JP2017144561A - Ceramic industry raw material, production method of fired body, and fired body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a practical compact in an additional production technology using a ceramic industry raw material.SOLUTION: A ceramic industry raw material, which is a ceramic industry raw material for producing a fired body by an additional production system, contains an inorganic binder. Preferably, the inorganic binder contains a silicate. According to this ceramic industry raw material, a practical pottery or a ceramic product can be obtained, by keeping the shape even at a firing time at 600°C or higher.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a ceramic material, a method for producing a fired body, and a fired body.

  In recent years, three-dimensional modeling using an additive manufacturing technique (3D printer) has attracted attention. In this technology, the shape of a thin section is calculated by a computer based on three-dimensional (3D) data, and materials are laminated based on the calculation result to produce a three-dimensional structure. .

  In this technique, for example, the following method is employed (see Patent Document 1). That is, a plurality of powder layers composed of modeling powder are stacked and formed, and in the stacking process, a predetermined patterning liquid (patterning liquid) is formed in a predetermined planar shape on each surface of the plurality of powder layers. ) Is being sprayed. By spraying this patterning liquid, the powder layers are bonded to each other to form a laminate (molded body).

As the material, for example, a powder material such as gypsum is used, and an organic binder such as polyvinyl alcohol (PVA) is used to fix the shape.
By the way, there is a demand for using ceramic raw materials as powder raw materials. In this case, it is considered that a molded body can be manufactured by applying a conventional additive manufacturing technique.

JP 2005-144870 A

  However, when ceramic raw materials are used as the powder raw material, when the conventional method is used, when the molded body is fired, the organic binder is decomposed so that the shape cannot be maintained, the shape collapses and cannot be fired. .

  This invention is made | formed in view of the said conventional situation, Comprising: It is an addition manufacturing technique using the ceramics raw material, and it aims at obtaining a sintered body which is shape-maintained also at the time of baking.

In view of the above prior art, the present inventors have developed a new ceramic material as a result of intensive research. And when the sintered body was manufactured by the additive manufacturing method using this ceramic raw material, the unexpected fact that the shape was maintained during firing and a practical fired body was obtained was found. The present invention has been made based on this finding.
That is, the ceramic raw material of the present invention is a ceramic raw material for producing a fired body by an additive production method, and contains an inorganic binder.
The manufacturing method of the present invention includes (1) a powder layer forming step of forming a powder layer having a predetermined thickness using a ceramic raw material, and (2) a spraying step of spraying a liquid on a predetermined region of the powder layer. It is a method for producing a fired body by repeating in order, laminating to form a shaped body, and firing the shaped body,
The ceramic raw material and / or the liquid contains an inorganic binder.
Moreover, the fired body of the present invention includes (1) a powder layer forming step of forming a powder layer having a predetermined thickness using a ceramic raw material, and (2) a spraying step of spraying a liquid on a predetermined region of the powder layer. It is a method for producing a fired body by repeating in order, laminating to form a shaped body, and firing the shaped body,
The ceramic raw material and / or the liquid is obtained by a method for producing a fired body containing an inorganic binder.

According to the ceramic raw material of the present invention, ceramics and ceramic products can be obtained by firing at 600 ° C. or higher.
According to the manufacturing method of the present invention, a ceramic or ceramic product having a high degree of freedom in shape using an additional manufacturing method can be obtained.
The fired body of the present invention is useful as a ceramic or ceramic product.

It is a conceptual diagram which shows a mode that a molded object is shape | molded by the addition manufacturing system using the ceramic industry raw material of this invention. It is a conceptual diagram which shows a mode that a molded object is shape | molded by the addition manufacturing system using the ceramic industry raw material of this invention. It is a conceptual diagram which shows a mode that a molded object is shape | molded by the addition manufacturing system using the ceramic industry raw material of this invention. It is a conceptual diagram which shows a mode that a molded object is shape | molded by the addition manufacturing system using the ceramic industry raw material of this invention. It is a conceptual diagram which shows a mode that a molded object is shape | molded by the addition manufacturing system using the ceramic industry raw material of this invention. It is a conceptual diagram which shows a mode that a molded object is shape | molded by the addition manufacturing system using the ceramic industry raw material of this invention. It is a conceptual diagram which shows a mode that a molded object is shape | molded by the addition manufacturing system using the ceramic industry raw material of this invention.

A preferred embodiment of the present invention will be described.
The ceramic raw material preferably contains a curing accelerator that accelerates the curing of the inorganic binder. When the curing accelerator is contained, curing of the inorganic binder is promoted, and the shape retention of the fired body is enhanced.

