KR20200035597A - Intermediate plate for ceramic support body, method for manufacturing same, ceramic support body comprising the intermediate plate and method for manufacturing same - Google Patents

Abstract

The present invention relates to a ceramic support and a method for manufacturing the same. More specifically, the present invention relates to: a ceramic support in which green sheets corresponding to channels and partition walls are alternately stacked and cut when manufacturing an intermediate plate, thereby being able to adjust the size of channels and the thickness of partition walls, and increase the bonding strength of the ceramic support; and a method for manufacturing the same.

Description

INTERMEDIATE PLATE FOR CERAMIC SUPPORT BODY, METHOD FOR MANUFACTURING SAME, CERAMIC SUPPORT BODY COMPRISING THE INTERMEDIATE PLATE AND METHOD FOR MANUFACTURING SAME}

The present invention relates to a ceramic support and its manufacturing method.

Currently, the water shortage phenomenon is intensifying in the world, and the importance of water treatment technology is increasing due to the serious water shortage phenomenon.

Among the water treatment technologies, the ceramic support for water treatment is actively used in fields where conventional paper filters or filters made of various polymers cannot be used because of excellent heat resistance and chemical properties.

In addition, it can be used as a variety of membranes when adjusting the pore amount or pore size of the ceramic support or coating a material having other fine pores.

A ceramic support used in a conventional water treatment or automobile exhaust gas treatment apparatus is provided with a honeycomb-type integral structure. In the honeycomb form, an extrusion molding method is used.

Ceramic molding methods include compression, extrusion, injection, injection molding, and tape casting. However, the production yield is not good because the green sheet produced through extrusion molding has a high defect rate such as warping or cracking during drying and heat treatment. Due to the high hardness and shear stress of the material itself, contamination and replacement costs are incurred due to wear of the mechanical device.

Korean Patent Publication No. 2014-0028705

An object of the present invention is to provide an intermediate plate for manufacturing a ceramic support, a method for manufacturing the same, a ceramic support including the intermediate plate, and a method for manufacturing the same.

An exemplary embodiment of the present invention includes the steps of alternately laminating a first green sheet 1 or more composed of a material removed by heat treatment and a second green sheet 2 or more comprising at least a portion of a material not removed by heat treatment; And cutting the first green sheet and the second green sheet stack in a direction perpendicular to the interface between the first green sheet and the second green sheet. .

In another exemplary embodiment of the present invention, as a method of manufacturing a ceramic support including a channel therein, an intermediate plate including a channel forming part and a partition forming part according to the manufacturing method of the intermediate plate for manufacturing the ceramic support Forming; Stacking upper and lower plates on one side and the other side of the intermediate plate, respectively; And it provides a method of manufacturing a ceramic support comprising the step of heat-treating a laminate including the upper plate, the intermediate plate and the lower plate.

In another exemplary embodiment of the present invention, a ceramic support manufactured according to the method for manufacturing a ceramic support of the present invention is provided.

According to the present invention, it is possible to adjust the channel size of the intermediate plate and the thickness of the partition wall according to the thickness of the flat plate to be stacked, and since the channel portion before firing is not left as an empty space, it is possible to increase the bonding strength of the support through a compression process. There is an advantage.

1 is a view schematically showing a method of manufacturing a ceramic support according to an exemplary embodiment of the present invention.
2 is a view schematically showing definitions of thickness, length, and width of the present invention.
3 is a view schematically showing the definition of a channel cross-section shape and spacing of a ceramic support.
4 to 6 are photographs showing the state of the ceramic support according to Comparative Examples 1 to 3.

In the present invention, two or more elements are sequentially provided, for example, the term “A and B sequentially provided”, wherein the elements A and B are arranged in the above order, and are different between A and B. When elements are interposed, it is also included, for example, when A and B and C are arranged in the above order.

