KR100638588B1 - Carbon-sintered body and manufacturing method thereof - Google Patents

Abstract

The present invention is to produce a carbon molded product of a plant-derived amorphous carbon material and resin-derived glassy hard carbon by mixing the plant-derived carbonized powder and thermosetting resin of fine particles in an appropriate ratio, and then molding the molded product under thermal pressure. It relates to a carbon molded product produced by the method and the production method.

 The carbon molded product produced by the above method can control and modify the specific properties of the plant-derived and resin-derived carbon materials by varying the thermosetting resin and carbide content and the carbonization temperature, thus providing high strength, structure, hardness, density, and electricity. Properties, adsorption, corrosion resistance, magnetic properties, chemical resistance and the like can be given, and can have a high moldability and far-infrared radiation characteristics, etc. can be used in various applications.

Carbon molded body, wood ceramic

Description

Carbon molded article and its manufacturing method {CARBON-SINTERED BODY AND MANUFACTURING METHOD THEREOF}             

1 is a process flowchart schematically showing a manufacturing process of a method for producing a carbon molded article of the present invention.

2 is a graph showing the results of ¹³ C CP / DD / MAS NMR spectra of charcoal carbonized powder.

3 is a view showing the results of X-ray change according to the carbonization temperature of oak.

Figure 4 is a view showing the SEM results of the powder of the carbon molding.

5 is a view showing a TEM result of the carbon molded powder.

The present invention relates to a method for producing a porous carbon molded article, and more particularly, to a porous carbon molded article including a step of forming a mixture of plant-derived carbon powder and a thermosetting resin under hot pressure and carbonizing the molded article. It relates to a method for producing a porous carbon molded article to be produced.

Wood ceramic, a new porous carbon material manufactured by carbonization at high temperature by impregnating thermosetting resin with plant-derived wood or wood materials, has higher strength, structure, hardness, density, adsorption, corrosion resistance, and corrosion resistance than conventional charcoal by controlling manufacturing conditions. Various industrial uses have been expected since chemical properties and electrical properties can be imparted.

Japanese Patent Laid-Open No. 4-164806 of the conventional wood ceramic manufacturing method relates to a method for producing wood ceramics, which is obtained by impregnating and hardening phenolic resin on wood or medium density fiberboard (MDF), and then carbonizing it. The above method of manufacturing impregnates the resin material into the wood material, resulting in difficult and uneven injection. As a method for resin impregnation, the resin is injected by putting wood into a sealed injection container and sucking air in the wood under low pressure or vacuum. In addition, there is a need for a manufacturing method such as improving the resin impregnation rate by imparting ultrasonic vibrations during impregnation under reduced pressure, which requires a lot of equipment and time related to resin impregnation, and also requires more time to improve the resin impregnation rate. . In addition, these methods also involve a non-uniform resin injection depending on the type, density, and orientation of the wood material due to the nature of the wood material, which is a natural material, which results in partial change of composition ratio of carbon derived from carbon and carbon derived from resin. This may cause splitting of the wood ceramic material and distortion of the shape during carbonization. In addition, by making the board first, by impregnating the thermosetting resin on the board to produce a wood ceramic, there are many molding restrictions such as the shape is limited to a single plate, the manufacturing process is complicated, and the shrinkage of the product during carbonization has a big problem.

The present invention for solving the above problems by using a homogeneous vegetable carbon powder and thermosetting resin as a raw material for the manufacture of wood ceramics as an industrial material that can reduce the material variation, such as the unique wood, at the time of manufacturing conventional wood ceramics It eliminates difficult resin impregnation process and dramatically improves non-uniform resin distribution due to different kinds, density, and orientation of wood materials, preventing splitting or twisting of molded products, free molding, resin content and carbonization temperature By controlling and modifying the unique properties of carbonaceous materials derived from plants and resins to control the carbon properties of carbon moldings having high strength, structure, hardness, density, electrical properties, adsorption, corrosion resistance, magnetic properties, chemical resistance, and far-infrared radiation properties. The purpose is to provide a manufacturing method.

