CN113183544A - Heat-conducting gasket and preparation method thereof - Google Patents
Heat-conducting gasket and preparation method thereof Download PDFInfo
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- CN113183544A CN113183544A CN202110436502.9A CN202110436502A CN113183544A CN 113183544 A CN113183544 A CN 113183544A CN 202110436502 A CN202110436502 A CN 202110436502A CN 113183544 A CN113183544 A CN 113183544A
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Images
Classifications
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- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
- B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0092—Metallizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/04—Punching, slitting or perforating
- B32B2038/047—Perforating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Fluid Mechanics (AREA)
- Plasma & Fusion (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Gasket Seals (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a heat-conducting gasket, which comprises a heat-conducting film and an adhesive layer; and optionally other thermally conductive fillers, wherein the thermally conductive film has a plurality of holes penetrating the upper and lower surfaces thereof, and the plurality of holes are filled with an adhesive. Therefore, the adhesives on different layers can be connected through the plurality of holes to form a continuous structure, the heat-conducting film is wrapped on a microscopic scale, the adhesives and the heat-conducting film can be strongly combined together without surface coating, and the problem of self layering of the heat-conducting film is avoided.
Description
Technical Field
The invention relates to a heat conduction gasket and a preparation method thereof, in particular to a longitudinal high-heat-conduction gasket with a reinforced heat conduction film, and belongs to the technical field of heat conduction and heat dissipation.
Background
The rapid development of mobile networks allows more and more electronic devices to be connected to the mobile networks, and a large number of new services and applications are generated. Especially, in the coming of the 5G era, the functions of mobile network equipment products are more powerful, the power consumption is synchronously increased, the design space size is smaller and smaller, and more heat energy is generated by electronic components in the using process. If the heat energy cannot be dissipated from the inside in time, the operation speed of the electronic element is reduced, and the service life of the electronic element is shortened. Therefore, how to effectively remove a large amount of heat from the components generating higher temperatures is a serious problem for thermal management of 5G electronic devices.
Thermal Interface Materials (TIM) is one of the key Materials for determining the heat dissipation efficiency of electronic products, and a Thermal pad is the most interesting material in the field of Thermal Interface Materials and the most studied material. The heat conductivity coefficient of the common heat conducting gasket product is difficult to reach 10W/(m.K), and the application in the 5G field is far from being satisfied. Although the carbon fiber reinforced heat conduction gasket adopted at present has a high heat conduction coefficient, the carbon fibers are in a dispersed state in the matrix instead of a continuous state, and the exertion of the heat conduction effect of the carbon fibers is limited, so that the heat conduction coefficient of the heat conduction gasket is difficult to further improve. Meanwhile, the high thermal conductivity carbon fiber is expensive and limited in purchasing.
On the other hand, the graphite heat-conducting film and the graphene heat-conducting film both have higher heat conductivity coefficients, and if the graphite heat-conducting film and the graphene heat-conducting film can be used as a continuous integral reinforced heat-conducting gasket, the heat conductivity coefficients of the graphite heat-conducting film and the graphene heat-conducting film can be increased certainly and greatly. In contrast, in International Journal of Heat and Mass Transfer 118(2018) 510-. However, the graphene thermal conductive film/epoxy resin composite material obtained by the method is a hard material, cannot be in full contact with an interface, has high thermal resistance and is not suitable for being used as a thermal conductive interface material. In addition, in the documents ACS Nano 2019,13,11561-11571, it is described that the graphene thermal conductive film is made into a corrugated shape, and the height and aggregation degree of the corrugations are controlled, so as to obtain a pure graphene material with longitudinal thermal conductivity. The heat conduction material obtained by the method can obtain a high heat conduction coefficient in the longitudinal direction, but cannot be in full contact with an interface due to rough surface, a large number of gaps among folds, hardness of the graphene film and the like, has high heat resistance, and is not suitable for serving as a heat conduction gasket material. In addition, although the graphene thermal conductive film is directly applied to longitudinal thermal conduction in the above documents, the graphene thermal conductive film is not suitable for a thermal conduction interface due to large thermal resistance, limited heat dissipation effect, and the like.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
In view of one or more of the problems in the prior art, the present invention provides a thermal pad that has excellent thermal conductivity, can be in full contact with an interface, has low thermal contact resistance, and has excellent thermal conduction and heat dissipation effects. In addition, the invention also provides a method for preparing the heat-conducting gasket.