In the present invention, when a part is said to “include” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

Hereinafter, preferred embodiments of the present invention will be described. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

The method for manufacturing an intermediate plate for manufacturing a ceramic support according to an exemplary embodiment of the present invention includes a first green sheet 1 or more composed of a material removed by heat treatment, and a second green sheet 2 or more comprising at least a portion of a material not removed by heat treatment. Alternately stacking; And cutting the first green sheet and the second green sheet stack in a direction perpendicular to the interface between the first green sheet and the second green sheet.

In the present invention, the first green sheet may be a channel forming portion of the intermediate plate.

In addition, in the present invention, the second green sheet may be a partition wall forming portion of the intermediate plate.

As described above, since the partitions and the channel portions are separately cast, it is easy to control the size of the channels and the thickness of the partitions without a process of uniformly controlling the partitions and the channel portions while performing multi casting. There is an advantage that can be done. In addition, thereafter, when manufacturing the ceramic support by attaching the upper or lower plate, there is an advantage that can control the thickness of the entire ceramic support.

In an exemplary embodiment of the present invention, the first green sheet may be manufactured by tape casting a removable material when heat-treating. For example, when the heat treatment is performed, as a removable material, a polymer material such as carbon black, graphite, or polyethylene may be used.

In an exemplary embodiment of the present invention, the thickness of the first green sheet may be adjusted, and the thickness of the first green sheet may be 1 mm to 10 mm, preferably 2 mm to 6 mm.

In the present invention, as shown in Fig. 2, thickness (a) means a relatively shorter shortest distance when viewed from the direction A, and width (c) is a relatively shorter shortest distance when viewed from the direction B. Means, and the length (b) means a relatively longer shortest distance when viewed in the A or B direction. The A direction means a direction perpendicular to the stacking direction, and the B direction means a direction parallel to the stacking direction.

In another exemplary embodiment of the present invention, the second green sheet may be manufactured by tape casting a material that is not partially removed when heat-treated. For example, alumina, zirconia, silica, or the like can be used as a material that is not removed at least partially during the heat treatment. After heat treatment of these materials, impurities, liquids, etc., which are not partially removed, remain so as not to affect the formation of the partition walls.

In one embodiment of the present invention, the thickness of the sheet of the second green sheet may be adjusted, and the thickness of the sheet of the second green sheet may be 0.5 mm to 5 mm, preferably 1 mm to 3 mm. .

In one embodiment of the present invention, the thickness of the laminate formed by alternately laminating the first green sheet 1 or more and the second green sheet 2 or more is 100 mm to 500 mm, preferably 100 mm to 300 mm. You can. In addition, the length of the laminate may be 1000 mm or more, preferably 1500 mm or more.

In an exemplary embodiment of the present invention, a method of cutting the laminate may use a multi-wire saw, and the distance between the multi-wire saws is 1 mm to 5 mm, preferably May be 1 mm to 3 mm. As described above, when using a multi-wire saw, it is possible to manufacture multiple interlayers at once, which has the advantage of improving productivity.

The present invention provides an intermediate plate for manufacturing a ceramic support in which the first green sheet manufactured by the method for manufacturing the intermediate plate for manufacturing the ceramic support is disposed at regular intervals. The distance between the first green sheets of the intermediate plate may be 0.5 mm to 5 mm, preferably 1 mm to 5 mm. That is, it means that the second green sheet is disposed at a distance.

In the intermediate plate for manufacturing a ceramic support of the present invention, the first green sheets may be arranged at equal intervals. That is, it means that the thickness of the second green sheet is constant.

Since the first green sheet of the intermediate plate is disposed at regular or equal intervals, the channels of the ceramic support can be arranged at regular or equal intervals. In this case, the function of imparting a binding force to the upper or lower plate and improving the strength of the ceramic support, but the number of barrier ribs capable of lowering the transmittance is adjustable, so that the permeability of the ceramic support is prevented from being excessively reduced, and the desired level It can have a uniform transmittance.

A method of manufacturing a ceramic support including a channel in the present invention includes forming an intermediate plate including a channel forming portion and a partition forming portion according to the above-described intermediate plate manufacturing method; Stacking upper and lower plates on one side and the other side of the intermediate plate, respectively; And it may include the step of heat-treating the laminate including the upper plate, the intermediate plate and the lower plate. Each step is schematically shown in FIG. 1.

