform compounding of graphene and aluminum and improve product performance, a new way needs to be created, and a proper scheme can be found only by considering the overall thinking and design of the dispersion problem, the binding force problem and the side reaction problem in the process of combining graphene and aluminum and considering the influence of all aspects. The method adopts a plasma coating technology to uniformly grow carbon on the surface of aluminum metal in a plasma form to form a graphene coating mode, can well realize aluminum coating, and is low in cost and capable of realizing large-scale production. In the method, the problem of dispersion is solved by uniform growth of plasma, the problem of binding force is solved by stable binding of charged particles, the processing temperature of the plasma process is in a lower problem range, and the occurrence of side reactions is reduced.
Disclosure of Invention
In view of the above problems, a main object of the present invention is to provide a method for preparing an aluminum metal composite material of vertically grown graphene, in which a graphene growth technology is combined with a metal metallurgy technology, and the aluminum metal is deeply and dispersedly combined with aluminum metal in the graphene formation process, and meanwhile, the vertical growth of graphene is also convenient for molten aluminum to flow into vertical graphene gaps in the later hot isostatic pressing process.
The invention solves the technical problems through the following technical scheme: a preparation method of an aluminum metal composite material with vertically grown graphene comprises the following steps: firstly, carrying out reduction cleaning on a base material, then growing a titanium layer on the surface of the base material after reduction cleaning, then growing a graphene layer, processing the graphene layer into a uniform workpiece through a later-stage powder metallurgy process, and carrying out various tests.
In a specific implementation example of the present invention, the specific steps include:
the method comprises the following steps: pure aluminum is selected as the aluminum substrate, and the aluminum substrate is treated for 1-3 hours in the mixed gas of hydrogen and argon at the temperature of 350-450 ℃ to ensure that the oxide is removed.
Step two: and (3) placing the aluminum substrate treated in the step one in a high-temperature inert atmosphere furnace, heating to the temperature of 400-500 ℃, and coating a metal titanium layer by using a plasma electroplating process to serve as a bonding layer of aluminum and graphene.
Step three: and (4) increasing the temperature to 550-600 ℃ on the basis of the second step, and vertically growing the graphene sheet material on the product obtained in the second step through a plasma growth process.
Step four: and finally, performing pre-pressing forming on the product obtained in the third step by adopting cold rolling, pressing the graphene-aluminum composite material into uniformly dispersed workpieces by a hot isostatic pressing process, and performing various tests.
In an embodiment of the present invention, the aluminum substrate in the first step is foamed aluminum, nano aluminum or aluminum foil; the surface of the aluminum substrate contains an aluminum oxide layer, and acid liquor is selected for cleaning during processing.
In an embodiment of the present invention, the aluminum foam in the first step is selected to be porous aluminum foam.
In the embodiment of the invention, the ratio of the hydrogen-argon mixture in the step one is hydrogen: argon is 5: 95.
in the embodiment of the invention, the inert atmosphere in the inert atmosphere furnace in the second step is one or a mixture of helium and argon.
In the specific implementation example of the invention, the temperature condition of the plasma treatment of the titanium alloy is 400-500 ℃, the treatment time is 2-3h, and the thickness of the titanium alloy is 100-200 nm.
In the specific implementation example of the invention, the furnace temperature for growing the graphene by the plasma is 550-600 ℃, the carbon source is a graphite material, the treatment time is 6-8h, the graphene layer is a vertical growth structure, and the thickness of the graphene layer is 200-1 μm.
In the embodiment of the invention, the cold rolling in the fourth step is performed at a pressure of 100MPa, and the hot isostatic pressing is performed at a pressure of 200 MPa.
In the embodiment of the invention, the test method in the fourth step comprises a tensile test, a modulus test, a hardness test, an electric conduction test and a heat conduction test.
The positive progress effects of the invention are as follows: according to the preparation method of the aluminum metal composite material for vertically growing the graphene, the titanium layer is used as a connecting layer between the metal aluminum and the graphene, a foundation is provided for growth of the graphene on the aluminum, the growth of the graphene below melting of the aluminum can be realized by adopting a plasma growth technology, the grown graphene is uniform and stable, and the vertical growth is beneficial to preparing and distributing uniformly workpieces in a later hot isostatic pressing process. The method has the advantages of high feasibility, low production cost, simple operation, improved product performance and convenient large-scale production and application.
