JP5927522B2 - Carbon material structural material manufacturing method and carbon material structural material - Google Patents

Description

  The present invention relates to a method for producing a carbon material structure and a carbon material structure.

Carbon materials include diamond composed of carbon having sp ³ hybrid orbitals, graphite (or graphite) composed of carbon having sp ² hybrid orbitals, carbine (or polyin) composed of carbon having sp hybrid orbitals, etc. It is an extremely diverse material composed of allotropes and their composites.

Furthermore, in recent years, sp ² carbon-based fullerenes, carbon nanotubes, and graphene have been named as new carbon materials.

Among these carbon materials, the ones that have been used for a relatively long time in the industry and have the largest and widest range of applications are glassy carbon, carbon fiber, and carbon-fiber-reinforced carbon materials (Carbon-Fiber-Reinforced Carbon Materials). , hereinafter referred to as CC material) it is primarily sp ² carbon material, such as.

These sp ² -based carbon materials are light because the specific gravity is usually smaller than that of metals, and have a relatively high Mohs hardness of 7, so that they have a considerable hardness, are chemically stable, are inert to living organisms, and are resistant to heat at about 1000 ° C. Because it has the features of maintaining practical strength up to high temperatures exceeding the temperature and withstanding repeated use, sports and leisure equipment such as fishing rods, tennis and badminton rackets, members of various industrial equipment and medical equipment related to X-rays, civil engineering architecture It is widely used for structural materials such as structural materials in the field of aerospace, electronic parts such as electrodes in the electrical industry, and electrodes of ion engines used in asteroid explorers and geostationary satellites.

However, sp ² -based carbon materials are essentially incompletely graphitized due to manufacturing limitations. Their surfaces are covered with a large number of grain boundaries of several nanometers to several micrometers, and each crystal has a large number of defect structures such as atomic defects. These grain boundaries and defect structures can be the starting point for physical erosion such as air friction and sputtering, and chemical corrosion such as oxidation. For this reason, the surface of the sp ² -based carbon material having a large number of grain boundaries and defect structures is significantly inferior in wear resistance and oxidation resistance as compared with a completely crystalline graphite surface. Further, there is due to structural imperfections of the surface of the sp ² carbon material, a problem that the gas barrier performance of the sp ² carbon material is inevitably limited and. Furthermore, due to the above problems, it has been pointed out that when products made of sp ² carbon materials are used under severe conditions, their lifetime is shorter than required.

With the development of technology in recent years, several methods for coating the surface of the sp ² -based carbon material have been put into practical use for the purpose of reducing the above problems. For example, Patent Document 1 discloses a technique for coating with a surface-treated silicon carbide (SiC) layer (Patent Document 1). Also disclosed is a technique for applying a graphite coating on the surface of an sp ² -based carbon material by a CVD (Chemical Vapor Deposition) method. For example, made from CC material, other (Patent Document 2) which coating techniques the surface of the crucible is reinforced with pyrolytic carbon is disclosed in Patent Document 2, Patent Document 3 improves the gas barrier properties of the sp ² carbon material For this reason, a coating technique using carbon derived from thermal CVD is disclosed (Patent Document 3).

Japanese Patent No. 3228489 JP 2000-351689 A JP 2003-183076 A

  However, the coating techniques disclosed in Patent Documents 1 to 3 described above have the following problems.

First, the coating of the sp ² -based carbon material with the SiC layer disclosed in Patent Document 1 has a problem that the conductivity is lost due to the coating. This is because SiC is a wide gap semiconductor and electrically semi-insulating. For this reason, when the sp ² based carbon material is used as an electrode, coating with an SiC layer cannot be employed.

Next, in Patent Document 2, a CVD process is performed on the surface of sp ² based carbon material with pyrolytic carbon using methane gas as a raw material for a long time of at least 50 hours and a growth temperature of 1800 ° C. is necessary. Therefore, this technique causes a problem that the apparatus cost and the material cost increase, and there are many problems from the viewpoint of resource saving and energy saving. Further, it is generally known that in the CVD method using hydrocarbon as a raw material, graphitization does not proceed without a metal catalyst such as copper or nickel. That is, the pyrolytic carbon film disclosed in Patent Document 2 is not carbonaceous crystalline but amorphous carbon. Therefore, wear resistance and oxidation resistance cannot be expected with this coating technology.

