CN115895262B - A thermal interface material with a vertically oriented structure and its preparation method - Google Patents
A thermal interface material with a vertically oriented structure and its preparation method Download PDFInfo
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Abstract
本发明属于热界面材料制备技术领域，公开了一种竖直取向结构热界面材料及其制备方法，所述竖直取向结构热界面材料包括有机聚合物基体和具有竖直片层取向结构的薄膜；首先制备高深宽比微管道阵列模具；配制纳米片分散液；将分散液注入微管道阵列模具中，然后流入至凝固液里，再经过冷冻干燥和高温热处理得到竖直片层取向结构的薄膜；然后将有机聚合物灌封于竖直片层取向结构的薄膜制备得到。本发明利用高深宽比微管道模具的尺寸限域影响和非牛顿流体在模具出口处的挤出膨胀效应，纳米片材料由开始的水平排布经过模具流出后得到内部具有高度有序竖直片层结构的薄膜，成本低，可实现大面积定制化的生产制备，可广泛应用于大功率电子器件等需要高效热管理的应用场景。
The invention belongs to the technical field of preparation of thermal interface materials, and discloses a thermal interface material with a vertical orientation structure and a preparation method thereof. The thermal interface material with a vertical orientation structure includes an organic polymer matrix and a film with a vertical lamellar orientation structure ; First prepare a high-aspect-ratio micro-channel array mold; prepare a nanosheet dispersion; inject the dispersion into the micro-channel array mold, then flow into the coagulation liquid, and then undergo freeze-drying and high-temperature heat treatment to obtain a film with a vertical sheet orientation structure ; Then the film prepared by potting the organic polymer in the vertical lamellar orientation structure. The present invention utilizes the size confinement effect of the high-aspect-ratio micro-pipeline mold and the extrusion expansion effect of non-Newtonian fluid at the outlet of the mold, and the nanosheet material flows out from the initial horizontal arrangement through the mold to obtain a highly ordered vertical sheet inside The thin film with layer structure has low cost and can realize large-area customized production and preparation, and can be widely used in high-power electronic devices and other application scenarios that require efficient thermal management.
Description
Technical Field
The invention belongs to the technical field of preparation of thermal interface materials, and particularly relates to a thermal interface material with a vertical orientation structure and a preparation method thereof.
Background
Currently, miniaturization and integration have become a trend in electronic devices. As the power of electronic devices increases, the amount of heat generated increases dramatically, which can severely shorten the life of the electronic device and the human use experience. Therefore, in order to improve the reliability of the device and make it perform optimally, it is necessary to ensure that the heat generated by the device can be dissipated in time, and heat dissipation has become the most critical problem and technical bottleneck that limit the service life and performance of the electronic device.
Thermal interface materials, also known as thermally conductive interface materials, are a material commonly used for IC packaging and electronic heat dissipation where only a small portion of the surface area is actually in contact when two solid surfaces are in contact due to the rough topography. The remainder of this area will be separated by an air-filled gap, with negligible heat transfer through the air interface, since the thermal conductivity of air (0.026W/mK) is about four orders of magnitude lower than that of metal. Most of the heat flux will pass through the actual contact points, and even for very low roughness substrates, severe thermal bottlenecks will occur. This is manifested in the difficulty in transferring heat at the interface and in the large temperature difference. Therefore, the thermal interface material is placed between the two metal surfaces to increase the thermal conductivity at the interface, plays an important role in the performance, service life and stability of the electronic device, and is particularly widely applied to high-power electronic power devices.
The current commercial thermal interface materials are usually silicon-based or resin-based high polymer materials, and the thermal conductivity of the materials is lower<0.6W·m -1 ·K -1 ) Some manufacturers develop phase change materials or resin matrix composite materials filled with ceramic particles, liquid metal, carbon materials and the like as heat conducting fillers, and heat dissipation capacity is improved by utilizing the heat conducting fillers, however, the heat conductivity of the filled thermal interface materials is also lower<10W·m -1 ·K -1 )。
However, due to the anisotropy of two-dimensional materials or carbon fibers, the thermal conductivity of these materials is high in the horizontal direction of the sheet and low in the vertical direction of the sheet, and the weak coupling between the anisotropic material and the polymer matrix creates a high thermal contact resistance, the random arrangement of the filler and the presence of the polymer resin severely reduces the thermal conductivity of the polymer-based thermal interface material in the vertical direction.
Therefore, how to use the thermal conductivity of the two-dimensional material itself to prepare thermal interface materials with thermal conductivity greater than 10W/mK in the vertical direction and apply them to high power electronic devices remains a great challenge.
Through the above analysis, the problems and defects existing in the prior art are as follows:
the existing thermal interface material has lower thermal conductivity, the weak coupling between the anisotropic material and the polymer matrix generates higher thermal contact resistance, and the random arrangement of the material and the existence of the polymer resin seriously reduce the thermal conductivity coefficient of the polymer-based thermal interface material in the vertical direction.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a thermal interface material with a vertical orientation structure and a preparation method thereof.
The invention is realized in that a thermal interface material with a vertical orientation structure is a composite thermal interface material of an organic polymer matrix and a film with a vertical lamellar orientation structure.
Further, the organic polymer is one of silica gel, rubber, gel, epoxy resin and phenolic resin.
Further, the film with the vertical lamellar orientation structure is made of one of graphene, boron nitride, ceramic plates and metal nano plates.
Further, the film with the vertical lamellar orientation structure accounts for 2-60 wt% of the composite thermal interface material in terms of mass percent.