Drawings
Fig. 1 is a schematic view of the overall structure of the present invention.
Detailed Description
The following provides a detailed description of the preferred embodiments of the present invention with reference to the accompanying drawings.
Fig. 1 is a schematic overall structure of the present invention, as shown in fig. 1: the invention provides a preparation method of an aluminum metal composite material with vertically grown graphene, which comprises the following steps: firstly, reducing and cleaning a base material, then growing a titanium layer on the surface of the base material after reduction and cleaning, then growing a graphene layer, processing the graphene layer into uniform workpieces through a later-stage powder metallurgy process, and carrying out various tests.
The method comprises the following specific steps:
the method comprises the following steps: selecting pure aluminum as an aluminum base material, firstly treating the aluminum base material in hydrogen-argon mixed gas at the temperature of 350-450 ℃ for 1-3h to ensure that oxides are removed;
step two: placing the aluminum substrate treated in the step one in a high-temperature inert atmosphere furnace, heating to the condition of 400-500 ℃, and coating a metal titanium layer by a plasma electroplating process to be used as a bonding layer of aluminum and graphene;
step three: raising the temperature to 550-600 ℃ on the basis of the step two, and vertically growing a graphene sheet material on the product obtained in the step two through a plasma growth process;
step four: and finally, performing pre-pressing forming on the product obtained in the third step by adopting cold rolling, pressing the graphene-aluminum composite material into uniformly dispersed workpieces by a hot isostatic pressing process, and performing various tests. In a specific implementation, the cold rolling is performed at a pressure of 100MPa and the hot isostatic pressing is performed at a pressure of 200 MPa. In specific implementations, the tests include tensile tests, modulus tests, hardness tests, electrical conductivity tests, and thermal conductivity tests.
In a specific implementation process, the aluminum substrate in the first step of the present invention may be foamed aluminum, nano aluminum or aluminum foil; the surface of the aluminum substrate contains an aluminum oxide layer, and acid liquor is selected for cleaning during processing; selecting porous foamed aluminum as the foamed aluminum in the first step; the proportion of the hydrogen-argon mixed gas in the first step is hydrogen: argon is 5: 95.
in a specific implementation process, the inert atmosphere in the inert atmosphere furnace in the second step of the invention is one or a mixture of helium and argon.
In the specific implementation process, the temperature condition of the plasma treatment of the titanium alloy is 400-500 ℃, the treatment time is 2-3h, and the thickness of the titanium alloy is 100-200 nm.
In the specific implementation process, the furnace temperature for growing the graphene by the plasma is 550-600 ℃, the carbon source is a graphite material, the treatment time is 6-8h, the graphene layer is a vertical growth structure, and the thickness of the graphene layer is 200-1 μm.
Example 1
1.1, pretreatment stage:
selecting 300g of foamed aluminum as an aluminum-based raw material, placing the aluminum-based raw material in a tube furnace, introducing a hydrogen-argon mixed gas (hydrogen/argon is 5/95), setting the flow rate to be 50slpm, setting the constant heating temperature to be 400 ℃, and setting the constant time to be 2h to ensure that an oxide layer on the surface of the metal aluminum is completely reduced.
1.2, transition layer processing stage:
connecting plasma generation equipment on the basis of an original tube furnace, taking titanium metal as a metal generation source, placing an aluminum substrate without aluminum oxide in the tube furnace without taking out, introducing an inert gas, namely helium and argon (50slpm) into the tube furnace, setting the heating temperature of the tube furnace to be 500 ℃, stabilizing the heating time to be 2h, and growing a metal titanium layer of 200nm by a plasma electroplating process to be used as a bonding layer of aluminum and graphene.
1.3, graphene growth stage:
after the growth of the titanium metal layer is finished, the growth source is replaced by a graphite material, the temperature is raised to 600 ℃ through a plasma growth process, the constant heating time is 8 hours, the graphene layer material is continuously grown, and the graphene layer material is vertically generated on the surface of the titanium metal.