In one embodiment of the present invention, the upper plate and the lower plate may be provided by stacking 2 to 7 sheets of green sheets having a thickness of 80 μm to 2 mm produced by tape casting.

In one embodiment of the present invention, the upper plate and the lower plate are, but are not limited to, alumina powder, TiO ₂ , SiC, and MgAl ₂ O ₄ . Can be manufactured. In addition, the upper plate may have a smaller particle size of the ceramic powder as it goes up, and the lower plate may have a smaller particle size of the ceramic powder as it goes down.

In one embodiment of the present invention, the upper plate and the lower plate, alumina powder, TiO ₂ , SiC and MgAl ₂ O ₄ Ceramic powder and carbon powder containing any one or more, starch powder, carbon black and spherical organic particles It may be prepared by a ceramic slurry containing a pore-forming agent containing any one or more of, but is not limited thereto. At this time, the upper plate may have a smaller content of the pore-forming agent as it goes up, and the lower plate may have a smaller content of the pore-forming agent as it goes down.

Preferably, the pore-forming agent may include 2 wt% to 30 wt%, and in the firing step, the carbon powder is oxidized to form pores on the upper plate and the lower plate. At this time, the upper plate and the lower plate may have a porosity of 28% to 100%. In addition, the difference in porosity may be 5% to 50%.

The porosity gradient may be, for example, the porosity decreases toward the upper portion of the upper plate with respect to the intermediate plate, and the porosity decreases toward the lower portion of the lower plate.

In addition, preferably, the ceramic powder may be provided with a particle size of 1.4 µm to 20 µm to form pores on the upper plate and the lower plate.

In the present invention, the upper portion of the upper plate means the opposite side of the surface opposite to the upper plate and the intermediate plate, and the lower portion of the lower plate means the opposite side of the surface opposite to the lower plate and the intermediate plate.

In the present invention, removal means that the material constituting the first green sheet is burned out by the heat treatment.

The heat treatment means a temperature higher than room temperature.

In one embodiment of the present invention, the heat treatment temperature may be 800 ° C to 1700 ° C, preferably 1000 ° C to 1700 ° C. In addition, the heat treatment time may be 30 minutes or more and less than 6 hours, preferably 2 hours or more and less than 4 hours. As the components of the first green sheet are removed by heat treatment at a temperature of 800 ° C. or higher, sintering of the laminate composed of the upper plate, the intermediate plate, and the lower plate starts, and the heat treatment is performed at a temperature of 1700 ° C. or lower to excessively sinter. It is possible to prevent the internal pores of the upper and lower plates from disappearing.

In the present invention, sintering means a phenomenon in which particles are brought into close contact with each other and hardened when heat-treated at a constant temperature.

In one embodiment of the present invention, after the step of laminating the upper plate and the lower plate on one side and the other side of the intermediate plate, respectively, before the step of heat-treating the laminate composed of the upper plate, the intermediate plate and the lower plate, the upper plate, the intermediate plate, and A process of applying pressure to the laminate made of the lower plate may be further included. Since the channel portion of the intermediate plate is not an empty space before the heat treatment, as a possible process, it is possible to increase the bonding strength of the ceramic support. For example, when using a uniaxial pressure press (press), it can be pressurized under conditions of 2MPa to 20MPa at 40 ° C to 80 ° C. More preferably, it may be uniaxially pressurized at 50 ° C to 60 ° C under the conditions of 10Mpa to 15Mpa.

In another exemplary embodiment of the present invention, a separation layer may be stacked on the outermost layer in addition to the upper plate and the lower plate, and heat-treated at the same time. This can simplify the process. The separation layer may be the same material as the upper and lower plates.

In one embodiment of the present invention, the top plate; The above-described intermediate plate provided on one surface of the top plate; And it provides a ceramic support precursor comprising a lower plate sequentially provided on the opposite side of the surface provided with the intermediate plate.

