A method for preparing a graphene reinforced aluminum-based gradient composite material with gradient nanostructure

Abstract

The application relates to a preparation method of a graphene reinforced aluminum-based gradient composite material with a gradient nanostructure and relates to a preparation method of an aluminum-based gradient composite material. The application aims to solve the problems that graphene is uniformly distributed or in a net shape at the grain boundaries in the aluminum matrix in the existing graphene reinforced aluminum-based composite material, that the graphene consumption of the block composite material is large for realizing comprehensive performance improvement, that the addition of a large amount of graphene reduces the compactness of the block composite material, that the plasticity of the material is greatly reduced, and that the processing performance is poor. The application aims to prepare the graphene reinforced aluminum-based gradient composite material by taking GO and an Al plate as raw materials, mechanically milling a working groove on the Al plate, electrophoretically depositing the GO, covering the GO / Al prefabricated plate with the Al plate and adopting a rolling composite method combined with surface mechanical treatment, so that the graphene reinforced aluminum-based gradient composite material has good mechanical properties, heat conduction performance and electric conductivity, and has the characteristics of structural function integration.

Description

Technical Field

[0001] This invention relates to a method for preparing an aluminum-based gradient composite material. Background Technology

[0002] The energy shortage problem places higher demands on the comprehensive performance of materials, often requiring the realization of multiple performance requirements in a single material, including structural and functional properties—that is, the integration of structure and function, and the functional integration of materials. This demand is particularly urgent in the energy sector. Al and its alloys are the most widely used non-ferrous metals. Due to their low density and relatively high specific strength, as well as relatively high thermal and electrical conductivity, they are widely used as low-cost structural components for heat and electricity conduction. However, whether as structural materials or thermal and electrical conductive materials, their strength, thermal conductivity, and electrical conductivity still need to be improved. Graphene has high thermal and electrical conductivity and strong electromagnetic response capabilities, capable of absorbing, reflecting, and scattering electromagnetic waves. Combining graphene with an Al matrix to prepare GO / Al-based composite materials allows for the integrated design and fabrication of structural components for both heat and electricity conduction.

[0003] Currently, the preparation of graphene-reinforced aluminum matrix composites mainly focuses on powder metallurgy technology and corresponding additive manufacturing. In the prepared composites, graphene is often uniformly or in a network distribution at the grain boundaries of the aluminum matrix, i.e., inside the composite material. To achieve comprehensive performance improvement, bulk composites require a large amount of graphene. However, the addition of a large amount of graphene will reduce the density of the bulk composite material, significantly reduce the material's plasticity, and worsen its processing performance. Summary of the Invention

[0004] The purpose of this invention is to address the problem that existing graphene-reinforced aluminum matrix composites have graphene uniformly or in a network distribution at the grain boundaries in the aluminum matrix. To achieve comprehensive performance improvement, bulk composites require a large amount of graphene, and the addition of a large amount of graphene reduces the density of the bulk composite, significantly reduces the plasticity of the material, and deteriorates the processing performance. Therefore, this invention provides a method for preparing graphene-reinforced aluminum matrix gradient composites with a gradient nanostructure.

[0005] A method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure is specifically carried out according to the following steps:

[0006] I. Surface mechanical milling treatment:

[0007] The Al plate is subjected to surface mechanical milling in a direction perpendicular to the plane to obtain an Al plate with a working groove with a depth of 0.1 mm to 1 mm;

[0008] II. Electrophoretic deposition of GO:

[0009] Electrophoretic deposition of GO was performed on an Al plate with a working groove of 0.1 mm to 1 mm depth, followed by drying, to obtain a GO / Al substrate with a GO deposition layer.

[0010] III. Preparation of GO / Al prefabricated panels;

[0011] ① Perform alkaline washing on another Al plate with the same length and width as the Al plate described in step one to obtain a surface-pretreated Al plate;

[0012] ② Cover the surface-pretreated Al plate onto the GO / Al substrate with the GO deposition layer, so that the GO deposition layer is in contact with the surface-pretreated Al plate, then use Al foil to wrap it, and finally roll it to obtain the GO / Al preform.

[0013] IV. Surface mechanical treatment:

[0014] By applying a load of 300N to 1000N in the direction perpendicular to the plane of the GO / Al preform and feeding at a rate of 0.5 to 5 mm / s in the direction parallel to the plane of the GO / Al preform multiple times for pressure friction treatment, and rotating the pressure friction head at a speed of 0 to 600 rpm, a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure is obtained.