1.4, metal processing stage:
and (3) performing cold rolling treatment on the grown composite raw material in cold rolling equipment at the pressure of 100MPa to press the composite raw material into a block material, and then putting the cold-rolled metal block into a mould to further press the metal block into the composite material through a hot isostatic pressing process under the pressure of 200 MPa.
1.5, testing stage:
pressing into rod-shaped material of 15cm × Φ 1cm, linear composite material of 1m × Φ 3mm, and disc-shaped material of 200 μm × Φ 2.5cm according to the test requirement. And respectively testing the mechanical strength, the electric conduction, the heat conduction and other properties of the sample. The tested conductivity was 8% higher compared to pure aluminum material, the thermal conductivity was 80% of pure aluminum material, the modulus was 200% higher, the mass was 14% lower, the graphene layer thickness was 700 nm.
Example 2
1.1, pretreatment stage:
the method comprises the steps of selecting 300g of nano aluminum powder and aluminum foil as aluminum-based raw materials, placing the aluminum-based raw materials in a tubular furnace, introducing hydrogen-argon mixed gas (hydrogen/argon is 5/95), setting the flow rate to be 50slpm, setting the constant heating temperature to be 400 ℃, and setting the constant time to be 3h, so as to ensure that an oxide layer on the surface of the metal aluminum is completely reduced.
1.2, transition layer processing stage:
connecting plasma generation equipment on the basis of an original tube furnace, taking titanium metal as a metal generation source, placing an aluminum substrate without aluminum oxide in the tube furnace, taking out the aluminum substrate, introducing an inert gas helium argon (50slpm) into the tube furnace, setting the heating temperature of the tube furnace to be 400 ℃, setting the stable heating time to be 3h, and growing a metal titanium layer with the thickness of 100nm by using a plasma electroplating process to serve as a bonding layer of aluminum and graphene.
1.3, graphene growth stage:
after the growth of the titanium metal layer is finished, the growth source is replaced by a graphite material, the temperature is raised to 550 ℃ through a plasma growth process, the constant heating time is 7 hours, the graphene layer material is continuously grown, and the graphene layer material is vertically generated on the surface of the titanium metal.
1.4, metal processing stage:
and (3) performing cold rolling treatment on the grown composite raw materials in a cold rolling device at the pressure of 100MPa to press the composite raw materials into a block material, and then putting the cold-rolled metal block into a mould to further press the metal block into the composite material through a hot isostatic pressing process under the pressure of 200 MPa.
1.5, testing stage:
pressing into rod-shaped material of 15cm × Φ 1cm, linear composite material of 1m × Φ 3mm, and disc-shaped material of 200 μm × Φ 2.5cm according to the test requirement. And respectively testing the mechanical strength, the electric conductivity, the heat conductivity and other properties of the sample. The tested conductivity was 5% higher compared to pure aluminum material, and the thermal conductivity was 72% of pure aluminum material, modulus was 150% higher, mass was 10% lower, and graphene layer thickness was 500 nm.
Example 3
1.1, pretreatment stage:
300g of aluminum foil is selected as an aluminum-based raw material and is placed in a tube furnace, hydrogen-argon mixed gas (hydrogen/argon is 5/95) is introduced, the flow is 50slpm, the constant heating temperature is set to be 400 ℃, the constant time is 1h, and the complete reduction of an oxide layer on the surface of the metal aluminum is ensured.
1.2, transition layer processing stage:
connecting plasma generation equipment on the basis of an original tube furnace, taking titanium metal as a metal generation source, placing an aluminum substrate without aluminum oxide in the tube furnace, taking out the aluminum substrate, introducing an inert gas helium argon (50slpm) into the tube furnace, setting the heating temperature of the tube furnace to be 500 ℃, setting the stable heating time to be 2 hours, and growing a metal titanium layer of 200nm by a plasma electroplating process to be used as a bonding layer of aluminum and graphene.
1.3, graphene growth stage:
and after the titanium metal layer is grown, replacing the growth source with a graphite material, raising the temperature to 550 ℃ by a plasma growth process, keeping the constant heating time for 6 hours, continuously growing, and vertically generating a graphene sheet layer material on the surface of the titanium metal.
