CN114940829B - Two-dimensional graphene/liquid metal/PDMS composite membrane and preparation method thereof - Google Patents
Two-dimensional graphene/liquid metal/PDMS composite membrane and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 157
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 title claims abstract description 131
- 239000004205 dimethyl polysiloxane Substances 0.000 title claims abstract description 122
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 title claims 8
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 title claims 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 title claims 6
- 239000012528 membrane Substances 0.000 title abstract description 9
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 25
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- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
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- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
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- 229910052582 BN Inorganic materials 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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Abstract
The invention relates to a two-dimensional graphene/liquid metal (GaIn)/PDMS composite membrane, and a preparation method and application thereof, wherein the composite membrane takes a photosensitive resin skeleton with a foldback-type bow-tie structure as a template, takes a 3D printing technology as a template preparation process, uniformly fills polydimethylsiloxane resin (PDMS) into the template after the template is prepared and molded, and separates the photosensitive resin skeleton from the PDMS after the PDMS is solidified at room temperature to obtain a flexible and stretchable PDMS membrane with the foldback-type bow-tie structure; and filling graphene, graphene oxide and liquid metal (GaIn) into the PDMS film to obtain the foldback type bowknot-shaped stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film. The graphene/liquid metal (GaIn)/PDMS composite film provided by the invention has a foldback type bow-tie structure, has an effective conduction network and a unique graphene two-dimensional auxetic structure, has excellent heat and electric conductivity and stretching rebound stability under lower graphene and liquid metal contents, and can be applied to flexible heat dissipation devices.
Description
Technical Field
The invention belongs to the field of heat dissipation of flexible electronic devices, and particularly relates to a foldback type bowknot-shaped stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film, and a preparation method and application thereof.
Background
With the rapid development of high-performance flexible electronic technology, the deformability and intellectualization of electronic devices are becoming a trend. However, high performance electronic devices generate excessive waste heat during operation, causing significant damage to themselves. In order to timely eliminate the adverse effect of waste heat, higher requirements are put forward on the high-heat-conductivity thermal interface material. Polydimethylsiloxane (PDMS) resin has the characteristics of deformability and flexibility, so that the Polydimethylsiloxane (PDMS) resin plays an important role in the field of heat dissipation of flexible electronic devices, but the application of the Polydimethylsiloxane (PDMS) resin in flexible electronic devices, such as the field of thermal interface materials, is severely restricted by the lower coefficient of thermal conductivity (0.2W/mK). In order to improve the heat conducting property, various high heat conductivity fillers such as boron nitride, graphene, liquid metal, carbon nanotubes and the like are added to prepare a heat conducting composite material, and the heat conducting composite material is applied to the field of heat management.
Among these heat conductive fillers, the characteristics of high intrinsic heat conductivity (4800W/mK) and high aspect ratio of graphene have been reported in the past to be particularly suitable for use in constructing a heat conductive network structure. The flexible matrix is constructed into a two-dimensional film, a directional structure array and a three-dimensional structure, and the graphene is added into the flexible matrix constructed into a conductive network, so that the heat conduction performance of the composite material can be remarkably improved. The conductive network structure can eliminate the contact thermal resistance between graphene sheets and provide a channel for smooth transmission of phonons in the material. However, a large friction force is generated between the graphene solid heat conduction filler and the flexible matrix, hysteresis phenomenon is generated, stress concentration is also caused in the process of stretching and releasing, so that the solid filler falls off, the mechanical property of the composite material is reduced, and meanwhile, the application of the flexible composite film in the field of heat dissipation of flexible electronic devices is also influenced. In addition, the graphene obtained by the current preparation method is unordered and porous in heat conduction structure, poor in mechanical property, complex in preparation and high in cost. Therefore, reasonable morphological design is required for the graphene heat conduction structure, the mechanical property of the structure is enhanced, and the material defects are reduced so as to meet the industrial application requirements of the high-performance heat conduction composite material. In order to solve the problem, special geometric structures such as corrugation, paper folding and spring structures are designed in the plane of the stretchable flexible composite material, so that the generation of contact thermal resistance between graphenes can be effectively reduced. These structures may allow the material to maintain the integrity of the phonon transport channels of the thermally conductive network during deformation. Meanwhile, the special geometric structure can reduce the generation of residual stress and cracks in the dynamic deformation process. Among the numerous geometries, negative poisson's ratio auxetic materials are of great interest due to their unique mechanical properties, including folded, hinged, foam structural materials, and the like. These structures are auxetic into two-dimensional or three-dimensional structures based on another oriented portion of the combined or rotary unit. Based on different materials, the negative poisson ratio auxetic structures can present negative poisson ratios with higher values of-20 to-4.