  Finally, in Patent Document 3, CVD is required for coating under severe conditions in which a high temperature of 1200 ° C. or higher, a hydrocarbon gas as a raw material, a hydrogen gas as a carrier gas, and a hydrogen chloride gas are allowed to flow. The Moreover, high temperature of 2000-3000 degreeC is required for the final graphitization of a coating layer. Therefore, like the problem in Patent Document 2, this technique causes a problem that the apparatus cost and the material cost increase, and there are many problems from the viewpoint of resource saving and energy saving. In addition, the use of dangerous gases such as hydrogen and hydrogen chloride is likely to have adverse health and environmental impacts.

  This invention is made | formed in view of the said subject, The objective is to provide the manufacturing method of a carbon material structural material with low manufacturing cost while it is mass-productivity and high quality.

  In order to solve the above-described problem, the first aspect of the present invention is as follows. (A) A carbon material matrix containing a carbon material is brought into contact with a liquid metal, and the metal is heated to heat the metal material. Carbon in the material is dissolved, and (b) the liquid metal is cooled to precipitate the carbon in the liquid metal on the surface of the carbon material base material, thereby coating the surface of the carbon material base material. This is a method for producing a carbon material structural material.

  The second aspect of the present invention is a carbon material structural material manufactured using the method for manufacturing a carbon material structural material according to the first aspect.

  According to the present invention, it is possible to provide a method for producing a carbon material structural material that is mass-productive, has high quality, and at the same time has low production costs.

It is a figure which shows the outline of the manufacturing method of the carbon material structural material 9 which concerns on this embodiment. It is a figure which shows the specific example of the manufacturing method of the carbon material structural material 9 which concerns on this embodiment. It is a photograph which shows the surface of the sample which concerns on Example 1, Comprising: (a) is the state before performing coating by a graphene film or a graphite film, (b) is the state after coating. It is an optical micrograph of the surface of the sample of FIG. 3, (a) respond | corresponds to the surface of FIG. 3 (a), (b) respond | corresponds to the surface of FIG.3 (b). It is a figure which shows the Raman spectrum of the sample of FIG. 3, Comprising: (a) respond | corresponds to Fig.3 (a), (b) respond | corresponds to FIG.3 (b). It is a figure which shows the relationship between the film thickness of a graphene film or a graphite film, and growth temperature. It is a figure which shows the temperature profile in the case of the coating of a graphene film or a graphite film. FIG. 7 is an optical micrograph of the surface of a sample when a graphene film or a graphite film is coated with the temperature profile shown in FIG. 7, and (a) shows a case where coating is performed with the temperature profile shown in FIG. FIG. 7B corresponds to the case where coating is performed with the temperature profile shown in FIG.

  DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail based on the drawings.

  First, the outline of the manufacturing method of the carbon material structural member 9 according to the present embodiment will be described with reference to FIG.

  The “carbon material structural material” here means a carbon-containing structural material, and the “structural material” means oxidation resistance, chemical resistance, heat resistance, impact resistance, and wear resistance. A material that requires chemical and mechanical properties such as sputtering resistance.

  First, as shown in FIG. 1A, a (liquid) metal 2 is arranged on the surface of a carbon material 1 containing carbon 3 (carbon material base material 5).

Here, the carbon material 1 may contain an element other than the carbon 3 or may be composed of only the carbon 3. Carbon 3 is a carbine (polyyne) type having sp hybrid orbitals, a graphite type having sp ² hybrid orbitals, or a diamond type having sp ³ hybrid orbitals, and a carbine type, a graphite type, or a diamond type is combined. You may do it.

  Next, the carbon material 1 on which the metal 2 is disposed is heated. Then, as shown in FIG. 1B, the carbon 3 is dissolved into the metal 2 from the surface layer of the carbon material 1. When heated at an appropriate temperature for an appropriate time, finally, the amount of carbon 3 required for coating dissolves in the metal 2 as shown in FIG. That is, the metal 2 functions as a flux for dissolving the carbon 3 in a liquid state.

