CN114621546A - Heat dissipation film, composite heat dissipation fin and preparation method of composite heat dissipation fin - Google Patents
Heat dissipation film, composite heat dissipation fin and preparation method of composite heat dissipation fin Download PDFInfo
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- CN114621546A CN114621546A CN202210332698.1A CN202210332698A CN114621546A CN 114621546 A CN114621546 A CN 114621546A CN 202210332698 A CN202210332698 A CN 202210332698A CN 114621546 A CN114621546 A CN 114621546A
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 95
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 38
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 38
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000003607 modifier Substances 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
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- 239000000243 solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
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- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229940055237 sodium 1-naphthalenesulfonate Drugs 0.000 claims description 3
- 229940080299 sodium 2-naphthalenesulfonate Drugs 0.000 claims description 3
- AZKQWFQWHHSLDU-UHFFFAOYSA-M sodium;2-aminonaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(N)=CC=C21 AZKQWFQWHHSLDU-UHFFFAOYSA-M 0.000 claims description 3
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 claims description 3
- DWHOIYXAMUMQTI-UHFFFAOYSA-L disodium;2-[(1-sulfonatonaphthalen-2-yl)methyl]naphthalene-1-sulfonate Chemical compound [Na+].[Na+].C1=CC2=CC=CC=C2C(S(=O)(=O)[O-])=C1CC1=CC=C(C=CC=C2)C2=C1S([O-])(=O)=O DWHOIYXAMUMQTI-UHFFFAOYSA-L 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims 1
- 150000003460 sulfonic acids Chemical class 0.000 abstract description 14
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- 239000001257 hydrogen Substances 0.000 abstract description 6
- 238000009825 accumulation Methods 0.000 abstract description 4
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- 238000001514 detection method Methods 0.000 description 2
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- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
- H05K7/20954—Modifications to facilitate cooling, ventilating, or heating for display panels
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention discloses a heat dissipation film, a composite heat dissipation fin and a preparation method of the heat dissipation film and the composite heat dissipation fin. Compared with the prior art, the heat dissipation film provided by the invention modifies graphene by adopting sulfonic acid compounds and/or sulfonate compounds, the main chain of the heat dissipation film contains an aromatic ring structure, the heat dissipation film can interact with graphene through pi-pi accumulation, meanwhile, the graphene modified by the sulfonic acid compounds and/or sulfonate compounds has negative charges, and stacking is avoided due to electrostatic repulsion among the graphene; on the other hand, the sulfonic acid compounds and/or the sulfonate compounds can be used as bridges for connecting graphene (pi-pi) and polyvinyl alcohol (hydrogen bond), so that the graphene in the solution is stabilized, the stacking of the graphene in the polyvinyl alcohol solution is avoided, and the uneven distribution of the graphene in the layer-by-layer blade coating process is also avoided; the film has good mechanical property, is not easy to age, can eliminate air thermal resistance, has excellent heat-conducting property, and has lower preparation process cost, easy operation and contribution to industrialization.
Description
Technical Field
The invention relates to the technical field of display, in particular to a heat dissipation film, a composite heat dissipation fin and a preparation method of the heat dissipation film and the composite heat dissipation fin.
Background
The Organic Light Emitting display device displays images by using Organic Light Emitting diodes (abbreviated as OLEDs), which are self-Emitting devices. In the working process of the OLED, a large amount of heat is generated due to light emission, the response time of the OLED can be delayed by the generated heat, the aging of electronic elements in the OLED can be accelerated when the OLED is in a high-temperature state for a long time, and the service life of the whole OLED is shortened.
Therefore, the corresponding heat dissipation treatment needs to be carried out on the OLED, and at present, the heat conduction connection between the heat radiator and the display panel, the electronic device and the like generally adopts the heat conduction silicone grease, but the heat conductivity of the heat conduction silicone grease is not high, and the maximum heat conductivity can only reach 4 W.m-1·K-1Moreover, the heat-conducting silicone grease is easy to mix with air when connecting the radiator with a display panel or an electronic device, and the like, so that air bubbles are generated, and the air bubbles are poor heat conductors, can increase thermal resistance, greatly reduce heat transfer and influence heat transfer.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a heat dissipation film with excellent thermal conductivity, a composite heat dissipation sheet and a method for manufacturing the same.