Because the 3D printing technology can realize accurate design and controllable preparation of materials, the material molding with the negative poisson's ratio structure can be realized. According to the method, a 3D printer is used for pre-designing a printing program and a printing model, and photosensitive resin is printed into a three-dimensional heat conduction network structure with a negative Poisson ratio structure, so that high-precision structure molding is realized. Although the special geometric structure is designed in the plane of the stretchable flexible composite material, the contact thermal resistance between the graphenes can be effectively reduced, and the high intrinsic thermal conductivity of the graphenes is utilized as much as possible, the graphenes belong to rigid fillers, and the compatibility between the graphenes and the flexible matrix is poor, so that stress concentration is generated in the stretching rebound process, and the mechanical property of the composite material is further reduced. Based on this, the present invention contemplates gallium liquid metal and gallium-based liquid metal alloys having high thermal conductivity that are liquid at room temperature. The liquid metal is compounded with the flexible matrix, and stress concentration can not occur in the stretch rebound process. And the liquid metal also has excellent electric conductivity and heat conductivity, and is widely used in the flexible heat dissipation field.
Disclosure of Invention
In order to solve the problems that disordered distribution of graphene in a flexible matrix can increase contact thermal resistance between graphene and large friction force between solid graphene and the flexible matrix can influence thermal conductivity and mechanical performance of a composite material, the invention provides a foldback-type stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film, and a preparation method and application thereof, wherein the composite film takes a photosensitive resin skeleton with a foldback-type bow-tie structure as a template, takes a 3D printing technology as a template preparation process, uniformly fills Polydimethylsiloxane (PDMS) resin into the template after the template is prepared and molded, and separates the photosensitive resin skeleton from PDMS after the PDMS is solidified at room temperature to obtain a flexible stretchable PDMS film with the foldback-type bow-tie structure; and filling graphene, graphene oxide and liquid metal (GaIn) into the PDMS film to obtain the foldback type bowknot-shaped stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film. The graphene/liquid metal (GaIn)/PDMS composite film provided by the invention has a foldback type bow-tie structure, has an effective conduction network and a unique graphene two-dimensional auxetic structure, has excellent heat and electric conductivity and stretching rebound stability under lower graphene and liquid metal contents, and can be applied to flexible heat dissipation devices. The unique two-dimensional auxetic structure of the composite material endows high stretchability (100%) in a stretching/releasing period, and has good heat conduction performance in stretching deformation, and the heat conductivity can reach 4.51W/mK under the condition of 30wt% of filler content. The heat-conducting material has stable heat-conducting performance and structural stability in the strain range of 0-100% in 100 cycles. In addition, the intrinsic high heat conductivity of the liquid metal and the three-dimensional heat conduction channel endowed by liquid property and 3D printing at room temperature cooperatively enhance the heat conductivity of the graphene/liquid metal (GaIn)/PDMS composite film, so that the graphene/liquid metal (GaIn)/PDMS composite film is more convenient to apply in the electronic industry. Vinyl-terminated polydimethylsiloxane hydride terminated poly (dimethylsiloxane)
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a foldback type bowtie-shaped stretchable flexible graphene/liquid metal (GaIn)/PDMS composite membrane comprises a flexible PDMS matrix, and graphene dispersion liquid and liquid metal poured onto the flexible PDMS matrix.
In the preferred embodiment of the invention, the flexible PDMS matrix is a photosensitive resin skeleton with a foldback bow-tie structure which is printed by using a 3D printing technology, a mixed solution of a PDMS prepolymer A component and a curing agent B component is dripped into the skeleton, and the mixture is obtained by demoulding after room temperature curing; more preferably, the component A is vinyl-terminated polydimethylsiloxane and a platinum catalyst, the component B is hydride-terminated poly (dimethylsiloxane), and the mixing mass ratio or volume ratio of the component A, B is 1:4-4:1; most preferably, the mixing mass ratio or volume ratio of A, B components is 1:1.
