TWI303273B - Metal matrix carbon composite material with high thermal conductivity and method for producing the same - Google Patents

Description

1303273 IX. Description of the invention [Technical field to which the invention pertains]: The invention relates to a high thermal conductivity carbon-containing metal matrix composite material and a method thereof, in particular to a high thermal conductivity carbon-containing metal matrix composite material applied to a heat dissipating component and Its manufacturing method. [Prior Art] "Hot" - is a problem that must be dealt with when electronic components work. The problem of heat dissipation has become a bottleneck for key technologies in the development of science and technology. At present, the heat dissipation path of the electronic components is transmitted to the surface layer through the material of the inner material, and the heat is transmitted to the outside of the heat source by using a larger heat spreader, and a Korean film or a fan is added. The effect of forced convection is achieved.

In recent years, the material of the heat dissipating component has become a hot topic. With the trend toward thinner, smaller, higher-functionalized, and higher-frequency electronic products, the heat generation per unit volume of electronic components has increased relatively, so a heat-dissipating material having a higher thermal conductivity is required. At present, aluminum extrusion type heat dissipating materials are widely used, for example, a type 6063 aluminum extruded heat dissipating material is used to manufacture various heat dissipating components. Since the heat transfer coefficient of the aluminum extruded heat-dissipating material is not high, it is only between 16 watts/meter of card temperature (W/mK) to 180 W/mK, which has long been unable to meet the new demand: Various improved processes have been developed for this aluminum extruded heat dissipating material, such as Bonding Fins process, Folding Fins process, Modified Die Casting, Forging process and planer type ( Skiving), etc., but still failed to solve the bottleneck problem of heat dissipation. 1303273 Since the high temperature generated in electronic circuits affects the working efficiency of electronic components, it is necessary to develop a thermal module to maintain the temperature of the electronic components below the critical safe temperature to avoid performance degradation due to overheating of the components; stable. However, due to the limited heat transfer coefficient of the heat dissipating component, a heat dissipation bottleneck occurs. Copper has a higher heat transfer coefficient than aluminum, and has a copper-based heat sink material of about 38 〇 W/mK ‘. In order to improve the heat transfer efficiency of the heat dissipating component, U.S. Patent No. 6,264,882 discloses a method of manufacturing a highly thermally conductive composite material for manufacturing a heat sink or a heat spreader of a high density integrated circuit ( Heat Spreader), and the composite material obtained from this process has a thermal conductivity between diamond and copper. The process basically comprises sputtering a metal layer on the diamond powder, then pressing into a porous body, and then infiltrating the copper alloy into the porous body in an infiltrated manner to form a diamond-steel composite having high thermal conductivity. material. China Patent Publication No. 573,025 discloses a carbon-containing copper-based composite material having a thermal expansion coefficient of φ and its application, which is based on copper powder, carbon powder and high-score polymer, respectively, depending on 70% to 95%. /. , 0. 01% ~ 10%, 5% ~ 3〇% ratio of evenly mixed, or steel powder and high molecular weight polymer containing carbon, respectively, according to the ratio of 7 G% ~ 95%, 5% ~ 鄕 mixed And through a number of high-temperature heat: work, the polymer polymer melts and evaporates, which constitutes a carbon-containing copper-based composite, material, and the thermal expansion coefficient of the composite material can vary with the ratio of the mixed raw materials and the heating temperature. And there are changes, so it can respond to the material requirements of different thermal expansion coefficients. China Patent Publication No. 561,207 discloses a carbon fiber having high thermal conductivity, mainly coated with polyacrylonitrile (P〇lyaCryl〇nitlile; pAN)-based carbon fiber 7 1303273 (Coating)-asphalt, asphalt derivative or high. After the molecular polymer is formed by carbonization and graphitization, the carbon fiber obtained has a thermal conductivity of between '20 W/mK and 500 W/mK. In short, the prior art improves the thermal conductivity of the composite by adding diamond powder or carbon powder. However, both the diamond powder and the carbon powder are in the form of granules. If only a small amount of diamond powder or carbon powder is added, it is difficult to form continuity in the composite material, and it is difficult to contribute to the thermal conductivity of the composite Lu material; if a large amount of diamond powder or carbon powder is added The shadow will ♦ the physical properties of the composite material. In addition, although the PAN-based carbon fiber is more continuous, the carbon fiber obtained by the graphitization treatment has a thermal conductivity of only between 2 〇 w/mK and 500 W/mK, which has a limited contribution to the thermal conductivity of the composite. In addition, conventional techniques often face problems of poor interface when carbon materials are combined with metal substrates. Therefore, there is an urgent need to develop a manufacturing method of a high thermal conductivity carbon-containing metal matrix composite material, in order to utilize a carbon material having a high thermal conductivity and good continuity, and to improve the interface problem of the carbon material in the metal substrate and improve The carbon-containing metal composite material appeals to the thermal conductivity, thereby improving the heat dissipation efficiency of the heat dissipating component fabricated using the carbon-containing metal matrix composite material. [Explanation] Therefore, one of the objects of the present invention is to disclose a high thermal conductivity carbon-containing metal matrix composite material and a method for producing the same, which are characterized by having a high thermal conductivity and a good connection, and a graphene gas Vap〇r Growll Carbon Fiber is used as an added carbon material, and a thin layer of carbonized metal is formed on the surface of the graphitized vapor-grown carbon fiber to improve the interface between the carbon material and the metal substrate, and to raise 1303273 high carbon material. The composite quality and the compounding ratio with the metal substrate greatly increase the thermal conductivity of the carbon-containing metal-based composite material, thereby making the heat dissipating component made of the metal-based composite material excellent in heat dissipation efficiency. According to the above object of the present invention, a high thermal conductivity carbon-containing metal matrix composite material is proposed. The high thermal conductivity carbon-containing metal matrix composite comprises at least between 1, and between 40% by weight of a thin layer of carbonized metal. Inked vapor grown carbon fiber, and from 60% by weight to 99.