The invention provides a heat dissipation film, which comprises a mixed material; the mixed material comprises:
1-20 parts by weight of graphene;
80-100 parts by weight of polyvinyl alcohol;
0.5-10 parts by weight of a graphene modifier;
the graphene modifier is a sulfonic acid compound and/or a sulfonate compound, and comprises an aromatic ring group.
Optionally, the aromatic ring group is a fused ring group.
Optionally, the graphene modifier is one or more of sodium methylene bis-naphthalene sulfonate, sodium alkyl naphthalene sulfonate, sodium 1-naphthalene sulfonate, sodium 2-naphthalene sulfonate and sodium 2-amino-1-naphthalene sulfonate.
The invention also provides a preparation method of the heat dissipation film, which comprises the following steps:
s1) mixing graphene and a graphene modifier in water to obtain a graphene aqueous solution;
s2) mixing the graphene aqueous solution with a polyvinyl alcohol aqueous solution to obtain a mixed slurry;
s3) carrying out blade coating on the mixed slurry to form a film, thus obtaining the heat dissipation film.
Optionally, the mixing in step S1) is ultrasonic mixing; the power of ultrasonic mixing is 100-500W; the ultrasonic mixing time is 10-60 min.
Optionally, the concentration of the polyvinyl alcohol aqueous solution is 0.5-5 wt%.
Optionally, the mixing in step S2) is ultrasonic mixing; the power of ultrasonic mixing is 100-500W; the ultrasonic mixing time is 10-60 min.
The present invention also provides a composite heat sink, comprising: the metal substrate and a heat dissipation film arranged on one side of the metal substrate.
Optionally, the metal substrate is selected from an aluminum plate or a copper foil.
The invention also provides a display panel comprising the heat dissipation film or the composite heat dissipation sheet.
The invention also provides a display device comprising the display panel.
Compared with the prior art, the heat dissipation film provided by the invention modifies graphene by adopting sulfonic acid compounds and/or sulfonate compounds, the main chain of the heat dissipation film contains an aromatic ring structure, the heat dissipation film can interact with graphene through pi-pi accumulation, meanwhile, the graphene modified by the sulfonic acid compounds and/or sulfonate compounds has negative charges, and stacking is avoided due to electrostatic repulsion among the graphene; on the other hand, the sulfonic acid compounds and/or the sulfonate compounds can be used as bridges for connecting graphene (pi-pi) and polyvinyl alcohol (hydrogen bond), so that the graphene in the solution is stabilized, the stacking of the graphene in the polyvinyl alcohol solution is avoided, and the uneven distribution of the graphene in the layer-by-layer blade coating process is also avoided; the film has good mechanical property, is not easy to age, can eliminate air thermal resistance, has excellent heat-conducting property, and has lower preparation process cost, easy operation and contribution to industrialization.
Drawings
FIG. 1 is a schematic view of a process for preparing a heat dissipation film according to the present invention;
FIG. 2 is a schematic flow chart of a process for preparing a heat dissipation film according to the present invention;
FIG. 3 is a top view of a composite heat sink provided by the present invention;
FIG. 4 is a cross-sectional view of a composite heat sink provided by the present invention;
FIG. 5 is a schematic diagram of a display panel according to the present invention;
fig. 6 is a schematic structural diagram of a display panel provided in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a heat dissipation film, which comprises a mixed material; the mixed material comprises 1-20 parts by weight of graphene; 80-100 parts by weight of polyvinyl alcohol; 0.5-10 parts by weight of a graphene modifier; the graphene modifier is a sulfonic acid compound and/or a sulfonate compound, and comprises an aromatic ring group.
In the invention, the content of graphene in the mixed material is optionally 1-15 parts by weight, and further optionally 1-10 parts by weight.
