CN110117810B - Method for preparing modified graphene oxide aluminum composite heat conduction material through electrophoresis - Google Patents
Method for preparing modified graphene oxide aluminum composite heat conduction material through electrophoresis Download PDFInfo
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- CN110117810B CN110117810B CN201910500732.XA CN201910500732A CN110117810B CN 110117810 B CN110117810 B CN 110117810B CN 201910500732 A CN201910500732 A CN 201910500732A CN 110117810 B CN110117810 B CN 110117810B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
Abstract
The invention provides a method for preparing a modified graphene oxide aluminum composite heat conduction material by electrophoresis, and belongs to the technical field of composite materials. Firstly, modifying the surface of graphene oxide by using a silane coupling agent to obtain a silane coupling agent-graphene oxide product, and then reacting the silane coupling agent-graphene oxide product with hydrazine hydrate to prepare a silane coupling agent-reduced graphene oxide; and finally, preparing a layer of controllable silane coupling agent modified graphene/aluminum composite material on the conductive matrix aluminum by adopting an electrophoretic deposition method. The silane coupling agent modified graphene/aluminum composite material prepared by the invention is uniform in distribution, does not contain other impurities, can obviously improve the thermal conductivity of an aluminum matrix, and has potential application value in heat dissipation materials.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of composite materials, in particular to a method for preparing a modified graphene oxide aluminum composite heat conduction material by electrophoresis.
[ background of the invention ]
With the development of science and technology, the requirement on equipment power is higher and higher, the heat dissipation problem of electronic devices becomes a serious problem for people, and the heat dissipation problem relates to the fields and industries of numerous national economy pillars such as smart grids, electric power engineering, transportation, industrial electrodes, wind power, solar energy and the like. Graphene is the best two-dimensional carbon material found at present, and the theoretical specific surface area is as high as 2600m2g-1And has excellent electrical performance (carrier mobility of 15000 cm)2V · s) (room temperature). In addition, graphene is the material with the highest thermal conductivity at present, the thermal conductivity coefficient of graphene is as high as 3000W/(m · K), the thermal conductivity of the composite material obtained simply by compounding metal and graphene at present is not good, and the essence is that graphene is a two-dimensional layered carbon material, and the layers are connected by weak van der waals force. Metal is an inorganic material, and metal atoms are bonded by metal bonds. Thus, the interaction between graphene and metal tends to be a weak van der waals force. Neither electrons nor phonons, which are conductive to heat, can be transported by van der waals forces, resulting in a large thermal resistance between the metal and the graphene. Silane Coupling Agents (SCAs) are the most common coupling agent materials that react with both inorganic (e.g., metals) and organic materials (e.g., resins). By means of the affinity property of the silane coupling agent with metal and graphene, a strong covalent bond can be constructed between the metal and the graphene, the transmission capability of phonons between the graphene and the metal is improved, and therefore the heat conduction capability of the graphene/metal composite heat conduction material can be greatly improved. Electrophoretic deposition (EPD) is an electrochemical deposition method, and is widely used in material processing due to its advantages of low cost, good versatility, easy combination with other preparation methods, etc. The graphene-based aluminum alloy heat-conducting composite material is synthesized by utilizing graphene oxide (graphene oxide) and a silane coupling agent through electrophoretic deposition, and is an effective way for improving the heat dissipation capacity of an aluminum alloy-based material.
