KR100435006B1 - Method for Manufacturing Homogeneous Preform of Reaction-Bonded Silicon Carbide Using the Powders of Multimodal Particle Size Distribution - Google Patents

Abstract

The present invention provides a preform of a uniformly packed structure for the production of reaction sintered silicon carbide by press molding, which uses a raw material powder having a multiple particle size distribution, which hardly separates constituent particles and hardly causes filling defects due to coarse particles. It is about how to get.

According to the present invention, when the raw material powder having a large difference in particle size or a large density difference is used for the purpose of use of reaction-sintered silicon carbide ceramic components, Particle separation due to size and density difference and early generation of coarse particles can result in suppressing filling defects and reducing filling efficiency. By this effect, it is possible to obtain an effect of minimizing the amount of residual silicon and less filling defects in the final sintered body produced using the preform of the present invention.

Description

Method for Manufacturing Homogeneous Preform of Reaction-Bonded Silicon Carbide Using the Powders of Multimodal Particle Size Distribution}

The present invention corresponds to a new process field of structural ceramics represented by a new material, and the conventional technique is usually press-molded using granules produced by a mechanical method (pelletizing).

Generally, fine powders are used to improve sinterability when manufacturing ceramic parts.However, in high temperature material parts such as sintering jig or reaction tube used at high temperature, coarse powder particles are dispersed to make creep resistance. Or improve thermal shock resistance. In order to add coarse powder and obtain high molding density, the filling principle of filling the pores formed by the coarse particles with the smaller medium particles and filling the pores formed by the medium particles with the smaller fine particles is used a lot. [Particle Packing Characteristics, RM German, pp. 147, Metal Powder Industries Federation, New Jersey.

Prerequisites for improving the packing density by reducing the pore volume by using such a powder having a multi-particle size distribution can be maintained in a state in which each component powder is uniformly mixed as a whole.

Various methods are used to achieve mixing uniformity, but dry mixing is commonly used. That is, a method of forming granules by polymer crosslinking by dry mixing various powders having different particle sizes and then repeatedly agglomeration and pulverizing mechanically while adding a small amount of the polymer binder solution thereto.

However, this method prevents premature contact between the coarse powders or maintains a sufficient distance between the coarse powder particles when the volume fraction of the coarse powder having a large hydrodynamic volume increases, thereby suppressing the reduction of the filling efficiency due to friction between the coarse particles during press molding. Not enough to do

Accordingly, an object of the present invention is to prepare a high density preform having a uniform packing structure from multiple particle size distribution raw material powders commonly used in reaction sintered silicon carbide production for improved physical properties and microstructure control.

1 is a scanning electron micrograph showing a packed structure of a preform for reaction sintered silicon carbide prepared by press molding a multi-particle size distribution raw material powder obtained by dry mixing.

Figure 2 is a scanning electron micrograph showing a uniform packing structure of the preform for reaction sintered silicon carbide prepared by pressing the granules prepared in the present invention.

The inventors of the present invention have repeatedly studied to achieve the above object, and as a result, using the raw powder having a multi-particle size distribution, granulates the early contact of the particle separation or coarse particles caused by the particle size difference of the powder sintered silicon carbide products The present invention was achieved by finding that the particle-filled structure of the reaction-sintered silicon carbide preform produced by the press molding by suppressing from the forming step can be obtained uniformly.

Therefore, the present invention forms a granule that maintains a uniform distribution of the remaining constituent powder while maintaining a sufficient distance between the coarse particles by using a wet mixing process, thereby filling efficiency by early contact between coarse particles, which is the main filling defect in the press molding process. A method for producing preforms with uniform particle filling structure by suppressing reduction and filling defects.

In the method for producing a uniform preform of the present invention, it is important to prepare uniform granules by suppressing constituent particle separation that may occur due to powder particle size differences from the mixing step.

The main cause of filling defects in the reaction-sintered silicon carbide preforms manufactured by the general press molding method is that there is a large amount of residual silicon in the sintered body due to the nonuniform distribution of coarse powder and the decrease in the filling efficiency of the fine powder, and in particular, early contact between coarse particles occurs. It is often found to act as a process defect that degrades the physical properties of the sintered compact.