% by weight a metal substrate between a hundred and a ratio, wherein the thermal conductivity of the high thermal conductivity carbon-containing metal matrix composite is between the thermal conductivity of the metal substrate and the thermal conductivity of the graphitized vapor-grown carbon fiber, and the graphitized gas phase The thermal conductivity of the growing carbon fiber is between 1000 W/mK and 1980 W/mK. In accordance with a preferred embodiment of the present invention, the carbon content of the graphitized vapor-growth carbon fibers having a thin layer of a metal carbide is generally between 7 and 99 weight percent. According to a preferred embodiment of the present invention, the metal of the metallized metal layer and the metal Φ substrate are substantially the same or different materials. According to a preferred embodiment of the present invention, the metal of the metallization layer may generally include, but is not limited to, tungsten (W), titanium (Ti), chromium (Cr), molybdenum (Mo), zirconium (Zr), vanadium (V). Or any combination thereof. According to a comparative embodiment of the present invention, the material of the metal substrate may generally include, but is not limited to, copper, aluminum, silver, gold or any combination thereof. According to the above object of the present invention, a method of producing a highly thermally conductive carbon-containing metal matrix composite material is further proposed. First, a graphite vapor-grown carbon fiber having a thin layer of a metal carbide is provided, wherein the heat of the graphitized vapor-grown carbon fiber is between 3, 3,273, 1000 W/mK and 198 〇w/mK. Then, performing a complex m ^ step of making the metal I material and the graphitized gas having a thin layer of carbonized metal into a high thermal conductivity carbon-containing metal matrix composite material, wherein the high thermal carbon-containing metal matrix composite material is thermally conductive Between the conductivity of the metal substrate, the coefficient and the thermal conductivity of the graphitized vapor-grown carbon fiber. According to a preferred embodiment of the present invention, before the step of providing the graphitized vapor-growth carbon fiber having the thin metal carbide thinner 9, the method further comprises the following steps: first opening the gas into the vapor-grown carbon fiber. Between 6 0 0 and 1 3 0 0 f, the temperature is in the presence of a reducing gas, and the carbon source material is formed by the catalyst to form a vapor-grown carbon fiber. Next, a graphitization step is carried out which is between 2400 t and 3,000. (: between the temperature and in the presence of a blunt gas, the vapor-grown carbon fiber is formed into a graphitized vapor-grown carbon fiber. Then, a thin layer of a metal carbide is formed on the surface of the graphitized vapor-grown carbon fiber by a sintering method. In a preferred embodiment of the invention, the catalyst is generally a transition metal such as iron, cobalt or nickel or a metal organic compound thereof. According to a preferred embodiment of the invention, the carbon source material is generally a gaseous or liquid sad hydrocarbon. The carbon source material may be, for example, carbon monoxide 'benzene, toluene, xylene, liquefied petroleum gas, acetylene or any combination thereof. According to a preferred embodiment of the present invention, the above thin layer of carbonized metal is the aforementioned graphitized gas phase. After the carbon fiber is added to the metal compound solution, the solvent is removed, the temperature is cracked and sintered, and the metal of the metal compound is generally, for example, tungsten (W), titanium (Ti), chromium (Cr), molybdenum (Mo), and hammer ( Zr), vanadium (V) or any combination of the above. Further, the above metal compound may be, for example, Ammonium Paratungstate or phosphotungstic acid (Tun Gstoph〇sphoric 1303273

Acid), Tungstic Acid, Tungsten Chloride, Titanium Isopropoxide, Chromocene, Ammonium Chromate, Chromium Chloride, (Chromium) Chloride), Chromium Acetylacetonate, Chromium Acetate, Chromium Nitrate Nonahydrate, Ammonium • Paramolybdate, Zirconium Chloride Zirconium Acetylacetonate, Zirconium t> Butoxide, Vanadyl Acetylacetonate or any combination thereof. According to a preferred embodiment of the present invention, the compounding and molding steps can be generally performed by a melting method, a squeeze casting method, a melt die casting method, a metal powder stamping (Compact Pressing) method or a metal powder injection molding (Metal Injection Molding; The MIM) method forms a highly thermally conductive carbon-containing metal-based composite material with a graphitized vapor-grown carbon fiber having a thin layer of a metal carbide on the surface and a metal substrate. According to a preferred embodiment of the present invention, the metal substrate and the graphitized vapor-grown carbon fiber having a carbonized sublayer are added to the compounding and molding step to further add an organic binder to assist in compounding and molding, wherein the organic bonding The combined amount of the agent is the weight percentage of ruthenium/ruthenium to the weight percentage of the total weight of the metal substrate and the graphitized fumed stone anti-fiber having a thin layer of carbonized metal. Applying the above high thermal conductivity carbon-containing metal matrix composite material and a manufacturing method thereof, improving the composite quality of the carbon material and the metal substrate by improving the high thermal conductivity of the graphitized vapor-grown carbon fiber and the interface between the carbon fiber and the metal substrate complex