In a preferred embodiment of the present invention, the graphene dispersion is obtained by adding graphene microplates to an aqueous graphene oxide solution; preferably, the concentration of the graphene oxide dispersion liquid is 10mg/ml, and the mass ratio of graphene to graphene oxide is 10:1.
In a preferred embodiment of the invention, graphene/liquid metal (GaIn) blend solution is uniformly poured into bowtie-like grooves of a flexible PDMS substrate; preferably, the mass ratio of graphene dispersion to liquid metal (GaIn) is 1:1; more preferably, the composition of the liquid metal (GaIn) is: ga 75.5wt.% In 24.5wt.%, melting point 16 ℃.
In a preferred embodiment of the invention, a mixed solution of a PDMS prepolymer A component and a curing agent B component is used for packaging flexible PDMS added with graphene and liquid metal (GaIn) to obtain a foldback type bow-tie stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film; preferably, the component A is vinyl-terminated polydimethylsiloxane and a platinum catalyst, the component B is hydride-terminated poly (dimethylsiloxane), and the mixing mass ratio or volume ratio of the component A, B is 1:4-4:1; most preferably, the mixing mass ratio or volume ratio of A, B components is 1:1.
In a preferred embodiment of the present invention, the photosensitive resin skeleton has a size of 10mm by 2mm and 10mm by 10mm; the length of the symmetrical bevel edge of a single bow tie in the foldback type bow tie-shaped flexible PDMS matrix membrane is 1.582mm, and a plurality of bow tie-shaped structures with an included angle of 120 degrees in the shape of an eight in the bow tie are sequentially arranged to jointly form a heat conducting channel (shown in figure 2).
In a preferred embodiment of the present invention, the polydimethylsiloxane having vinyl ends reacts with the hydride end-capped poly (dimethylsiloxane) curing agent under the catalysis of the platinum catalyst, the vinyl double bond is opened to form a new silicon-carbon bond, and then a crosslinked network structure is formed, and finally the Polydimethylsiloxane (PDMS) resin is obtained.
The invention also provides a preparation method of the foldback-shaped stretchable flexible graphene/liquid metal (GaIn)/PDMS composite membrane, which specifically comprises the following steps:
(1) Preparation of graphene oxide by Hummers method: mixing graphite, sodium nitrate and potassium permanganate, adding sulfuric acid, fully stirring for 5-8 hours, and keeping the reaction temperature at 35-60 o C, adding deionized water after the reaction is finished, and raising the temperature to 85-95 o C, maintaining for 10-15 minutes, adding hydrogen peroxide and deionized water after the solution is cooled to room temperature, washing with water for three times, taking out the product, and freeze-drying to obtain graphene oxide;
(2) Preparing graphene dispersion liquid: dispersing 0.1g of graphene oxide obtained in the step (1) in 10 ml deionized water to prepare a 10mg/ml graphene oxide aqueous solution, adding 1g graphene microplates, and dispersing for 30 min by using tip ultrasound to obtain graphene dispersion liquid with stable properties and uniform dispersion;
(3) Preparation of PDMS matrix film: firstly, respectively preparing photosensitive resin frameworks with bow-tie structures and different sizes of 10mm by 2mm and 10mm by using a 3D printer according to the thickness requirements required by different samples of a heat conduction test and a mechanical test; secondly, preparing a mixed solution of a component A, which is prepared by mixing vinyl-terminated polydimethylsiloxane and a platinum catalyst according to a mass ratio or a volume ratio of 1:1, and a component B, which is prepared by mixing a hydride-terminated poly (dimethylsiloxane) curing agent, uniformly pouring the mixed solution into a bowknot-shaped groove of a photosensitive resin skeleton, curing at room temperature, and demolding to obtain a PDMS matrix film with a two-dimensional foldback bowknot-shaped structure (shown in figure 2);
(4) Uniformly pouring the graphene dispersion liquid obtained in the step (2) into the PDMS matrix film obtained in the step (3), and removing the moisture in the graphene dispersion liquid by means of a vacuum oven to uniformly disperse the graphene into the PDMS matrix film;
(5) Casting of liquid metal (GaIn): uniformly injecting liquid metal (GaIn) into the PDMS matrix film in the step (4) by using an injector;
(6) Preparing a mixed solution of vinyl-terminated polydimethylsiloxane and a platinum catalyst in a mass ratio or a volume ratio of 1:4-4:1, wherein the component A is hydrogenated-terminated polydimethylsiloxane, the solution is poured onto the surface of the PDMS matrix film added with graphene and liquid metal (GaIn) in the step (5) to encapsulate the graphene and the liquid metal to prevent leakage of the graphene and the liquid metal, curing the graphene and the liquid metal for 4-6 hours at room temperature, and freeze-drying to remove residual moisture, thereby obtaining the foldback-type bow-tie-shaped stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film.