Another object of the present invention is to provide a method for preparing a vertically oriented structural thermal interface material, the method comprising the steps of:
step one, preparing a micro-pipe mold with high aspect ratio;
step two, preparing a nano sheet material dispersion liquid;
step three, injecting the dispersion liquid obtained in the step two into the micro-pipe mold in the step one, then flowing out into the coagulating liquid, and then performing freeze drying and high-temperature heat treatment to obtain the film with the vertical lamellar orientation structure;
step four, if the film material in the step three is boron nitride, the boron nitride film can be formed by taking the graphene film with the vertical lamellar orientation structure obtained in the step three as a template, boric acid provides a boron source for a precursor, ammonia gas provides a nitrogen source and is converted into a boron nitride film by a direct chemical vapor deposition method, and then the crystallinity of the boron nitride is improved by high-temperature heat treatment, so that the boron nitride film with the vertical lamellar orientation structure is obtained;
and fifthly, encapsulating the organic polymer in the film with the vertical lamellar orientation structure obtained in the step three or the step four, and curing to obtain the thermal interface material with the vertical orientation structure.
Further, the preparation method of the high aspect ratio micro-pipe mold in the first step comprises the following steps:
providing a micro-channel rectangular fin array;
providing an upper cover plate, an inlet runner and an outlet runner which are matched with the fin array; providing a mask plate matched with the micro-pipeline array;
and assembling the rectangular fin array, the upper cover plate, the inlet runner and the outlet runner to obtain the micro-pipe mold with high aspect ratio.
Further, the thickness of the fins in the micro-channel rectangular fin array is 100-300 mu m, the height of the fins is 1-50 mm, the distance between the fins is 100-250 mu m, the total length of the fin array is 1-20 cm, and the total width of the fin array is 0.5-2 cm.
Further, the length and width of the upper cover plate are kept consistent with those of the micro-pipe rectangular fin array, and the thickness is 1mm-5mm.
Further, the aperture of the inlet flow passage of the fin is 2mm-5.4mm, the length of the inlet flow passage is consistent with the total length of the fin array, and the width is consistent with the height of the fin;
the length of the outlet flow passage is one-fourth to one-half of the length of the fin array.
Further, the micro-channel fin array is processed and prepared by adopting a CNC diamond wire-electrode cutting process, a CNC relieved tooth process or a three-dimensional photo-curing molding 3D printing technology.
Further, the length of the vertical lamellar oriented structure film in the third step is determined by the outflow speed of the nano lamellar dispersion liquid, the outflow speed is 100 mu m/s-4mm/s, and the width is determined by the width of the pipeline array of the high aspect ratio micro pipeline mould in the first step.
Further, the mass of boric acid in the step of tetraboric acid is 2g-4g in the precursor.
Further, the flow rate of the ammonia gas in the direct chemical vapor deposition method in the step four is 20-50sccm, the flow rate of the argon gas is 100-250sccm, the conversion temperature is 830-1200 ℃, and the conversion time is 1-3h;
the heat treatment temperature of the boron nitride film is 1500-1700 ℃.
In combination with the above technical solution and the technical problems to be solved, please analyze the following aspects to provide the following advantages and positive effects:
first, aiming at the technical problems in the prior art and the difficulty in solving the problems, the technical problems solved by the technical proposal of the invention are analyzed in detail and deeply by tightly combining the technical proposal to be protected, the results and data in the research and development process, and the like, and some technical effects brought after the problems are solved have creative technical effects. The specific description is as follows:
the alignment of the thermally conductive filler within the thermal interface material to increase the thermal conductivity and maintain a low compression modulus of the material is currently an effective solution. The current mainstream technology is as follows: (1) And treating the heat conducting filler particles with magnetism by using an external magnetic field to enable the heat conducting filler particles to be orderly arranged along the magnetic field direction. (2) ordering the filler by using ice crystals as templates. At present, although the heat conduction additives are ordered by using an external magnetic field and an ice crystal template method and the heat conduction coefficient of the material is effectively improved, the ordering degree of the heat conduction particles in the material prepared by the two methods is too low, so that the proportion of the filler is still too large, and the two methods are too high in preparation cost in large area and difficult to experiment and realize large-scale industrialized production.
According to the invention, the micro-scale pipeline with large area and high depth-to-width ratio is used as a mould, the influence of the size limit of the micro-pipeline mould with high depth-to-width ratio and the extrusion swelling effect of non-Newtonian fluid at the outlet of the mould are utilized, the nano-sheets are subjected to shearing force in the vertical direction after flowing out from the initial horizontal arrangement through the micro-pipeline mould, the nano-sheets rotate and form a highly ordered vertical lamellar structure, the vertically arranged sheets can obviously improve the heat conductivity of the thermal interface material in the vertical direction, and the heat conductivity of the thermal interface material in the vertical direction reaches 10-30W/(m.K) under the condition that the graphene filling amount is not more than 10wt%, so that the thermal interface material exceeds the current commercial heat conducting gasket. The boron nitride film thermal interface material provided by the invention is insulated, has higher breakdown resistance field strength reaching 50KV/mm, and can be used in the fields of high-power electronic devices, aerospace and the like;
according to the invention, the thermal interface materials of the vertical lamellar orientation structures with different sizes and thicknesses can be prepared in a customized manner by selecting the size of the mold, and the prepared thermal interface materials are good in interface combination, have excellent heat conducting performance and reduce weight. And the preparation method is simple and easy to expand, has low cost and can realize large-scale industrial production.
Secondly, the technical scheme is regarded as a whole or from the perspective of products, and the technical scheme to be protected has the following technical effects and advantages:
the thermal interface material provided by the invention has better heat conduction performance in the vertical direction, and the preparation method is simple and easy to expand, has low cost and can realize large-scale industrial production.
Thirdly, as inventive supplementary evidence of the claims of the present invention, the following important aspects are also presented:
(1) The expected benefits and commercial values after the technical scheme of the invention is converted are as follows:
the method can be widely applied to high-power electronic equipment and any application scene requiring thermal management.