[ summary of the invention ]
The invention aims to: aiming at the problems, the invention provides a method for preparing a modified graphene oxide aluminum composite heat conduction material by electrophoresis, wherein silane coupling agent is adopted to modify the surface of graphene oxide, and the surface-modified redox graphene is prepared by reaction with hydrazine hydrate; and finally, preparing a layer of controllable silane coupling agent modified graphene/aluminum composite material on the conductive matrix aluminum by adopting an electrophoretic deposition method. The prepared silane coupling agent modified graphene/aluminum composite material is uniform in distribution, does not contain other impurities, and has potential application value in heat dissipation materials.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a modified graphene oxide aluminum composite heat conduction material by electrophoresis comprises the following steps:
(1) mixing graphene oxide with ultrapure water to obtain a dispersion liquid A, adding a silane coupling agent into the dispersion liquid A, heating to 70-90 ℃ under stirring, and fully and uniformly mixing to obtain a mixture A;
(2) vacuum filtering the uniformly mixed mixture A obtained in the step (1), cleaning the filtered product, and drying the obtained product in a vacuum oven at 70-90 ℃ to obtain a silane coupling agent-graphene oxide product;
(3) adding water into a silane coupling agent-graphene oxide product to obtain a dispersion liquid B, mixing the dispersion liquid B with hydrazine hydrate, and stirring in an aqueous solution at 85-95 ℃ for reduction to obtain a mixture B;
(4) vacuum-filtering and cleaning the mixture B obtained in the step (3), and drying the obtained product in a vacuum oven at 70-90 ℃ to obtain a silane coupling agent-reduced graphene oxide product;
(5) degreasing the aluminum matrix in degreasing liquid, and cleaning with deionized water; activating the deoiled aluminum matrix in an activating solution, and then cleaning the aluminum matrix with deionized water;
(6) subjecting the aluminum substrate treated in the step (5) to pulse electrophoresis in an electrophoretic deposition electrophoresis solution for 5-20 minutes at a current density of 0.5-2.5A/dm2The polar distance is 3cm, and the silane coupling agent-reduced graphene oxide/aluminum composite is prepared by electrophoretic depositionCombining materials; wherein, the electrophoretic deposition electrophoretic fluid is: 0.3-0.4g/L, TW-601-1.5 mg/L of silver nitrate and 0.5-0.7g/L of silane coupling agent-reduced graphene oxide;
(7) and (4) drying the modified reduced graphene oxide/aluminum composite material treated in the step (6) to obtain a final product.
In the present invention, preferably, in the dispersion liquid a in the step (1), the mass concentration of graphene oxide is 0.1-0.2%; the silane coupling agent is KH550 with the concentration of 5.5-6.3g/L, and the pH is adjusted to 4.0 by acetic acid; the volume ratio of the silane coupling agent to the dispersion liquid A is 2-3: 400-500.
In the present invention, preferably, in the dispersion liquid B in the step (3), the mass ratio of the silane coupling agent-graphene oxide to water is 1-2: 200-260, the volume ratio of hydrazine hydrate to the dispersion liquid B is 1-2: 200-260.
In the present invention, it is preferable that the pore size of the filter paper is 0.45 μm when vacuum-filtering in the steps (2) and (4).
In the invention, preferably, the deoiling liquid in the step (5) is a mixed liquid containing 30-80g/L of trisodium phosphate, 20-60g/L of sodium carbonate and 1.0-2.0g/L of Op-10 emulsifier; when oil is removed, the temperature of the oil removing liquid is 55-65 ℃, and the oil removing time is 2 minutes.
In the invention, the activating solution is preferably 40-50g/L sodium hydroxide, and the activating time is preferably 2 minutes.
In the present invention, preferably, the power supply parameters of the pulse electrophoresis in step (7) are: the frequency is 10Hz, the forward current is 0.15A, the reverse current is 0.05A, the forward direction is 97ms, the reverse direction is 3ms, and the duty ratio is 100%.
In the present invention, preferably, the drying in steps (2), (4) and (7) is performed in a vacuum oven at 75-85 ℃ for 3-5 hours, and the step of irradiating the composite material with an infrared lamp in air for natural drying is further included before the vacuum drying in step (7).
The invention also provides the modified graphene oxide aluminum composite heat conduction material prepared by the method, and the composite material can be applied to preparation of heat conduction materials.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, a layer of silane coupling agent modified graphene composite material is controllably prepared on the conductive substrate by using an electrophoretic deposition mode, and an Al-O-Si-O-C covalent bond is constructed between the aluminum substrate and the reduced graphene oxide, so that the interface thermal resistance can be effectively reduced, the prepared silane coupling agent modified graphene/aluminum composite material has a higher thermal conductivity coefficient, and the thermal conductivity of the material is improved.