In a preferred embodiment of the invention, in the step (1), the mass ratio of graphite, sodium nitrate and potassium permanganate is 1:1:3.
In a preferred embodiment of the present invention, in step (3), the mass or volume ratio of the components of the Polydimethylsiloxane (PDMS) resin matrix A, B is preferably 1:1.
In a preferred embodiment of the invention, in steps (4) and (5), the mass ratio of the poured graphene dispersion to the liquid metal is 1:1, the liquid metal is GaIn with a melting point of 16 ℃, wherein the gallium content is 75.5wt.% and the indium content is 24.5 wt.%.
The invention also comprises application of the foldback bow-tie stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film as a heat conduction packaging material in 5G communication equipment and high-power electronic equipment.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, a photosensitive resin skeleton is printed by a 3D printing technology, then a Polydimethylsiloxane (PDMS) resin matrix is poured into the skeleton, and after being cured at room temperature, the matrix is demoulded to obtain a flexible PDMS matrix, and the matrix endows a heat conduction channel filled with heat conduction filler, so that the contact thermal resistance among the fillers is reduced, and the heat conductivity is increased.
(2) According to the invention, graphene and liquid metal (GaIn) are added into the PDMS flexible matrix, high thermal conductivity and electrical conductivity of the composite material can be realized under the mass fraction of the total content of the graphene and the liquid metal (GaIn) as low as 30wt%, and meanwhile, compared with a graphene/PDMS mixed composite material, the graphene/liquid metal (GaIn)/PDMS composite film has better deformation recovery capability, so that the composite film has important significance in the use of the composite film in flexible heat conducting materials.
(3) The product of the invention has better heat conduction performance, and in the X-axis direction of the horizontal direction of the graphene/liquid metal (GaIn)/PDMS composite film, the heat conductivity of the product is 4.51W/mK and is 17.4 times higher than that of a blended sample with the same graphene content due to the synergistic effect of a bowknot-shaped heat conduction network, graphene and liquid metal. It is noted that in the Y-axis direction, the thermal conductivity of PDMS is only 0.27W/(mK) due to the layer-by-layer barrier effect of the PDMS, and thus the PDMS composite film has anisotropy in thermal conductivity (as shown in fig. 3 and 4).
(4) The product of the invention has better deformation recovery capability and stretching-releasing cycle stability, and after 100 stretching/releasing cycles, the residual strain of the pure PDMS film is 33.8 percent, and the residual strain of the graphene/liquid metal (GaIn)/PDMS composite film is 23.4 percent (shown in figures 5 and 6).
(5) The product of the invention has the advantages of convenient preparation, low cost, no toxicity, environmental protection, high heat conduction performance, suitability for commercial application, and applicability as a heat conduction packaging material and a heat interface material to 5G communication equipment and high-power electronic equipment.
Drawings
The following is further described with reference to the accompanying drawings:
fig. 1 is a flow chart of simulation preparation of a graphene/liquid metal (GaIn)/PDMS composite film with a two-dimensional turn-back bow-tie structure.
FIG. 2 is a diagram of 3D printed photosensitive resin backbone feature sizes.
Fig. 3 is a schematic diagram of heat transfer along the X, Y axis direction of a flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film that is folded back, bow-tie-shaped, stretchable.