(2) The technical scheme of the invention fills the technical blank in the domestic and foreign industries:
the main current orientation arrangement technology for controlling the heat conduction filler comprises the following steps: (1) And treating the heat conducting filler particles with magnetism by using an external magnetic field to enable the heat conducting filler particles to be orderly arranged along the magnetic field direction. (2) ordering the filler by ice crystal template method. The same technology as the patent is not reported at home and abroad.
(3) Whether the technical scheme of the invention solves the technical problems that people want to solve all the time but fail to obtain success all the time is solved:
the graphene film with the large-area highly ordered vertical lamellar structure is prepared, and the difficulty of amplifying and preparing the existing process for preparing the vertical oriented film with the high heat conduction lamellar is overcome.
Drawings
FIG. 1 is a flow chart of a method for preparing a vertically oriented structured thermal interface material according to an embodiment of the present invention;
FIG. 2 is a three-view of a high aspect ratio micro-pipe array in CAD software according to an embodiment of the present invention;
FIG. 3 is a three-dimensional view of an inlet flow channel in CAD software according to an embodiment of the present invention;
FIG. 4 is a three-dimensional view of an outlet flow path in CAD software in accordance with one embodiment of the present invention;
FIG. 5 is a schematic three-dimensional diagram of an aluminum alloy fin array mold in Solidworks software according to an embodiment of the present invention;
FIG. 6 is a simulation diagram of an embodiment provided by an embodiment of the present invention in Comsol software.
FIG. 7 is a microscopic optical image of a physical image and a cross section of an aluminum alloy fin array mold used in the first embodiment provided by the embodiment of the invention;
FIG. 8 is an SEM image of a cross section of a graphene film of a vertical platelet orientation structure according to an embodiment of the present invention;
FIG. 9 is an SEM image of a cross section of a boron nitride film of a vertical lamellar orientation structure according to an embodiment of the invention;
FIG. 10 is a Raman spectrum of a boron nitride film of a vertical lamellar orientation structure in embodiment one provided by the embodiment of the invention;
fig. 11 is a physical diagram of a thermal interface material with a graphene film with a vertical lamellar orientation structure in a first embodiment provided by an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
1. The embodiments are explained. In order to fully understand how the invention may be embodied by those skilled in the art, this section is an illustrative embodiment in which the claims are presented for purposes of illustration.
As shown in fig. 1, the preparation method of the vertical orientation structure thermal interface material provided by the embodiment of the invention includes:
s101, preparing a micro-pipe mold with high depth-to-width ratio;
s102, preparing a nano sheet material dispersion liquid;
s103, injecting the dispersion liquid obtained in the second step into the micro-pipe mold in the first step, then flowing out into the coagulating liquid, and then performing freeze drying and high-temperature heat treatment to obtain the film with the vertical lamellar orientation structure;
s104, if the film material in the third step is boron nitride, the boron nitride film can be formed by taking the graphene film with the vertical lamellar orientation structure obtained in the third step as a template, boric acid provides a boron source for a precursor, ammonia gas provides a nitrogen source and is converted into a boron nitride film by a direct chemical vapor deposition method, and then the crystallinity of the boron nitride is improved by high-temperature heat treatment, so that the boron nitride film with the vertical lamellar orientation structure is obtained;
and S105, encapsulating the organic polymer in the film with the vertical lamellar orientation structure obtained in the step three or the step four, and curing to obtain the thermal interface material with the vertical orientation structure.
The preparation method of the high aspect ratio micro-pipe die in the embodiment of the invention specifically comprises the following steps:
providing a micro-channel rectangular fin array;
providing an upper cover plate, an inlet runner and an outlet runner which are matched with the fin array;
and assembling the rectangular fin array, the upper cover plate, the inlet runner and the outlet runner to obtain the micro-pipe mold with high aspect ratio.
In the rectangular fin array in the embodiment of the invention, the thickness of the fins is 100-300 mu m, the height of the fins is 1-50 mm, the distance between the fins is 100-250 mu m, the total length of the fin array is 1-20 cm, and the total width of the fin array is 0.5-2 cm;
the length and width of the upper cover plate in the embodiment of the invention are consistent with those of the micro-pipe rectangular fin array, and the thickness is 1mm-5mm; the aperture of the fin inlet runner is 2mm-5.4mm, the length of the inlet runner is consistent with the total length of the fin array, the width is consistent with the dimension of the fin height, the length of the outlet runner is one fourth to one half of the length of the fin array (for example, the length of the fin array is 5cm, the length of the outlet runner is 1.25cm-2.5cm, the width is consistent with the dimension of the fin height, and the wall thickness of the inlet runner and the outlet runner is 3 mm).
The micro-channel fin array in the embodiment of the invention can be processed and prepared by technologies such as a CNC diamond wire-electrode cutting process, a CNC relieved tooth process or three-dimensional light curing forming (SLA) 3D printing.
The length of the vertical lamellar oriented structure film in the step S103 in the embodiment of the invention is determined by the outflow speed of the nano lamellar dispersion, the outflow speed is 100 mu m/S-4mm/S, and the width is determined by the width of the pipeline array of the high aspect ratio micro pipeline mould in the step S101.
In the step S104 of the embodiment of the invention, the mass of the boric acid serving as a precursor is 2g-4g.
In the embodiment of the invention, in the step S104, the flow of the ammonia gas of the direct chemical vapor deposition method is 20-50sccm, the flow of the argon gas is 100-250sccm, the conversion temperature is 830-1200 ℃, and the conversion time is 1-3h.
The heat treatment temperature of the boron nitride film of the vertical lamellar orientation structure in the step S104 in the embodiment of the invention is 1500-1700 ℃.
2. Application example. In order to prove the inventive and technical value of the technical solution of the present invention, this section is an application example of the specific product or related technology application of the claim technical solution.