According to an aspect of the present invention, there is provided a thermal conductive gasket comprising a thermal conductive film and an adhesive layer; and optionally other thermally conductive fillers, wherein the thermally conductive film has a plurality of holes penetrating the upper and lower surfaces thereof, and the plurality of holes are filled with an adhesive. Therefore, the adhesives on different layers can be connected through the plurality of holes to form a continuous structure, the heat-conducting film is wrapped on a microscopic scale, the adhesives and the heat-conducting film can be strongly combined together without surface coating, and the problem of self layering of the heat-conducting film is avoided.
Wherein the heat conducting film and the adhesive are stacked in a staggered manner layer by layer.
The heat conduction film is selected from one of graphite or graphene heat conduction films and boron nitride heat conduction films, and the graphite or graphene heat conduction film is preferred.
Wherein the thickness of the heat conducting film is 4-60 μm, preferably 10-50 μm, and more preferably 15-40 μm.
Wherein the size of a plurality of pores of the heat conduction film is 0.5-200 μm, preferably 5-100 μm, more preferably 10-50 μm, and the pore spacing is 5-200 μm, preferably 10-150 μm, more preferably 20-100 μm.
Wherein the binder comprises at least one component selected from silicone oil, silicone gel, polydimethylsiloxane, alpha, omega-dihydroxypolydimethylsiloxane, polydiphenylsiloxane, alpha, omega-dihydroxypolymethyl (3,3, 3-trifluoropropyl) siloxane, cyanosiloxysilane, and alpha, omega-diethylpolydimethylsiloxane, wherein silicone oil is preferred.
Wherein the other heat conductive filler is selected from one of alumina, boron nitride, graphite, silica, zinc oxide, beryllium oxide, aluminum nitride or a mixture thereof, and alumina, aluminum nitride, boron nitride or a mixture thereof is preferred.
Wherein the thickness of the heat-conducting gasket is 0.25-3mm, preferably 0.5-2 mm.
According to another aspect of the present invention, there is provided a method of manufacturing a thermal gasket, comprising the steps of:
(1) forming a plurality of holes penetrating through the upper and lower surfaces of the heat-conducting film on the heat-conducting film;
(2) laminating an adhesive layer on the heat-conducting film formed in the step (1), then continuously laminating the heat-conducting film formed in the step (1) on the adhesive layer, and repeating the layer-by-layer alternate lamination process to form a stacked body;
(3) performing compression molding on the stacked body obtained in the step (2), and performing vulcanization treatment;
(4) slicing the formed body obtained in the step (3) along a direction perpendicular to the plane of the heat-conducting film;
(5) and (4) carrying out secondary vulcanization treatment on the slices obtained in the step (4), and optionally carrying out surface grinding treatment to obtain the heat-conducting gasket.
Wherein the binder layer further contains other heat-conducting filler, and the heat-conducting filler is selected from one of alumina, boron nitride, graphite, silica, zinc oxide, beryllium oxide, aluminum nitride or a mixture thereof, wherein the alumina, the aluminum nitride, the boron nitride or the mixture thereof is preferred.
Among them, a plurality of holes are preferably formed on the heat conductive film by a laser technique. The perforation may be performed by other methods.
In the step (2), an adhesive is laminated on the heat conductive film formed in the step (1) by coating or spraying.
Wherein the temperature of the vulcanization treatment in the step (3) is 100-150 ℃. The secondary vulcanization temperature is 120-200 ℃.