  The ceramic raw material preferably contains silicate as an inorganic binder. By including the silicate, shape retention during firing is improved.

The bulk density of the fired body is preferably 1.0 g / cm ³ or more. When the bulk density is within this range, it becomes a practical ceramic or ceramic product.

  The fired body preferably has a stacking trace in the cross section and a stacking pitch of 5 mm or less. Such a structure has sufficient strength and good appearance.

Hereinafter, embodiments of the present invention will be described in detail.
[1] Ceramic Industry Raw Material The ceramic industry material of the present invention is a ceramic industry material for producing a fired body by an additive production method. The ceramic raw material contains an inorganic binder.

  The ceramic raw material is not particularly limited as long as it is a raw material used for the ceramic industry. Examples of raw materials include skeleton-forming raw materials such as porcelain stone, feldspar, silica stone, wax stone, chamotte, ban shale, kaolin, plastic raw materials such as glazed clay, kibushi clay, kaolin, wollastonite, limestone, anorthite, etc. Calcium raw materials, sintering aid raw materials such as feldspar, dolomite and the like. Preferable examples include inorganic materials such as morokite, feldspar, calcined clay, clay, alumina powder, quartz powder, talc, and aggregate. These raw materials may be used individually by 1 type, and 2 or more types may be mixed and used for them. Usually, a mixture of two or more is used.

  In the present invention, when the total amount of ceramic raw materials other than the inorganic binder is 100 parts by mass, the plastic raw material is preferably 60 parts by mass or less. Here, examples of the plastic raw material include clay, glazed clay, and kaolin. The plastic raw material is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. When it is within this range, the laminated state of the molded body becomes good.

  In the present invention, the mixing ratio of each raw material is preferably 5 to 70 parts by weight of morokite and 40 to 70 parts by weight of feldspar when the total amount of ceramic raw materials other than the inorganic binder is 100 parts by weight, and more preferably Is 10-60 parts by mass of morokite and 45-55 parts by mass of feldspar. When it is within this range, the laminated state of the molded body becomes good, and a desired fired body is obtained.

  The maximum particle size of the ceramic raw material is not particularly limited. The maximum particle size of the ceramic raw material is preferably 2 times or less, more preferably 1 time or less, and even more preferably 0.9 times or less the lamination pitch of the additive production method. In general, the maximum particle size of the ceramic raw material is 1/1000 times or more the stacking pitch of the additive manufacturing method. When the maximum particle size of the ceramic raw material is within this range, the density of the molded body can be improved.

  The maximum particle size of the ceramic raw material is not particularly limited, but when the lamination pitch is 100 μm, it is preferably 0.01 to 200 μm, more preferably 0.1 to 200 μm, and still more preferably 0.1 to 100 μm. It is. If the maximum particle size of the ceramic raw material is too small, the ceramic raw material will flutter and tend to be difficult to mold in the additive manufacturing method, while if too large, the density of the molded body tends to be small. Therefore, the above range is preferable as the maximum particle size of the ceramic raw material.

  The particle size distribution in the ceramic material is not particularly limited. Preferably, coarse particles can be 60 to 80 parts by mass, fine particles can be 40 to 20 parts by mass, and more preferably, coarse particles can be 65 to 80 parts by mass and fine particles can be 35 to 20 parts by mass. More preferably, the coarse particles can be 70 to 80 parts by mass and the fine particles can be 30 to 20 parts by mass. This range is preferable because the density of the molded body is improved.

  Here, “coarse particles” mean particles having a particle diameter of 50 μm or more and 100 μm or less determined by a sedimentation method when the lamination pitch is 100 μm. “Fine particles” means particles having a particle size of 0.01 μm or more and 5 μm or less determined by a sedimentation method.

  You may adjust the powder particle size of a ceramic raw material by granulation. It does not specifically limit as a granulation method, A well-known method can be selected suitably. For example, wet granulation and dry granulation can be employed. In the case of granulation, the powder layer can be compressed to increase the packing property and the density.

  Although the angle of repose of the ceramic raw material is not particularly limited, it is preferably 20 to 70 degrees, more preferably 30 to 70 degrees, and further preferably 30 to 60 degrees. Within this range, the fluidity of the ceramic raw material will be in an appropriate range, and the lamination state by the additive manufacturing method will be good.

  The angle of repose can be measured with a powder tester (manufactured by Hosokawa Micron Corporation) TYPE PT-E.