1.4, metal processing stage:
and (3) performing cold rolling treatment on the grown composite raw material in cold rolling equipment at the pressure of 100MPa to press the composite raw material into a block material, and then putting the cold-rolled metal block into a mould to further press the metal block into the composite material through a hot isostatic pressing process under the pressure of 200 MPa.
1.5, testing stage:
pressing into rod-shaped material of 15cm × Φ 1cm, linear composite material of 1m × Φ 3mm, and disc-shaped material of 200 μm × Φ 2.5cm according to the test requirement. And respectively testing the mechanical strength, the electric conductivity, the heat conductivity and other properties of the sample. The tested conductivity was 5% higher than that of pure aluminum material, the thermal conductivity was 78% higher than that of pure aluminum material, the modulus was 100% higher, the mass was 20% lower, and the thickness of graphene plating layer was 1 μm.
Example 4
1.1, pretreatment stage:
300g of foamed aluminum is selected as an aluminum-based raw material, the aluminum-based raw material is placed in a tube furnace, a hydrogen-argon mixed gas (hydrogen/argon is 5/95) is introduced, the flow rate is 50slpm, the constant heating temperature is set to be 400 ℃, the constant time is 2 hours, and the complete reduction of an oxide layer on the surface of the metal aluminum is ensured.
1.2, transition layer processing stage:
connecting plasma generation equipment on the basis of an original tube furnace, taking titanium metal as a metal generation source, placing an aluminum substrate without aluminum oxide in the tube furnace without taking out, introducing an inert gas, namely helium and argon (50slpm) into the tube furnace, setting the heating temperature of the tube furnace to be 500 ℃, stabilizing the heating time to be 2h, and growing a metal titanium layer of 200nm by a plasma electroplating process to be used as a bonding layer of aluminum and graphene.
1.3, graphene growth stage:
and after the titanium metal layer is grown, replacing the growth source with a graphite material, raising the temperature to 550 ℃ by a plasma growth process, keeping the constant heating time for 6 hours, continuously growing, and vertically generating a graphene sheet layer material on the surface of the titanium metal.
1.4, metal processing stage:
and (3) performing cold rolling treatment on the grown composite raw materials in a cold rolling device at the pressure of 100MPa to press the composite raw materials into a block material, and then putting the cold-rolled metal block into a mould to further press the metal block into the composite material through a hot isostatic pressing process under the pressure of 200 MPa.
1.5, testing stage:
pressing into rod-shaped material of 15cm × Φ 1cm, linear composite material of 1m × Φ 3mm, and disc-shaped material of 200 μm × Φ 2.5cm according to the test requirement. And respectively testing the mechanical strength, the electric conductivity, the heat conductivity and other properties of the sample. Compared with a pure aluminum material, the tested conductivity is improved by 3%, the thermal conductivity is 60% of that of the pure aluminum material, the modulus is improved by 120%, the mass is reduced by 10%, and the thickness of a graphene layer is 200 nm.
Comparative example 1
1.1, pretreatment stage:
300g of foamed aluminum is selected as an aluminum-based raw material, the aluminum-based raw material is placed in a tube furnace, a hydrogen-argon mixed gas (hydrogen/argon is 5/95) is introduced, the flow rate is 50slpm, the constant heating temperature is set to be 400 ℃, the constant time is 2 hours, and the complete reduction of an oxide layer on the surface of the metal aluminum is ensured.
1.2, transition layer processing stage:
connecting plasma generation equipment on the basis of an original tubular furnace, placing an aluminum substrate without aluminum oxide in the tubular furnace without taking out the aluminum substrate by using a graphite generation source, introducing an inert gas, namely helium and argon (50slpm), into the tubular furnace, raising the temperature to 600 ℃ by using a plasma growth process, keeping the constant heating time for 8 hours, continuously growing, and vertically generating a graphene sheet material on the surface of titanium metal.
1.3, graphene-free growth stage:
1.4, metal processing stage:
and (3) performing cold rolling treatment on the grown composite raw materials in a cold rolling device at the pressure of 100MPa to press the composite raw materials into a block material, and then putting the cold-rolled metal block into a mould to further press the metal block into the composite material through a hot isostatic pressing process under the pressure of 200 MPa.