In the invention, the content of the polyvinyl alcohol in the mixed material is 85-99 parts by weight, and is further optional, 90-99 parts by weight; optionally, the molecular weight of the polyvinyl alcohol is 90000-100000, further 90200-98000, further 90200-94000 and further 90200-93280; the polymerization degree of the polyvinyl alcohol is 1800-2200, 1850-2150, 1900-2150 and 1980-2120; the alcoholysis degree of the polyvinyl alcohol can be 98-100%.
The method takes sulfonic acid compounds and/or sulfonate compounds containing aromatic ring groups as graphene modifiers; the graphene modifier contains an aromatic ring structure which can interact with graphene through pi-pi accumulation, and the graphene modified by the sulfonic acid compound and/or the sulfonate compound has negative charges, so that the modified graphene is prevented from being stacked due to electrostatic repulsion; and the sulfonic acid compounds and/or the sulfonate compounds can be used as a bridge for connecting graphene (pi-pi) and polyvinyl alcohol (hydrogen bond), so that graphene in a system is stabilized, stacking of the graphene is avoided, and further the phenomenon that the graphene in the heat dissipation film is unevenly distributed can be avoided. In the present invention, optionally, the aromatic ring group is a fused ring group, and further optionally, the aromatic ring group is a naphthyl group; in the invention, optionally, the graphene modifier is a naphthalene sulfonate compound; further optionally, the graphene modifier is one or more of sodium methylenedinaphthalene sulfonate, sodium alkyl naphthalenesulfonate, sodium 1-naphthalenesulfonate, sodium 2-naphthalenesulfonate and sodium 2-amino-1-naphthalenesulfonate.
The heat dissipation film provided by the invention modifies graphene by adopting sulfonic acid compounds and/or sulfonate compounds, the main chain of the heat dissipation film contains an aromatic ring structure, the heat dissipation film can interact with graphene through pi-pi accumulation, meanwhile, the graphene modified by the sulfonic acid compounds and/or sulfonate compounds has negative charges, and stacking is avoided due to electrostatic repulsion among the graphene; on the other hand, the sulfonic acid compounds and/or the sulfonate compounds can be used as bridges for connecting graphene (pi-pi) and polyvinyl alcohol (hydrogen bond), so that the graphene in the solution is stabilized, the stacking of the graphene in the polyvinyl alcohol solution is avoided, and the uneven distribution of the graphene in the layer-by-layer blade coating process is also avoided; the film has good mechanical property, is not easy to age, can eliminate air thermal resistance, has excellent heat-conducting property, and has lower preparation process cost, easy operation and contribution to industrialization.
The invention also provides a preparation method of the heat dissipation film, which comprises the following steps: s1) mixing graphene and a graphene modifier in water to obtain a graphene aqueous solution; s2) mixing the graphene aqueous solution with a polyvinyl alcohol aqueous solution to obtain a mixed slurry; s3) blade coating the mixed slurry to form a film, and obtaining the heat dissipation film.
Referring to fig. 1 and 2, fig. 1 and 2 are schematic views illustrating a process for preparing a heat dissipation film according to the present invention.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available. The types and contents of the graphene, the graphene modifier and the polyvinyl alcohol are the same as those described above, and are not described herein again.
Mixing graphene and a graphene modifier in water to obtain a graphene aqueous solution; wherein the concentration of graphene in the graphene aqueous solution is specifically 0.5-10 wt%, further specifically 0.5-5 wt%, and further specifically 0.7-2 wt%; the mixing method is a method of resin for those skilled in the art, and is not particularly limited, and in the present invention, ultrasonic mixing is optionally adopted; the power of ultrasonic mixing is specifically 100-500W, more specifically 200-300W; the ultrasonic mixing time is specifically 10-60 min.
Mixing the graphene aqueous solution with a polyvinyl alcohol aqueous solution to obtain a mixed slurry; in the invention, the concentration of the polyvinyl alcohol aqueous solution is 0.5-5 wt%, the concentration of the polyvinyl alcohol aqueous solution is 0.5-3 wt%, and the concentration of the polyvinyl alcohol aqueous solution is 1-2 wt%; the polyvinyl alcohol aqueous solution is prepared by the following method: heating and mixing polyvinyl alcohol powder and water to obtain a polyvinyl alcohol aqueous solution; the temperature of the heating and mixing is specifically 80-120 ℃, more specifically 90-110 ℃, and further specifically 100 ℃; the heating and mixing time is 30-80 min, more specifically 50-60 min. The method for mixing the graphene aqueous solution and the polyvinyl alcohol aqueous solution is a resin method of a person skilled in the art, and is not particularly limited, and in the invention, ultrasonic mixing is optionally adopted; the power of ultrasonic mixing is specifically 100-500W, more specifically 200-300W; the ultrasonic mixing time is specifically 10-60 min.