Fig. 4 is a thermal conductivity comparison of a pure PDMS film, a graphene/PDMS hybrid composite (30 wt.% graphene content), a foldback bow-tie stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film of the present invention (30 wt.% total graphene and liquid metal content).
Fig. 5 is a tensile/release cyclic stress-strain curve of a foldback-like stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film (30 wt% total content of graphene and liquid metal (GaIn)).
FIG. 6 is a periodic table of stress cycles for a foldback-like stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the attached drawings so that the advantages and features of the present invention will be more readily understood by those skilled in the art, thereby making a clearer definition of the scope of the present invention.
Example 1:
(1) 10 g of graphite, 10 g of sodium nitrate and 30 g of potassium permanganate are mixed in a flask, 300 ml of sulfuric acid is added, stirring is carried out for 6 hours, and the reaction temperature is kept at 45 ℃. Deionized water was added after the reaction was completed and the temperature was raised to 90 ℃ for 15 minutes. After the solution is cooled to room temperature, adding hydrogen peroxide and deionized water, washing for three times, taking out the product, and putting the product into a freeze dryer for drying to obtain graphene oxide;
(2) Firstly, dispersing the graphene oxide obtained in the step (1) of 0.5 g in 50ml of deionized water to prepare a graphene oxide aqueous solution of 10 mg/ml; based on the mass ratio of graphene to graphene oxide of 10:1, adding 5g of graphene microplates, and dispersing for 30 min by using tip ultrasound to obtain graphene dispersion liquid with stable properties and uniform dispersion;
(3) Firstly, according to the thickness requirements of different samples of a heat conduction test and a mechanical test, respectively preparing photosensitive resin frameworks (shown in figure 2) with different sizes of 10mm by 2mm and 10mm by a 3D printer; secondly, preparing a mixed solution of a component A, a component B and a component B, wherein the mixed solution comprises vinyl-terminated polydimethylsiloxane, a platinum catalyst and a hydride-terminated poly (dimethylsiloxane) curing agent according to the mass ratio of 1:1, pouring the mixed solution into a photosensitive resin template, curing at room temperature, and demolding to obtain the PDMS matrix film with a two-dimensional foldback bow-tie structure;
(4) Preparing a graphene dispersion liquid-liquid metal (GaIn) mixed solution based on the mass ratio of the graphene dispersion liquid obtained in the step (2) to the liquid metal (GaIn) of 1:1, and then uniformly pouring the mixed solution into the PDMS matrix film obtained in the step (3) to be cured for 4-6 hours at room temperature;
(5) Preparing a mixed solution of vinyl-terminated polydimethylsiloxane and a platinum catalyst as an A component and a hydride-terminated poly (dimethylsiloxane) curing agent as a B component according to the mass ratio of 1:1, and uniformly pouring the mixed solution onto the surface of the PDMS matrix film added with graphene and liquid metal (GaIn) in the step (4) to encapsulate the graphene and the liquid metal. Solidifying for 4-6 hours at room temperature, and then freeze-drying to remove residual moisture to obtain a foldback type bowknot-shaped stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film; the simulation preparation flow chart of the composite membrane is shown in figure 1.