1.5, testing stage:
pressing into rod-shaped material of 15cm × Φ 1cm, linear composite material of 1m × Φ 3mm, and disc-shaped material of 200 μm × Φ 2.5cm according to the test requirement. And respectively testing the mechanical strength, the electric conduction, the heat conduction and other properties of the sample. Compared with a pure aluminum material, the tested electrical conductivity is not obviously improved, the thermal conductivity is not obviously changed in the pure aluminum material, the modulus is improved by 50%, the mass is reduced by 2%, and the graphene coating does not uniformly grow on the aluminum substrate and is only distributed sporadically.
Comparative example 2
1.1, pretreatment stage:
300g of foamed aluminum is selected as an aluminum-based raw material, the aluminum-based raw material is placed in a tube furnace, a hydrogen-argon mixed gas (hydrogen/argon is 5/95) is introduced, the flow rate is 50slpm, the constant heating temperature is set to be 400 ℃, the constant time is 2 hours, and the complete reduction of an oxide layer on the surface of the metal aluminum is ensured.
1.2, transition layer processing stage:
connecting plasma generation equipment on the basis of an original tube furnace, taking titanium metal as a metal generation source, placing an aluminum substrate without aluminum oxide in the tube furnace, taking out the aluminum substrate, introducing an inert gas helium argon (50slpm) into the tube furnace, setting the heating temperature of the tube furnace to be 500 ℃, setting the stable heating time to be 2 hours, and growing a metal titanium layer of 200nm by a plasma electroplating process to be used as a bonding layer of aluminum and graphene.
1.3, graphene-free growth stage:
1.4, metal processing stage:
and (3) performing cold rolling treatment on the grown composite raw material in cold rolling equipment at the pressure of 100MPa to press the composite raw material into a block material, and then putting the cold-rolled metal block into a mould to further press the metal block into the composite material through a hot isostatic pressing process under the pressure of 200 MPa.
1.5, testing stage:
pressing into rod-shaped material of 15cm × Φ 1cm, linear composite material of 1m × Φ 3mm, and disc-shaped material of 200 μm × Φ 2.5cm according to the test requirement. And respectively testing the mechanical strength, the electric conductivity, the heat conductivity and other properties of the sample. The tested electrical conductivity is reduced by 5% compared with a pure aluminum material, the thermal conductivity is 50% of that of the pure aluminum material, the modulus is improved by 30%, the mass is reduced by 5%, and no graphene coating is formed.
The composite materials in the examples and the comparative examples are detected in all instruments, and the performance results of the examples and the comparative examples are obtained by comparing the test results with the detection results of pure aluminum through calculation.
The embodiment shows that the graphene-aluminum composite material disclosed by the invention has good electric and heat conducting properties, and the properties such as strength and hardness are obviously improved, compared with the prior art, the graphene-aluminum composite material has the advantages of less side reaction, uniform dispersion, strong binding force and the like, and the used material is low in cost, simple in processing process, and has very high practical value and wide market.
Aiming at the defects of the existing graphene-aluminum composite material, the inventor finds that the graphene-aluminum composite material prepared by the plasma technology can reduce side reactions, reduce graphene defects and improve the bulk phase dispersion capacity of graphene and aluminum, and compared with the existing mode that graphene and aluminum nano can be directly and physically mixed, the electric conduction and heat conduction performance is improved by multiple times. And the metal titanium is adopted as a transition layer, so that the binding force of the graphene and the aluminum is better improved, and the mechanical property of the material is improved, thereby completing the invention.
According to the aluminum metal composite material for vertically growing the graphene, disclosed by the invention, before growth, hydrogen and argon mixed gas needs to be introduced into a pure aluminum material in advance to reduce an aluminum oxide layer on the surface of aluminum, so that the content of oxygen is reduced. The required aluminum base materials comprise foamed aluminum, nano aluminum powder, aluminum foil and the like, wherein the foamed aluminum can realize the effect of uniform growth inside and outside due to the porous structure of the foamed aluminum, and the growth is more uniform. And the aluminum foil is used as a substrate to form a graphene aluminum multilayer stacked structure after growth.