The present invention devised to achieve the above object is a porous, characterized in that for preparing a porous carbon molded body comprising a step of forming a mixture of plant-derived carbon powder and a thermosetting resin at a hot pressure, and carbonizing the molded product It provides a method for producing a carbon molded article.

And it provides a method for producing a porous carbon molded body characterized in that the mixture obtained by filling the inorganic powder to the plant-derived carbon powder and thermosetting resin.

In addition, the temperature of the hot pressing process of the mixture is 120 to 180 ℃, the molding pressure provides a method for producing a porous carbon molded body, characterized in that 10 kgf / cm ² or more.

And it provides a method for producing a porous carbon molded body characterized in that the molding process and the carbonization process can be performed by a single process by setting the hot pressure temperature of the mixture to 400 ° C or more.

On the other hand it provides a porous carbon molded body characterized in that it is produced by the above-mentioned method for producing a porous carbon molded body.

Hereinafter, the porous carbon molded product manufacturing method of the present invention will be described in detail.

1 is a process flow chart schematically showing a manufacturing process of the method for producing a carbon molded article of the present invention, the porous carbon molded article manufacturing method of the present invention is largely as shown in Figure 1 the mixing process of the carbon powder and the thermosetting resin, the molding process of the mixture, molding Carbonization process.

[Step 1] Mixing Step

The mixing step is a step of uniformly mixing the plant-derived carbon powder and the thermosetting resin.

The plant-derived carbonized powder is obtained by pulverizing carbides obtained by carbonizing plant-derived raw materials such as wood, coconut shell, sawdust and the like in a grinder to a desired particle size, and the plant-derived carbonized powder has a water content of less than 5%, and It is preferable to use carbonized to be 90% or more and pulverized to 100 mesh or less, which is mixed evenly with the thermosetting resin to produce a uniform product to obtain a product having excellent physical properties such as strength and hardness For sake.

The thermosetting resin may use various thermosetting resins such as phenol resin, melamine resin, epoxy resin, urethane resin, furan resin, unsaturated polyester resin, and vegetable tar may also be used.

In particular, it is preferable to use a phenolic resin which is uniform in carbon in a solid state, has excellent mechanical strength and chemical resistance, and forms glassy carbon.

In addition, the mixing ratio of the plant-derived carbon powder and the thermosetting resin is not particularly limited and may be mixed and used at an appropriate ratio depending on the intended use.

Meanwhile, in order to add various properties, inorganic fillers such as ocher, germanium, elvan, ceramic, zeolite, feldspar, and silica may be used alone or in a mixed form, such as carbonized powder and thermosetting resin derived from the plant, and inorganic fillers. Unlike carbonized material, is not carbonized and remains in itself or in a reduced form in the produced carbon molded product.

[Step 2] Molding Process

The molding process is a process of molding a plant-derived carbon powder, a thermosetting resin or a mixture of inorganic fillers into a predetermined shape by thermopressing the mixture, injecting the mixture into a mold and curing by applying a pressure under a predetermined temperature. At this time, the molding temperature, the molding pressure, and the molding time are closely related to the density, porosity, and strength of the carbon molded body. In addition, it will be natural to change the mold to match the shape to be manufactured by using carbonized powder.

The mold temperature for molding the mixture is 120 to 180 ° C., in which the phenol resin, which is a thermosetting resin, is softened and cured, and the molding pressure is 10 kgf / cm ² or more in consideration of the thickness, density, and pore characteristics of the final product. It is preferable.

The molding time is short when the thickness of the molded article is thin, and lengthened when the thickness of the molded article is all or part thick, and then demolded.