(6) Selecting a bowknot-shaped photosensitive resin skeleton with the characteristic dimension of 10mm x 2mm according to the thickness requirement of a heat conduction test to prepare a bowknot-shaped graphene/liquid metal (GaIn)/PDMS composite film, and performing a heat conductivity test on the composite film; as shown in fig. 3, a schematic heat transfer diagram of the flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite film in the X, Y axial direction is shown; in addition, thermal conductivity tests were compared for pure PDMS films, graphene/PDMS mixed composites (graphene content 30 wt.%), and the inventive foldback bow-tie stretchable flexible two-dimensional graphene/liquid metal (GaIn)/PDMS composite films (total graphene and liquid metal content 30 wt.%), as shown in fig. 4, the thermal conductivity of pure PDMS was only 0.26 (W/m×k) since PDMS is an insulating polymer. The graphene/PDMS blend composite material containing 30wt% has a thermal conductivity of only 1.02 (W/m×k) because the graphene sheets inside the composite material are blocked by PDMS and cannot form an effective thermal conductive network. The graphene composite material with the two-dimensional turn-back bow-tie structure, which contains 30wt.% of graphene and liquid metal in total, has a thermal conductivity of 4.51 (W/m×k) in the X-axis direction of the horizontal direction (as shown in fig. 3) due to the effect of the graphene and liquid metal thermal conduction network, which is 17.4 times higher than that of a blended sample with the same graphene content. It is noted that the thermal conductivity of the graphene/liquid metal (GaIn)/PDMS composite film of the present invention (30 wt.% total graphene and liquid metal content, heat transfer along the Y-axis direction, as shown in fig. 3) is only 0.27 (W/m x K). As described above, the graphene microplates and the liquid metal form a bow-tie structure in the PDMS resin that is periodically arranged, which helps phonons to propagate along the X-axis direction in the network of graphene and liquid metal. The graphene sheets are bridged together before polymer encapsulation, and the gaps between the graphene sheets are filled with liquid metal, so that the contact thermal resistance and phonon scattering phenomena are reduced. In contrast, for the Y-axis direction, the path of thermal conduction needs to penetrate the multilayer graphene and PDMS phases, with a significant increase in thermal resistance due to the thermally insulating nature of PDMS, and exhibiting a significant difference in thermal conductivity from the X-axis direction.
(7) According to the thickness requirement of the mechanical test, selecting a bowknot-shaped photosensitive resin skeleton with the characteristic size of 10mm*10mm*10mm to prepare a bowknot-shaped graphene/liquid metal (GaIn)/PDMS composite film, and carrying out a stretching/releasing cycle test and a cycle stability test on the composite film. To evaluate the mechanical properties of a two-dimensional foldback bowtie graphene/liquid metal (GaIn)/PDMS composite film (30 wt% total graphene and liquid metal content) the tensile/release cyclic stress-strain test of the composite film is shown in fig. 5. It can be seen that the pure PDMS film exhibits a pronounced hysteresis loop under cyclic stress, i.e., the tensile stress-strain curve and the relief stress-strain curve form a closed loop, rather than being superimposed. The area formed by the hysteresis loop represents the energy dissipation of the material during cyclic stretching. For pure PDMS films, the energy dissipation is mainly due to internal losses that are overcome when the polymer segments slip during stretching. The sample cannot recover to the original length during release due to energy dissipation. When the stress is zero, a significant residual strain is shown. It can be seen that the residual strain of the pure PDMS film after ten stretch release cycles was 33.8%. It is notable that the hysteresis loop area of the two-dimensional foldback-like graphene/liquid metal (GaIn)/PDMS composite film of the present invention (total content of graphene and liquid metal 30 wt%) is significantly smaller than that of the pure PDMS sample, meaning lower energy dissipation. It can be seen that the residual strain of the graphene/liquid metal (GaIn)/PDMS composite film after 100 cycles of stretch-release was reduced to 23.4%. The reduction of residual strain is beneficial to reconstruction of graphene and liquid metal heat conduction networks, and loss of residual stress of graphene is reduced. Therefore, the composite film prepared by the invention has better strain recovery capability. In addition, in order to evaluate the mechanical properties of the two-dimensional foldback-like bowtie graphene/liquid metal (GaIn)/PDMS composite film (total content of graphene and liquid metal 30 wt%), the stress cycle chart of the composite film is shown in fig. 6, and fig. 6 shows a graph of stress versus cycle number of the graphene/liquid metal (GaIn)/PDMS composite film in 100 tensile stress-strain tests. The graphene/liquid metal (GaIn)/PDMS composite film has a mechanical tensile strength of about 2 MPa, maintains good structural integrity and mechanical strength in the whole complete cycle period, proves excellent elastic recovery performance, and shows potential as a scalable thermal management material.
Example 2: the implementation method is the same as that of the embodiment 1, the mass ratio of the graphene dispersion liquid and the liquid metal (GaIn) in the step (4) is changed to 1:2, a graphene dispersion liquid-liquid metal (GaIn) mixed solution is prepared, and then the mixed solution is uniformly poured into the PDMS matrix film obtained in the step (3), and other components and the mass are unchanged.
