TW574283B - Super high thermal conductive polymer matrix composite and method for making the same. - Google Patents

Description

574283 A7 B7 V. Description of the Invention (Field of the Invention The present invention relates to a polymer polymer composite material that can be used in thermal management applications' and to a method for manufacturing such a polymer polymer composite material. The Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Background of the printed invention Composite materials have been widely known in the past for structural applications. In recent years, 'composite materials have also been used in thermal management applications. For example, composite materials can be used for heat dissipation in electronic packaging. Typical The heat expansion material used for electronic packaging will have the problem of matching the coefficient of thermal expansion, but because the coefficient of thermal expansion of the composite material can be adjusted by changing the quantity, type and structure of the reinforcing material, the problem of matching the coefficient of thermal expansion is avoided. Conventional carbon fibers, silicon carbide particles, silicon carbide particles, boron nitride particles, titanium nitride particles, and diamond particles are used. However, these reinforcement materials are used. The composites made are not very solid Improved thermal conductivity. Therefore, in recent years, some people have studied the application of new carbon fibers, that is, vapor-grown carbon fibers, in thermal management. Vapor-grown carbon fibers (abbreviated as VGCF) are permeated with hydrocarbon gas (hydrocarbon gas). It grows by pyrolysis on metal catalyst. VGCF has higher thermal conductivity than any other carbon fiber, and VGCF can be produced at a lower cost. VGCF also has the highest of all known carbon fibers. Carbon fiber with the highest degree of graphitic perfection.

4NCKU / 200101TW This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 2 Read the notes on the back of the paper I · Fill · ····· 574283 A7 -------- B7 V. Description of the invention (&gt;) As disclosed in U.S. Pat. No. 5,8H, 408, aluminum matrix composites (aluminum matrix composite) and a carbon matrix composite (carbon matrix composite) have been Made of carbon fiber, and the composite material has high thermal conductivity. However, both composites are conductive, a feature that is not allowed in many applications. In addition, the manufacture of aluminum-based composites requires a temperature above the aluminum solidus (aluminum solidus), approximately 660 ° C or 1220 ° F, and high pressure must be applied to die-cast aluminum in the molten state. In addition, a protective environment full of inert gas must be provided to prevent oxidation of aluminum. The manufacture of carbon-based composite materials also requires temperatures higher than 110 ° C or 201 ° F, and requires a lower pressure <reduced pressure>. At the same time, the manufacture of aluminum-based composite materials or carbon-based composite materials requires a preliminary Forming <pref〇rm>. In addition, aluminum-based composite materials need to be heated separately from aluminum and preforms, and carbon-based composite materials often need to be heated separately from carbon materials and preforms. These will be added to the cost. The composite material technology used must still be modified. In addition, the improved technology must provide a composite material with higher thermal conductivity, low-density, low-cost production. ~ 丨 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The purpose and description of the invention-the purpose of the present invention is to provide-a high molecular polymer compound, a molecular polymer composite material with high thermal conductivity, and complex characteristics, surface and low density characteristics.

Another object of the present invention is to provide 4NCKU / 200101TW 2 suitable for __ applications. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by 574283 A7 _ B7. 5. Description of the invention (3)) Preparation method of high molecular polymer composite material . The present invention satisfies the needs of applications by providing a high molecular polymer composite material, which has a high thermal conductivity, a low density, and an electrically insulating surface. The preparation of this high molecular polymer composite requires no pre-forming and requires only atmospheric pressure. The polymer composite material of the present invention is particularly useful in a variety of thermal management applications requiring electrical insulation and low density. The polymer polymer composite material of the present invention is composed of a stack of in-situ woven and graphitized vapor-grown carbon fibers (abbreviated as VGCF). Therefore, post growth interweaving and pre-forming can be avoided. Manufacturing.