  Here, as the metal 2, a carbon hardly soluble metal having extremely low carbon solubility even at a high temperature is used. In general, the carbon solubility of a hardly-soluble metal is not known, but experience has estimated that it is in the range of 0.1 to 10 ppm at a temperature of 800 ° C. The reason for using a metal having low carbon solubility is that the surface layer of the carbon material 1 is not scraped more than necessary for coating. Thereby, even if it coats, it becomes possible to maintain the original shape of carbon material 1.

  Next, it cools to such an extent that the metal 2 in which the carbon 3 is dissolved is not solidified. Then, as shown in FIG. 1 (d), the carbon solubility in the metal 2 decreases and becomes supersaturated, so that the carbon 3 starts to precipitate on the surface layer of the carbon material 1. When an appropriate time has elapsed, as shown in FIG. 1 (e), the total amount of carbon 3 dissolved in the metal 2 is finally crystallized on the surface of the carbon material 1 as graphene or graphite. Coating with the graphene film or the graphite film 4 completes the carbon material structure 9.

  Here, regarding the formation of the graphene film or the graphite film 4 described above, during cooling, the carbon 3 in the metal 2 precipitates as graphene or graphite having a dense two-dimensional crystal structure, and does not precipitate as amorphous amorphous carbon. This is because the metal 2 as a flux acts as a catalyst for graphene formation in a liquid state.

  In addition, since the graphene film or the graphite film 4 grows starting from defects or crystal grain boundaries in the surface layer of the carbon material 1, the interface between the surface layer of the carbon material 1 and the graphene film or the graphite film 4 has an infinite number of covalent bonds. Are firmly connected. Further, the thermal expansion coefficients of the carbon material 1 and the graphene film or the graphite film 4 are almost the same.

  Therefore, the graphene film or the graphite film 4 is not peeled off or cracked from the carbon material 1 even if there is a violent temperature rise or fall or physical impact, and the coating according to the present invention has high heat resistance and impact resistance. Will have sex. Further, since the graphene film or the graphite film 4 is defect-free, the coating according to the present invention is also resistant to chemical reactions such as oxidation resistance.

  In addition, the other element which the carbon material 1 may contain at the time of cooling of FIG.1 (d) does not usually precipitate. This is because when the other element is a metal element, the solubility in the metal 2 is at a level of several percent to several tens of percent even at room temperature, and is not oversaturated. In addition, when the other elements are light elements such as hydrogen, oxygen, and nitrogen, the solubility in the metal 2 is high, and part of the gas is released from the metal 2 after being heated and dissolved. As a result, the graphene film or the graphite film 4 to be coated is also free from impurities and is highly purified.

  The above is summarized as follows. That is, the carbon 3 that is in the surface layer of the carbon material 1 and contains defects and impurities and has various bonding modes is once dissolved in the metal 2 by heating, and the original surface layer of the carbon material 1 is defected by cooling. It is the gist of the present invention to reconstitute as a dense and crystalline graphene film or graphite film that does not contain any impurities. This method is a kind of liquid phase growth method, and has a lower production cost than that of a CVD method, which is a kind of vapor phase growth method, and enables high quality coating.

  The above is the outline of the method for manufacturing the carbon material structural member 9 according to the present embodiment.

  Next, the manufacturing method of the carbon material structural member 9 will be described more specifically with reference to FIG.

  First, as shown in FIG. 2A, a carbon material base material 5 including a carbon material 1 to be coated and formed into a desired shape is prepared.

  Here, the carbon material base material 5 is preferably surface-polished. This treatment is for enhancing the adhesion between the carbon material base material 5 and the metal 2 in a liquid state. The surface roughness after polishing is appropriately the same as the film thickness of the coating layer, that is, the film thickness of the graphene film or the graphite film 4. However, polishing is not particularly required if the unevenness of the surface of the carbon material base material 5 is within 1 μm.