Blade-coating the mixed slurry to form a film, and obtaining a heat dissipation film; wherein the blade coating is blade coating layer by layer; the thickness of the coating after blade coating is specifically 0.1-2 mm; after blade coating, preferably drying to obtain a heat dissipation film; the drying temperature is specifically 50-80 ℃, more specifically 60-70 ℃; the drying time is specifically 5-20 min, more specifically 8-15 min, and further specifically 10 min; optionally, the thickness of the heat dissipation film is 10-200 μm; the graphene of the polyvinyl alcohol solution and the sulfonic acid compound and/or sulfonate compound modifier generates strong electrostatic attraction in the blade coating layer by layer, and then a layer of thermal interface material can be formed on a substrate, particularly a metal substrate, so that a heat dissipation film is obtained, and the heat dissipation film and the substrate eliminate bubbles in the blade coating layer by layer process, so that the heat dissipation film is tightly combined and has excellent heat conductivity.
The present invention also provides a composite heat sink, comprising: the heat dissipation film is arranged on one side of the metal substrate; the heat dissipation film is the same as the above, and is not described in detail here.
Referring to fig. 3 and 4, fig. 3 is a top view of the composite heat sink provided by the present invention; FIG. 4 is a cross-sectional view of a composite heat sink provided by the present invention; in fig. 3 and 4, 1 is a heat dissipation film, and 2 is a metal substrate.
In the present invention, the metal substrate is a metal substrate known to those skilled in the art, and is not particularly limited, and optionally, the metal substrate is an aluminum plate or a copper foil; the thickness of the metal substrate can be 0.5-2.5 mm.
The radiating film is arranged on one side of the metal substrate and completely covers the metal substrate, and due to the electrostatic attraction, the combination is tight, and meanwhile, the heat-conducting silicone grease can be omitted, the air thermal resistance is reduced, the heat-conducting performance is excellent, and the production cost is reduced. Optionally, the thickness of the heat dissipation film is 10-200 μm.
The present invention further provides a display panel, including the heat dissipation film or the composite heat dissipation sheet, as shown in fig. 5 and 6, fig. 5 and 6 are schematic structural views of the display panel provided by the present invention; in FIG. 6, 1 is a heat dissipating film, 2 is a metal substrate, and 3 is a panel.
The invention also provides a display device comprising the display panel.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preparation method
1g of graphene and 0.5g of 1-naphthalenesulfonic acid sodium salt are ultrasonically stirred for 20min in 200mL of deionized water at 200W to obtain a graphene aqueous solution.
Adding polyvinyl alcohol powder (molecular weight is 90200-93280, polymerization degree is 2050 +/-70, alcoholysis degree is 98% -100%) into 600mL of deionized water, and heating at 100 ℃ for 1h to prepare a polyvinyl alcohol aqueous solution with mass fraction of 1 wt%.
And mixing and stirring the graphene aqueous solution and the polyvinyl alcohol aqueous solution according to a specific volume ratio (shown in table 1) of 200W, ultrasonically treating for 30min, then carrying out layer-by-layer blade coating on an aluminum plate/copper foil, and drying for 10min at 60 ℃ to obtain the composite radiating fin.