Preferably, the heat conducting film is subjected to surface treatment, and the surface treatment is at least one of surface metallization treatment and plasma treatment; preferably, the metallization treatment is selected from at least one of copper plating, nickel plating, iron plating and silver plating; preferably, the thickness of the metal plating layer is 0.1 to 2 μm, preferably 0.5 to 1 μm; preferably, the plasma treatment is performed under an air atmosphere, a nitrogen atmosphere, or an oxygen atmosphere; preferably, the plasma power of the plasma treatment is in the range of 1-10KW, preferably 3-8KW
According to yet another aspect of the present invention, there is provided a method of bonding a membrane structure to a polymeric material, comprising the steps of:
(1) forming a plurality of holes on the membrane structure penetrating through the upper and lower surfaces of the membrane structure;
(2) laminating a polymer material on the film structure formed in step (1), wherein the polymer material covers at least the plurality of holes; and
(3) the lamination of the film structure or other material is optionally continued.
The film structure is selected from one of a graphite or graphene heat-conducting film and a boron nitride heat-conducting film, and the graphite or graphene heat-conducting film is preferred; the high polymer material is a binder.
According to this method, the membrane structure can be easily combined with other interfaces or other materials.
According to still another aspect of the present invention, there is provided an electronic apparatus including a heat source, a heat dissipation member, and the heat conductive gasket of the present invention interposed between the heat source and the heat dissipation member.
The invention has the following beneficial effects:
(1) due to the fact that the holes in the micron level are formed in the heat conduction film, the heat conduction film is well combined with the adhesive such as silicon oil or silicon gel while the whole continuity and integrity of the heat conduction film are guaranteed, the heat conduction coefficient of the heat conduction gasket is improved, and the heat resistance is reduced.
(2) The adhesive and the heat-conducting film are mutually combined in a layer-by-layer staggered and laminated mode, so that the problem of hardness of the graphite or graphene heat-conducting film is solved, the whole material has good mechanical elasticity, can be in good contact with an interface, and reduces contact thermal resistance.
(3) The concept of the invention also provides a new idea and a new method for combining other membrane structure materials with high polymer materials.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a heat-conducting film according to the present invention after through holes are punched on the surface;
FIG. 2 is a schematic view of a layer-by-layer, compression molded stack in which a plurality of holes are filled with an adhesive and integrated with a peripheral adhesive;
fig. 3 is a schematic view of the heat conductive gasket of the present invention formed after slicing, in which the heat conductive films are arranged along the longitudinal direction of the gasket.
Description of reference numerals: 1: a thermally conductive gasket; 2: a stack; 10: a thermally conductive film; 11: an aperture; 12: an adhesive layer; 12 a: and an adhesive filled in the hole.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
First, the heat conductive pad of the present invention will be explained.
As shown in fig. 3, the heat conductive pad 1 of the present invention includes a heat conductive film 10 and an adhesive layer 12, wherein a plurality of holes 11 penetrating through the upper and lower surfaces of the heat conductive film 10 are formed on the heat conductive film 10, and the plurality of holes 11 are filled with an adhesive 12 a. The thickness of the heat conducting pad 1 is 0.25 to 3mm, preferably 0.5 to 2 mm.
As the heat conductive film of the present invention, a heat conductive film commonly used in the art may be used, for example, any one of a graphite or graphene heat conductive film and a boron nitride heat conductive film is selected, and a graphite or graphene heat conductive film is preferable.
The length and width of the heat conductive film are not particularly limited and may be selected as desired. The thickness of the thermally conductive film can be selected as desired, and is preferably in the range of 4 to 60 μm, for example, 10 to 50 μm or 5 to 40 μm.
The manner of forming the plurality of holes in the thermally conductive film is not particularly limited, and the holes are preferably formed by laser, from the viewpoint of accuracy and effect, and the holes have a size of 0.5 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm, and a hole pitch of 5 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm, where the hole pitch is a distance between adjacent edges of two adjacent holes. The micron-level hole formed in this way can ensure the integral integrity of the heat-conducting film, provide a continuous heat-conducting channel and greatly improve the heat-conducting coefficient of the heat-conducting gasket.
In addition, a surface treatment, which is at least one of a surface metallization treatment and a plasma treatment, may be applied to the heat conductive film as necessary.
The metallization treatment may be, for example, copper plating, nickel plating, iron plating, silver plating. The thickness of the metal plating layer may be 0.1 to 2 μm, preferably 0.5 to 1 μm.