2. According to the invention, ultrapure water is used as a dispersing agent to disperse graphene oxide, and compared with the prior art in which an organic solvent is used, the preparation cost is reduced and the harm of the organic solvent to a human body in the preparation process is reduced on the premise that the performance of the material can be maintained.
3. The silane coupling agent modified graphene/aluminum composite material prepared by the invention also has better corrosion resistance.
[ description of the drawings ]
FIG. 1 is a schematic structural diagram of an electrophoretic deposition cell in an embodiment;
fig. 2 is a Raman spectrum (Raman) of the silane coupling agent graphene/aluminum composite material obtained in the example;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the silane coupling agent graphene/aluminum composite material obtained in the example;
FIG. 4 is an infrared spectrum (FTIR) of the silane coupling agent graphene/aluminum composite material obtained in the example;
FIG. 5 is a Tafel plot of the silane coupling agent graphene/aluminum composite material obtained in the example tested in a 3.5% sodium chloride solution;
FIG. 6 is an X-ray photoelectron spectrum (XPS) of the silane coupling agent graphene/aluminum composite material obtained in the example;
fig. 7 is a graph of thermal conductivity of the silane coupling agent graphene/aluminum composite obtained in example 2 and comparative example 3.
Fig. 8 is a graph of thermal conductivity of the silane coupling agent graphene/aluminum composite materials obtained in comparative example 1 and comparative example 2.
[ detailed description ] embodiments
In order that the invention may be more clearly expressed, the invention will now be further described by way of specific examples.
Example 1
A method for preparing a modified graphene oxide aluminum composite heat conduction material by electrophoresis comprises the following steps:
(1) mixing graphene oxide with ultrapure water to obtain a dispersion liquid A, wherein the mass concentration of the graphene oxide in the dispersion liquid A is 0.1%; adding a silane coupling agent into the dispersion liquid A, wherein the silane coupling agent adopts KH550 with the concentration of 5.5g/L, acetic acid is used for adjusting the pH value to 4.0 before use to achieve the best hydrolysis effect, and the volume ratio of the silane coupling agent to the dispersion liquid A is 2: 400, heating to 70 ℃ under magnetic stirring, and keeping stirring for 4 hours to fully mix the mixture uniformly to obtain a mixture A;
(2) vacuum filtering the uniformly mixed mixture A obtained in the step (1) by using filter paper with the aperture of 0.45 micrometer, cleaning a filtered product, and drying the obtained product in a vacuum oven at 70 ℃ for 5 hours to obtain a silane coupling agent-graphene oxide product;
(3) adding water into a silane coupling agent-graphene oxide product to obtain a dispersion liquid B, wherein in the dispersion liquid B, the mass ratio of the silane coupling agent-graphene oxide to the water is 1: 200 of a carrier; adding hydrazine hydrate into the dispersion liquid B, wherein the volume ratio of the hydrazine hydrate to the dispersion liquid B is 1-2: 200, and then stirring the mixture forcibly at the temperature of 90 ℃ for reduction to obtain a mixture B;
(4) performing vacuum filtration on the mixture B in the step (3) by using filter paper with the pore diameter of 0.45 micrometer, cleaning, and drying the obtained product in a vacuum oven at 70 ℃ for 5 hours to obtain a silane coupling agent-reduced graphene oxide product;
(5) deoiling an aluminum matrix in deoiling liquid, wherein the deoiling liquid is mixed liquid containing 30g/L of trisodium phosphate, 60g/L of sodium carbonate and 1.0g/L of Op-10 emulsifier; when oil is removed, the temperature of the oil removing liquid is 55 ℃, and the oil removing time is 2 minutes; cleaning with deionized water after oil removal; activating the deoiled aluminum matrix in an activating solution, wherein the activating solution is 40g/L sodium hydroxide, the activating time is 2 minutes, and then cleaning the aluminum matrix by using deionized water;
(6) subjecting the aluminum matrix treated in the step (5) to electrophoresis precipitationPulse electrophoresis in the electrophoresis solution for 5 minutes, wherein the electrophoresis is carried out by using the device shown in figure 1, and the current density is 2.5A/dm2The polar distance is 3cm, the frequency is 10Hz, the forward current is 0.15A, the reverse current is 0.05A, the forward direction is 97ms, the reverse direction is 3ms, the duty ratio is 100 percent, and the silane coupling agent-reduced graphene oxide/aluminum composite material is prepared by electrophoretic deposition; wherein, the electrophoretic deposition electrophoretic fluid is: 0.3g/L, TW-601.2 mg/L of silver nitrate and 0.6g/L of silane coupling agent-reduced graphene oxide, and it can be seen from FIG. 1 that a layer of black film is covered on the surface of the silane coupling agent-reduced graphene oxide/aluminum composite material after electrophoretic deposition;
(7) and (3) irradiating and drying the silane coupling agent-reduced graphene oxide/aluminum composite material treated in the step (6) for 1 hour by using an infrared lamp, drying in a vacuum oven at the temperature of 75 ℃ for 5 hours, and drying to obtain a final product.