Examples 1 to 6 and comparative examples 1 to 12 were prepared by the above method, and the raw material ratios and the results of performance test of the heat-dissipating film are shown in table 1, wherein the in-plane thermal conductivity was measured by a Netzsch LFA447 thermal conductivity tester (Netzsch, germany), the test samples were circular with a diameter of 25mm, the thermal diffusivity was measured at 25 ℃, each sample was required to be tested to obtain at least 3 effective thermal conductivities, and the average value and the standard deviation were calculated; tensile Strength measured according to GB1040.1-2018, dynamic thermo-mechanical analysis (TA, USA) of TA Q850, using a film stretching mode at a stretching rate of 0.1 N.min-1。
TABLE 1 test results of the composition and the performance of the heat-dissipating film after drying of examples 1 to 6
As can be seen from table 1, the in-plane thermal conductivity of the composite material linearly increases with the increase of the addition amount of the naphthalene sulfonate modified graphene, and when the addition amount of the naphthalene sulfonate modified graphene is 10 wt%In-plane thermal conductivity of 16.8 W.m-1·K-1. This is mainly due to the fact that at low filler contents, the filler is present in the polymer matrix like "islands" and does not form an efficient heat conducting path. The low affinity between the rigid filler and the softer polymer matrix results in poor interfacial compatibility, phonon scattering and therefore not high thermal conductivity. With the increase of the filler content, the heat conduction path is better formed, and the heat conductivity is naturally improved. The Young's modulus steadily increases with the filling amount of the composite material, and when the filler content exceeds 5 wt%, the tensile strength of the composite material decreases. This may be due to the early onset of failure occurring in the interface and region of the filler clusters in the form of voids and cracks, resulting in a decrease in tensile strength.
TABLE 2 detection results of the composition of comparative examples 1 to 6 and the performance of the heat-dissipating film without the addition of the sulfonate
As can be seen from table 2, the composite material prepared from graphene that is not modified with a sulfonate substance has lower thermal conductivity and tensile strength than the composite material prepared from graphene that is modified with a sulfonate substance at the same content. The naphthalene sulfonate substance has an aromatic ring structure in a main chain, and can interact with graphene through pi-pi stacking. The graphene modified by the naphthalenesulfonate is negatively charged, and stacking is avoided due to electrostatic repulsion among the graphene; on the other hand, the naphthalene sulfonate substance can be used as a bridge for connecting graphene (pi-pi) and polyvinyl alcohol (hydrogen bond), so that graphene in the solution is stabilized, stacking of the graphene in the polyvinyl alcohol solution is avoided, and uneven distribution of the graphene in the layer-by-layer blade coating process is also avoided, and the heat conductivity and tensile strength of the composite material prepared from the graphene modified by the naphthalene sulfonate substance are obviously improved.
TABLE 3 detection results of the components of comparative examples 7 to 12 and the performance of the heat-dissipating film obtained by adding a sulfonate containing no aromatic ring as a modifier
As can be seen from table 3, when the aromatic ring-free sulfonate is added to modify graphene, the thermal conductivity and tensile strength are improved compared to those of the composite materials without any modification (comparative examples 1 to 6), but the properties are lower than those of the composite materials prepared from aromatic ring-containing sulfonate-modified graphene (examples 1 to 6). The sulfonate without aromatic ring is used as dispersant, which is beneficial to improving the performance of the composite material. However, the sulfonate containing no aromatic ring can not interact with graphene through pi-pi stacking, so that the sulfonate cannot serve as a bridge for connecting graphene and polyvinyl alcohol, cannot play a role in stabilizing graphene in a solution, cannot effectively avoid stacking of graphene in a polyvinyl alcohol solution, can cause uneven distribution of graphene in a layer-by-layer blade coating process, and causes poor mechanical and heat dissipation performance of comparative examples 7-12 as compared with examples 1-6.
As can be seen from tables 1 to 3, the heat dissipation film provided by the present invention modifies graphene by using sulfonic acid compounds and/or sulfonate compounds, and can interact with graphene through pi-pi stacking, and the graphene modified by the sulfonic acid compounds and/or sulfonate compounds has negative charges, and stacking is avoided due to electrostatic repulsion between the graphene; on the other hand, the sulfonic acid compounds and/or the sulfonate compounds can be used as bridges for connecting graphene (pi-pi) and polyvinyl alcohol (hydrogen bond), so that the graphene in the solution is stabilized, the stacking of the graphene in the polyvinyl alcohol solution is avoided, and the uneven distribution of the graphene in the layer-by-layer blade coating process is also avoided; the film has good mechanical property, is not easy to age, can eliminate air thermal resistance, has excellent heat-conducting property, and has lower preparation process cost, easy operation and contribution to industrialization.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (11)
1. A heat dissipating film comprising a mixture of materials; the mixed material comprises:
1-20 parts by weight of graphene;
80-100 parts by weight of polyvinyl alcohol;
0.5-10 parts by weight of a graphene modifier;
the graphene modifier is a sulfonic acid compound and/or a sulfonate compound, and comprises an aromatic ring group.