The temperature between the two is in the presence of a reducing gas, and the carbon source material is formed into a vapor-grown carbon fiber by a catalyst in a reaction apparatus made of, for example, quartz, alumina or I. (Mun (10). The reducing gas of the society is generally hydrogen. The catalyst is generally a transition metal or a metal of the ancient genus, and it is preferred to use iron, cobalt, nickel or a metal organic compound thereof. The material of the stone source is generally gaseous or liquid stone, and it is preferably carbon monoxide, stupid, petroleum gas, B-speed or any combination of the above. Stupid 1303273 proportionally The thermal conductivity of the carbon-metal composite material further improves the heat dissipation efficiency of the heat-dissipating component made of the carbon-containing metal-based composite material. [Embodiment] The high thermal conductivity carbon-containing metal matrix composite material of the present invention and a method for producing the same Firstly, a high thermal conductivity graphitized vapor-grown carbon fiber is produced, and a thin layer of carbonized gold is formed on the surface by a sintering method, thereby improving the interface between the carbon fiber and the metal substrate. The composite quality and compounding ratio of the high carbon material and the metal substrate, and further, the graphitized vapor-grown carbon fiber having a thin layer of carbonized metal formed on the surface is composited with the metal substrate, and (4) the W thermal carbon-containing metal matrix composite material enables the use of the carbonaceous material The heat dissipating component made of the metal matrix composite material has excellent heat dissipation rate. The high thermal conductivity carbon-containing metal matrix composite material of the present invention and the manufacturing method thereof will be described in detail below with reference to the first to third figures. , which is a flow chart showing the process of the high thermal conductivity carbon-containing metal matrix composite material according to the preferred embodiment of the present invention. First, as shown in the step ι〇ι, a vapor-grown carbon fiber is formed, which is between 6〇. 〇t to 〇〇3〇〇ιtoluene, liquid 12 1303273 Next, the above vapor-grown carbon fiber is placed in, for example, a graphitization furnace at a temperature of between 24 〇 0. (: to 300 (TC) and blunt The graphitization step is carried out in the presence of a gas such as argon, and the vapor-grown carbon fibers are formed into graphitized vapor-grown carbon fibers as shown in step 103. The graphitization step can be carried out using process parameters used in conventional processes. Therefore, the thermal conductivity of the vapor-grown carbon fiber can be increased to between 1 〇〇〇W/mK and 1980 W/mK after the above-described graphitization step. The obtained graphitized vapor-grown carbon fiber is slender. , hollow, graphite-curled structure, and its single graphitized vapor-grown carbon fiber diameter between 0.01//111 to 10/zm, length between = 10 cm, aspect ratio (Aspect Rati 〇) Between 1〇〇 and ι〇, 〇〇〇. If the aspect ratio of graphitized vapor-grown carbon fiber is too low, it is difficult to form a continuous path, such as the aspect ratio of graphitized vapor-grown carbon fiber is too high. However, it is easy to correct 2 = poor dispersion, so the graphitized vapor-grown carbon fiber of the present invention is between 0.1/m and the length of the mixture is between 5 〇 " melon to 2 茁 、, long A diameter ratio of between 500 and 2,000 is preferred. In general, when conventional carbon materials are combined with metal substrates, they often face the problem of good interface. Therefore, in the present invention, after the graphitization step, as in the step, a thin layer of a metal carbide is formed on the surface of the graphitized vapor-grown carbon fiber, which improves the problem of poor interface between the slave material and the metal substrate. Further, when forming a thin layer of deuterated metal, the graphitized vapor-phase-growth carbon obtained above is added to the metal compound solution, and the solvent in the metal compound=liquid is distilled off under uniform stirring, and is graphitized. The surface of the vapor-grown carbon fiber is uniformly attached to the thin layer of the genus genus, and then the thin layer of the metal compound adhered to the surface of the carbon fiber is converted into a thin layer of the carbonized metal bonded to the carbon fiber by a sintering method. The solvent described in 13 1303273 is well known to those of ordinary skill in the art and may be, for example, water or an organic solvent, and thus will not be further described. The metal of the above metal compound is a metal which is easy to form a carbide. Generally, it may include, but is not limited to, tungsten (W), titanium (Ti), chromium (Cr), _ (Mo), ytterbium (Zr), vanadium (V) or Any combination thereof. Further, the above metal compound may be, for example, Ammonium Paratungstate, Tungstophosphoric Acid, Tungstlc Acid, Tungsten Chloride, Isopropyltitanate. (Titanium IS0pr0p0Xide), Chr〇m〇cene, Ammonium Chromate, Chromium Chl〇ride, Chromium Acetylacetonate, Chrome Acetate , Chromium Nitrate Nonahydrate, Ammonium Param〇iybdate, Zirc〇nium

Chloride), zirconium Acetylacetonate, Zirconium t_Butoxide, vanadyl Acetylacetonate or any combination thereof. However, the metal compound of the present invention is not limited to those mentioned herein, and any one of ordinary skill in the art can understand that other metal compounds which are easy to form carbides can also be used in the present invention. In the presence of an inert gas or a reducing gas as described above, the temperature is raised in, for example, a heat treatment furnace to crack a thin layer of the metal compound to remove components other than the metal, and the metal component and the graphite remain at a high temperature. The vaporized carbon fiber is sintered and converted into a thin layer of a solid carbonized metal. The sintering temperature and time are determined depending on the metal to be used. For example, when the metal component is chromium metal, it can be sintered at 1500 ° C for 3 hours. 