As for the plasma treatment, it is preferable to carry out under an air atmosphere, a nitrogen atmosphere or an oxygen atmosphere, and the plasma power may be 1 to 10KW, preferably 3 to 8 KW.
The binder used in the present invention may be at least one member selected from the group consisting of silicone, polyurethane, polyacrylate, and polyolefin elastomer, and silicone is preferable. The silicone gum may be at least one silicone oil, silicone gel, polydimethylsiloxane, α, ω -dihydroxypolydimethylsiloxane, polydiphenylsiloxane, α, ω -dihydroxypolymethyl (3,3, 3-trifluoropropyl) siloxane, cyanosiloxysilane, α, ω -diethylpolydimethylsiloxane.
In addition, the binder may contain other additives as needed, for example, other thermally conductive fillers such as alumina, boron nitride, graphite, silica, zinc oxide, beryllium oxide, aluminum nitride, or mixtures thereof, and the like, preferably alumina, aluminum nitride, boron nitride, or mixtures thereof, may be added.
As a method of applying (laminating) the adhesive to the thermally conductive film, a process such as coating or spraying may be employed, and other methods known in the art may be employed as long as the adhesive can be laminated substantially uniformly) to the thermally conductive film. In the process of applying the adhesive, the adhesive enters the plurality of holes of the heat-conducting film and is integrated with the adhesive on the upper (lower) surface and the periphery of the heat-conducting film, so that the problem that the heat-conducting film cannot be combined with the adhesive such as silicon oil or silicon gel is effectively solved, good contact between the heat-conducting gasket and a heat dissipation interface is provided, and the contact thermal resistance is reduced.
In addition, the mode of stacking the heat-conducting film and the binder layer in a staggered manner for a plurality of layers layer by layer solves the problem of heat-conducting hardness of graphite or graphene, so that the heat-conducting gasket has good mechanical elasticity, the compressibility is improved, and the longitudinal high-heat-conducting gasket is provided.
An exemplary method of making a thermal gasket of the present invention comprises the steps of:
(1) forming a plurality of holes 11 penetrating the upper and lower surfaces of the heat conductive film 10 on the heat conductive film, as shown in fig. 1;
(2) an adhesive layer 12 is laminated on the thermally conductive film 10 formed in step (1), and then the thermally conductive film 10 formed in step (1) is laminated on the adhesive layer. This step may cause the adhesive 12a to enter the plurality of holes 11. Repeating the layer-by-layer alternating lamination process to form a stacked body 2, as shown in fig. 2;
(3) performing compression molding on the stacked body 2 obtained in the step (2), and performing vulcanization treatment;
(4) slicing the formed body obtained in the step (3) along a direction perpendicular to the plane of the heat-conducting film (as shown by an arrow in fig. 2), as shown in fig. 2;
(5) and (4) carrying out secondary vulcanization treatment on the slices obtained in the step (4), and optionally carrying out surface grinding treatment to obtain the heat-conducting gasket 1 (shown in figure 3).
The compression molding in step (3) may be, but not limited to, compression molding, and other methods known in the art may also be used.
Wherein, the temperature of the sulfurization treatment in the step (3) is 100-150 ℃, such as 110-140 ℃, 120-130 ℃, etc.
Wherein, the temperature of the secondary vulcanization treatment in the step (5) is 120-200 ℃, such as 140-180 ℃ or 150-170 ℃, and the like.
Wherein, the slicing process in the step (4) has no special requirements, and the ultrasonic cutting process is preferentially adopted from the aspects of cutting precision, continuity and the like. The thickness of the slices may be as conventional in the art, such as 0.5-5mm, or may be cut to a suitable thickness, such as 1-2mm, as desired. In addition, preferably, the slices can be polished to obtain a heat conduction gasket with a smoother surface, which helps to further reduce the contact thermal resistance.
According to yet another aspect of the present invention, there is provided a method of bonding a membrane structure to other polymeric materials, comprising the steps of:
(1) forming a plurality of holes on the membrane structure penetrating through the upper and lower surfaces of the membrane structure;
(2) laminating a polymer material on the film structure formed in step (1), wherein the polymer material covers at least the plurality of holes; and
(3) the lamination of the film structure or other material is optionally continued.