  Second, as shown in FIG. 2B, the carbon material base material 5 is immersed in a container 7 filled with the metal 2 in a liquid state and heated at an appropriate temperature for an appropriate time. The surface carbon of 5 is dissolved in metal 2. When the container 7 is covered with the lid 6, evaporation of the metal 2 during heating can be prevented. Note that the carbon-containing raw material 8 may be added to the metal 2 for the purpose of increasing the thickness of the coating layer.

  As described above, the metal 2 has a role as a flux for melting the carbon 3, and uses a carbon hardly soluble metal having a carbon solubility of ppm level.

  Examples of such metals include gallium (Ga), indium (In), tin (Sn), aluminum (Al), zinc (Zn), cadmium (Cd), mercury (Hg), thallium (Tl), lead ( At least one selected from the group of Pb) and bismuth (Bi) can be used.

However, if the influence on the environment and human body is taken into consideration, gallium (Ga), indium (In), tin (Sn), aluminum (Al), zinc (Zn), bismuth (Bi), or an alloy thereof Is desirable. Among them, gallium has the characteristics that the temperature range in the liquid state is 29.8 to 2403 ° C., which is the widest among the single elements, and the vapor pressure is considerably low even at high temperatures (for example, 10 ⁻³ Pa at 800 ° C.). Have. These features mean that the temperature range acting as a flux is very wide and that the loss due to evaporation during heating is very low, so gallium and its alloys are particularly desirable as the metal 2 material.

  In the step of immersing the carbon material base material 5 in the metal 2, it is easy to handle the metal 2 that is liquid near room temperature. For example, as a metal that is liquid near room temperature, gallium-indium alloy (melting point: about 15.7 ° C.), gallium-indium-tin alloy (melting point: 19 ° C.), gallium-aluminum alloy (melting point: 26.5 ° C.) ), Gallium (melting point: 29.8 ° C.), bismuth / lead / tin / cadmium / indium alloy (melting point: about 46.7 ° C.), and the like. However, when the immersion process is handled under appropriate heating, it is not always necessary to use a metal having a melting point near room temperature.

As the carbon-containing raw material 8, any material that basically contains carbon may be used. Examples include carbon allotropes such as amorphous carbon, glassy carbon, crystalline graphite, single-walled carbon nanotubes, multi-walled carbon nanotubes, fullerenes, diamonds, nanodiamonds, low molecular organic compounds such as metallocenes, naphthalenes, anthracenes, pentacenes, Teflon (registered) Trademarks), PMMA (polymethyl methacrylate), artificial high molecular organic compounds such as polyethylene, natural high molecular organic compounds such as proteins, nucleic acids, fat lipids, polysaccharides, silicon carbide (SiC), boron carbide (B ₄ C) Aluminum carbide (Al ₄ C ₃ ), titanium carbide (TiC), zirconium carbide (ZrC). Hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tantalum carbide (TaC), chromium carbide (CrC), molybdenum carbide (MoC), tungsten carbide (WC), carbon nitride (C ₃ N ₄ ) And having at least one selected from the group consisting of inorganic compounds containing carbon such as carbon boron nitride (BCN). However, those having a carbon content of 20% or more are desirable, and the above-mentioned carbon allotrope composed only of carbon is more desirable.

  Examples of the heating method include heating by heat radiation of an electric furnace or the like, laser heating, high frequency, electromagnetic wave heating by microwave exposure. The heating temperature is suitably 900 to 1700 ° C., and the heating time is suitably 30 minutes to 3 hours.

  The graphene film or the graphite film 4 which is a coating layer becomes thicker as the heating temperature is higher. In general, a graphene film having a number of layers of about 1 to 10 at 1000 ° C. or lower, and a graphite film having a number of layers higher than 1000 ° C. More specifically, for example, the heating temperature is about 0.5 nm at 900 ° C., about 10 nm at 1100 ° C., about 100 nm at 1300 ° C., about 700 nm at 1500 ° C., about 5 μm at 1700 ° C. That is, it means that the film thickness of the coating layer can be controlled by the heating temperature. Further, as described in the embodiments, it is possible to control the film thickness of the coating layer by changing the temperature profile.