14 1303273 - If the carbon content in the graphitized vapor-grown carbon fiber with a thin layer of carbonized metal is less than 70% by weight, the excessive thin layer of carbonized metal will affect the thermal conductivity; otherwise, if the carbon content is higher than 99% by weight However, the thin layer of the metal layer will not significantly improve the problem that the carbon material is poor in the metal substrate. Therefore, the graphitized vapor-growth carbon fiber having a thin layer of carbonized metal obtained on the surface of the present invention generally has a carbon content of between about 100% by weight and a percentage by weight of 99% by weight. It is preferred to be between 90% by weight of the scent. In the subsequent process, the graphitized vapor-grown carbon fiber having a thin layer of deuterated metal on the surface of the present invention can significantly improve the interface problem of the carbon material in the metal substrate. * Then, a compounding and molding step 107 is performed in which the graphitized vapor-growth carbon fiber having the surface of the metallized layer is formed by differently forming a preformed mold with a metal base: Thermally conductive carbon-containing metal matrix composite. In an example of the present invention, a heat dissipating member of a highly thermally conductive carbon-containing gold-based composite material can be produced by a smelting method, a Φ squeezing method or a melt-casting method. First, the metal substrate is placed in a refining furnace. • Heated and melted in a presence of an inert gas and uniformly mixed with a graphitized vapor-grown carbon fiber having a thin layer of a metal carbide to form a composite material, wherein the content of the metal substrate is: f The content is between 60% by weight and 99% by weight, and the content of the graphitized vapor-growth carbon fiber having a thin layer of metal carbide is between 1% by weight and 40% by weight. The material of the metal substrate is generally preferably a metal having a high 孰 conductivity, and may be, for example, copper, aluminum, silver, gold or any combination thereof. Further, in the case of the metal substrate and the metal of the thin layer of the metal carbide, the materials of the two may be substantially the same or different, and the present invention is not limited thereto. The composite material described above can be directly removed from the melting furnace by 15 1303273 and pressed into a mold to form a composite heat dissipating component of a desired shape. Alternatively, the composite material may be first formed into an ingot, and then melted into a mold to form a composite heat dissipating member of a desired shape. In another example of the present invention, a metal powder stamping method or a Metal Injection Molding (MIM) method can be used to manufacture a heat dissipating component of a high thermal conductivity carbon-containing metal matrix composite material, depending on the desired product shape. Depending on the complexity. First, the metal substrate powder and the graphitized vapor-grown carbon fiber having a thin layer of carbonized metal are uniformly mixed into a mixture, wherein the content of the metal substrate powder is between 60% by weight and 99% by weight, and has a The content of the graphitized vapor-growth carbon fiber of the thin metal layer is between 1% by weight and 40% by weight. Alternatively, an organic binder of from 1% by weight to 1% by weight based on the total weight of the above mixture may be added to aid in compounding and molding. Suitable organic binders may generally include, but are not limited to, stearic acid, stearic acid, lithium stearate, MiCrocrystamne Wax, paraffin Wax, paraffin oil. , rubber, plastic or any combination thereof. After the above ingredients are uniformly mixed, the mixture is placed in a mold and directly formed into a composite heat-dissipating element body of a desired shape. Alternatively, the above components may be uniformly mixed, and then heated and kneaded to form a composite feedstock (Feedst〇ck), which is injected into a mold by an injection molding machine to form a composite heat dissipating component body body of a desired shape. . After the composite body heat-dissipating element body of the desired shape is formed by metal #end molding or metal ❺纟 injection molding, a De-Wax de-Binding step, such as heating to 6 尚, is required. Hey. 〇约ι小16 1303273, in order to remove the organic binder contained in the embryo body. Thereafter, a Sintering step is performed in which the dewaxed and degreased embryo body is placed in, for example, a sintering furnace, for example, at 1000 ° C for sintering, for example, about 1 hour, to form a neck joint between the metal particles, and shrink. Densification into a porous body. Subsequently, an infiltrating step is performed, which utilizes the same or different metal substrate to melt and fill the pores of the porous body, thereby forming a high thermal conductivity carbon-containing metal-based composite heat dissipating component, wherein the high thermal conductivity The thermal conductivity of the carbon-containing metal matrix composite heat dissipating component is between the thermal conductivity of the metal substrate and the thermal conductivity of the graphitized vapor-grown carbon fiber. Yi Luzhi' The carbon-containing metal matrix composite of the present invention first produces a highly thermally conductive graphitized vapor-grown carbon fiber, and then forms a thin layer of carbonized metal on the surface thereof by a sintering method, thereby improving the interface between the carbon fiber and the metal substrate, and improving the carbon. The composite quality and composite ratio of the material and the metal substrate are then combined with the metal substrate to obtain a carbon-containing metal matrix composite material having a high thermal conductivity, so that the heat dissipating component made of the carbon-containing metal matrix composite material has excellent heat dissipation efficiency. In one embodiment of the present invention, when the material of the metal substrate is copper, the resulting carbon-containing metal matrix composite may have a thermal conductivity of between 400 W/mK and 1 00 w/mK. In the following, several examples are given to illustrate the high thermal conductivity stone-containing metal-based composite material of the present invention and a method for producing the same, but the following examples are not intended to limit the scope of the present invention, and the scope of the present invention is This is subject to the definition of the scope of the patent application. Embodiment 1 Please refer to Fig. 2, which is a schematic view showing the structure of a reaction apparatus for vapor-phase-forming carbon fibers according to Embodiment 1 of the present invention. The reverse phase 130 1303273 of the vapor-grown carbon fiber is a fluidized bed type reaction tube device, and further, for example, an upright oxidation reaction tube. The reaction apparatus 2 一般 一般 generally includes at least a reaction tube 20 1 and a heater 2 〇 3 on the periphery of the reaction tube 20 1 . At one end of the reaction tube 20 1 ; a raw material introduction tube 205 and a carrier gas inlet 207 are provided, and the other end of the reaction tube 201 is a collection tank 209, and one side of the collection tank 209 is provided with an exhaust port "211. The material of the tube 2G1 is generally oxidized, quartz or mullite _ (Mullite). In this embodiment, the reaction tube 201 is made of, for example, a purity of 99.8% ♦, and its outer diameter is, for example, 762 cm. The inner diameter is, for example, 69 melon, and the length is, for