The shear stress of the ceramic raw material is not particularly limited, but is preferably 40 kPa or more. Usually, it is 100 kPa or less.
Here, the shear stress is a value measured as follows. That is, it is a value measured with a nano-seeds powder shear force measuring apparatus NS-S500 type. As measurement conditions, the sample is 50 g, and the load is 50 N, 100 N, and 150 N.

The internal friction of the ceramic raw material is not particularly limited, but is preferably 30 to 40.
Here, the internal friction is a value measured as follows. That is, it is a value measured with a nano-seeds powder shear force measuring apparatus NS-S500 type. As measurement conditions, the sample is 50 g, and the load is 50 N, 100 N, and 150 N.

The loose bulk density of the ceramic material is not particularly limited. The loose bulk density of the ceramic raw material is preferably 0.5 g / cm ³ or more, more preferably 0.7 g / cm ³ or more, and further preferably 1.0 g / cm ³ or more. Moreover, the loose bulk density of the ceramic raw material is usually 2.0 g / cm ³ or less. Within this range, the filling property of the ceramic raw material becomes an appropriate range, and the laminated state by the additive manufacturing method becomes good.

  The loose bulk density in the present invention is a packing density in a state where the powder is naturally dropped into a predetermined container, and is a value measured by the following method using a powder characteristic measuring instrument. Specifically, a value measured with a powder tester (manufactured by Hosokawa Micron Corporation) TYPE PT-E can be employed.

  In the present invention, the method of mixing the ceramic raw materials is not particularly limited. Both dry mixing and wet mixing can be employed. Dry mixing is preferred from the viewpoint of production efficiency. In addition, it is preferable to select a raw material having a known particle size distribution in advance before dry mixing.

[Inorganic binder]
The ceramic raw material of the present invention is characterized by containing an inorganic binder. The inorganic binder is not particularly limited. For example, silicate, phosphate, silica sol, and cement can be preferably used. These may be used alone or in combination of two or more.

  Although it does not specifically limit as a silicate, For example, sodium silicate, potassium silicate, lithium silicate, magnesium silicate, aluminum silicate, calcium silicate etc. are mentioned. Among the silicates, alkali metal silicic acid is preferable, and sodium silicate is particularly preferably used.

  The phosphate is not particularly limited, but aluminum phosphate, calcium phosphate, magnesium phosphate, potassium phosphate, lithium phosphate, sodium hexametaphosphate, sodium pyrophosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, sodium ultraphosphate Etc. Among the phosphates, aluminum phosphate is preferably used.

  The cement is not particularly limited. For example, alumina cement, magnesia cement, ordinary Portland cement, early strength Portland cement, super early strength Portland cement, moderately hot Portland cement, sulfate resistant Portland cement, white Portland cement, ultrafast cement And various cements such as expanded cement, acidic phosphate cement, silica cement, blast furnace cement, fly ash cement, keens cement and the like.

  The amount of inorganic binder added is not particularly limited. Preferably it is 0-60 mass parts with respect to 100 mass parts of ceramic raw materials other than an inorganic binder, More preferably, it is 0-30 mass parts, More preferably, it is 0-10 mass parts. By setting the additive for the inorganic binder within this range, the molded product can be baked in a state in which the shape is kept good.

[Curing accelerator]
The curing accelerator for promoting the curing of the inorganic binder is an arbitrary additive, and is appropriately selected according to the type of the inorganic binder. Only one type of curing accelerator may be used, or two or more types may be used in combination.

When alkali metal silicate is used as the inorganic binder, examples of the curing accelerator include oxides such as Zn (zinc), Mg (magnesium), and Ca (calcium); Zn (zinc) and Mg (magnesium) , Hydroxides such as Ca (calcium) and Al (aluminum); silicides such as Na (sodium), K (potassium) and Ca (calcium); Na (sodium), K (potassium) and Ca (calcium) Illustrative examples include silicofluorides: phosphates such as Al (aluminum) and Zn (zinc); borate salts such as Ca (calcium), Ba (barium) and Mg (magnesium); alum and the like.
Among these, aluminum tripolyphosphate, zinc oxide, aluminum hydroxide, and alum are preferably used.

[2] Manufacturing method of fired body The manufacturing method of the molded body of the present invention includes (1) a powder layer forming step of forming a powder layer of a predetermined thickness using a ceramic raw material, and (2) a predetermined powder layer. This is a method for manufacturing a fired body in which a spraying process of spraying a liquid onto a region is repeated in order, laminated to form a molded body, and the molded body is fired. The ceramic material and / or liquid contains an inorganic binder.

  A method for manufacturing a fired body will be described with reference to FIGS.