  In general, for the purpose of improving the heat resistance, impact resistance, chemical resistance, and oxidation resistance of a carbon material, it is better that the coating layer covering the carbon material has a larger film thickness. That is, it is desirable to form a graphite film as a coating layer because a thick graphite film has higher performance than an ultrathin graphene film. Accordingly, the heating temperature is preferably 1000 ° C. or higher, and more preferably 1200 ° C. or higher. However, this is not the case when the graphene film is coated on the surface of the carbon material so that the physical properties peculiar to graphene that are not found in bulk graphite are expressed.

The material of the container 7 and the lid 6 is a heat resistant material. For example, oxides such as quartz (SiO ₂ ), alumina and sapphire (Al ₂ O ₃ ), nitrides such as boron nitride (BN) and aluminum nitride (AlN), silicon carbide (SiC), tungsten carbide (WC), etc. Carbides, glassy carbon, mica, etc. When heating at 1500 ° C. or higher, alumina, sapphire, boron nitride, or glassy carbon is desirable.

  Third, as shown in FIG. 2 (c), the carbon dissolved in the metal 2 on the surface of the carbon material base material 5 is crystallized as a graphene film or a graphite film 4 by cooling to such an extent that the metal 2 does not solidify. Let

  The cooling rate is suitably within 100 ° C./min. In order to improve the film quality of the graphene film or the graphite film 4, a smaller cooling rate is desirable.

Fourth, the carbon material base material 5 coated with the graphene film or the graphite film 4 is taken out from the metal 2 in a liquid state, and the metal 2 remaining on the surface is washed with an acid, an alkali, etc. As shown in (d), finally, a carbon material structural material 9 in which the carbon material base material 5 is coated with the graphene film or the graphite film 4 is obtained.

As an acid for dissolving the residue of the metal 2 in the carbon material base material 5, hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ), nitric acid (HNO ₃ ), or the like can be used. When the metal 2 is an amphoteric metal such as gallium or aluminum, an aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (KOH), or tetramethylammonium hydroxide can be used. When the carbon material base material 5 as a whole is immersed in the cleaning liquid under appropriate heating, the cleaning effect is high.

In addition, the metal 2 after coating use can be reused as a flux. In particular, when gallium (Ga), which is a rare metal, is used, flux regeneration has the effect of significantly reducing manufacturing costs.

  Thus, according to the present embodiment, the carbon material structural member 9 has the carbon material in the metal by bringing the liquid metal 2 into contact with the carbon material base material 5 including the carbon material 1 and heating the metal 2. It is produced by dissolving the carbon 3 in the liquid and cooling the liquid metal 2 to precipitate the carbon 3 in the liquid metal 2 on the surface of the carbon material base material 5 and coating the surface of the carbon material base material 5 Is done.

  Therefore, the original surface layer of the carbon material 1 (the carbon material base material 5) can be reconfigured as a graphene film or a graphite film that does not contain defects and impurities and has a dense and crystalline film thickness controlled.

  Further, since this method is a kind of liquid phase growth method, the manufacturing cost is lower than that of the CVD method which is a kind of vapor phase growth method, and high quality coating is possible with energy saving and low environmental load.

  Hereinafter, based on an Example, this invention is demonstrated in detail.

Example 1
First, based on the manufacturing method shown in FIG. 1 or FIG. 2, the surface of the CC material substrate was coated with a graphene film or a graphite film. The CC material was 15 × 15 × 1 mm in size, and was polished before coating until the level difference of surface irregularities was about 100 nm. Next, gallium was disposed on the polished surface of the CC material within a central radius of 12 mm, heated in an exhausted electric furnace at 1300 ° C. for 1 hour, and then cooled at a rate of 5 ° C./min. The gallium residue on the surface was dissolved in hydrochloric acid heated to 80 degrees.

  The results are as follows. FIG. 3 (a) is a photograph of the CC material before coating, and FIG. 3 (b) is a photograph of the CC material after coating. As shown in FIG. 3, only the portion in contact with gallium during heating / cooling changed from black to silver white. This change suggests that a graphene film or a graphite film was formed by the method according to the present invention.