The thermal interface material with the vertical orientation structure provided by the embodiment of the invention can be applied to application scenes such as high-power electronic devices, aerospace, 5G communication equipment and the like which need efficient thermal management.
3. Evidence of the effect of the examples. The embodiment of the invention has a great advantage in the research and development or use process, and has the following description in combination with data, charts and the like of the test process.
The PDMS related to the invention is purchased from the dakangning, and the rest medicines are all sold in the market. The model of the 3D printer for the preferable three-dimensional photo-curing molding is Form3, and the model of the pressure sampler is Elveflow OB1 MK3. The cooling liquid circulating pump and the freeze dryer are all domestic commercial instruments.
Preferably, graphene is used as the nano-sheet material in the following embodiments, and boron nitride is converted by chemical vapor deposition using a graphene film having a vertically oriented structure as a template.
Embodiment one:
a preparation method of a vertical orientation structure thermal interface material comprises the following steps:
(1) Preparing a high aspect ratio aluminum alloy micro-pipe mold: and processing the aluminum alloy part by adopting a numerical control relieved tooth to obtain a rectangular fin array, wherein the thickness of fins in the rectangular fin array is 100 mu m, the height of the fins is 1mm, the distance between the fins is 100 mu m, the total length of the fin array is 5cm, and the total width of the fin array is 1.5cm (shown in figure 2). And then printing an upper cover plate and an inlet runner which are matched with the fin array by adopting a photocuring rapid prototyping 3D printing technology, wherein the aperture of the inlet runner is 5.4mm, the length of the inlet runner is consistent with the total length of the fin array and is 5cm, the width and the height of the fins are consistent with each other and are 1mm, and the wall thickness of the inlet runner is 3mm. And assembling the upper cover plate, the inlet runner and the rectangular fin array to obtain the aluminum alloy micro-pipe mold containing the micro-pipe array.
(2) A modified Hummer's method was used to prepare a high concentration graphene oxide dispersion having a concentration of 10mg/ml.
(3) Injecting the graphene dispersion liquid obtained in the step (2) into the micro-pipe mold in the step (1) by adopting a pressure injector, controlling the speed of the graphene fluid flowing out of the aluminum alloy micro-pipe mold by controlling the pressure applied to the fluid, wherein the input pressure of the pressure injector is 1500Pa, the outflow speed is 200 mu m/s, the graphene flows out into a coagulating liquid after being sequenced by the mold, and the coagulating bath is Cetyl Trimethyl Ammonium Bromide (CTAB) and calcium chloride (CaCl) 2 ) Is a 50wt% ethanol aqueous solution, CTAB and CaCl 2 The concentration and mass fraction of the graphene oxide film are respectively 0.5mg/ml and 0.8wt%, after standing for 20min, the graphene oxide film with the vertical lamellar orientation structure is transferred to liquid nitrogen for freezing, then freeze drying is carried out for 24h, and after drying, high-temperature heat treatment at 2800 ℃ is carried out for 1h under the argon atmosphere, so that the graphene film with the vertical lamellar orientation structure is obtained.
(4) At normal pressure, preparing a boron nitride film by adopting a direct chemical vapor deposition method, adding boric acid powder with the mass of 2g into one end of a quartz tube, and putting the graphene film obtained in the step (3) into the other end of the quartz tube to serve as a template for transforming and growing the boron nitride film. The tube was first heated to 150℃and held at this temperature for 30 minutes, and the air and moisture remaining in the tube were removed at a flow rate of 300sccm of argon. Then, an end region of the graphene film was placed and heated to 1000 ℃ at a heating rate of 10 ℃/min. Meanwhile, heating the region at one end of the boric acid to 600 ℃ at a heating rate of 10 ℃/min, simultaneously introducing ammonia gas into the quartz tube, wherein the flow rate of the ammonia gas is 50sccm, the flow rate of Ar is reduced to 250sccm, maintaining for 2 hours, naturally cooling the system to room temperature under the argon flow, and finally carrying out high-temperature heat treatment for 2 hours at 1700 ℃ to obtain the boron nitride film with the vertical lamellar orientation structure.
(5) PDMS prepolymer and curing agent according to 10:1, encapsulating the mixed PDMS in the graphene film in the step (3) or the boron nitride film in the step (4), wherein the content of the graphene film in the vertical lamellar orientation structure is 30wt%, the content of the boron nitride film in the vertical lamellar orientation structure is 30wt%, then vacuum degassing and defoaming are carried out, the thermal interface material is obtained after curing for 4 hours at 65 ℃, the thermal conductivity of the thermal interface material in the vertical direction is tested by adopting ASTM E1461-2013 (test method for measuring solid thermal diffusivity by using a flash method), the thermal conductivity of the graphene film in the vertical lamellar orientation structure is 30.2W/(m.K), the thermal conductivity of the boron nitride film in the vertical lamellar orientation structure is 6.7W/(m.K), and the breakdown field strength is 40KV/mm.
FIG. 2 is a three-dimensional schematic diagram of a high aspect ratio micro-pipe mold in CAD software in the first embodiment, wherein the high-order vertical lamellar structure is obtained by using the size limit influence of the high aspect ratio micro-pipe mold and the extrusion expansion effect of high-concentration graphene non-Newtonian fluid at the outlet of the mold, wherein graphene lamellar layers can be arranged horizontally from the beginning and flow out through the mold;
FIG. 3 is a three-dimensional view of an aluminum alloy fin array mold in CAD for the first embodiment, which is fabricated by numerical control machining;
FIG. 4 is a three-view of the inlet flow path in CAD in accordance with the first embodiment;
FIG. 5 is a three-dimensional schematic diagram of an aluminum alloy fin array mold in Solidworks software in accordance with an embodiment I;
fig. 6 is a simulation of computational fluid dynamics according to the die size simulation of example one using the Comsol software, and the results of the cross-sectional fluid dynamics simulation of the pipe outlet show that the non-newtonian fluid expands as it passes through the pipe outlet, thus experiencing strong stretching shear forces (dVz/dz) at the outlet in a direction perpendicular to the fluid flow direction, which is why the nanoplatelets deflect and thus orient in a vertical alignment.