The film structure can be selected from one of a graphite or graphene heat conduction film and a boron nitride heat conduction film, and the graphite or graphene heat conduction film is preferred; the high polymer material is a binder.
According to the invention, the heat-conducting film such as graphite or graphene is applied to the heat-conducting gasket in a continuous state, so that an internal heat-conducting channel network is formed, and thus the longitudinal heat conductivity coefficient of the gasket is greatly improved; a plurality of micron-sized holes are formed in the heat-conducting film, so that the silicone oil or silicone gel can be tightly bonded with the heat-conducting film to form a stable integral structure; in addition, since the sheet is cut along the perpendicular direction in which the heat conductive films are arranged, a gasket material having high heat conductivity in the longitudinal direction can be obtained. In addition, due to the existence of micron-sized or submicron-sized holes, the problem that the heat-conducting film is hard due to small thickness (0.25-3mm) when vertically arranged in the heat-conducting gasket is solved, and the contact thermal resistance can be further reduced due to the mechanical properties such as flexibility and elasticity which are completely expressed by the cured silicone oil or silicone gel. Meanwhile, the preparation method of the invention also optimizes the process steps of orientation and surface treatment in the existing heat conducting gasket manufacturing process.
The present invention is described in detail below with reference to more specific examples.
Example 1:
in this embodiment, the preparation process of the graphene heat-conducting film reinforced longitudinal high-thermal-conductivity gasket includes the following steps:
1) perforating a graphene heat-conducting film with the thickness of 4 microns by a laser technology, and penetrating the upper surface and the lower surface, wherein the size of each hole is 200 microns, and the distance between the holes is 200 microns;
2) uniformly mixing the silica gel with heat-conducting alumina powder, and performing defoaming treatment to obtain mixed silica gel, wherein the alumina content is 70%;
3) uniformly coating the mixed silica gel obtained in the step 2) on the surface of the perforated graphene heat-conducting film in the step 1) in a blade coating manner, and stacking the graphene heat-conducting films in a staggered manner to form a stacked body;
4) placing the stacked body in the step 3) in a mould, and performing hot-press molding at 60 ℃ after vacuum defoaming;
5) directly carrying out vulcanization treatment on the basis of the step 4), wherein the vulcanization temperature is 125 ℃;
6) after cooling, taking out the vulcanized sample, and slicing the vulcanized sample along the direction vertical to the plane of the graphene heat-conducting film in an ultrasonic cutting mode to obtain a sheet material with the thickness of 0.25-3 mm;
7) carrying out secondary vulcanization on the flaky material, wherein the vulcanization temperature is 200 ℃;
8) and polishing the surface of the sheet material subjected to secondary vulcanization to obtain the graphene heat-conducting film reinforced longitudinal high-heat-conductivity gasket.
Example 2:
in this embodiment, the preparation process of the graphene heat-conducting film reinforced longitudinal high-thermal-conductivity gasket includes the following steps:
1) punching a graphene heat-conducting film with the thickness of 60 micrometers by a laser technology, and penetrating the upper surface and the lower surface, wherein the size of each hole is 0.5 micrometer, and the distance between the holes is 5 micrometers;
2) uniformly mixing silica gel and heat-conducting aluminum nitride, and performing defoaming treatment to obtain mixed silica gel, wherein the content of aluminum nitride is 60%;
3) uniformly coating the mixed silica gel obtained in the step 2) on the surface of the perforated graphene heat-conducting film in the step 1) in a blade coating manner, and stacking the graphene heat-conducting films in a staggered manner to form a stacked body;
4) placing the stacked body in the step 3) in a mould, and performing hot-press molding at 80 ℃ after vacuum defoaming;
5) directly carrying out vulcanization treatment on the basis of the step 4), wherein the vulcanization temperature is 100 ℃;
6) after cooling, taking out the vulcanized sample, and slicing the vulcanized sample along the direction vertical to the plane of the graphene heat-conducting film in an ultrasonic cutting mode to obtain a sheet material with the thickness of 0.25-3 mm;
7) carrying out secondary vulcanization on the flaky material, wherein the vulcanization temperature is 200 ℃;
8) and polishing the surface of the sheet material subjected to secondary vulcanization to obtain the graphene heat-conducting film reinforced longitudinal high-heat-conductivity gasket.