[0015] The principle of this invention:

[0016] This invention aims to prepare graphene-reinforced aluminum-based gradient composite materials using GO and Al plates as raw materials. This is achieved by mechanically milling working grooves on the Al plate and electrophoretically depositing GO, then covering the GO / Al prefabricated plate with the Al plate and employing a rolling composite process combined with surface mechanical treatment. The key features of this invention are: 1. The deposition thickness of graphene (GO) on the Al plate can be controlled using the working groove processing and electrophoretic deposition method, while effectively solidifying the GO deposition and ensuring good interfacial bonding; 2. The use of a cover plate combined with encapsulation treatment effectively prevents GO loss, achieving good rolling mechanical-metallurgical bonding and effective GO encapsulation; 3. Surface mechanical treatment improves the surface properties of the GO / Al prefabricated plate, simultaneously forming a gradient distribution of matrix grain size and reinforcement volume fraction, exhibiting excellent comprehensive performance; 4. The GO volume fraction gradient can be controlled by selecting the GO deposition amount, cover plate thickness, and surface mechanical treatment process parameters.

[0017] The present invention has the following advantages:

[0018] I. The method of the present invention can efficiently prepare graphene-reinforced aluminum-based gradient composite materials with gradient nanostructures. The production process is simple and easy to implement, pollution-free, and low-cost.

[0019] II. The graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure prepared by this invention is dense and has good mechanical properties, thermal conductivity, and electrical conductivity, and has the characteristics of integrated structure and function.

[0020] Third, the thickness of the graphene-reinforced aluminum-based gradient composite material with gradient nanostructure prepared by this invention can be controlled by adjusting the Al substrate, the cover plate, and the rolling deformation amount. The graphene volume fraction gradient can be controlled by electrophoretic deposition and surface mechanical treatment process parameters to obtain graphene-reinforced aluminum-based gradient composite materials with gradient nanostructures with different structural parameter characteristics, thereby controlling the material cost and mechanical, thermal and electrical properties.

[0021] IV. The surface hardness of the graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure prepared by this invention can reach 70–90 HV, which is more than 100% higher than that of the aluminum matrix; the thermal conductivity can reach 240–282 W / (m·K), which is 2%–20% higher than that of the aluminum matrix; and the electrical conductivity can reach up to 3.9 × 10⁻⁶. 7 S / m, 5% higher than that of aluminum matrix. Attached Figure Description

[0022] Figure 1 The image shows a microstructure of a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure prepared in Example 1. (a) is a cross-sectional view and (b) is a surface view.

[0023] Figure 2 The microhardness gradient is shown in Example 1 for a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure. Detailed Implementation

[0024] Specific Implementation Method 1: This implementation method provides a method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure, specifically completed according to the following steps:

[0025] I. Surface mechanical milling treatment:

[0026] The Al plate is subjected to surface mechanical milling in a direction perpendicular to the plane to obtain an Al plate with a working groove with a depth of 0.1 mm to 1 mm;

[0027] II. Electrophoretic deposition of GO:

[0028] Electrophoretic deposition of GO was performed on an Al plate with a working groove of 0.1 mm to 1 mm depth, followed by drying, to obtain a GO / Al substrate with a GO deposition layer.

[0029] III. Preparation of GO / Al prefabricated panels;

[0030] ① Perform alkaline washing on another Al plate with the same length and width as the Al plate described in step one to obtain a surface-pretreated Al plate;

[0031] ② Cover the surface-pretreated Al plate onto the GO / Al substrate with the GO deposition layer, so that the GO deposition layer is in contact with the surface-pretreated Al plate, then use Al foil to wrap it, and finally roll it to obtain the GO / Al preform.

[0032] IV. Surface mechanical treatment:

[0033] By applying a load of 300N to 1000N in the direction perpendicular to the plane of the GO / Al preform and feeding at a rate of 0.5 to 5 mm / s in the direction parallel to the plane of the GO / Al preform multiple times for pressure friction treatment, and rotating the pressure friction head at a speed of 0 to 600 rpm, a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure is obtained.

[0034] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the thickness of the Al plate mentioned in step one is 2mm to 8mm. The other steps are the same as in Specific Implementation Method One.

[0035] Specific Implementation Method Three: This implementation method differs from Specific Implementation Method One or Two in that the width and length of the working groove described in step one are processed according to the design dimensions. The other steps are the same as in Specific Implementation Method One or Two.