FIG. 7 is a physical diagram of a high aspect ratio microchannel mold used in the first embodiment, wherein high concentration graphene fluid is introduced into the mold to change the ordering of graphene sheets to prepare a thermal interface material with a vertical sheet orientation structure;
fig. 8 is an SEM image of a cross section of a graphene film with a vertical lamellar orientation structure in the first embodiment, from which it can be seen that graphene lamellae are vertically arranged, which illustrates that graphene nano-sheets can be well vertically and orderly arranged after flowing out of a high aspect ratio micro-pipe die, and because of anisotropy of the nano-sheets, the thermal conductivity in the lamellar direction is high, the thermal conductivity in the direction perpendicular to the lamellar direction is low, and because the lamellae are vertically arranged, the graphene film has higher thermal conductivity in the vertical direction;
fig. 9 is an SEM image of a cross section of a boron nitride film with a vertical lamellar orientation structure in the first embodiment, which shows that after the graphene film is converted into a boron nitride film by direct chemical vapor deposition, the boron nitride film can still have a complete and good vertical ordering structure, and a heat conduction network is formed between the nano-sheets, so that better heat conduction performance in the vertical direction is realized, and the intrinsic heat conductivity of the boron nitride is low, so that the heat conductivity coefficient of the material is reduced to some extent, but the boron nitride film is insulated, and the boron nitride film is suitable for a thermal management scene of electrical insulation;
FIG. 10 is a Raman spectrum of a boron nitride film having a vertical lamellar orientation structure in example one, the position of the Raman peak being 1367cm -1 Indicating that the graphene film is completely converted into the boron nitride film through a direct chemical vapor deposition method;
fig. 11 is a thermal interface material physical diagram of a graphene film with a vertical lamellar orientation structure in the first embodiment, PDMS is completely filled in the pores between graphene lamellar layers, and the surface of the material is smooth and flat.
Embodiment two:
a preparation method of a vertical orientation structure thermal interface material comprises the following steps:
(1) Preparing a high aspect ratio microchannel mold: and (3) processing the aluminum alloy part by adopting numerical control diamond wire cutting to obtain a rectangular fin array, wherein the thickness of fins in the rectangular fin array is 200 mu m, the heights of the fins are 3mm, the intervals of the fins are 200 mu m, the total length of the fin array is 5cm, and the total width of the fin array is 1.5cm. And then printing an upper cover plate and an inlet runner which are matched with the fin array by adopting a photocuring rapid prototyping 3D printing technology, wherein the aperture of the inlet runner is 5.4mm, the length of the inlet runner is consistent with the total length of the fin array, the width of the inlet runner is consistent with the height of the fins by 1mm, the length of the outlet runner is one fourth of the length of the fin array by 1.25cm, the width of the outlet runner is consistent with the height of the fins by 1mm, and the wall thicknesses of the inlet runner and the outlet runner are all 3mm. And assembling the upper cover plate, the inlet runner and the rectangular fin array to obtain the aluminum alloy micro-pipe mold containing the micro-pipe array.
(2) A modified Hummer's method was used to prepare a high concentration graphene oxide dispersion having a concentration of 10mg/ml.
(3) Injecting the graphene dispersion liquid obtained in the step (2) into the micro-pipe mold in the step (1) by adopting a pressure injector, controlling the speed of the graphene fluid flowing out of the aluminum alloy micro-pipe mold by controlling the pressure applied to the fluid, wherein the input pressure of the pressure injector is 2000Pa, the outflow speed is 190 mu m/s, and the graphene flows out into the coagulating liquid after being sequenced by the mold, thereby coagulatingThe solid bath is Cetyl Trimethyl Ammonium Bromide (CTAB) and calcium chloride (CaCl) 2 ) Is a 50wt% ethanol aqueous solution, CTAB and CaCl 2 The concentration and mass fraction of the graphene oxide film are respectively 0.5mg/ml and 0.8wt%, after standing for 20min, the graphene oxide film with the vertical lamellar orientation structure is transferred to liquid nitrogen for freezing, then freeze drying is carried out for 24h, and after drying, high-temperature heat treatment at 2800 ℃ is carried out for 1h under the argon atmosphere, so that the graphene film with the vertical lamellar orientation structure is obtained.
(4) At normal pressure, preparing a boron nitride film by adopting a direct chemical vapor deposition method, adding boric acid powder with the mass of 3g into one end of a quartz tube, and putting the graphene film obtained in the step (3) into the other end of the quartz tube to serve as a template for transforming and growing the boron nitride film. The tube was first heated to 150℃and held at this temperature for 30 minutes, and the air and moisture remaining in the tube were removed at a flow rate of 300sccm of argon. Then, an end region of the graphene film was placed and heated to 1000 ℃ at a heating rate of 10 ℃/min. Meanwhile, heating the region at one end of the boric acid to 600 ℃ at a heating rate of 10 ℃/min, simultaneously introducing ammonia gas into the quartz tube, wherein the flow rate of the ammonia gas is 50sccm, the flow rate of Ar is reduced to 250sccm, maintaining for 2 hours, naturally cooling the system to room temperature under the argon flow, and finally carrying out high-temperature heat treatment for 2 hours at 1700 ℃ to obtain the boron nitride film with the vertical lamellar orientation structure.