In another exemplary embodiment of the present invention, there is provided a ceramic support having a distance of 0.5 mm to 5 mm between channels made of the above-described ceramic support precursor. The distance between the channels may be more preferably 1 mm to 5 mm. In this case, the ceramic support may have a uniform transmittance, and the bonding strength is excellent.

The ceramic support of the present invention may have an equal interval between channels. This means that the number of barrier ribs is adjustable, as described above, to prevent the permeability of the ceramic support from being lowered, and to have a desired level of uniform permeability.

In an exemplary embodiment of the present invention, a ceramic support having a square or rectangular cross-sectional shape of the channel may be provided.

In an exemplary embodiment of the present invention, a ceramic support having a rectangular cross-sectional shape of the channel may be provided. When the cross-section of the channel is rectangular, it is easy to reduce the number of partition walls, which further prevents the permeability from being reduced.

The cross-sectional shape refers to a shape when a channel of a ceramic support is vertically viewed from an empty space. As shown in Fig. 3, it means the shape when the ceramic support is cut and viewed vertically from C to C '. In FIG. 3, a relatively dark part means a channel (channe), and t1 to t4 mean a space between channels. That is, the vertical distance from the end of a section of a channel to the end of a section of an adjacent channel is defined as the distance between the channels. However, the number of channels is not limited to FIG. 3.

Hereinafter, examples will be described in detail to specifically describe the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not interpreted to be limited to the embodiments described below. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

<Example 1>

3 to 7 green tapes produced by tape casting carbon black having a width of 50 mm, a length of 50 mm and a thickness of 200 μm to 500 μm are stacked to form 3 to 7 green tapes, 50 mm in width, 50 mm in length, and 2 to 5 mm in thickness. A first green sheet of ㎜ is prepared. In addition, a green tape (tape) prepared by mixing a ratio of alumina and carbon black having a width of 50 mm, a length of 50 mm, and a thickness of 200 μm to 500 μm in a ratio of 8: 2 was stacked with 3 to 7 sheets, and a width of 50 mm, A second green sheet having a length of 50 mm and a thickness of 1 mm to 2 mm is prepared.

After this, the outermost sheet is a second green sheet, and the first green sheet and the second green sheet are alternately stacked to produce a green body having a thickness of 50 mm, and the multi-body saw having a thickness of 5 mm between the green bodies ( Multi Wire Saw). The rest of the cut parts, except the outermost, are used as intermediate plates.

The upper and lower plates were manufactured in the same manner as the second green sheet, except that the thickness was 1.5 mm. After stacking in the order of the lower plate, the intermediate plate and the upper plate from below, the final laminate is prepared by uniaxially pressing under the conditions of 60 ° C. and 10 Mpa. The final laminate was sintered at 1500 ° C. for 4 hours to prepare a ceramic support.

<Example 2>

A ceramic support was prepared in the same manner as in Example 1, except that the green sheet having a thickness of 50 µm was laminated on the top and the bottom of the top plate, and then to the separation layer, the bottom plate, the middle plate, the top plate, and the separation layer from below. To manufacture.

<Comparative Example 1>

A green sheet having a width of 35 mm and a thickness and a thickness of 200 µm is manufactured by multi-tape casting while alternately arranging a 5 mm wide ceramic slurry and a carbon black slurry. Seven green sheets are stacked to prepare an intermediate plate having a thickness of 1.5 mm.

Then, a final laminate was prepared in the same manner as in Example 1, and sintered under the same conditions as in Example 1 to prepare a ceramic support. The appearance of the ceramic support of Comparative Example 1 is shown in Figure 4.

<Comparative Example 2>

In the green sheet made of the same material as the second green sheet of Example 1, a part corresponding to a channel is cut at intervals of 5 mm, and the part is removed to prepare an intermediate plate.

In the same order as in Example 1, the lower plate, the intermediate plate, and the upper plate were laminated, and uniaxially pressed under conditions of 60 ° C. and 2 Mpa to prepare a final laminate. The final laminate was sintered under the same conditions as in Example 1 to prepare a ceramic support. The appearance of the ceramic support of Comparative Example 2 prepared is shown in FIG. 5.