2. The heat spreading film of claim 1, wherein the aromatic ring group is a fused ring group.
3. The heat dissipation film of claim 1, wherein the graphene modifier is one or more of sodium methylenedinaphthalene sulfonate, sodium alkyl naphthalene sulfonate, sodium 1-naphthalene sulfonate, sodium 2-naphthalene sulfonate, and sodium 2-amino-1-naphthalene sulfonate.
4. A method for preparing the heat dissipating film of claim 1, comprising:
s1) mixing graphene and a graphene modifier in water to obtain a graphene aqueous solution;
s2) mixing the graphene aqueous solution with a polyvinyl alcohol aqueous solution to obtain a mixed slurry;
s3) carrying out blade coating on the mixed slurry to form a film, thus obtaining the heat dissipation film.
5. The production method according to claim 4, wherein the mixing in step S1) is ultrasonic mixing; the power of ultrasonic mixing is 100-500W; the ultrasonic mixing time is 10-60 min.
6. The method according to claim 4, wherein the concentration of the aqueous polyvinyl alcohol solution is 0.5 to 5 wt%.
7. The production method according to claim 5, wherein the mixing in step S2) is ultrasonic mixing; the power of ultrasonic mixing is 100-500W; the ultrasonic mixing time is 10-60 min.
8. A composite heat sink, comprising: the heat dissipation film is arranged on one side of the metal substrate; the heat dissipation film is the heat dissipation film as set forth in any one of claims 1 to 3 or the heat dissipation film prepared by the preparation method as set forth in any one of claims 4 to 7.
9. The composite heat sink as recited in claim 8 wherein the metal substrate is selected from the group consisting of aluminum or copper foil.
10. A display panel comprising the heat dissipating film according to any one of claims 1 to 3, the heat dissipating film produced by the production method according to any one of claims 4 to 7, or the composite heat dissipating sheet according to any one of claims 8 to 9.
11. A display device comprising the display panel of claim 10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWM390642U (en) * | 2010-01-25 | 2010-10-11 | Shiu Li Technology Co Ltd | Thermal structure and a radiation film thereon |
| CN203149247U (en) * | 2013-02-19 | 2013-08-21 | 京东方科技集团股份有限公司 | Display panel and display device |
| US20170018327A1 (en) * | 2015-07-13 | 2017-01-19 | National University Corporation Nagoya University | Conducting film and method for producing the same |
| CN111925697A (en) * | 2019-05-13 | 2020-11-13 | 中国科学院化学研究所 | Graphene/water-soluble polymer composite material and preparation method thereof |
| WO2021137685A1 (en) * | 2019-12-31 | 2021-07-08 | Universiti Putra Malaysia | A method of preparing a water-dispersible graphene nanoplatelet and uses thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWM390642U (en) * | 2010-01-25 | 2010-10-11 | Shiu Li Technology Co Ltd | Thermal structure and a radiation film thereon |
| CN203149247U (en) * | 2013-02-19 | 2013-08-21 | 京东方科技集团股份有限公司 | Display panel and display device |
| US20170018327A1 (en) * | 2015-07-13 | 2017-01-19 | National University Corporation Nagoya University | Conducting film and method for producing the same |
| CN111925697A (en) * | 2019-05-13 | 2020-11-13 | 中国科学院化学研究所 | Graphene/water-soluble polymer composite material and preparation method thereof |
| WO2021137685A1 (en) * | 2019-12-31 | 2021-07-08 | Universiti Putra Malaysia | A method of preparing a water-dispersible graphene nanoplatelet and uses thereof |
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