According to a preferred embodiment of the present invention, a high molecular polymer composite material is provided. The high molecular polymer composite material includes a stack of graphitized VGCF parent woven mats; Void. The VGCF pads in this stack are preferably composed of semi-aligned and semi-continuous vgCF. These VGCFs are inter-woven in the field during the growth process. These fibers are preferably graphitized, that is, heat-treated at a temperature of about 2600 ° C or higher to convert a part of the carbon contained in this carbon fiber into graphitic carbon. The room temperature thermal conductivity of the VGCF pad of the present invention is preferably higher than woo W / m-K. The polymer composite material thus produced has a thermal conductivity higher than 400 W / m-K. 4NCKU / 200101TW. This applies to China National Standard (CNS) A4 specification (210 X 297 public) (Please read the precautions on the back first # &lt; Fill this page)

574283 A7 V. Description of the invention (+) The present invention also provides a method for manufacturing the polymer polymer composite material. This method-generally includes the step of providing at least ~ graphitization vgc to degrade _ good polymerization _ material permeate this stone Spoon the VGCF pad into the gap. This

In the preferred embodiment, the high-molecular polymer material is infiltrated into the graphitized VGCF pad by hot pressing technology '. In the hot-pressing technology, the high molecular polymer material is the same as the VGCF, and the temperature is higher than the melting point of the high molecular polymer material. When the stacking of the polymer material and the graphitized VGCF pad reaches the required state, the stacking of the polymer material and the graphitized VGCF pad is performed in an atmospheric environment.

Pressure is applied to initiate the infiltration procedure. The method of the present invention is cost-effective and highly efficient due to the use of high-molecular polymer materials without the need for high temperature, pre-forming, environmental protection, lower pressure or high pressure, and separate heating. In addition, the use of VGCF mats eliminates the need to mechanically weave individual carbon fibers to form mats before using VGCF in composites. The printing of such hot-pressing technology by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs makes the fiber volume percentage <fiber loading> fall in a useful range, that is, from 10 volume percentage (v〇lume percent) to 60 volume percentage, and allows a single direction <Uni-directional> or in-piane orthogonal (two-directional) fiber structure without inhomogeneous infiltration. This also allows the thermal expansion coefficient and the characteristics of other composite materials to be controlled within a wide range, thereby increasing the number of types of applications where this composite material can be used.

4NCKU / 200101TW This paper size is applicable to China National Standard (CNS) A4 (210 X 297 meals)

574283 V. Description of the invention (5) In addition, the 砂 _sand polymer composite material mt has a significantly higher thermal conductivity than any other carbon fiber composite material. In addition, the forced blue molecular polymer composite has a lower density than other composite materials for thermal management. This composite material can be used in many thermal management applications, including Q-boat appliances, spacecraft, electronic components, and portable electronics. Based on this, a feature of the present invention is to provide a fine-molecular-molecular polymer composite material made of interlaced VGCF, and the polymer-polymer composite material is Pogoconductor, and can be modified. = Invention ^ Another-㈣ is a cost-effective application for the production of quasi-molecular polymer composites. Those familiar with this technology will have a clear understanding of these and other features and advantages of the present invention after reading the following detailed description and referring to the drawings and cap patents. Brief description of the drawings FIG. 1A is a photomicrograph illustrating the VGCF pad of the present invention to show the direction of the VGCF; FIG. 2A illustrates a stacking structure with unidirectional fibers; FIG. 2B illustrates an orthogonal fiber with the same plane Figure 3A is a schematic diagram when the mold of the present invention is opened, and the polymer material is placed on the bottom of the mold;

Figure 3B is a schematic diagram of the mold when the present invention is opened. The polymer aggregate material is placed on the bottom of the mold. The polymer material is VGCF 4NCKU / 2〇〇〇〇xw. The paper size is applicable to Chinese national standards. (CNS) A4 specification ⑽χ 297 public love) Read the precautions on the back first, and then ii. Page ii Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by employee consumer cooperatives 574283 A7 5. Description of the invention (L) Stacking of pads; and Figure 3C series This is a schematic diagram when the mold of the present invention is opened, polymer polymer (please read the precautions on the back before filling this page)