<Comparative Example 3>

An intermediate plate and a ceramic support were prepared in the same manner as in Comparative Example 2, except that the final laminate was not uniaxially pressed. The appearance of the ceramic support of Comparative Example 3 is shown in Figure 6.

In the case of Comparative Example 1, as can be seen through FIG. 4, due to the difference in rheological properties of the ceramic slurry and the carbon black slurry in the process of multi-tape casting, the width of the line of the stacked slurry varies, and the channel It was confirmed that the (channel) spacing was not constant, and the cross-sectional shape was not rectangular. In addition, the gap could not be adjusted to less than 5 mm. This means that it is difficult to manufacture a ceramic support having a desired channel spacing, and the transmittance is uneven.

In the case of Comparative Example 2, it can be confirmed from FIG. 5 that the channel is slightly distorted. That is, when the ceramic support is prepared by the method of Comparative Example 2, since the channel portion is uniaxially pressed in an empty state, a pressure greater than 2 Mpa cannot be applied, and the bonding force between the lower plate, the middle plate and the upper plate is weakened.

In addition, it was confirmed that when the pressure is not applied as in Comparative Example 3, cracks are often generated in the ceramic support as shown in FIG. 6.

From Examples 1 to 3, it was confirmed that a ceramic support having a constant channel spacing and a rectangular cross-section shape and having a channel spacing of less than 5 mm was possible. In addition, by using a multi wire saw, it was possible to manufacture multiple intermediate plates at once. That is, it was found that it is easy to control the spacing of the channels and the process efficiency is excellent. In addition, as compared with the comparative example, it was formed by applying a high pressure, it was confirmed that the bonding strength is excellent.

Claims (11)

Alternately stacking the first green sheet 1 or more made of a material removed by heat treatment and the second green sheet 2 or more comprising at least a portion of the material not removed by heat treatment; And
Cutting a stack of the first green sheet and the second green sheet in a direction perpendicular to the interface between the first green sheet and the second green sheet.
Method for manufacturing an intermediate plate for manufacturing a ceramic support comprising a. According to claim 1,
The method of cutting the laminate is a method of manufacturing an intermediate plate for manufacturing a ceramic support, which uses a multi wire saw. According to claim 1,
The first green sheet has a thickness of 1 mm to 10 mm, and the second green sheet has a thickness of 0.5 mm to 5 mm. According to claim 1,
The thickness of the laminate formed by alternately laminating the first green sheet and the second green sheet is 100 mm to 500 mm. An intermediate plate for manufacturing a ceramic support in which the first green sheets manufactured by the manufacturing method according to any one of claims 1 to 4 are disposed at intervals of 0.5 mm to 5 mm. The method of claim 5,
The first green sheet is an intermediate plate for manufacturing a ceramic support, arranged at equal intervals. As a method of manufacturing a ceramic support including a channel (channel) therein,
Forming an intermediate plate comprising a channel forming portion corresponding to the first green sheet and a partition forming portion corresponding to the second green sheet by the manufacturing method according to any one of claims 1 to 4;
Stacking upper and lower plates on one side and the other side of the intermediate plate, respectively; And
Heat-treating the laminate including the upper plate, the intermediate plate, and the lower plate.
Method for manufacturing a ceramic support comprising a. The method of claim 7,
After the step of stacking the upper plate and the lower plate on one side and the other side of the intermediate plate, applying pressure to the laminate composed of the upper plate, the intermediate plate and the lower plate before the step of heat-treating the laminate composed of the upper plate, the intermediate plate and the lower plate, respectively. Method for manufacturing a ceramic support further comprising a process. Tops; The intermediate plate according to claim 5 provided on one surface of the top plate; And a lower plate sequentially provided on the opposite side of the surface provided with the intermediate plate. A ceramic support having a distance of 0.5 mm to 5 mm between channels manufactured by claim 9. The method of claim 10,
A ceramic support having a square or rectangular cross-section shape of the channel.

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