Example 3:
in this embodiment, the preparation process of the graphene heat-conducting film reinforced longitudinal high-thermal-conductivity gasket includes the following steps:
1) punching a graphene heat-conducting film with the thickness of 30 micrometers by a laser technology, and penetrating the upper surface and the lower surface, wherein the size of each hole is 25 micrometers, and the distance between the holes is 20 micrometers;
2) uniformly mixing silica gel with boron nitride powder and alumina powder, and performing defoaming treatment to obtain mixed silica gel, wherein the content of boron nitride is 20%, and the content of alumina is 50%;
3) uniformly coating the mixed silica gel obtained in the step 2) on the surface of the perforated graphene heat-conducting film in the step 1) in a blade coating manner, and stacking the graphene heat-conducting films in a staggered manner to form a stacked body;
4) placing the stacked body in the step 3) in a mould, and performing hot-press molding at 70 ℃ after vacuum defoaming;
5) directly carrying out vulcanization treatment on the basis of the step 4), wherein the vulcanization temperature is 140 ℃;
6) after cooling, taking out the vulcanized sample, and slicing the vulcanized sample along the direction vertical to the plane of the graphene heat-conducting film in an ultrasonic cutting mode to obtain a sheet material with the thickness of 0.25-3 mm;
7) carrying out secondary vulcanization on the flaky material, wherein the vulcanization temperature is 180 ℃;
8) and polishing the surface of the sheet material subjected to secondary vulcanization to obtain the graphene heat-conducting film reinforced longitudinal high-heat-conductivity gasket.
Example 4:
in this embodiment, the preparation process of the graphene heat-conducting film reinforced longitudinal high-thermal-conductivity gasket includes the following steps:
1) punching a graphene heat-conducting film with the thickness of 15 micrometers by a laser technology, and penetrating the upper surface and the lower surface, wherein the size of each hole is 10 micrometers, and the distance between the holes is 25 micrometers;
2) uniformly mixing silica gel and alumina powder, and performing defoaming treatment to obtain mixed silica gel, wherein the alumina content is 80%;
3) uniformly coating the mixed silica gel obtained in the step 2) on the surface of the perforated graphene heat-conducting film in the step 1) in a blade coating manner, and stacking the graphene heat-conducting films in a staggered manner to form a stacked body;
4) placing the stacked body in the step 3) in a mould, and performing hot-press molding at 75 ℃ after vacuum defoaming;
5) directly carrying out vulcanization treatment on the basis of the step 4), wherein the vulcanization temperature is 150 ℃;
6) after cooling, taking out the vulcanized sample, and slicing the vulcanized sample along the direction vertical to the plane of the graphene heat-conducting film in an ultrasonic cutting mode to obtain a sheet material with the thickness of 0.25-3 mm;
7) carrying out secondary vulcanization on the flaky material, wherein the vulcanization temperature is 200 ℃;
8) and polishing the surface of the sheet material subjected to secondary vulcanization to obtain the graphene heat-conducting film reinforced longitudinal high-heat-conductivity gasket.
The high thermal conductive gasket obtained in each of the above examples was subjected to the following performance tests.
And (3) testing the heat conductivity coefficient: according to the testing method, the apparent thermal conductivity coefficient is obtained by testing under different thicknesses by adopting ASTMD 5470-17.
Testing thermal resistance: test method the overall thermal resistance of a 2mm thick sample at 50% strain was tested using astm d 5470-17.
And (3) testing the compression performance: with reference to ASTM D575-1991, a sample was compressed to a strain of 50% at a compression rate of 0.5mm/s and observed for compression after holding for 10 min.
Adhesion testing: after the compression performance test was completed, the pressure head was moved upward to measure the tensile stress, and the adhesion was evaluated according to astm d 575-1991.