example, 150 cm. In the process of vapor-grown carbon fiber, first, after the air in the reaction tube 201 is replaced with nitrogen, the reaction tube 2〇1 is heated by the heater 2〇3. And maintained at about n 〇 (rc. Then, the nitrogen gas is turned off, and the hydrogen gas having a flow rate of 10 liters/min (L/min) is introduced into the reaction tube 2〇1 to form a reducing atmosphere in the tube. Then, it will contain 4 The weight percentage of ferrocene (Ferr〇eene) in xylene solution is continuously fed into the reaction tube at a flow rate of 8 ml/min (mL/min) to form a gas phase by catalytic cracking of the ferrocene catalyst at a high temperature. : long _ carbon fiber, and the resulting vapor-grown carbon fiber falls into the collection tank 2〇9. Please refer to Figure 3. It is a scanning electron micrograph showing a 10,000-fold magnification of the vapor-grown carbon fiber of the first embodiment of the present invention. The results of the third graph show that the diameter of the obtained vapor-grown carbon fiber is between 〇〇i#m and 0.3. Between /zm, and the length is between 60/zin and 1 mm. After that, the vapor-grown carbon fiber obtained above is placed in a graphitization furnace, and the furnace is in an argon atmosphere at 1 (TC/min). The heating rate was heated to 28 〇〇. (:, and held for 1 hour, thereby vaporizing the vapor-grown carbon fiber. The obtained graphitized vapor-grown carbon fiber has a thermal conductivity of 1 850 w/mK. 18 1303273 Subsequently, The graphitized vapor-grown carbon fiber is added to an aqueous chromic acid solution, wherein the chromium carbonate aqueous solution has a chromium content of 11% by weight, and the weight ratio of the graphitized vapor-grown carbon fiber to the ferrous chromium acetate solution is 1:1. The vapor-grown carbon fiber oxychromic acid aqueous solution is placed in a rotary evaporator and heated at 120 ° C for 2 hours to evaporate the water to make the stone

The surface of the vaporized vapor-grown carbon fiber leaves a thin layer of acetic acid. Next, the graphitized vapor-grown carbon fiber having a thin layer of chromite acetate was placed in a high-temperature heat treatment furnace, and sintered at 1500 ° C for 3 hours under a hydrogen atmosphere, thereby obtaining a graphitized gas having a thin layer of solid chromium carbide on the surface. The phase-grown carbon fiber, wherein the graphitized vapor-growth carbon fiber having a thin layer of solid chromium carbide on the surface has a carbon content of 90% by weight. Example 2 First, 10 g of graphitized vapor-growth carbon fiber having a thin layer of chromium carbide obtained on the surface obtained in Example 1, a copper powder having an average particle diameter of 2 〇/zm of 9 gram, and 0.5 gram of stearic acid were used, for example, by mixing. The machine is evenly mixed. Then, for example, a press molding machine, the above-mentioned 15 gram of the mixed powder is formed by the pressure (four) of Μ (eight): 千 坪 square centimeters, to obtain a flat carbon-containing copper-based composite material body body, then, in a volume ratio The embryo body was degreased to G. 5 hours under a nitrogen/hydrogen atmosphere of 9/1. Thereafter, the degreased embryo = under the H atmosphere is sintered to obtain a porous body, which is taken out after the cold portion. The sintered carbon-containing copper-based composite porous body is placed in a mold of a carbon-containing steel-based composite porous body powder.铗尨4· 叫 上 上 上 上 上 上 上 上 上 上 上 上 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 130 19 19 Next, the carbon powder is melt-infiltrated into the pores of the porous body by, for example, 98 (TC is subjected to an infiltration step to 55 hours) to form a carbon-containing metal-based composite heat dissipating member. The obtained carbon-containing metal-based composite heat dissipating member is, for example, Netzsch [FA 447

The Nan〇Flash laser measuring instrument has a thermal conductivity of 6〇2 w/mK, which is between the thermal conductivity of copper and silver and the thermal conductivity of graphitized vapor-grown carbon fiber. First of all, first, take 300 g of graphitized vapor-grown carbon fiber with a thin layer of chromium carbide obtained on the surface of Example 1, and put it into a vacuum melting furnace together with 7 g of aluminum ingot, and heat and melt under agitation. . Next, a rod-shaped ingot is formed (1 is called 〇〇, wherein the ingot has a thermal conductivity of 556 W/mK. Subsequently, the ingot can be remelted and die-formed according to the shape of several heat sinks to form a desired shape. Carbon-containing metal-based composite heat-dissipating component. Comparative example - 10 g of graphitized vapor-grown carbon fiber with no thin layer of carbonized metal, 9 g of copper powder with an average particle size of 2 〇/zm, and stearic acid 〇·5 gram is uniformly mixed by, for example, a mixer, and the above-mentioned 15 g of the mixed powder is press-formed in the same manner as in the second embodiment. However, the preform of the carbon-containing steel-based composite material prepared is formed. Poor and easy to delamination. Another way is to change the graphitized vapor-growth carbon fiber gram with a thin layer of carbonized metal on the surface, 95 gram of copper powder with an average particle size of 20 # m, and 公·5 gram of stearic acid using, for example, mixing. After the machine was uniformly mixed, the above-mentioned 15 g of the mixed powder was press-formed in the same manner as in Example 2. The heat transfer coefficient of the 1303273 carbon-containing copper-based composite material obtained was only 38 〇W/ mK. From the above hair It understood the preferred embodiment, the high thermal conductivity of the present invention is applied

The stone-containing anti-metal matrix composite material and the manufacturing method thereof have the advantages that the added graphitized vapor-grown carbon fiber has high thermal conductivity and has a thin layer of carbonized metal on the surface thereof, thereby improving the carbon material in the metal substrate. The composite quality and the composite ratio' thus greatly increase the thermal conductivity of the carbon-containing metal matrix composite material, thereby further improving the heat dissipation efficiency of the heat dissipation component manufactured using the carbon-containing metal matrix composite material. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make various changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing the process of a high thermal conductivity sound-containing carbon-metal composite material according to a preferred embodiment of the present invention; A schematic diagram of the structure of a reaction apparatus for vapor-grown carbon fibers; and FIG. 3 is a scanning electron micrograph showing the vapor-grown carbon fibers of the first embodiment of the present invention. [Description of main component symbols] 101: Step 103 of forming vapor-grown carbon fibers: Graphitization step 21 1303273 105: Step of forming a metal carbide layer on the surface of the graphitized vapor-grown carbon fiber - 107: Compounding and molding step 201: Reaction Tube 205: raw material introduction pipe 209 ··collection tank ^ 200 : reaction device '203 : heater " 2 0 7 : carrier gas inlet 2 11 : exhaust port ·e