Example 2
A method for preparing a modified graphene oxide aluminum composite heat conduction material by electrophoresis comprises the following steps:
(1) mixing graphene oxide with ultrapure water to obtain a dispersion liquid A, wherein the mass concentration of the graphene oxide in the dispersion liquid A is 0.1%; adding a silane coupling agent into the dispersion liquid A, wherein the silane coupling agent adopts KH550 with the concentration of 6.0g/L, acetic acid is used for adjusting the pH value to 4.0 before use to achieve the best hydrolysis effect, and the volume ratio of the silane coupling agent to the dispersion liquid A is 3: 500, heating to 80 ℃ under magnetic stirring, and keeping stirring for 4 hours to fully mix the mixture uniformly to obtain a mixture A;
(2) vacuum filtering the uniformly mixed mixture A obtained in the step (1) by using filter paper with the aperture of 0.45 micrometer, cleaning a filtered product, and drying the obtained product in a vacuum oven at 80 ℃ for 4 hours to obtain a silane coupling agent-graphene oxide product;
(3) adding water into a silane coupling agent-graphene oxide product to obtain a dispersion liquid B, wherein in the dispersion liquid B, the mass ratio of the silane coupling agent-graphene oxide to the water is 1: 200 of a carrier; adding hydrazine hydrate into the dispersion liquid B, wherein the volume ratio of the hydrazine hydrate to the dispersion liquid B is 1-2: 200, and then stirring the mixture forcibly at the temperature of 90 ℃ for reduction to obtain a mixture B;
(4) performing vacuum filtration on the mixture B in the step (3) by using filter paper with the pore diameter of 0.45 micrometer, cleaning, and drying the obtained product in a vacuum oven at 80 ℃ for 4 hours to obtain a silane coupling agent-reduced graphene oxide product;
(5) deoiling an aluminum matrix in deoiling liquid, wherein the deoiling liquid is mixed liquid containing 50g/L of trisodium phosphate, 50g/L of sodium carbonate and 1.5g/L of Op-10 emulsifier; when oil is removed, the temperature of the oil removing liquid is 60 ℃, and the oil removing time is 2 minutes; cleaning with deionized water after oil removal; activating the deoiled aluminum matrix in an activating solution, wherein the activating solution is 45g/L sodium hydroxide, the activating time is 2 minutes, and then cleaning the aluminum matrix by using deionized water;
(6) subjecting the aluminum substrate treated in step (5) to pulse electrophoresis in an electrophoretic deposition solution for 15 minutes, wherein the electrophoresis is carried out by using the device shown in FIG. 1 and the current density is 1.5A/dm2The polar distance is 3cm, the frequency is 10Hz, the forward current is 0.15A, the reverse current is 0.05A, the forward direction is 97ms, the reverse direction is 3ms, the duty ratio is 100 percent, and the silane coupling agent-reduced graphene oxide/aluminum composite material is prepared by electrophoretic deposition; wherein, the electrophoretic deposition electrophoretic fluid is: 0.3g/L, TW-601 mg/L of silver nitrate and 0.5g/L of silane coupling agent-reduced graphene oxide, and it can be seen from FIG. 1 that a layer of black film is covered on the surface of the silane coupling agent-reduced graphene oxide/aluminum composite material after electrophoretic deposition;
(7) and (3) irradiating and drying the silane coupling agent-reduced graphene oxide/aluminum composite material treated in the step (6) for 1-2 hours by using an infrared lamp, drying in a vacuum oven at the temperature of 75-85 ℃ for 3-5 hours, and drying to obtain a final product.