The composite material is placed on the bottom of the mold. There is a stack of VGCF pads on the polymer material, and there is another layer of polymer material on the stack of VGCF pads. Detailed description of the stomach month The matrix composite material reinforced with vapor-grown carbon fibers according to the present invention can provide more advantages than the use of other matrix materials, such as aluminum, or the use of other reinforcing materials, such as traditional carbon fiber composite materials condition. For example, processing polymers requires very low temperatures and does not require a protected environment and lower or high pressure. In addition, the use of VGCF pad stacks eliminates the need for preform fabrication. In addition, the VGCF pad has the highest thermal conductivity of all carbon fibers, which also results in a composite material with high thermal conductivity. In addition, other carbon fibers must be interwoven mechanically before being used in composite materials. The VGCF mat of the present invention is composed of semi-continuous fibers, which have been interwoven when growing on site, and do not need to be interwoven after growing. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to this, the production cost of the polymer composite material of the present invention is much lower than the cost production of traditional composite materials. The polymer composite contains a stack of graphitized VGCF interwoven mats. I should understand that this composite can have different shapes depending on its final use. These VGCF mats are composed of semi-aligned and semi-continuous Vgcf. As shown in Figure 7 ^ in the mat, most of the fibers have the same alignment direction, but some will show different degrees of alignment. 4NCKU / 2001 〇1 xw This paper size applies Chinese National Standard (CNS) A4 ϋ〇x 297 mm) 574283 A7 B7 V. Description of the invention (〇 <mis-orientation or mis-aiignment>. The arrangement direction and weaving of the fibers in the mat can be determined by the fibers The gas flow conditions are controlled during growth. I should understand that the number of VGCF pads in the stack can be changed according to the desired composite material size and end use. The size of individual VGCF pads can also be modified as needed. VGCF 塾 Better It is grown on a substrate, which has been seeded with seed particles composed of iron particles, or the substrate will be placed near a substrate full of iron seeds. The substrate is placed in a reactor. In, and under 1GGGt: the flowing gas mixture of carbon sutures and hydrogen attracts people with the degree of instability. The young compound of this post is 曱 ㉖ <Edit ^>. During the growth process, __ 杂 AKE The squall line <price bargaining> grows and interweaves. Result_ During the growth process, the intertwined fibers are thickened, which results in the formation of fiber mats. Seed prescription: In a blunt atmosphere, heat treatment with bribe temperature VGC is used to graphitize it. The interweaving will be run as shown in Figure 2B-the number of materials to form-end ®, as shown in Figure 2A and Figure 2B. Among them, Figure 2Δ Yang 28 and 2B respectively replace the list. ~ The structure and the same plane orthogonal fiber rack bottle. Lixiang's Ministry of Fiber Economy, Intellectual Property Bureau, employees, consumer cooperatives, printed polymer polymer composites can be tested with this package. As shown in Fig. 3A. Then :: Sub: = material material-to the top of the opened sub-polymer material, the number of fiber pads to the high score has the appropriate size and is indicated by L1, where all fiber pads ====; Fiber alignment direction. Then add the secondary gripper material to the aforementioned VGCF stack

4NCKU / 200101TW 574283 A7

V. Description of the invention (g) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and then covered with a mold to cover the mold with sandwich-like polymer materials Heating to a temperature higher than the melting point of the polymer material. When the temperature is reached, a positive force is applied to the mold gland to allow the molten polymer material to penetrate into the voids of the VGCF pad. This forward force is preferably in the range of about atmospheric pressure to about 70 atmospheres. I should understand that the pressure and temperature required for infiltration can vary depending on the specific high-molecular polymer materials and stack characteristics used. Then, the mold is cooled, and the polymer material is re-solidified. The polymer matrix is then removed from the mold. I should note that the order of stacking can be changed. This polymer material and graphitized VGCF pad can also be inserted into the mold with each VGcf pad inserted into two layers of polymer material. Any stacking order that allows the high molecular polymer material to be evenly distributed in the mat is within the scope of the present invention. For thicker polymer composites, this stacking process can be performed more than once before heating and pressing the mold and its contents. The resulting polymer composite material may have a thermal conductivity between about 400-700 W / m-K. The polymer composite material of the present invention is particularly suitable for use in electronic components and packaging, aviation appliances, spacecraft, and portable electronic products. The following examples are intended to illustrate the invention &apos; and should not be considered as limiting the scope of the accompanying patent application. 4NCKU / 200101TW 8 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back before filling this page) -I ϋ n ϋ · ϋ 1 I * 574283 A7 B7 V. Description of the invention (Example 1 Now an epoxy resin (Epoxy resin) matrix composite is prepared in accordance with the present invention. First, a VGCF mat is grown and removed from the reactor. Then at 2600 ° C Temperature, heat treat <graphitization> this VGCF pad in an argon atmosphere. Cut a small VGCF pad with a size of 5 cm by 10 cm square from a graphitized, large VGCF pad, and use this small VGCF The mats form a stack. This stack is then placed in a mold that has been pre-loaded with the desired amount of epoxy resin. Then epoxy resin is added on top of this VGCF 塾 stack, as shown in Figure 3C The mold is then closed and heated to 180 ° C. When the temperature is reached, a pressure of i atmosphere to 70 atmospheres is applied to the mold, so that the epoxy resin begins to penetrate into the voids of the VGCF pad. Then cool this Mold, remove the shape from the mold Epoxy resin matrix composite material. Seven composite materials were formed according to this method. The results are listed in Table 1. It can be seen from Table 1 that the use of VGCF pads greatly increases the thermal conductivity of epoxy resins, among which epoxy resins The original thermal conductivity of the ester is lower than 〇1 w / m_K. By using less than 14 fiber volume percentage of VGCF, the thermal conductivity of epoxy resin has increased by 200,000% compared to pure epoxy resin. (Please read the back first Notes (Fill in this page)-Binding: Printed by Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs

4NCKU / 200101TW This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇X 297 mm) 574283 A7 B7 V. Description of the invention (\ 0) Architecture density (g / cc) &amp; Gap thermal conductivity (W / mK) -5 ^ Thermal expansion coefficient (ppm / K)

(Please read the notes on the back first, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

In Table 1, X represents the primary fiber direction <the primary ―>, and Y represents the direction perpendicular to X on the same plane. Vf represents the volume ratio of VG-CF. 1D and buckle respectively represent one-dimensional (single direction) and two-dimensional (plane orthogonal). Please note that the density of this polymer composite is about! · 2 to its inspection position 5,814, the number of medium-wound composite low density means lower weight, this feature is more favorable for -like-style gambling. Although in the above embodiments, we use sub-polymer materials, we will also understand that the selection of === Γ materials in the scope of the present invention is also feasible. All illustrated implementations illustrate the invention. Those skilled in the art will understand that without departing from the scope defined by the patent application, the method of the present invention can be modified and changed. 4NCKU / 200101TW ^ Paper size applies to China National Standard (CNS) A4 specification (21〇 X 297mm Fill out this page)-Pack · 10

Claims (1)

574283; X2 A8 B8 C8 D8 Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to apply for patents 1. A polymer polymer composite material includes: at least one graphitized vapor-grown carbon fiber mat, the graphitized vapor-grown carbon fiber mat There are voids therein; and a high molecular polymer material; wherein the high molecular polymer material penetrates into the voids of the graphitized vapor-grown carbon fiber mat. 2. The high-molecular polymer composite material as described in item 1 of the scope of the patent application, wherein the graphitized vapor-grown carbon fibers are interwoven at the growing site <in-situ>. 3. The high-molecular polymer composite material according to item 1 of the scope of patent application, wherein the graphitized vapor-grown carbon fiber has a thermal conductivity higher than 1500 W / m-K at room temperature. 4. The high molecular polymer composite material described in item 1 of the patent application scope has a thermal conductivity higher than 400W / m-K. 5. The high-molecular polymer composite material according to item 1 of the patent application scope, wherein the graphitized vapor-grown carbon fiber is at least partially semi-aligned and semi-continuous to form the graphitized vapor-grown carbon fiber mat. 6. The high molecular polymer composite material according to item 1 of the scope of patent application, wherein the graphitized vapor-grown carbon fiber is graphitized at a temperature higher than 260 ° C. 7. A method for manufacturing a High polymer composite materials, this method 4NCKU / 200101TW 11 Please read the first note. I Page gutter. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) 574283 A8 B8 C8 D8. 6. The scope of patent application includes The following steps: Provide at least one graphitized vapor-grown carbon fiber mat with voids therein; and infiltrate with the polymer polymer material at a temperature higher than the melting point of a polymer polymer material Into the gap. 8. The method according to item 7 in the scope of the patent application, wherein the graphitized vapor-grown carbon fibers are interwoven in the field during growth. 9. The method according to item 7 in the scope of patent application, wherein the Graphitized vapor-grown carbon fibers are at least partially semi-aligned and semi-continuous. 10. The method as described in item 7 of the scope of patent application, wherein The step of infiltrating the macromolecular polymer material into the void further includes the following steps: placing the graphitized vapor-grown carbon fiber mat in a mold previously loaded with the macromolecular polymer material; adding the macromolecular polymer material On the graphitized vapor-grown carbon fiber mat in the mold; cover the mold with a mold gland; printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the mold on the cover is heated higher than the polymer The temperature and temperature of the melting point of the material; and a positive force is applied to the mold gland. 4NCKU / 200101TW 12 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)