On the other hand, in order to shorten the manufacturing time by simultaneously performing the molding process and the carbonization process described below, and to eliminate the hassle of carbonizing the molded article formed by the molding process into the atmosphere and the like, the pressure of the mold temperature is 400 ° C or higher. Therefore, the molding and the carbonization process may be performed at the same time, and carbonization is preferably performed to at least 800 ° C. At this time, the temperature increase rate should be maintained gently, because it can impart strength or hardness of the product by preventing splitting or twisting during carbonization and forming a large amount of crystalline carbon phase clusters.

[Step 3] Carbonization Process

The carbonization process is a process for producing a porous carbon molded body by inserting the molded product into an atmosphere that can be precisely controlled or into a heat treatment furnace to apply a heat to the molded product to cause a carbonization reaction. To the temperature of the furnace up to 2500 ℃ to control the temperature in the furnace to maintain a uniform and accurate to complete the carbonization after cooling to produce the final carbon molded product.

In addition, it is desirable to obtain a carbonized molded article having excellent physical properties such as flexural strength and brinell hardness by suppressing the occurrence of splitting due to shrinkage during firing by increasing the temperature during the carbonization to 200 to 600 ° C. or less at 10 ° C./min.

In addition, when the phenol resin is carbonized, water is released from 180 ° C., and volatile gases are actively released at around 400 to 500 ° C., and small amounts of about 700 to 800 ° C. Therefore, a sudden dimensional change occurs between 400 and 500 ° C., so there is a high possibility of splitting or warping, and thus the temperature rising temperature during carbonization is more preferably gradually increased to 450 to 600 ° C.

And it is most preferable that the temperature increase rate is 5 ℃ / min, when the temperature rise rate is less than 5 ℃ / min is less occurrence of splitting and distortion and the physical properties are good, but if it exceeds 5 ℃ / min possibility of splitting or distortion This becomes large and there is a possibility of deterioration of physical properties and defective products.

As described above, the carbon molded product of the present invention is not impregnated with phenolic resin in wood or fiberboard, but is injected into a mold by mixing carbonized powder and phenolic resin, so as to impregnate a high pressure impregnation container and a vacuum pump for reducing pressure. No equipment is required, and since the carbon powder and the phenol resin are uniformly mixed, the defect rate is greatly reduced, as there is no fear of splitting or warping of the product at the time of carbonization due to uneven injection of phenol resin into wood. Not only can it be made, but the shape is not limited to a single plate, there is an advantage in that the moldability, such as can be produced in various shapes.

Hereinafter, the present invention will be described in detail with reference to the following Examples, and the scope of the present invention is not limited to the following examples, but should be understood by those skilled in the art within the scope of the claims. It is obvious that the deformation is possible.

Example 1

The oak was carbonized at a temperature of 800 ° C. or higher, and the carbide having a water content of 5% and a final carbon content of 90% was pulverized to 100 mesh or less using a grinder to obtain a charcoal carbonized powder. In addition, ¹³ C CP / DD / MAS NMR and X-ray were measured to examine the thermal decomposition characteristics of the charcoal carbonized powder thus obtained, and the results of ¹³ C CP / DD / MAS NMR spectrum of the charcoal carbonized powder are shown in FIG. 2. The result of X-ray change according to carbonization temperature of oak is shown in FIG. 3.

The oak was observed to be aromatized with increasing carbonization temperature from ¹³ C CP / DD / MAS NMR of Figure 2, the X-ray results of Figure 3 after 2 ° = 26 ° and 43 ° slowly after 400 ℃ Shows that the intensity of the peak is increasing. This is due to weak diffraction due to the {002} (2θ = 26 °) plane and laminates derived from {101}, {100} (2θ = 43 °). As the carbonization temperature increases, the atomic arrangement of the oak develops. It is present. Significant increase in {002} diffraction at 1500 to 2500 [deg.] C. means that the stack height Lc and the crystal cluster arrangement are achieved. Therefore, it can be seen that the strength and hardness are excellent when the carbon molded body is manufactured using carbonized powder of charcoal prepared at a high temperature of 800 ° C. or higher.