Example 3
A method for preparing a modified graphene oxide aluminum composite heat conduction material by electrophoresis comprises the following steps:
(1) mixing graphene oxide with ultrapure water to obtain a dispersion liquid A, wherein the mass concentration of the graphene oxide in the dispersion liquid A is 0.2%; adding a silane coupling agent into the dispersion liquid A, wherein the silane coupling agent adopts KH550 with the concentration of 6.3g/L, acetic acid is used for adjusting the pH value to 4.0 before use to achieve the best hydrolysis effect, and the volume ratio of the silane coupling agent to the dispersion liquid A is 2: 500, heating to 90 ℃ under magnetic stirring, and keeping stirring for 4 hours to fully mix the mixture uniformly to obtain a mixture A;
(2) vacuum filtering the uniformly mixed mixture A obtained in the step (1) by using filter paper with the aperture of 0.45 micrometer, cleaning a filtered product, and drying the obtained product in a vacuum oven at 90 ℃ for 3 hours to obtain a silane coupling agent-graphene oxide product;
(3) adding water into a silane coupling agent-graphene oxide product to obtain a dispersion liquid B, wherein in the dispersion liquid B, the mass ratio of the silane coupling agent-graphene oxide to the water is 2: 260 of a nitrogen atom; adding hydrazine hydrate into the dispersion liquid B, wherein the volume ratio of the hydrazine hydrate to the dispersion liquid B is 2: 260, and then stirring vigorously at the temperature of 90 ℃ for reduction to obtain a mixture B;
(4) performing vacuum filtration on the mixture B in the step (3) by using filter paper with the pore diameter of 0.45 micrometer, cleaning, and drying the obtained product in a vacuum oven at 90 ℃ for 3 hours to obtain a silane coupling agent-reduced graphene oxide product;
(5) deoiling an aluminum matrix in deoiling liquid, wherein the deoiling liquid is mixed liquid containing 80g/L of trisodium phosphate, 20g/L of sodium carbonate and 2.0g/L of Op-10 emulsifier; when oil is removed, the temperature of the oil removing liquid is 65 ℃, and the oil removing time is 2 minutes; cleaning with deionized water after oil removal; activating the deoiled aluminum matrix in an activating solution, wherein the activating solution is 50g/L of sodium hydroxide, the activating time is 2 minutes, and then cleaning the aluminum matrix by using deionized water;
(6) subjecting the aluminum substrate treated in step (5) to pulse electrophoresis in an electrophoretic deposition solution for 20 minutes, wherein the electrophoresis is carried out by using the apparatus shown in FIG. 1 and the current density is 2.5A/dm2The polar distance is 3cm, the frequency is 10Hz, the forward current is 0.15A, the reverse current is 0.05A, the forward direction is 97ms, the reverse direction is 3ms, the duty ratio is 100 percent, and the silane coupling agent-reduced graphene oxide/aluminum composite material is prepared by electrophoretic deposition; wherein, the electrophoretic deposition electrophoretic fluid is: 0.3g/L, TW-601.5 mg/L of silver nitrate and 0.7g/L of silane coupling agent-reduced graphene oxide, and it can be seen from FIG. 1 that a layer of black film is covered on the surface of the silane coupling agent-reduced graphene oxide/aluminum composite material after electrophoretic deposition;
(7) and (3) irradiating and drying the silane coupling agent-reduced graphene oxide/aluminum composite material treated in the step (6) for 2 hours by using an infrared lamp, drying in a vacuum oven at 85 ℃ for 3 hours, and drying to obtain a final product.