(5) PDMS prepolymer and curing agent according to 10:1, encapsulating the mixed PDMS in the graphene film in the step (3) or the boron nitride film in the step (4), wherein the content of the graphene film in the vertical lamellar orientation structure is 25wt%, the content of the boron nitride film in the vertical lamellar orientation structure is 25wt%, vacuum degassing and defoaming are carried out, curing is carried out at 65 ℃ for 4 hours, the thermal interface material is obtained, the thermal conductivity of the thermal interface material in the vertical direction is tested by adopting ASTM E1461-2013 (test method for measuring solid thermal diffusivity by using a flash method), and the thermal conductivity of the graphene film in the vertical lamellar orientation structure is 24.6W/(m.K), and the thermal conductivity of the boron nitride film in the vertical lamellar orientation structure is 4.7W/(m.K).
Embodiment III:
a preparation method of a vertical orientation structure thermal interface material comprises the following steps:
(1) Preparing a high depth ratio micro-pipe mold: and processing the aluminum alloy part by adopting a numerical control relieved tooth process to obtain a rectangular fin array, wherein the thickness of fins in the rectangular fin array is 150 mu m, the heights of the fins are 3mm, the intervals of the fins are 150 mu m, the total length of the fin array is 5cm, and the total width of the fin array is 1.5cm. And then printing an upper cover plate and an inlet runner which are matched with the fin array by adopting a photocuring rapid prototyping 3D printing technology, wherein the aperture of the inlet runner is 5.4mm, the length of the inlet runner is consistent with the total length of the fin array, the width of the inlet runner is consistent with the height of the fins by 3mm, the length of the outlet runner is one fourth of the length of the fin array by 1.25cm, the width of the outlet runner is consistent with the height of the fins by 3mm, and the wall thicknesses of the inlet runner and the outlet runner are all 3mm. And assembling the upper cover plate, the inlet runner and the rectangular fin array to obtain the aluminum alloy micro-pipe mold containing the micro-pipe array.
(2) A modified Hummer's method was used to prepare a high concentration graphene oxide dispersion having a concentration of 10mg/ml.
(3) Injecting the graphene dispersion liquid obtained in the step (2) into the micro-pipe mold in the step (1) by adopting a pressure injector, controlling the speed of the graphene fluid flowing out of the aluminum alloy micro-pipe mold by controlling the pressure applied to the fluid, wherein the input pressure of the pressure injector is 2300Pa, the outflow speed is 160 mu m/s, the graphene flows out into a coagulating liquid after being sequenced by the mold, and the coagulating bath is Cetyl Trimethyl Ammonium Bromide (CTAB) and calcium chloride (CaCl) 2 ) Is a 50wt% ethanol aqueous solution, CTAB and CaCl 2 The concentration and mass fraction of the graphene oxide film are respectively 0.5mg/ml and 0.8wt%, after standing for 20min, the graphene oxide film with the vertical lamellar orientation structure is transferred to liquid nitrogen for freezing, then freeze drying is carried out for 24h, and after drying, high-temperature heat treatment at 2800 ℃ is carried out for 1h under the argon atmosphere, so that the graphene film with the vertical lamellar orientation structure is obtained.
(4) At normal pressure, preparing a boron nitride film by adopting a direct chemical vapor deposition method, adding boric acid powder with the mass of 3.5g into one end of a quartz tube, and putting the graphene film obtained in the step (3) into the other end of the quartz tube to serve as a template for transforming and growing the boron nitride film. The tube was first heated to 150℃and held at this temperature for 30 minutes, and the air and moisture remaining in the tube were removed at a flow rate of 300sccm of argon. Then, an end region of the graphene film was placed and heated to 1000 ℃ at a heating rate of 10 ℃/min. Meanwhile, heating the region at one end of the boric acid to 600 ℃ at a heating rate of 10 ℃/min, simultaneously introducing ammonia gas into the quartz tube, wherein the flow rate of the ammonia gas is 50sccm, the flow rate of Ar is reduced to 250sccm, maintaining for 2 hours, naturally cooling the system to room temperature under the argon flow, and finally carrying out high-temperature heat treatment for 2 hours at 1700 ℃ to obtain the boron nitride film with the vertical lamellar orientation structure.
(5) PDMS prepolymer and curing agent according to 10:1, encapsulating the mixed PDMS in the graphene film in the step (3) or the boron nitride film in the step (4), wherein the content of the graphene film in the vertical lamellar orientation structure is 30wt%, the content of the boron nitride film in the vertical lamellar orientation structure is 30wt%, then vacuum degassing and defoaming are carried out, curing is carried out at 65 ℃ for 4 hours, the thermal interface material is obtained, the thermal conductivity of the thermal interface material in the vertical direction is tested by adopting ASTM E1461-2013 (test method for measuring solid thermal diffusivity by using a flash method), the thermal conductivity of the graphene film in the vertical lamellar orientation structure is 27.5W/(m.K), and the thermal conductivity of the boron nitride film in the vertical lamellar orientation structure is 5.5W/(m.K).
Embodiment four:
a preparation method of a vertical orientation structure thermal interface material comprises the following steps:
(1) Preparing a high aspect ratio microchannel mold: and processing the aluminum alloy part by adopting a numerical control relieved tooth process to obtain a rectangular fin array, wherein the thickness of fins in the rectangular fin array is 250 mu m, the height of the fins is 1mm, the distance between the fins is 250 mu m, the total length of the fin array is 10cm, and the total width of the fin array is 1.5cm. And then printing an upper cover plate and an inlet runner which are matched with the fin array by adopting a photocuring rapid prototyping 3D printing technology, wherein the aperture of the inlet runner is 5.4mm, the length of the inlet runner is 10cm consistent with the total length of the fin array, the width of the inlet runner is 1.5mm consistent with the height of the fins, the length of the outlet runner is 2.5cm which is one fourth of the length of the fin array, the width of the outlet runner is 1mm consistent with the height of the fins, and the wall thickness of the inlet runner and the wall thickness of the outlet runner are 3mm. And assembling the upper cover plate, the inlet runner and the rectangular fin array to obtain the aluminum alloy micro-pipe mold containing the micro-pipe array.