Therefore, in the present invention, a raw powder having a multi-particle size distribution having a different particle size and a phenol resin used as a carbon source are uniformly mixed in an alcohol solution and added to a non-solvent to prepare granules at high speed, thereby obtaining the wet mixing process. Uniformity can be obtained even in the granular state.

Specifically, in order to prevent particle separation and early contact of coarse particles, in the present invention, the powder is dispersed in an alcohol solution of phenol resin, and the resulting slurry is added dropwise to 70-90 ° C. water or water to which a curing agent is added. Granules are obtained which retain their uniformity in. The phenol contained in the granules dropped into the water is soluble in alcohol but not in water, so that the alcohol is eluted from the granules and the water is penetrated into the granules, thereby maintaining the mixing degree of the first dropped in the water.

According to the present invention, hot press molding using the uniform granules prepared as described above promotes deformation of the granules and rearrangement of the constituent particles to obtain a uniform molded body, which is degreased under an inert gas atmosphere or vacuum to obtain silicon carbide. A uniform reaction sintered silicon carbide production preform composed of and carbon can be obtained.

As described above, the present invention uses a raw material powder having a multi-particle size distribution, and there is almost no separation of the constituent particles and little filling defects due to premature contact between coarse particles. It is about how to get the preform.

Specifically, the preform manufacturing method of the uniformly packed structure for the reaction sintered silicon carbide production by pressure molding of the present invention

1) providing a homogeneous mixture comprising raw powder, phenol resin and alcohol with multiple particle size distribution,

2) dropping the mixture into water or water containing a curing agent to form granules while maintaining the mixed state of the powder,

3) separating the granules from the mixture of step 2) by filtration or precipitation and washing them to remove residual alcohol,

4) drying the separated granules of step 3) at room temperature to a temperature of about 70 ℃ to remove the liquid medium contained in the granules,

5) putting the granules obtained in step 4) into the required amount mold and applying a pressure of 0.1 to 50 MPa at a temperature of 80 to 140 ° C. for 5 to 60 minutes to produce a molded article having a uniform packing structure; and

6) thermally decomposing the molded product obtained in step 5) at 400 to 1350 ° C. in an inert gas atmosphere or a vacuum atmosphere to obtain residual carbon and to give strength to the preform by densification of the residual carbon.

It includes.

Specifically, in step 1), the silicon carbide raw material powder of the appropriate size is weighed in an appropriate fraction, 1 to 20% of phenol resin is added according to the purpose of use, and then dry ball milling, followed by adding ethyl alcohol or butyl alcohol and strongly Stir to produce a homogeneous mixture.

In step 2), the mixed slurry is added dropwise to water or water at 70 to 90 ° C. containing a curing agent, and stable granules are formed with vigorous stirring for about 5 to 30 minutes. At this time, the higher the ratio of the amount of water to the amount of alcohol used in the slurry, the easier the formation of granules and the more stable the shape of the granules.

At this time, the temperature of the water is about 70 to 90 ℃ is suitable and maintaining a strong stirring for about 10 minutes to help maintain the granule form while speeding up the speed of replacing the alcohol in the droplets with water. Adding a curing agent to water to promote the formation of granules makes granule formation easier.

In step 3), the granules can be separated after filtration or precipitation, and after the separation, new water is added to remove the alcohol remaining in the granules as much as possible to prevent changes in the shape of the granules or the intergranular bonds during drying. It helps. In general, it is preferable to repeat the process of adding water to the state capable of stirring about 2 to 3 times, stirring vigorously, and then filtering.

In step 4), the separated granules are dried at room temperature or dried at 70 ° C. or lower to completely remove the liquid medium.

In step 5), the mold is filled with the required amount of granules and subjected to a pressure of 0.1 to 50 MPa at a temperature of 80 to 140 ° C. for 5 to 60 minutes to obtain a molded article having a uniform filling structure.

In step 6), the molded body obtained in step 5) is heat-treated at 400 to 1350 ° C. under an inert gas atmosphere or vacuum atmosphere to pyrolyze the phenol resin to obtain residual carbon, and to give strength to the preform by densification of the residual carbon. At this time, if the heat treatment temperature is increased according to the size of the product or the necessity of further processing, the strength of the preform increases as the densification of residual carbon proceeds.

The present invention will be described in more detail with reference to the following examples. These examples are merely illustrative of the present invention, and the present invention is not limited thereto.