  Next, in order to investigate the details of the coated part, observation with an optical microscope was performed. FIG. 4A is an optical microscope image of the surface of the CC material before coating, and FIG. 4B is a surface of the CC material after coating. In FIG. 4 (a) before coating, it was clearly observed that the carbon fibers were dispersed in the carbon material of the matrix, whereas in FIG. 4 (b) after coating, the entire CC material surface was graphene. It was observed that it was coated with a film or a graphite film.

Furthermore, the qualitative change of the carbon material before and after coating was analyzed by micro Raman spectroscopy. 5 (a) is prior to coating, FIG. 5 (b) Ru Raman spectra der of CC material surface after coating. In co Computing front of FIG. 5 (a), a large D band relative intensity, broad G band, the relative intensities are significantly smaller 2D bands were observed broad. These characteristics mean that the carbon material is amorphous carbon-like. On the other hand, in FIG. 5B after coating, the D band was not observed, but a sharp G band having a high relative intensity and a 2D band having a shoulder on the low wave number side were observed. These features are unique to defect-free crystalline graphite.

  From the above results, according to the present invention, an extremely high quality graphite film could be formed on the surface of the CC material. As will be described later, it is added that when the growth temperature of the coating layer is lowered, a graphene film having a smaller number of layers than the graphite film can be formed on the surface of the carbon material.

(Example 2)
As described above, the film thickness of the graphene film or the graphite film increases as the heating temperature increases. In order to show this quantitatively, the heating temperature dependence of the film thickness of the graphene film or the graphite film was measured. The experimental conditions were the same as in Example 1, and only the heating temperature was changed.

  FIG. 6 shows the relationship between the film thickness of the graphene film or graphite film and the growth temperature. As apparent from FIG. 6, the film thickness of the graphene film or the graphite film increases exponentially with respect to the heating temperature. According to actual measurement, the heating temperature is about 0.5 nm at 900 ° C., about 10 nm at 1100 ° C., about 100 nm at 1300 ° C., about 700 nm at 1500 ° C., about 5 μm at 1700 ° C. Therefore, it was proved that the thickness of the graphene film or the graphite film can be controlled by the heating temperature. When the heating temperature is 1000 ° C. or less, the number of layers formed is about several to several tens of layers. Therefore, the graphene film is responsible for coating, and the graphite film is responsible for coating when the temperature exceeds 1000 ° C. It is.

(Example 3)
Next, the temperature profile dependence of heating / cooling of the film thickness of the graphene film or graphite film as a coating layer was measured.

  Specifically, the temperature profile at the time of coating the graphite film is the two temperature profiles shown in FIGS. 7A and 7B, and how the graphite film coating on the surface of the CC material is changed by an optical microscope. Observed at.

  7A shows a monotonous heating / cooling temperature profile, and FIG. 7B shows a temperature profile in which heating / cooling is repeated.

  FIG. 8A shows an optical microscope image of the surface of the CC material when coating is performed with the temperature profile shown in FIG. 7A. FIG. 7B shows the coating with a temperature profile that repeats heating and cooling as shown in FIG. 7B. FIG. 8B shows an optical microscope image of the surface of the CC material when it is performed.

  In both cases, the maximum value of the heating temperature is 1200 ° C., and although the time from the temperature rise to the high temperature is almost the same, a remarkable difference appears in the surface morphology. In FIG. 8 (a), graphite pieces having a relatively small area accumulate and cover the surface of the CC material, whereas in FIG. 8 (b), a monolithic graphite film covers the surface of the CC material. Was observed. This observation result means that the growth of graphite having a large crystal size can be promoted by repeating heating and cooling for a short time. Therefore, it can be concluded that coating with a graphite film with fewer crystal grain boundaries and fewer defects is possible by devising a temperature profile such as repeated heating and cooling for a short time.

Example 4
In this example, the sputtering resistance of the CC material coated with the present invention to Xe ⁺ ions was examined.