Example 3: the implementation method is the same as that of the embodiment 1, the mass ratio of the graphene dispersion liquid and the liquid metal (GaIn) in the step (4) is changed to 1:3, a graphene dispersion liquid-liquid metal (GaIn) mixed solution is prepared, and then the mixed solution is uniformly poured into the PDMS matrix film obtained in the step (3), and other components and the mass are unchanged.
Example 4: the implementation method is the same as that of the embodiment 1, the mass ratio of the graphene dispersion liquid and the liquid metal (GaIn) in the step (4) is changed to 1:4, a graphene dispersion liquid-liquid metal (GaIn) mixed solution is prepared, and then the mixed solution is uniformly poured into the PDMS matrix film obtained in the step (3), and other components and the mass are unchanged.
Example 5: the implementation method is the same as that of the embodiment 1, the mass ratio of the graphene dispersion liquid and the liquid metal (GaIn) in the step (4) is changed to 2:1, a graphene dispersion liquid-liquid metal (GaIn) mixed solution is prepared, and then the mixed solution is uniformly poured into the PDMS matrix film obtained in the step (3), and other components and the mass are unchanged.
Example 6: the implementation method is the same as that of the embodiment 1, the mass ratio of the graphene dispersion liquid and the liquid metal (GaIn) in the step (4) is changed to 3:1, a graphene dispersion liquid-liquid metal (GaIn) mixed solution is prepared, and then the mixed solution is uniformly poured into the PDMS matrix film obtained in the step (3), and other components and the mass are unchanged.
Example 7: the implementation method is the same as that of the embodiment 1, the mass ratio of the graphene dispersion liquid and the liquid metal (GaIn) in the step (4) is changed to 4:1, a graphene dispersion liquid-liquid metal (GaIn) mixed solution is prepared, and then the mixed solution is uniformly poured into the PDMS matrix film obtained in the step (3), and other components and the mass are unchanged.
Example 8: the method was carried out in the same manner as in example 1, and only the graphene dispersion was cast into the PDMS base film obtained in step (3), without casting the liquid metal (GaIn), and without changing the other components and the quality.
Example 9: the implementation method is the same as that of the example 1, and only the liquid metal (GaIn) is poured into the PDMS matrix film obtained in the step (3) without pouring the graphene dispersion liquid, and other components and qualities are unchanged.
The test results of the heat conducting property and the mechanical property of the obtained composite film are shown in table 1.
Table 1 results of composite film Performance test
The performance test results of Table 1 show that the composite film prepared by the invention has high thermal conductivity and high mechanical tensile strength. By comparing examples 1-4 with example 9, it can be stated that: with the increase of the content of liquid metal in the graphene/liquid metal mixed solution, the thermal conductivity and the tensile strength of the composite film are reduced to a certain extent, and the reason is that after the liquid metal exceeds the critical addition amount, the composite film can leak liquid metal in the stretching process, so that the thermal conductivity and the tensile strength of the composite film are reduced. By comparing examples 1, 5, 6, 7 with example 8, it can be stated that: with the increase of the graphene content in the graphene/liquid metal mixed solution, the tensile strength of the composite film is increased due to the intrinsic excellent mechanical property of the graphene, but the continuously increased graphene content causes the aggregation phenomenon of the graphene in the composite film, so that the thermal conductivity of the composite film tends to be reduced. Thus, as can be seen from the data in Table 1, example 1 is the most preferred formulation.
The foregoing embodiments illustrate and describe the basic principles and principal features of the invention and advantages of the invention. It will be appreciated by persons skilled in the art that the present invention is not limited to the embodiments described above, and that the embodiments and descriptions described above are merely illustrative of the principles of the invention and not in any way limiting the scope of the invention, and that various changes and modifications may be made therein without departing from the scope of the invention, which is defined by the claims.