twenty two

Claims (1)

1303273,-—η ^±3 X. Patent application: 1. A high thermal conductivity carbon-containing metal matrix composite 'at least · one thin layer of carbonized metal, graphitized vapor phase growth, anti-fiber (Vapor Grown Carbon) Fiber), wherein the content of the graphitized vapor-growth carbon fiber having the thin layer of the metal carbide is between 1% by weight and 40% by weight, and the thermal conductivity of the graphitized vapor-grown carbon fiber is based on 1000W/ Between mK and 1980 W/mK, the diameter of the graphitized vapor-grown carbon fiber is between 0·1 // m and 1 // m, and the length is between 50 // m and 2 mm, and the long diameter a ratio of between 5 Å and 2 Å; and a metal substrate of which the content of the metal substrate is between 6 Å and 99% by weight; wherein the high thermal conductivity carbon-containing metal group The thermal conductivity of the composite material is between the thermal conductivity of the uhai metal substrate and the guiding coefficient of the graphitized vapor grown carbon fiber. w, Bi Ren Lr Please apply the carbon content of the high thermal conductivity carbon-containing metal-based fiber described in the patent scope 帛1 between 7G inkized and grown carbon. "70% by weight to 99% by weight of the composite material", as in the patent application of the composite material, wherein the carbon content of the carbonized gold thermally conductive carbon-containing metal-based fiber is between 8Q ^ 〃 graphitized milk phase growth carbon ratio Up to 90% by weight of 23 1303273. The compound of the high thermal conductivity cutting metal base described in the above-mentioned patent scope 帛1 is different or the metal of the second carbonized metal layer is substantially the same as the metal substrate. The high thermal conductivity carbon-containing metal matrix composite material according to the invention of claim 2, wherein the metallization layer is selected from the group consisting of tungsten, titanium, chromium molybdenum, niobium, vanadium and any combination thereof. The high thermal conductivity carbon-containing metal matrix composite material according to claim 1, wherein the material of the gold alloy substrate is selected from the group consisting of copper, aluminum, silver, gold, and any combination thereof. Form a group of people. 7. A method for producing a high thermal conductivity carbon-containing metal matrix composite, comprising: providing a graphitized vapor-grown carbon fiber having a thin layer of a carbonized metal, wherein a thermal conductivity of the graphitized vapor-grown carbon fiber is Between 1000 W/mK and 1980 W/mK, the graphitized vapor-grown carbon fiber has a diameter between 0.1 // m and 1 // m, a length between 50//m and 2 mm, and a long diameter a ratio between 500 and 2, 〇〇〇; and a compounding and forming step of compounding a metal substrate and a mixture of the graphitized vapor-grown carbon fibers having the thin layer of carbonized metal in different ways And molding into a mold to make the mixture into the high-conductivity 24 1303273 thermal carbon-containing metal-based composite material, wherein the content of the metal substrate is between 60% by weight and 99% by weight, and The content of the graphitized vapor-growth carbon fiber of the thin metal carbide layer is between 1% by weight and 40% by weight, and the thermal conductivity of the high thermal conductivity carbon-containing metal matrix composite is between the guiding of the metal substrate Coefficient of thermal conductivity of gas phase between the long carbon fibers graphitized. For example, the manufacturing method of the high thermal conductivity carbon-containing metal-based composite material described in the seventh paragraph of the patent scope, wherein before the step of providing the graphitized vapor-growth carbon fiber having the thin layer of the carbonized metal, at least The method comprises: forming a vapor-grown carbon fiber, which is formed between a range of 6〇〇〇c to 13〇(^c and in the presence of a reducing gas, forming a carbon source material by a catalyst The vapor-grown carbon fiber; the step of graphitization is carried out in a range of between 24 〇〇c > c and 3 〇〇 (rc) and in the presence of a blunt gas, the vapor-grown carbon fiber Forming the stone art ink vapor-grown carbon fiber; and forming a thin layer of the carbonized metal on the surface of the graphitized vapor-grown carbon fiber by a sintering method. • The high thermal conductivity content as described in the patent (4) The method for manufacturing a metal-based complex a material, wherein the reducing gas is nitrogen gas, and the method for producing a high thermal conductivity carbon-containing metal base according to the eighth aspect of the invention, wherein the catalyst is selected from the group consisting of Metals described by transition metals and above 25 1303273 11. The method of manufacturing a high thermal conductivity carbon-containing metal-based composite material according to claim 8, wherein the catalyst is selected from the group consisting of iron, cobalt, nickel, and the like. A method for producing a high thermal conductivity carbon-containing metal-based composite material according to claim 8 wherein the carbon source material is a gaseous hydrogen absorbing compound or a liquid The method for producing a high thermal conductivity carbon-containing metal-based composite material according to claim 8, wherein the carbon source material is selected from the group consisting of anti-odd, stupid, stupid, and A method for producing a high thermal conductivity carbon-containing metal odor composite material according to the invention, wherein the pure gas is selected from the group consisting of acetylene, liquefied petroleum gas, acetylene, and any combination thereof. And a method for producing a high thermal conductivity carbon-containing gold composite material according to claim 8, wherein the carbonized metal layer is formed 'Soil contains··1 less forms a thin layer of a metal compound on the surface of the graphitized vapor-grown ruthenium fiber, which is added to a metal compound = 26 1303273 liquid and then removed under uniform stirring. a solvent of one of the metal compound solutions; and