And (3) testing the rebound rate: the thickness after recovery was observed by releasing the pressure after holding the sample for 30min after compressing it to 50% strain according to ASTM D395.
Testing thermal resistance reliability:
and (3) high-temperature aging: 125 ℃ for 1000h
High temperature and high humidity: 85 ℃/85% RH, 1000h
Temperature cycle: temperature change rate of-40 deg.C to 125 deg.C, 10 to 15 deg.C/min, 1000 cycles
After the aging experiment, the change rate of the thermal resistance of the heat conduction gasket is examined.
The test results are summarized in the table below.
| Performance parameter | Example 1 | Example 2 | Example 3 | Example 4 |
| Coefficient of thermal conductivity (W.m)-1·K-1) | 88.61 | 104.52 | 93.52 | 110.37 |
| Thermal resistance (K.in)2·W-1) | 0.083 | 0.061 | 0.069 | 0.056 |
| Compressive stress (psi) | 15.34 | 26.69 | 21.03 | 19.46 |
| Adhesion (psi) | 12.11 | 11.94 | 13.24 | 10.94 |
| Rebound resilience (%) | 91.39 | 95.72 | 96.32 | 92.18 |
| Thermal resistance increase after aging (%) | 8.94 | 7.45 | 9.13 | 8.87 |
As can be seen from the above table, the thermal conductivity of the heat conductive pad (thermal conductivity generally not more than 10 W.m) is comparable to that of the prior art-1·K-1) Compared with the prior art, the heat-conducting gasket has excellent heat conductivity coefficient (up to 88.61 W.m)-1·K-1The heat conducting gasket has extremely low thermal resistance and excellent mechanical performance, is a heat conducting gasket with excellent heat conducting and radiating performance, and is very suitable for various electronic equipment needing high heat conducting gaskets.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be obvious to those skilled in the art that modifications may be made in the technical solutions described in the above embodiments, or some technical features may be equivalently replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. A heat conductive gasket comprises a heat conductive film and an adhesive layer; and optionally other thermally conductive fillers, wherein the thermally conductive film has a plurality of holes penetrating the upper and lower surfaces thereof, and the plurality of holes are filled with an adhesive.
2. The thermal gasket of claim 1, wherein the thermal film and the adhesive are stacked in layers in an alternating manner.
3. The thermally conductive gasket of claim 1 or 2, wherein the thermally conductive film is selected from one of a graphite thermally conductive film, a graphene thermally conductive film, a boron nitride thermally conductive film, preferably graphite or graphene thermally conductive film;
preferably, the thickness of the heat-conducting film is 4 to 60 μm, preferably 10 to 50 μm, more preferably 15 to 40 μm;
preferably, the size of the plurality of pores of the thermally conductive film is 0.5 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm, and the pore pitch is 5 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm.
4. The thermal conductive pad of any one of claims 1 to 3, wherein said adhesive comprises at least one selected from silicone oils, polyurethanes, polyacrylates, polyolefin elastomers, with silicone oils being preferred, wherein preferably said silicone oils are selected from at least one of silicone oils, silicone gels, polydimethylcyclosiloxanes, polydimethylsiloxanes, α, ω -dihydroxypolydimethylsiloxanes, polydiphenylsiloxanes, α, ω -dihydroxypolymethyl (3,3, 3-trifluoropropyl) siloxanes, cyanosiloxysilanes, α, ω -diethylpolydimethylsiloxanes;
and/or the presence of a gas in the gas,
the other heat conducting filler is selected from one of alumina, boron nitride, graphite, silica, zinc oxide, beryllium oxide, aluminum nitride or a mixture thereof, wherein alumina, aluminum nitride, boron nitride or a mixture thereof is preferred.