The present invention was applied to a CC material grid used for an acceleration electrode of an ion engine. The experimental conditions were the same as in Example 1, but the experiment was conducted at a heating temperature of 1500 ° C. in order to increase the thickness of the coating layer. In order to examine the sputtering resistance of the CC material grid, the surface of the CC material was exposed to Xe ⁺ ions accelerated to 1800 V in vacuum, and the amount of C ⁺ ions jumping from the surface of the CC material was measured with a mass spectrometer.

When comparing the coated CC grid with the uncoated CC grid, the relative amount of C ⁺ ions was reduced to about one-fourth of the latter. The reason why the sputtering resistance improved in the coated CC material is that the graphite film as the coating layer is structurally strong due to few defects such as atomic defects and crystal grain boundaries, and the graphite as the coating layer. This is probably because the flatness of the film is high, and the probability that Xe ⁺ ions are incident at 90 ° with a low sputtering yield is increased. Therefore, from the above results, it is proved that the lifetime of the CC material grid is improved by about 4 times.

  Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments and examples, and various modifications based on the technical idea of the present invention are possible. is there.

  The present invention is an intermediate material composed of carbon materials typified by carbon fiber reinforced carbon materials (CC materials), for example, sports and leisure products such as fishing rods, tennis and badminton rackets, various industrial equipment and X-ray related products. Examples include medical equipment components, civil engineering and aerospace structural materials, and electronic components such as electrodes in the electrical industry. In particular, in an ion engine mounted on a geostationary satellite for the purpose of asteroid probe, weather observation, etc., the present invention can be applied to an application for improving the wear resistance against sputtering of a CC material grid (electrode) used for ion acceleration.

DESCRIPTION OF SYMBOLS 1 Carbon material 2 Metal 3 Carbon 4 Graphite film 5 Carbon material base material 6 Lid 7 Container 8 Carbon containing raw material 9 Carbon material structural material

Claims (7)

(A) A liquid metal to which a carbon-containing raw material is added is brought into contact with a carbon material base material containing a carbon material, and the carbon in the carbon material base material is dissolved in the metal by heating the metal. ,
(B) A method for producing a carbon material structural material, wherein the carbon in the liquid metal is precipitated on the surface of the carbon material base material by cooling the metal in the liquid, and the surface of the carbon material base material is coated. . The carbon-containing raw material is amorphous carbon, glassy carbon, crystalline graphite, single-walled carbon nanotube, multi-walled carbon nanotube, fullerene, diamond, nanodiamond, metallocene, naphthalene, anthracene, pentacene, Teflon (registered trademark), PMMA (poly Methyl methacrylate), polyethylene, proteins, nucleic acids, fat lipids, polysaccharides and other natural high molecular organic compounds, silicon carbide (SiC), boron carbide (B ₄ C), aluminum carbide (Al ₄ C ₃ ), titanium carbide ( TiC), zirconium carbide (ZrC). Hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tantalum carbide (TaC), chromium carbide (CrC), molybdenum carbide (MoC), tungsten carbide (WC), carbon nitride (C ₃ N ₄ ) The manufacturing method of the carbon material structural material of Claim 1 which has at least 1 chosen from the group which consists of carbon boron nitride (BCN).   3. The carbon material structural material according to claim 1, wherein (b) deposits the carbon in the metal as graphene or graphite on the surface of the carbon material base material and coats the surface of the carbon material base material. Manufacturing method. (C) removing the metal from the surface of the carbon material base material coated with the carbon;
The manufacturing method of the carbon material structural material as described in any one of Claims 1-3 which has these.   Said (a) is a manufacturing method of the carbon material structural material as described in any one of Claims 1-4 whose temperature to heat is 900 degreeC or more.   6. The carbon material according to claim 1, wherein the carbon material has at least one selected from the group consisting of carbine, diamond, amorphous carbon, glassy carbon, carbon fiber, and carbon fiber reinforced carbon composite material. Manufacturing method of carbon material structural material.   The metal is made of gallium (Ga), indium (In), thallium (Tl), tin (Sn), aluminum (Al), lead (Pb), bismuth (Bi), zinc (Zn), Cd (cadmium). The manufacturing method of the carbon material structural material as described in any one of Claims 1-6 which has at least 1 chosen from a group.

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