[0036] Specific Implementation Method Four: This implementation method differs from Specific Implementation Methods One to Three in that the electrophoretic deposition of GO in step two is as follows: An Al plate with a working tank having a depth of 0.1 mm to 1 mm is immersed in the deposition solution, and deposition is performed for 10 s to 240 s under conditions of a voltage of 100V to 150V and the working tank facing the electrode plate. The Al plate is then removed and dried to obtain a GO / Al substrate with a GO deposition layer. Other steps are the same as in Specific Implementation Methods One to Three.

[0037] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that the deposition solution is a mixture of graphene, Al(NO3)3, and anhydrous ethanol, wherein the mass-to-volume ratio of graphene, Al(NO3)3, and anhydrous ethanol is (0.2g~0.5g):(0.05g~0.2g):400mL. The other steps are the same as in Specific Implementation Methods One to Four.

[0038] Specific Implementation Method Six: The difference between this implementation method and Specific Implementation Methods One to Five is that the alkaline washing process described in step three① is as follows: the Al plate is immersed in a 5% NaOH solution for 5 to 10 seconds, then rinsed with water until neutral, and then dried to obtain a surface-pretreated Al plate. Other steps are the same as in Specific Implementation Methods One to Five.

[0039] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the thickness of the Al plate used for surface pretreatment in step three① is 0.2mm to 1mm. The other steps are the same as in Specific Implementation Methods One to Six.

[0040] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that the thickness of the Al foil mentioned in step three, step two, is 0.01 mm to 0.05 mm. The other steps are the same as in Specific Implementation Methods One to Seven.

[0041] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the rolling temperature in step three ② is 25℃~200℃, and the deformation during rolling is 30%~80%. The other steps are the same as in Specific Implementation Methods One to Eight.

[0042] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One to Nine in that the number of pressure friction treatments described in step four is 1 to 100 times. The other steps are the same as in Specific Implementation Methods One to Nine.

[0043] The technical effects of the present invention are verified using the following embodiments:

[0044] Example 1: A method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure, specifically completed according to the following steps:

[0045] I. Surface mechanical milling treatment:

[0046] The surface is mechanically milled in a direction perpendicular to the plane of the Al plate to obtain an Al plate with a working groove;

[0047] The dimensions of the Al plate mentioned in step one are 50mm × 100mm × 4mm;

[0048] The working groove mentioned in step one has a length of 90mm, a width of 44mm, and a depth of 0.2mm;

[0049] II. Electrophoretic deposition of GO:

[0050] Electrophoretic deposition of GO was performed on an Al plate with a working tank, followed by drying, to obtain a GO / Al substrate with a GO deposition layer;

[0051] The electrophoretic deposition of GO in step two is as follows: an Al plate with a working tank is immersed in the deposition solution, and deposition is carried out for 60 seconds under the condition of 110V voltage and the working tank facing the electrode plate. Then the Al plate is taken out and placed in a vacuum drying oven to dry, thereby obtaining a GO / Al substrate with a GO deposition layer. The deposition solution is a mixture of graphene, Al(NO3)3 and anhydrous ethanol, wherein the mass-volume ratio of graphene, Al(NO3)3 and anhydrous ethanol is 0.3g:0.1g:400mL.

[0052] III. Preparation of GO / Al prefabricated panels;

[0053] ① An Al plate of the same size as the Al plate described in step one is subjected to alkaline washing to obtain a surface-pretreated Al plate;

[0054] The alkaline washing process described in step 3① is as follows: the Al plate is immersed in a 5% NaOH solution for 5 seconds, then rinsed with water until neutral, and then dried to obtain a surface-pretreated Al plate.

[0055] The dimensions of the Al plate used for surface pretreatment in step 3① are 50mm × 100mm × 0.5mm;

[0056] ② Cover the surface-pretreated Al plate onto the GO / Al substrate with the GO deposition layer, so that the GO deposition layer is in contact with the surface-pretreated Al plate, then use Al foil to wrap it, and finally roll it to obtain the GO / Al preform.

[0057] The thickness of the Al foil mentioned in step 3② is 0.01 mm;

[0058] The rolling temperature in step 3② is 25℃, and the deformation during rolling is 50%.

[0059] IV. Surface mechanical treatment:

[0060] A graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure was obtained by applying a load of 500 N perpendicular to the plane of the GO / Al preform and feeding at a rate of 1 mm / s parallel to the plane of the GO / Al preform multiple times with pressure friction treatment and a pressure friction head rotation speed of 600 rpm.

[0061] The pressure friction treatment described in step four is performed twice.