(2-1) Powder Layer Forming Step In the powder layer forming step, the powder layer 1 having a predetermined thickness is formed using a ceramic material (see FIG. 1). At this time, the powder layer 1 is usually formed by spreading ceramic raw materials using a recoater.
This step is specifically performed as follows, for example. First, a ceramic raw material (mixed powder for three-dimensional modeling) is filled in, for example, a layer having a thickness of 0.01 to 5 mm on the vertical upper side (upper side in the z-axis direction) of the base 3 of the molding apparatus. Next, the ceramic raw material is scraped off with a scissors or the like to form a powder layer 1 having a desired thickness.
The stacking pitch is preferably 0.1 to 5 mm in order to produce a large molded body. By making it within this range, the production speed can be improved.
Note that the powder layer 1 may be compressed after the ceramic material is spread.

  As the ceramic raw material in this step, those described in the above [1] Ceramic raw material can be used. The above-mentioned [1] ceramic materials are limited to those containing an inorganic binder.

In the method for producing a fired body of the present invention, the ceramic material is not limited to a ceramic material containing an inorganic binder, and a ceramic material that does not contain an inorganic binder can also be used. When using the ceramic raw material which does not contain an inorganic binder, the liquid 7 in the process of (2-1) mentioned later contains the inorganic binder.
In this case, the ceramic raw material not containing the inorganic binder is not particularly limited as long as it is a raw material used for the ceramic industry. Examples of raw materials include skeleton-forming raw materials such as porcelain stone, feldspar, silica stone, wax stone, chamotte, ban shale, kaolin, plastic raw materials such as glazed clay, kibushi clay, kaolin, wollastonite, limestone, anorthite, etc. Calcium raw materials, sintering aid raw materials such as feldspar, dolomite and the like. Preferable examples include inorganic materials such as morokite, feldspar, calcined clay, clay, alumina powder, quartz powder, talc, and aggregate. These raw materials may be used individually by 1 type, and 2 or more types may be mixed and used for them. Usually, a mixture of two or more is used.
In ceramic raw materials that do not contain an inorganic binder, the above-mentioned [1] description of "preferable mixing ratio of each raw material" in the ceramic raw materials, description of "maximum particle size of ceramic raw materials", "maximum particle size of ceramic raw materials" Description regarding “particle size distribution in ceramic materials” Description regarding “repose angle of ceramic materials” Description regarding “shear stress of ceramic materials” Description regarding “internal friction of ceramic materials” “Loose bulk density of ceramic materials "And the description about" how to mix ceramic materials "can be applied as they are.

(2-1) Spraying process In the spraying process, the liquid 7 is sprayed on the predetermined area | region of the powder layer 1 (refer FIG. 2). A liquid (modeling liquid) 7 is ejected (dropped) from the head 5 to a portion to be solidified in the powder layer 1, that is, a position corresponding to a part of the three-dimensional modeled object to be molded, and the part is layered. Formed as a solidified product. In FIG. 2, the solidified portion of the powder layer 1 is indicated by hatching.

  At this time, the liquid 7 is ejected while the head 5 is moved in the xy plane with respect to the base 3 by the head driving mechanism, so that the layered solidification corresponding to a part of the three-dimensional object to be molded is obtained. Things are formed.

Here, the liquid 7 will be described. When a ceramic raw material containing an inorganic binder is used, the liquid 7 can be a solvent alone or a solution obtained by dissolving an inorganic binder in a solvent.
When a ceramic raw material not containing an inorganic binder is used, as the liquid 7, a solution in which an inorganic binder is dissolved in a solvent is used.

  As the inorganic binder that may be contained in the solution used here, the inorganic binder described in the above-mentioned [1] ceramic raw materials can be suitably used. When using a ceramic material that contains an inorganic binder, the inorganic binder contained in the ceramic material and the inorganic binder contained in the solution may be the same or different. Good. Moreover, the inorganic binder added to a solution may be used by a single type, and may be used together 2 or more types.

  Moreover, you may add suitably the hardening accelerator described in the above-mentioned [1] ceramic industry raw material to the liquid 7. FIG. In this case, the curing accelerator added to the liquid 7 may be used alone or in combination of two or more.

  The solvent is not particularly limited. For example, water can be used. Moreover, it is good also as a mixed solvent of water and another solvent. The other solvent may be either an inorganic solvent or an organic solvent, and specific examples include solvents such as alcohol and ketone. Thus, when it is set as the mixed solvent of water and another solvent, content of water is not specifically limited. The content of water is preferably 1 to 99 parts by mass, more preferably 30 to 99 parts by mass, and particularly preferably 50 to 99 parts by mass when the total mixed solvent is 100 parts by mass.