(2) A modified Hummer's method was used to prepare a high concentration graphene oxide dispersion having a concentration of 10mg/ml.
(3) Injecting the graphene dispersion liquid obtained in the step (2) into the micro-pipe mold in the step (1) by adopting a pressure injector, controlling the speed of the graphene fluid flowing out of the aluminum alloy micro-pipe mold by controlling the pressure applied to the fluid, wherein the input pressure of the pressure injector is 3000Pa, the outflow speed is 100 mu m/s, the graphene flows out into a coagulating liquid after being sequenced by the mold, and the coagulating bath is Cetyl Trimethyl Ammonium Bromide (CTAB) and calcium chloride (CaCl) 2 ) Is a 50wt% ethanol aqueous solution, CTAB and CaCl 2 The concentration and mass fraction of the graphene oxide film are respectively 0.5mg/ml and 0.8wt%, after standing for 20min, the graphene oxide film with the vertical lamellar orientation structure is transferred to liquid nitrogen for freezing, then freeze drying is carried out for 24h, and after drying, high-temperature heat treatment at 2800 ℃ is carried out for 1h under the argon atmosphere, so that the graphene film with the vertical lamellar orientation structure is obtained.
(4) At normal pressure, preparing a boron nitride film by adopting a direct chemical vapor deposition method, adding boric acid powder with the mass of 4g into one end of a quartz tube, and putting the graphene film obtained in the step (3) into the other end of the quartz tube to serve as a template for transforming and growing the boron nitride film. The tube was first heated to 150℃and held at this temperature for 30 minutes, and the air and moisture remaining in the tube were removed at a flow rate of 300sccm of argon. Then, an end region of the graphene film was placed and heated to 1000 ℃ at a heating rate of 10 ℃/min. Meanwhile, heating the region at one end of the boric acid to 600 ℃ at a heating rate of 10 ℃/min, simultaneously introducing ammonia gas into the quartz tube, wherein the flow rate of the ammonia gas is 50sccm, the flow rate of Ar is reduced to 250sccm, maintaining for 2 hours, naturally cooling the system to room temperature under the argon flow, and finally carrying out high-temperature heat treatment for 2 hours at 1700 ℃ to obtain the boron nitride film with the vertical lamellar orientation structure.
(5) PDMS prepolymer and curing agent according to 10:1, encapsulating the mixed PDMS in the graphene film in the step (3) or the boron nitride film in the step (4), wherein the content of the graphene film in the vertical lamellar orientation structure is 30wt%, the content of the boron nitride film in the vertical lamellar orientation structure is 30wt%, then vacuum degassing and defoaming are carried out, curing is carried out at 65 ℃ for 4 hours, the thermal interface material is obtained, the thermal conductivity of the thermal interface material in the vertical direction is tested by adopting ASTM E1461-2013 (test method for measuring solid thermal diffusivity by using a flash method), and the thermal conductivity of the graphene film in the vertical lamellar orientation structure is 25W/(m.K), and the thermal conductivity of the boron nitride film in the vertical lamellar orientation structure is 5.1W/(m.K).
Example 5:
a preparation method of a vertical orientation structure thermal interface material comprises the following steps:
(1) Preparing a high aspect ratio microchannel mold: and processing the aluminum alloy part by adopting a numerical control relieved tooth process to obtain a rectangular fin array, wherein the thickness of fins in the rectangular fin array is 250 mu m, the height of the fins is 1mm, the distance between the fins is 250 mu m, the total length of the fin array is 10cm, and the total width of the fin array is 1.5cm. And then printing an upper cover plate and an inlet runner which are matched with the fin array by adopting a photocuring rapid prototyping 3D printing technology, wherein the aperture of the inlet runner is 5.4mm, the length of the inlet runner is 10cm consistent with the total length of the fin array, the width of the inlet runner is 1.5mm consistent with the height of the fins, the length of the outlet runner is 2.5cm which is one fourth of the length of the fin array, the width of the outlet runner is 1mm consistent with the height of the fins, and the wall thickness of the inlet runner and the wall thickness of the outlet runner are 3mm. And assembling the upper cover plate, the inlet runner and the rectangular fin array to obtain the aluminum alloy micro-pipe mold containing the micro-pipe array.
(2) A modified Hummer's method was used to prepare a high concentration graphene oxide dispersion having a concentration of 10mg/ml.
(3) Injecting the graphene dispersion liquid obtained in the step (2) into the micro-pipe mold in the step (1) by adopting a pressure injector, controlling the speed of the graphene fluid flowing out of the aluminum alloy micro-pipe mold by controlling the pressure applied to the fluid, wherein the input pressure of the pressure injector is 3000Pa, the outflow speed is 100 mu m/s, and the graphene flows out into the coagulating liquid after being sequenced by the mold, and the coagulating bathIs Cetyl Trimethyl Ammonium Bromide (CTAB) and calcium chloride (CaCl) 2 ) Is a 50wt% ethanol aqueous solution, CTAB and CaCl 2 The concentration and mass fraction of the graphene oxide film are respectively 0.5mg/ml and 0.8wt%, after standing for 20min, the graphene oxide film with the vertical lamellar orientation structure is transferred to liquid nitrogen for freezing, then freeze drying is carried out for 24h, and after drying, high-temperature heat treatment at 2800 ℃ is carried out for 1h under the argon atmosphere, so that the graphene film with the vertical lamellar orientation structure is obtained.