Comparative example 1
1) Taking graphene oxide, ultrasonically dispersing the graphene oxide into dimethylformamide, and preparing graphene oxide dispersion liquid with the mass concentration of 0.1% for later use;
2) uniformly mixing graphene oxide dispersion liquid and a silane coupling agent KH550 in a volume ratio of 1:15, controlling the temperature of 80-90 ℃ in a water bath, stirring for reaction for 20-24 hours, and performing ultrasonic dispersion to obtain a silane coupling agent grafted graphene oxide solution for later use;
3) uniformly mixing a silane coupling agent grafted graphene oxide solution and a reducing agent hydrazine hydrate in a volume ratio of 45:1, controlling the temperature of 90 ℃ in a water bath, and stirring for reaction for 20 hours to obtain a silane coupling agent grafted graphene solution for later use;
4) uniformly mixing deionized water and alcohol in a volume ratio of 1:6 to obtain an aqueous solution, adjusting the pH value to 7 in advance, and mixing deionized water and alcohol in a volume ratio of 1: 5, uniformly mixing the silane coupling agent grafted graphene solution and the alcohol-water solution, controlling the temperature at 45 ℃, carrying out hydrolysis reaction for 3 hours, and cooling to room temperature to obtain graphene/silane coupling agent treatment liquid for later use;
5) polishing, deoiling, washing, hydroxylating the surface of an aluminum substrate and drying for later use; the surface hydroxylation refers to immersing the aluminum matrix in a 0.5 mass percent NaOH solution for 2 minutes.
6) And (3) immersing the aluminum substrate into the graphene/silane coupling agent treatment solution for 250s, and drying to obtain the graphene/silane molecular self-assembly material on the surface of the aluminum.
Comparative example 2
Compared with comparative example 1, the difference is that the silane coupling agent-graphene oxide product is not subjected to hydrazine hydrate reduction treatment, i.e., the silane coupling agent-graphene oxide/aluminum composite material is prepared by an immersion method.
Comparative example 3
Compared with the embodiment 2, the difference lies in that hydrazine hydrate reduction treatment is not carried out on the silane coupling agent-graphene oxide product, and the electrophoresis solution adopted during electrophoresis is a mixed solution containing 0.3g/L, TW-6010 mg/L of silver nitrate and 0.5g/L of silane coupling agent-graphene oxide, so as to prepare the silane coupling agent modified graphene oxide/aluminum composite material.
Performance testing
(1) And (3) Raman spectrum testing:
raman spectrum tests were performed on raw material unmodified graphene oxide, KH 540-graphene oxide prepared in example 2, and KH540-r graphene oxide prepared in comparative example 3 (i.e., silane coupling agent-reduced graphene oxide, the same applies to below), respectively, and the test results are shown in fig. 2, which shows that the peak positions of the D peak and the G peak were hardly changed in graphene oxide, KH 540-graphene oxide, and KH540-r graphene oxide. KH540-r graphene oxide (ID/IG ═ 0.960) has an ID/IG greater than that of graphene oxide (ID/IG ═ 0.907). Due to the reduced oxygen content of the reduced graphene oxide, the structure tends to be ordered.
(2) Analysis by scanning Electron microscope
Scanning electron microscope analysis is respectively carried out on unmodified graphene oxide, KH 540-graphene oxide prepared in example 2 and KH540-r graphene oxide prepared in comparative example 3, and the test results are shown in figure 3, which shows that the surface of the graphene oxide is smooth and flaky, and the graphene composite modified by KH550 has small protrusions with different degrees, which shows that the roughness of KH 550-graphene oxide/Al and KH550-r graphene oxide/Al is obviously increased after KH550 modification.