Then, the powdered phenol resin was mixed in the carbonized powder of charcoal prepared as described above, and injected into a mold by 30% of the weight of the molding, and then molded at 180 ° C and 40 kgf / cm ² , and left at room temperature for 24 hours. The carbon molded product was prepared by carbonization at a temperature increase rate / min and carbonization at 800 ° C. for 4 hours. The carbon molded product thus produced did not generate splitting or twisting, and had excellent quality such as carbon composition rate of 92.5% and density of 0.82 g / cm ³ .

In order to confirm the formation of crystalline carbon clusters in the carbon molded product thus prepared, the prepared carbon molded product was pulverized and pulverized, and SEM and TEM were observed for the powder. The SEM results of the carbon molded powder are shown in FIG. 4, and the TEM results are shown in FIG. 5. It can be confirmed that the voids are formed in the carbon molded body manufactured by the SEM result of FIG. 3, and the crystalline carbon phase clusters can be observed from the TEM result of FIG. 4. It can be seen that it is a process capable of producing high-quality wood ceramic products in an optimal range in which crystal phase clusters between the phenol resin and the phenol resin are formed.

Example 2

Unlike Example 1, carbonized at a temperature of 800 ℃ or more to prepare a charcoal carbonized powder having a final carbon content of 90% and a water content of 3%, and mixed the powdered phenol resin with 50% by weight of the molding to the mold charcoal carbonized powder After injection, it was molded at 180 ° C and 40 kgf / cm ² and left at room temperature for 24 hours, and then carbonized at 5 ° C / min in a vacuum firing furnace and carbonized at 800 ° C. for 4 hours to prepare carbon molded products. This did not occur, the carbon composition rate was 94.1%, the density was 0.85 g / cm ³ Its excellent properties such as physical properties.

As described above, the present invention uses a high homogeneity of plant-derived carbonized powder and thermosetting resin as an industrial material capable of reducing material variations, such as wood, as a raw material for producing carbon molded products, It eliminates difficult resin impregnation process and drastically improves non-uniform resin injection due to density and directional differences peculiar to wood materials, thereby preventing splitting or twisting of molded products and free molding. In addition, carbonization significantly reduces distortion and shrinkage compared to conventional wood ceramic manufacturing methods, and adjusts the resin content and carbonization temperature to control and modify the unique properties of carbon materials derived from plants and resins. There is an effect that can produce a carbon molding having a density, electrical properties, adsorption properties, corrosion resistance, magnetic properties, chemical resistance, far infrared radiation characteristics.

In addition, by filling the carbonaceous powder and thermosetting resin of the plant-derived inorganic filler to produce a carbon molded body, there is an effect that can be produced a carbon molded body with various functionalities.

When the mixture of the carbonized powder and the thermosetting resin is formed at a temperature of 120 to 180 ° C. and a molding pressure of 10 kgf / cm ² or more, the molding can be performed smoothly and an excellent carbon property can be obtained. There is.

In addition, the molding temperature of the mixture is set at 400 ° C or higher, thereby shortening the manufacturing process by eliminating the trouble of transporting and injecting the molded product into a sintering furnace to undergo the carbonization process by performing the molding process and the carbonization process in a single process. It is effective.

Such a carbon molded product of the present invention can be used as a wide range of industrial uses, such as heat insulating material, packaging material, structural material, various filters, reaction catalysts, friction materials, soundproof walls, electromagnetic shielding materials, antistatic materials.

Claims (5)

And a step of forming a mixture of the plant-derived carbon powder and the thermosetting resin under hot pressure, and carbonizing the molded product. A method for producing a porous carbon molded article, characterized in that the molding step and the carbonization step can be performed by a single step by setting the hot pressure temperature of the mixture to 400 ° C or higher. The method of claim 1, wherein the carbonaceous powder derived from a plant and the thermosetting resin are filled with an inorganic filler, and the mixture is molded at a thermostatic pressure. delete delete delete

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