(4) At normal pressure, preparing a boron nitride film by adopting a direct chemical vapor deposition method, adding boric acid powder with the mass of 4g into one end of a quartz tube, and putting the graphene film obtained in the step (3) into the other end of the quartz tube to serve as a template for transforming and growing the boron nitride film. The tube was first heated to 150℃and held at this temperature for 30 minutes, and the air and moisture remaining in the tube were removed at a flow rate of 300sccm of argon. Then, an end region of the graphene film was placed and heated to 1000 ℃ at a heating rate of 10 ℃/min. Meanwhile, heating the region at one end of the boric acid to 600 ℃ at a heating rate of 10 ℃/min, simultaneously introducing ammonia gas into the quartz tube, wherein the flow rate of the ammonia gas is 50sccm, the flow rate of Ar is reduced to 250sccm, maintaining for 2 hours, naturally cooling the system to room temperature under the argon flow, and finally carrying out high-temperature heat treatment for 2 hours at 1700 ℃ to obtain the boron nitride film with the vertical lamellar orientation structure.
(5) PDMS prepolymer and curing agent according to 10:1, encapsulating the mixed PDMS in the graphene film in the step (3) or the boron nitride film in the step (4), wherein the content of the graphene film in the vertical lamellar orientation structure is 5wt%, the content of the boron nitride film in the vertical lamellar orientation structure is 5wt%, then vacuum degassing and defoaming are carried out, curing is carried out at 65 ℃ for 4 hours, the thermal interface material is obtained, the thermal conductivity of the thermal interface material in the vertical direction is tested by adopting ASTM E1461-2013 (test method for measuring solid thermal diffusivity by using a flash method), the thermal conductivity of the graphene film in the vertical lamellar orientation structure is 9.3W/(m.K), and the thermal conductivity of the boron nitride film in the vertical lamellar orientation structure is 2.6W/(m.K).
In the embodiments of the present invention, table 1 shows that the thermal conductivity of the thermal interface material of each embodiment is compared with that of pure silicone PDMS, which shows that the thermal interface material of the present invention has extremely high thermal conductivity in the vertical direction, and has obvious advantages compared with the thermal interface material prepared in the prior art.
TABLE 1
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (5)
1. The preparation method of the vertical orientation structure thermal interface material is characterized in that the vertical orientation structure thermal interface material is a composite thermal interface material of an organic polymer matrix and a film with a vertical lamellar orientation structure;
the organic polymer is one of rubber, gel, epoxy resin and phenolic resin;
the film with the vertical lamellar orientation structure is made of one of graphene, boron nitride, a ceramic plate and a metal nano plate;
the preparation method of the vertical orientation structure thermal interface material comprises the following steps:
step one, preparing a micro-pipe mold with high aspect ratio;
step two, preparing a nano sheet material dispersion liquid;
step three, injecting the dispersion liquid obtained in the step two into the micro-pipe mold in the step one, then flowing out into the coagulating liquid, and then performing freeze drying and high-temperature heat treatment to obtain the film with the vertical lamellar orientation structure;
step four, if the film material in the step three is boron nitride, the boron nitride film can be formed by taking the graphene film with the vertical lamellar orientation structure obtained in the step three as a template, boric acid provides a boron source for a precursor, ammonia gas provides a nitrogen source and is converted into a boron nitride film by a direct chemical vapor deposition method, and then the crystallinity of the boron nitride is improved by high-temperature heat treatment, so that the boron nitride film with the vertical lamellar orientation structure is obtained;
encapsulating the organic polymer in the film with the vertical lamellar orientation structure obtained in the third step or the fourth step, and curing to obtain the thermal interface material with the vertical orientation structure;
the preparation method of the micro-pipeline die with the high aspect ratio in the first step comprises the following steps:
providing a micro-channel rectangular fin array;
providing an upper cover plate, an inlet runner and an outlet runner which are matched with the fin array; providing a mask plate matched with the micro-channel rectangular fin array;
assembling the rectangular fin array, the upper cover plate, the inlet runner and the outlet runner to obtain a micro-pipe mold with high aspect ratio;
the thickness of the fins in the micro-channel rectangular fin array is 100-300 mu m, the height of the fins is 1-50 mm, the distance between the fins is 100-250 mu m, the total length of the fin array is 1-20 cm, and the total width of the fin array is 0.5-cm-2 cm;
the length and width of the upper cover plate are consistent with those of the micro-pipe rectangular fin array, and the thickness is 1mm-5mm;
the aperture of the fin inlet runner is 2mm-5.4mm, the length of the inlet runner is consistent with the total length of the fin array, and the width is consistent with the height of the fins;
the length of the outlet runner is one quarter to one half of the length of the fin array;
the micro-pipe rectangular fin array is processed and prepared by adopting a CNC diamond wire-cut electrical discharge machining process, a CNC relieved tooth process or a three-dimensional photo-curing forming 3D printing technology.
2. The method for preparing a thermal interface material with a vertical orientation structure according to claim 1, wherein the film with the vertical lamellar orientation structure accounts for 2-60wt% of the composite thermal interface material.
3. The method of claim 1, wherein the length of the vertical lamellar oriented structure film in the third step is determined by the outflow speed of the nano-lamellar dispersion, the outflow speed is 100 μm/s-4mm/s, and the width is determined by the width of the pipe array of the high aspect ratio micro-pipe mold in the first step.
4. The method for preparing a thermal interface material of vertically oriented structure of claim 1, wherein the mass of boric acid in the precursor of step four is 2g-4g.
5. The method for preparing a thermal interface material with a vertically oriented structure according to claim 1, wherein the flow of ammonia gas in the step four direct chemical vapor deposition method is 20-50sccm, the conversion temperature is 830-1200 ℃, and the conversion time is 1-3h;
the heat treatment temperature of the boron nitride film is 1500-1700 ℃.
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