The titanium metal layer is the key point that graphene can grow on an aluminum substrate, because aluminum metal is difficult to form a graphene growth site, after titanium metal grows, graphene can nucleate and grow on the titanium metal, the titanium metal is vertically arranged, and the sheet layer is larger and larger along with the extension of processing time.
The growth temperature of the graphene is controlled between 550 ℃ and 600 ℃, so that the aluminum substrate is not fused and adhered, the graphene material can be grown at the maximum efficiency, and the occurrence of side reactions can be reduced as much as possible in the temperature range.
The process adopting cold rolling and hot isostatic pressing is a traditional metal metallurgy processing process, but the required pressure is higher than the normal aluminum metal processing pressure due to the fact that the hardness of the added graphene is improved.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined by the appended claims and their equivalents.
Claims (10)
1. A preparation method of an aluminum metal composite material with vertically grown graphene is characterized by comprising the following steps: the preparation method of the aluminum metal composite material with the vertically grown graphene comprises the following steps: firstly, reducing and cleaning a base material, then growing a titanium layer on the surface of the base material after reduction and cleaning, then growing a graphene layer, processing the graphene layer into uniform workpieces through a later-stage powder metallurgy process, and carrying out various tests.
2. The method for preparing an aluminum metal composite material of vertically grown graphene according to claim 1, wherein: the method comprises the following specific steps:
the method comprises the following steps: selecting pure aluminum as an aluminum substrate, firstly treating the aluminum substrate in a hydrogen-argon mixed gas at the temperature of 350-450 ℃ for 1-3h to ensure that oxides are removed;
step two: placing the aluminum substrate treated in the step one in a high-temperature inert atmosphere furnace, heating to the condition of 400-500 ℃, and coating a metal titanium layer by a plasma electroplating process to be used as a bonding layer of aluminum and graphene;
step three: raising the temperature to 550-600 ℃ on the basis of the step two, and vertically growing a graphene sheet material on the product obtained in the step two through a plasma growth process;
step four: and finally, performing pre-pressing forming on the product obtained in the third step by adopting cold rolling, pressing the graphene-aluminum composite material into uniformly dispersed workpieces by a hot isostatic pressing process, and performing various tests.
3. The method for preparing the aluminum metal composite material with the vertically grown graphene according to claim 2, wherein the method comprises the following steps: the aluminum base material in the first step is foamed aluminum, nano aluminum or aluminum foil; the surface of the aluminum base material contains an aluminum oxide layer, and acid liquor is selected for cleaning during processing.
4. The method for preparing the aluminum metal composite material with the vertically grown graphene according to claim 3, wherein the method comprises the following steps: and selecting the foamed aluminum in the step one as porous foamed aluminum.
5. The method for preparing the aluminum metal composite material of the vertically grown graphene according to claim 2, wherein: the proportion of the hydrogen-argon mixed gas in the first step is hydrogen: argon is 5: 95.
6. the method for preparing the aluminum metal composite material of the vertically grown graphene according to claim 2, wherein: and in the second step, the inert atmosphere in the inert atmosphere furnace is one or a mixture of helium and argon.
7. The method for preparing the aluminum metal composite material of the vertically grown graphene according to claim 2, wherein: the temperature condition of the plasma treatment titanium alloy is 400-500 ℃, the treatment time is 2-3h, and the thickness of the titanium alloy is 100-200 nm.
8. The method for preparing the aluminum metal composite material with the vertically grown graphene according to claim 2, wherein the method comprises the following steps: the furnace temperature for growing the graphene by the plasma is 550-600 ℃, the carbon source is a graphite material, the treatment time is 6-8h, the graphene layers are vertical growth structures, and the thickness of the graphene layer is 200-1 mu m.
9. The method for preparing the aluminum metal composite material of the vertically grown graphene according to claim 2, wherein: in the fourth step, the pressure of cold rolling is 100MPa, and the pressure of hot isostatic pressing is 200 MPa.
10. The method for preparing the aluminum metal composite material of the vertically grown graphene according to claim 2, wherein: the test in the fourth step comprises a tensile test, a modulus test, a hardness test, an electric conduction test and a heat conduction test.
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