performing a sintering step of converting the thin layer of the metal compound into the thin layer of the metal carbide by the presence of a blunt gas or the reducing gas. The method for producing a high thermal conductivity carbon-containing metal matrix composite according to Item 15, wherein the metal of the metal compound is selected from the group consisting of tungsten (W), titanium (Ti), chromium (Cr), and molybdenum (Mo). And a method of manufacturing a high thermal conductivity carbon-containing metal matrix composite material according to claim 16 of the patent application scope, wherein the method of manufacturing the high-heat conductivity carbon-containing metal matrix composite material according to claim 16 The metal compound is selected from the group consisting of Ammonium Paratungstate, Tungstophosphoric Acid, Tungstic Acid, Tungsten Chloride, Titanium Isopropoxide. Chromocene, Ammonium Chromate, Chromium Chloride, Chromium Acetylacetonate, Chromium Acetate, Chromium Nitrate Nonahydrate ), Ammonium Paramolybdate, Zirconium Chloride, Zirconium Acetylacetonate, Zirconium t-But ox ide, Vanadyl Acetyl Ace to nate) and any combination of the above. The method for producing a high thermal conductivity carbon-containing metal 27 1303273 composite material according to claim 15, wherein the solvent of the metal compound solution is water or an organic solvent. The manufacturing method of the high thermal conductivity carbon-containing metal matrix composite material according to claim 7, wherein the carbonized content of the graphitized vapor-grown carbon fiber having the thin layer of the metal carbide is 7〇 Weight percentage to between 99 weight percent. 20. The method for producing a high thermal conductivity carbon-containing metal matrix composite according to claim 7, wherein the carbon content of the graphitized vapor-grown carbon fiber having the thin layer of the metal carbide is 8 〇 Percentage to 9 〇 weight percent. The method for producing a high thermal conductivity carbon-containing metal-based composite material according to claim 7, wherein the metal of the carbonized metal layer is different or similar. It is made up of cranes, dragonflies, chrome, and scorpions. The method for manufacturing a high thermal conductivity carbon-containing metal-based composite material according to claim 7, wherein the metal of the metallized metal layer is selected from the group consisting of erroneous, hunger, and any combination thereof. The material of the high thermal conductivity carbon-containing metal-based metal substrate is selected from the manufacturing method of the composite material according to the patent application scope, wherein the 28 1303273 copper 'aluminum, silver, gold and the above The _ group consisting of any combination. [24] The method for producing a high thermal conductivity carbon-containing metal matrix composite according to claim 7, wherein the compounding and molding step is performed by a melting method, a squeeze casting method or a melt casting method. To form the high thermal conductivity carbon-containing metal matrix composite. The method for producing a high thermal conductivity carbon-containing metal matrix composite according to claim 7, wherein the compounding and molding step is performed by a metal powder compacting method or a metal powder injection method. A Metal Injection Molding (MIM) method to form the high thermal conductivity carbon-containing metal matrix composite. 26. The method of claim 1, wherein the mixture further comprises at least one organic viscous gel-forming agent, and one of the organic binders is the metal. 1% by weight to 10% by weight of the total weight of the substrate and the graphitized vapor-growth carbon fiber having the thin layer of the metal carbide. The method for producing a high thermal conductivity carbon-containing metal matrix composite according to claim 26, wherein the organic binder is selected from the group consisting of stearic acid, zinc stearate, and stearic acid. Lithium acid, microcrystalline Wax, Paraffin Wax, ParafTin Oil, rubber, plastic, and any combination of the above 29 1303273 group. The method of manufacturing a base composite according to claim 26, wherein the mixture further comprises: forming the mixture into an embryo body; De-Wax de-Binding step to remove the organic binder in the ~body; and Sintering (4) to degrease the body of the body to form the south thermal conductivity Carbon-containing metal matrix composite. 29) A method for manufacturing a heat dissipating component of a high thermal conductivity carbon-containing metal matrix composite material, comprising at least: Forming a vapor-grown carbon fiber which is formed in a range of from 6 〇〇t to i3〇〇c>c and in the presence of a reducing gas, a carbon source is formed by a catalyst The milk phase grows carbon fiber, and the straightness/system of the graphitized vapor-grown carbon fiber is between 0.1 /zm and 1 #m, the length is between melon and 2 mm, and the aspect ratio is between 5〇〇. Between 2 and 〇〇〇; performing a graphitization step, which is between 24 ° C and 3000. (: between μ degrees and in the presence of a blunt gas, the vapor-grown carbon fiber is formed into the graphitized vapor-grown carbon fiber, and a thin layer of a carbonized metal is formed by the sintering method in the graphitized gas phase/ The surface of human fiber and crucible, in which the graphitized vapor-grown carbon fiber, the thermal conductivity of the dimension is between lOOOW/mK and 198〇w/mK, and 30 1303273 for a compounding and forming step, Mixing a first metal substrate and one of the graphitized vapor-grown carbon fibers having the thin layer of carbonized metal in a different manner and placing it into a mold to form the mixture into the thermally conductive carbon-containing metal The composite heat dissipating component, wherein the thermal conductivity of the high thermal conductivity stone-containing anti-metal-based heat dissipating component is between the thermal conductivity of the metal substrate and the thermal conductivity of the graphitized vapor-grown carbon fiber. The method for producing a high thermal conductivity carbon-containing metal matrix composite heat dissipating component according to claim 29, wherein the reducing gas is hydrogen gas. 31. The high thermal conductivity as described in claim 29 A method for producing a heat-dissipating member of a carbon-containing metal-based composite material, wherein the catalyst is selected from the group consisting of a transition metal and the above-mentioned metal organic compound. 32. High thermal conductivity as described in claim 29 The method for producing a heat-dissipating component of a carbon-containing metal-based composite material, wherein the catalyst is selected from the group consisting of iron, cobalt, nickel, and the above-mentioned metal organic compound. 