Claims (1)
1. The preparation method of the foldback type bow-tie stretchable flexible graphene/liquid metal GaIn/PDMS composite film is characterized by comprising the following steps of:
(1) Mixing 10 g of graphite, 10 g of sodium nitrate and 30 g of potassium permanganate in a flask, adding 300 ml of sulfuric acid, fully stirring for 6 hours, and keeping the reaction temperature at 45 ℃; adding deionized water after the reaction is finished, and raising the temperature to 90 ℃ for 15 minutes; after the solution is cooled to room temperature, adding hydrogen peroxide and deionized water, washing for three times, taking out the product, and putting the product into a freeze dryer for drying to obtain graphene oxide;
(2) Firstly, dispersing the graphene oxide obtained in the step (1) of 0.5 g in 50ml of deionized water to prepare a graphene oxide aqueous solution of 10 mg/ml; based on the mass ratio of graphene to graphene oxide of 10:1, adding 5g of graphene microplates, and dispersing for 30 min by using tip ultrasound to obtain graphene dispersion liquid with stable properties and uniform dispersion;
(3) Firstly, respectively preparing photosensitive resin frameworks with different sizes of 10mm by 2mm and 10mm by using a 3D printer according to the thickness requirements required by different samples of a heat conduction test and a mechanical test; secondly, preparing a mixed solution of a component A, a component B and a component B, wherein the mixed solution comprises vinyl-terminated polydimethylsiloxane, a platinum catalyst and a hydride-terminated poly (dimethylsiloxane) curing agent according to the mass ratio of 1:1, pouring the mixed solution into a photosensitive resin template, curing at room temperature, and demolding to obtain the PDMS matrix film with a two-dimensional foldback bow-tie structure;
(4) Preparing a graphene dispersion liquid-liquid metal GaIn mixed solution based on the mass ratio of the graphene dispersion liquid obtained in the step (2) to the liquid metal GaIn of 1:1, and then uniformly pouring the mixed solution into the PDMS matrix film obtained in the step (3) to be cured for 4-6 hours at room temperature;
(5) Preparing a mixed solution of vinyl-terminated polydimethylsiloxane and platinum catalyst as the A component and hydride-terminated poly (dimethylsiloxane) curing agent as the B component according to the mass ratio of 1:1, uniformly pouring the solution onto the surface of the PDMS matrix film added with graphene and liquid metal GaIn in the step (4) for packaging the graphene and the liquid metal,
solidifying for 4-6 hours at room temperature, and then freeze-drying to remove residual moisture to obtain the foldback type bowknot-shaped stretchable flexible two-dimensional graphene/liquid metal GaIn/PDMS composite film.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108753262A (en) * | 2018-06-27 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene-based heat-conductive composite material and preparation method thereof |
| CN109455948A (en) * | 2017-09-06 | 2019-03-12 | 香港理工大学 | Redox graphene, preparation method and the device comprising it |
| CN110358302A (en) * | 2019-08-27 | 2019-10-22 | 宁波石墨烯创新中心有限公司 | A kind of heat-conducting silica gel sheet and preparation method thereof |
| CN110862532A (en) * | 2019-12-03 | 2020-03-06 | 上海大学 | Degradable 3D printing resin |
| CN112981207A (en) * | 2019-12-12 | 2021-06-18 | 有研工程技术研究院有限公司 | Liquid metal thermal interface material with self-packaging function and preparation method thereof |
Family Cites Families (1)
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109455948A (en) * | 2017-09-06 | 2019-03-12 | 香港理工大学 | Redox graphene, preparation method and the device comprising it |
| CN108753262A (en) * | 2018-06-27 | 2018-11-06 | 中国科学院宁波材料技术与工程研究所 | A kind of graphene-based heat-conductive composite material and preparation method thereof |
| CN110358302A (en) * | 2019-08-27 | 2019-10-22 | 宁波石墨烯创新中心有限公司 | A kind of heat-conducting silica gel sheet and preparation method thereof |
| CN110862532A (en) * | 2019-12-03 | 2020-03-06 | 上海大学 | Degradable 3D printing resin |
| CN112981207A (en) * | 2019-12-12 | 2021-06-18 | 有研工程技术研究院有限公司 | Liquid metal thermal interface material with self-packaging function and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Yasaman Sargolzaeiaval et al."High Thermal Conductivity Silicone Elastomer Doped with Graphene Nanoplatelets and Eutectic GaIn Liquid Metal Alloy".Journal of Solid State Science and Technology.2019,第8卷(第6期),第357-362页. * |
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