(3) FTIR spectroscopic analysis
FTIR spectra of KH 550-graphene oxide, KH 550-reduced graphene oxide and KH 550-reduced graphene oxide/Al prepared in example 2 were analyzed, and the results are shown in FIG. 4, wherein C-N (1385 cm in each FTIR spectrum) existed in KH 550-graphene oxide, KH 550-reduced graphene oxide and KH 550-reduced graphene oxide/Al-1，1384cm-1And 1384cm-1) This illustrates the incorporation of a silane coupling agent. Furthermore, KH 550-reduced graphene oxide/Al was found at 1033cm-1，1055cm-1Additional tensile vibration peaks are shown, demonstrating the formation of Si-O-Al bonds. Considering Si-O-C (688 cm)-1) In the presence of the catalyst, we can obtain the success in KH 550-reduction of graphene oxide/AlAnd constructing a conclusion of the Al-O-Si-O-C covalent bond.
(4) Corrosion resistance
Electrochemical tests are respectively carried out on an aluminum alloy matrix, the silane coupling agent-reduced graphene oxide/aluminum composite material prepared in the example 2 and the silane coupling agent modified graphene oxide/aluminum composite material prepared in the comparative example 3 in a 3.5% sodium chloride solution, the tafel curve in fig. 5 shows that the corrosion resistance of the silane coupling agent modified graphene oxide/aluminum composite material is obviously enhanced, and the silane coupling agent-reduced graphene oxide/aluminum composite material prepared in the example 2 has the best corrosion resistance.
(5) XPS spectral analysis
The KH 550-graphene oxide, KH 550-reduced graphene oxide and KH 550-reduced graphene oxide/Al prepared in example 2 were analyzed by XPS spectrum, and the results are shown in FIG. 6, wherein Al 2p in XPS spectrum indicates the existence of Al-O bond, directly demonstrating the formation of Al-O-Si covalent bond between Al and KH 550. The Si 2p spectrum can show that a Si-O-C covalent bond (101.6eV) component is formed in KH550-GO/Al and KH550-rGO/Al, and the structure of a metal-carbon interface and a covalent bond is confirmed. XPS results confirm the successful construction of the Al-O-Si-O-C covalent bond, which can be attributed to the coexistence of Si-O-C covalent bonds and Al-O-Si covalent bonds.
(6) Test of Heat conductivity
The aluminum substrate, the composite materials prepared in example 2 and comparative examples 1 to 4 were prepared to a specification of 0.2mm × 10mm × 10mm, the thermal conductivity of the sample was measured in a thermal conductivity tester, and the thermal conductivity of each material was analyzed, and the results are shown in fig. 7 to 8, respectively.
Referring to fig. 7, which is a graph comparing thermal conductivity of the aluminum matrix, the composites prepared in example 2 and comparative example 3, it is apparent from fig. 7 that the reduced graphene oxide composite modified with KH550 has the highest thermal conductivity compared to other samples. Secondly, the heat conductivity coefficients of KH550-rGO/Al are respectively 212.6W/mK, 201.2W/mK, 201.0W/mK and 202.4W/mK at 50 ℃, 100 ℃, 150 ℃ and 200 ℃, which are respectively improved by 9.5%, 5.2%, 7.5% and 18.8% compared with the Al matrix at corresponding temperatures.
See fig. 8, which is a graph comparing the thermal conductivity of the aluminum matrix, the composites prepared in comparative examples 1 and 2. It can be seen that the thermal conductivity of the reduced graphene oxide composite modified with KH550 is also the highest compared to the other samples.
Comparing fig. 7 and fig. 8, it can be seen that the composite material obtained by the electrophoresis method has a higher thermal conductivity than the composite material obtained by the immersion method, and the thermal conductivity of the KH550 modified reduced graphene oxide composite material prepared by the immersion method is 196W/m · K, 187W/m · K, 185W/m · K and 177W/m · K respectively at 50 ℃, 100 ℃, 150 ℃ and 200 ℃, and is lower than the thermal conductivity of the composite material obtained by the embodiment of the present invention at the corresponding temperatures.
The above description is intended to describe in detail the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the claims of the present invention, and all equivalent changes and modifications made within the technical spirit of the present invention should fall within the scope of the claims of the present invention.