[0062] Example 2: The difference between this example and Example 1 is that the length of the working tank in step one is 90mm, the width is 44mm, and the depth is 0.5mm; in step two, deposition is carried out for 150s under the conditions of 110V voltage and the working tank facing the electrode plate; the dimensions of the Al plate for surface pretreatment in step three① are 50mm×100mm×1mm. All other steps and parameters are the same as in Example 1.

[0063] Example 3: The difference between this example and Example 1 is as follows: In step two, the electrophoretic deposition of GO is performed by immersing an Al plate with a working tank into the deposition solution and depositing for 30 seconds under conditions of 120V voltage and the working tank facing the electrode plate. In step four, a load of 500N is applied in the direction perpendicular to the plane of the GO / Al preform, and the feed rate in the direction parallel to the plane of the GO / Al preform is 0.5mm / s for multiple pressure friction treatments. The pressure friction head rotates at 300rpm, and the number of pressure friction treatments in step four is 10 times, resulting in a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure. Other steps and parameters are the same as in Example 1.

[0064] Comparison with Example 1: The difference between this embodiment and Example 1 is that step two, i.e., the electrophoretic deposition of GO, is omitted. All other steps and parameters are the same as in Example 1.

[0065] Comparison with Example 2: The difference between this embodiment and Example 1 is that step four, i.e., the surface mechanical treatment, is omitted. All other steps and parameters are the same as in Example 1.

[0066] The surface hardness, thermal conductivity, and electrical conductivity of the graphene-reinforced aluminum-based gradient composite materials with gradient nanostructures prepared in Examples 1-3 and Comparative Examples 1-2 are listed in Table 1.

[0067] Table 1

[0068]

Claims

1. A method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure, characterized in that... The preparation method is specifically carried out according to the following steps: I. Surface mechanical milling treatment: The Al plate is subjected to surface mechanical milling in a direction perpendicular to the plane to obtain an Al plate with a working groove with a depth of 0.1 mm to 1 mm; II. Electrophoretic deposition of GO: Electrophoretic deposition of GO was performed on an Al plate with a working groove of 0.1 mm to 1 mm depth, followed by drying, to obtain a GO / Al substrate with a GO deposition layer. III. Preparation of GO / Al preforms; ① Perform alkaline washing on another Al plate with the same length and width as the Al plate described in step one to obtain a surface-pretreated Al plate; ② Cover the surface-pretreated Al plate onto the GO / Al substrate with the GO deposition layer, so that the GO deposition layer is in contact with the surface-pretreated Al plate, then use Al foil to wrap it, and finally roll it to obtain the GO / Al preform. IV. Surface mechanical treatment: By applying a load of 300N to 1000N in the direction perpendicular to the plane of the GO / Al preform and feeding at a rate of 0.5 to 5 mm / s in the direction parallel to the plane of the GO / Al preform multiple times for pressure friction treatment, and rotating the pressure friction head at a speed of 0 to 600 rpm, a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure is obtained.

2. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The thickness of the Al plate mentioned in step one is 2mm to 8mm.

3. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The width and length of the working groove mentioned in step one are manufactured according to the design dimensions.

4. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The electrophoretic deposition of GO described in step two is as follows: an Al plate with a working tank of 0.1 mm to 1 mm depth is immersed in the deposition solution, and deposition is carried out for 10 to 240 seconds under the conditions of a voltage of 100 V to 150 V and the working tank facing the electrode plate. The Al plate is then removed, dried, and a GO / Al substrate with a GO deposition layer is obtained.

5. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 4, characterized in that... The deposition solution is a mixture of graphene, Al(NO3)3 and anhydrous ethanol, wherein the mass-volume ratio of graphene, Al(NO3)3 and anhydrous ethanol is (0.2g~0.5g):(0.05g~0.2g):400mL.

6. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The alkaline washing process described in step 3① is as follows: Immerse the Al plate in a 5% NaOH solution for 5 to 10 seconds, remove it, rinse it with water until neutral, and then dry it to obtain a surface-pretreated Al plate.

7. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The thickness of the Al plate used for surface pretreatment in step 3① is 0.2mm to 1mm.

8. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The thickness of the Al foil mentioned in step 3② is 0.01mm to 0.05mm.

9. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The rolling temperature described in step 3② is 25℃~200℃, and the deformation during rolling is 30%~80%.

10. The method for preparing a graphene-reinforced aluminum-based gradient composite material with a gradient nanostructure according to claim 1, characterized in that... The pressure friction treatment described in step four is performed 1 to 100 times.

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