<Example 1>

In the production of silicon carbide / carbon centrifugal bodies for the production of reaction-sintered silicon carbide, thermosetting resins such as phenol resins are thermally decomposed in an inert atmosphere or a vacuum atmosphere to provide excellent properties as carbon raw materials.

In the present invention, silicon carbide powders (Japan Showa Denko, GC) having particle sizes of 350, 60 and 8 microns were mixed as shown in the following Table 1 and used as a multi-particle size distribution silicon carbide raw material powder.

Silicon carbide powders with average particle diameters of 350, 60 and 8 microns were weighed in different weight ratios and dry mixed in a ball mill for 2 hours. 100 g of the mixed powder was added to a solution in which a phenol resin (Kolon Emulsification, KNG 100) corresponding to 5% of the weight of the powder was dissolved in butyl alcohol, and wet mixed at room temperature for 30 minutes.

The wet-mixed mixture was added dropwise to an aqueous solution of about 85 ° C. to which a curing agent (hexamethyleneamine) was added and maintained for 10 minutes with strong stirring. After cooling to room temperature, filtration and washing were repeated three times using water. The filtered granules were dried at 70 ^° C. for 10 hours to prepare granules for press molding.

The granules were hot pressed to a size of 50 × 25 × 7 mm with a pressure of about 10 MPa at 120 ^° C. for 40 minutes. The molded body was kept at 100 ° C. for 12 hours in a dryer to induce complete curing of the phenol resin, and a preform for producing reaction sintered silicon carbide was prepared by heat treatment at 1200 ° C. for 1 hour under vacuum.

Molding density of the press-formed product obtained a range of 2.13 to 2.33 g / cm ³ as shown in Table 1 according to the raw material powder composition. At this time, when the same technique using the conventional technique, that is, a simple dry mixing method, a molding density of 5% to 10% lower than the method according to the present invention was obtained.

1 is a scanning electron micrograph showing a packed structure of a preform for reaction sintered silicon carbide prepared by press molding a multi-particle size distribution raw material powder obtained by dry mixing of the prior art.

In contrast, FIG. 2 is a scanning electron micrograph showing a uniform packing structure of a preform for reaction sintered silicon carbide prepared by press molding granules prepared using the composition of Table 7 in the present invention. It can be seen that the prepared preforms show a more uniform filling structure than the preforms prepared by the prior art.

Forming Density of Hot Pressed Molded Body According to Composition of Silicon Carbide Powder Psalm Number Raw Material Composition of Silicon Carbide Powder (wt%) Molding Density (g / cm ³ ) Average particle size350 microns Average particle size60 micron Average particle size 8 micron One 65 25 10 2.13 2 61 30 9 2.18 3 70 22 8 2.11 4 62 23 15 2.27 5 55 30 15 2.27 6 55 25 20 2.33 7 60 15 25 2.33

According to the present invention, when the raw material powder having a large difference in particle size or a large density difference is used for the purpose of use of reaction-sintered silicon carbide ceramic components, Particle separation due to size and density difference and early generation of coarse particles can result in suppressing filling defects and reducing filling efficiency. By this effect, in the final sintered body manufactured using the preform of the present invention, it is possible to obtain an effect of minimizing the amount of residual silicon, which has less filling defects and lowers the room temperature and the high temperature strength.

Claims (3)

1) providing a homogeneous mixture comprising silicon carbide raw material powder having a multiple particle size distribution, 1 to 20% of the weight of the raw material powder and an alcohol, 2) dropping the mixture into water or water containing a curing agent and forming uniform granules while stirring, 3) separating the granules from the mixture of step 2) by filtration or precipitation and washing them to remove residual alcohol, 4) a drying step of drying the separated granules of step 3) to remove the liquid medium contained in the granules, 5) filling the mold obtained in step 4) into a mold, and applying a pressure of 0.1 to 50 MPa while heating to prepare a molded article having a uniform packing structure, and 6) heat-treating the molded product obtained in step 5) under an inert gas atmosphere or vacuum to pyrolyze the phenol resin to obtain residual carbon and to give strength to the preform by densification of the residual carbon. A preform manufacturing method of a uniform filling structure for reaction sintered silicon carbide production by pressure molding comprising a. delete The method of claim 1 wherein the temperature of the water of step 2) is from 70 to 90 ° C.