5. A thermal gasket according to any one of claims 1 to 4, having a thickness of 0.25-3mm, preferably 0.5-2 mm.
6. A method of making a thermal gasket comprising the steps of:
(1) forming a plurality of holes penetrating through the upper and lower surfaces of the heat-conducting film on the heat-conducting film;
(2) laminating an adhesive layer on the heat-conducting film formed in the step (1), then laminating the heat-conducting film formed in the step (1) on the adhesive layer, and repeating the layer-by-layer alternate lamination process to form a stacked body;
(3) performing compression molding on the stacked body obtained in the step (2), and performing vulcanization treatment;
(4) slicing the formed body obtained in the step (3) along a direction perpendicular to the plane of the heat-conducting film;
(5) and (4) carrying out secondary vulcanization treatment on the slices obtained in the step (4), and optionally carrying out surface grinding treatment to obtain the heat-conducting gasket.
7. The method of claim 6, wherein the thermally conductive film is selected from one of a graphite or graphene thermally conductive film, a boron nitride thermally conductive film, preferably a graphite or graphene thermally conductive film;
preferably, the thickness of the thermally conductive film is 4 to 60 μm, preferably 10 to 50 μm, more preferably 15 to 40 μm.
Preferably, the size of the plurality of pores of the thermally conductive film is 0.5 to 200 μm, preferably 5 to 100 μm, more preferably 10 to 50 μm, and the pore pitch is 5 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm.
8. The method according to claim 6 or 7, wherein the binder comprises at least one component selected from the group consisting of silicone oils, silicone gels, polyurethanes, polyacrylates, polyolefin elastomers, wherein silicone gels are preferred, preferably the silicone gels are selected from at least one of silicone oils, silicone gels, polydimethylcyclosiloxanes, polydimethylsiloxanes, α, ω -dihydroxypolydimethylsiloxanes, polydiphenylsiloxanes, α, ω -dihydroxypolymethyl (3,3, 3-trifluoropropyl) siloxanes, cyanosiloxysilanes, α, ω -diethylpolydimethylsiloxanes;
and/or the presence of a gas in the gas,
the adhesive layer also contains other heat-conducting fillers, and the heat-conducting fillers are selected from one of alumina, boron nitride, graphite, silica, zinc oxide, beryllium oxide, aluminum nitride or a mixture thereof, wherein the alumina, the aluminum nitride, the boron nitride or the mixture thereof are preferred.
9. A method according to any one of claims 6 to 8, wherein the thickness of the thermal pad is 0.25-3mm, preferably 0.5-2 mm.
10. The method according to any one of claims 6 to 9, wherein a plurality of holes are formed on the thermally conductive film by a laser technique.
11. The method according to any one of claims 6 to 10, wherein in the step (2), an adhesive is laminated on the thermally conductive film formed in the step (1) by coating or spraying;
and/or the temperature of the vulcanization treatment in the step (3) is 100-150 ℃, and the temperature of the secondary vulcanization is 120-200 ℃.
12. The method according to any one of claims 6 to 11, wherein the heat conductive film is subjected to a surface treatment, the surface treatment being at least one of a surface metallization treatment, a plasma treatment;
preferably, the metallization treatment is selected from at least one of copper plating, nickel plating, iron plating and silver plating; preferably, the thickness of the metal plating layer is 0.1 to 2 μm, preferably 0.5 to 1 μm;
preferably, the plasma treatment is performed under an air atmosphere, a nitrogen atmosphere, or an oxygen atmosphere; preferably, the plasma power of the plasma treatment is in the range of 1-10KW, preferably 3-8 KW.
13. A method of bonding a membrane structure to a polymeric material, comprising the steps of:
(1) forming a plurality of holes on the membrane structure penetrating through the upper and lower surfaces of the membrane structure;
(2) laminating a polymer material on the film structure formed in step (1), wherein the polymer material covers at least the plurality of holes; and optionally
(3) The lamination of the film structure or other material is continued.
14. The method according to claim 13, wherein the film structure is selected from one of a graphite or graphene thermally conductive film, a boron nitride thermally conductive film, preferably a graphite or graphene thermally conductive film; the high polymer material is a binder.
15. An electronic device comprising a heat source, a heat sink, and an insulating heat-conducting pad sandwiched between the heat source and the heat sink, wherein the heat-conducting pad is the insulating heat-conducting pad according to any one of claims 1 to 5 or the method according to any one of claims 6 to 12.
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