33. As claimed in claim 29 The method for manufacturing a heat-conducting element of a high thermal conductivity carbon-containing metal-based composite material, wherein the carbon source material is a gaseous hydrocarbon or a liquid hydrocarbon. 34. The high thermal conductivity as described in claim 33 A method for producing a carbonaceous metal 31 1303273 composite heat dissipating component, wherein the carbon source material is selected from the group consisting of carbon monoxide, benzene, toluene, hydrazine, liquefied petroleum gas, acetylene, and any combination thereof. 35. The method for manufacturing a high thermal conductivity carbon-containing metal-based composite heat dissipating component according to claim 29, wherein the obtuse gas is selected from the group consisting of a group of gases, helium, argon, and helium. 6 · A method for manufacturing a heat-conducting component of a high thermal conductivity carbon-containing metal-based composite material according to claim 29, wherein the carbonized metal is formed The step of layer further comprises: forming a thin layer of a metal compound on the surface of the graphitized vapor-grown carbon fiber, adding the graphitized vapor-growth carbon fiber to a metal compound solution, and removing the metal compound under uniform stirring a solvent in the solution; and performing a sintering step of converting the thin layer of the metal compound into the thin layer of the metal carbide in the presence of the inert gas or the reducing gas. 37. The method for manufacturing a high thermal conductivity carbon-containing metal-based composite heat dissipating component, wherein the metal compound of the metal compound is derived from tungsten (W), titanium (Ti), chromium (Cr), molybdenum (Mo), and (ζΓ), hunger (V), and any combination of the above. 38. The method of manufacturing a high thermal conductivity carbon-containing metal 32 1303273 according to claim 36, wherein the metal compound is selected from the group consisting of T ammonium metatungstate, phosphotungstic acid, tungstic acid, and gas. Tungsten, titanium isopropoxide, ferrocene - bismuth: bismuth ammonium, vaporized chromium, acetonitrile acetonate, ruthenium acetate, chrome nonachrome, • pair] ammonium, zirconium chloride, zirconium acetonide, A group consisting of zirconium tert-butoxide, acetamidineacetone, vanadium, and any combination of the foregoing. * _9. The method for producing a high thermal conductivity carbon-containing metal-based heat dissipating component according to claim 36, wherein the metal compound solution is water or an organic solvent. 4. The graphitized vapor-grown carbon fiber is manufactured to a ratio of 99% by weight of the composite heat-dissipating component of the patent application. The high thermal conductivity carbonaceous metal method of claim 29, wherein the carbon content in the thin layer of the metal carbide is 70% by weight 41 ·If you apply for the patent scope of the 29th 美 ϋ ι ι αι # ^ , 述 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲The ratio of carbon in the graphitized vapor-growth carbon fiber of the thin layer of the metal carbide is between (10) weight percent. The method of manufacturing a heat dissipating component of a composite material according to item 29 of the present invention, wherein the thermally conductive carbonaceous material is substantially different from the first metal substrate or a phase metal layer. Phnom Penh 33 1303273 person * Shen Qing patent scope 帛 29 items of high thermal conductivity carbon-containing metal 2::: manufacturing method of material heat-dissipating component 'where the carbonized metal layer - gold from the crane, titanium, network, Indium, erroneous, strontium, and any of the above combinations constitute a group. 44· *Application of the patent scope 帛29, the high thermal conductivity impeding metal = composite heat dissipating component manufacturing method, wherein the first metal substrate material is selected from the group consisting of m fine and any combination thereof a group of people. Person, 45. For the towel, please refer to the high thermal conductivity of the patented item No. 29: the manufacturing method of the material heat dissipating component, wherein the molding step is performed by using - φ = a die casting method or a melt casting method, To form the high thermal conductivity rabbit-containing composite heat dissipating component. 46. The method for manufacturing a high thermal conductivity carbon-containing two-heat-dissipating component according to claim 29, wherein the compounding and molding step is formed by n private stamping or metal powder injection molding to form The thermally conductive carbon-containing metal matrix composite heat dissipating component. The method of manufacturing a high thermal conductivity carbon-containing metal-organic crucible according to the item 46, wherein the mixture further comprises at least an organic binder, and the layer has a thin layer of the carbonized metal. The stone? The content of one of the metals, the metal substrate and the total weight of the gas-vapor-grown carbon fibers of ε. 1 34 1303273 by weight to 1 〇 by weight. 48. The method for producing a high thermal conductivity carbon-containing metal matrix composite heat dissipating component according to claim 47, wherein the organic binder is selected from the group consisting of stearic acid, zinc stearate, and lithium stearate. , a group of microcrystalline wax, paraffin wax, stone oil, rubber, plastic and a combination of the above. The method for manufacturing a high thermal conductivity carbon-containing metal-based composite 5 material heat dissipating component according to claim 47, wherein after the mixture is molded by the mold, the method further comprises: forming the mixture into an embryo body And a dewaxing and degreasing step, wherein the organic bond in the embryo body is removed for a sintering step to convert the dewaxed and degreased body into a "pore body"; and an infiltrating step By using the pores of the -second metal porous body, the high thermal conductivity carbon-containing metal-based a-material heat-dissipating element is formed. • If you apply for a patent, it's if you only have a high thermal conductivity, carbon d, a sputum, a material, a heat-dissipating component, the first 4 広 忒苐 忒苐 忒苐 金属 金属 金属 金属 金属 金属 金属 金属 金属 乐 乐 基材The same material. 5 1 . The method for manufacturing a high thermal conductivity carbon-containing 35 1303273 composite heat dissipating component according to claim 49, wherein the material of the second metal substrate is selected from the group consisting of copper, aluminum, silver, A group of gold and any combination of the above. 36