Claims (10)
1. A method for preparing a modified graphene oxide aluminum composite heat conduction material through electrophoresis is characterized by comprising the following steps:
(1) mixing graphene oxide with ultrapure water to obtain a dispersion liquid A, adding a silane coupling agent into the dispersion liquid A, heating to 70-90 ℃ under stirring, and fully and uniformly mixing to obtain a mixture A;
(2) vacuum filtering the uniformly mixed mixture A obtained in the step (1), cleaning the filtered product, and drying the obtained product in a vacuum oven at 70-90 ℃ to obtain a silane coupling agent-graphene oxide product;
(3) adding water into a silane coupling agent-graphene oxide product to obtain a dispersion liquid B, mixing the dispersion liquid B with hydrazine hydrate, and stirring in an aqueous solution at 85-95 ℃ for reduction to obtain a mixture B;
(4) vacuum-filtering and cleaning the mixture B obtained in the step (3), and drying the obtained product in a vacuum oven at 70-90 ℃ to obtain a silane coupling agent-reduced graphene oxide product;
(5) degreasing the aluminum matrix in degreasing liquid, and cleaning with deionized water; activating the deoiled aluminum matrix in an activating solution, and then cleaning the aluminum matrix with deionized water;
(6) subjecting the aluminum substrate treated in the step (5) to pulse electrophoresis in an electrophoretic deposition electrophoresis solution for 5-20 minutes at a current density of 0.5-2.5A/dm2And the polar distance is 3cm, and preparing the silane coupling agent-reduced graphene oxide/aluminum composite material by electrophoretic deposition; wherein, the electrophoretic deposition electrophoretic fluid is: 0.3-0.4g/L, TW-601-1.5 mg/L of silver nitrate and 0.5-0.7g/L of silane coupling agent-reduced graphene oxide;
(7) and (4) drying the modified reduced graphene oxide/aluminum composite material treated in the step (6) to obtain a final product.
2. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 1, wherein the method comprises the following steps: in the dispersion liquid A in the step (1), the mass concentration of the graphene oxide is 0.1-0.2%; the silane coupling agent is KH550 with the concentration of 5.5-6.3g/L, and the pH is adjusted to 4.0 by acetic acid; the volume ratio of the silane coupling agent to the dispersion liquid A is 2-3: 400-500.
3. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 1, wherein the method comprises the following steps: in the dispersion liquid B in the step (3), the mass ratio of the silane coupling agent-graphene oxide to water is 1-2: 200-260, the volume ratio of hydrazine hydrate to the dispersion liquid B is 1-2: 200-260.
4. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 1, wherein the method comprises the following steps: and (3) during vacuum filtration in the steps (2) and (4), the pore diameter of the filter paper is 0.45 micrometer.
5. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 1, wherein the method comprises the following steps: the deoiling liquid in the step (5) is a mixed liquid containing 30-80g/L of trisodium phosphate, 20-60g/L of sodium carbonate and 1.0-2.0g/L of OP-10 emulsifier; when oil is removed, the temperature of the oil removing liquid is 55-65 ℃, and the oil removing time is 2 minutes.
6. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 1, wherein the method comprises the following steps: the activating solution is 40-50g/L sodium hydroxide, and the activating time is 2 minutes.
7. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 1, wherein the method comprises the following steps: the power supply parameters of the pulse electrophoresis in the step (6) are as follows: the frequency is 10Hz, the forward current is 0.15A, the reverse current is 0.05A, the forward direction is 97ms, the reverse direction is 3ms, and the duty ratio is 100%.
8. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 1, wherein the method comprises the following steps: and (3) drying in the steps (2), (4) and (7) for 3-5 hours in a vacuum oven at 75-85 ℃.
9. The method for preparing the modified graphene oxide aluminum composite heat conduction material by electrophoresis according to claim 8, wherein the method comprises the following steps: in the step (7), before vacuum drying, the composite material is irradiated by an infrared lamp in the air to carry out natural drying.
10. The modified graphene oxide aluminum composite heat conduction material prepared by any one of claims 1 to 8.
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