  The concentration of the solution is not particularly limited, but is preferably 0 to 20 parts by mass of the inorganic binder, more preferably 0 to 10 parts by mass of the inorganic binder, and particularly preferably the inorganic binder with respect to 100 parts by mass of the solvent. 0 to 5 parts by mass. When the concentration of the solution is within a preferable range, the injection state from the nozzles of the head 5 is good.

  In this manufacturing method, the powder layer forming step and the spraying step are repeated in order (see FIGS. 3 to 4), and the state shown in FIG. 5 is obtained, and the molded body 9 as shown in FIG. 6 is taken out from the state shown in FIG.

  Specifically, the base 3 is lowered vertically by a thickness corresponding to each layer of the layered solid material (downward in the z-axis direction). Hereinafter, by repeating the powder layer forming step and the spraying step, the layered solidified product is sequentially laminated to form a three-dimensional shaped product, and the ceramic material that has not been solidified is removed to form a molded body. 9 (three-dimensional modeled object) is obtained. And as shown in FIG. 7, it is preferably set as a glazed product by glazing on the surface of the molded body 9. Reference numeral 11 indicates a soot layer. The method of glazing is not particularly limited, and a known method such as spray coating, dip coating, roll coating, spin coating, roll coating or the like can be appropriately selected and employed. The eaves layer may be a single layer or multiple layers. Note that the glazing is not necessarily performed.

  The glaze is not particularly limited. A well-known glaze can be suitably selected according to a use. Examples of glazes include, for example, ash glazes containing feldspar, silica stone and the like, colorless transparent glazes such as lime glazes, green glazes obtained by adding copper oxide to transparent glazes, iron glazes using iron as a colorant, and the like. The

(2-3) Firing step In the firing step, the molded body is fired to obtain a fired body.
The firing temperature is not particularly limited. For example, it can be set to 600-1350 degreeC. In the present invention, since the binder is an inorganic material, the shape of the molded body is maintained without breaking even in the firing step.

  As in the past, when an organic binder such as polyvinyl alcohol (PVA) was used, the organic binder was decomposed in the firing step, and the shape of the molded body could not be maintained, and the shape collapsed and could not be fired. When an inorganic binder is used as in the present invention, firing can be performed without causing shape collapse.

[3] Firing body The fired body of the present invention includes (1) a powder layer forming step of forming a powder layer having a predetermined thickness using ceramic raw materials, and (2) spraying a liquid on a predetermined area of the powder layer. A method for manufacturing a fired body in which the steps are repeated in order, forming a formed body by stacking, and firing the formed body, wherein the ceramic raw material and / or liquid contains an inorganic binder. Obtained by. About each term described in the manufacturing method of a sintered body, the description of [2] the manufacturing method of a sintered body can be applied as it is.

The bulk density of the fired body is not particularly limited, but is preferably 0.5 g / cm ³ or more, more preferably 0.8 g / cm ³ or more, and further preferably 1.0 g / cm ³ or more.
The bulk density of the fired body is usually 2.5 g / cm ³ or less.
By setting the bulk density within this range, the fired body can be practically used for a wide range of applications.
The bulk density is a value calculated by measuring mass and volume.

The porosity of the fired body is not particularly limited. The porosity is preferably 80% or less, more preferably 60% or less, and still more preferably 50% or less.
By setting the porosity within this range, the fired body can be used for a wide range of applications.
The porosity can be calculated from the bulk density and true specific gravity.

  It is preferable that stacking traces remain in the cross section of the fired body and the stacking pitch is 5 mm or less. By setting the lamination pitch within this range, the strength is increased, the appearance is improved, and the dimensional accuracy is increased.

  Hereinafter, the present invention will be described more specifically with reference to examples.

1. Examination of various inorganic binders <Experimental Examples 1-5>
5 parts by mass of various inorganic binders are added to a raw material preparation system of 50 parts by mass of molocite and 50 parts by mass of Masui feldspar, and a molded article (laminated model) is 5 cm square and 1 cm thick with a commercially available 3D printer ProJet160 (manufactured by 3D Systems). ) Was shaped and fired at 600 ° C. Then, it was confirmed whether the shape of the molded body could be maintained.
The conditions and results of Experimental Examples 1 to 5 are shown in Table 1. The evaluation is as follows. Experimental examples 2 to 5 are examples, and experimental example 1 is a reference example.
○: The shape can be maintained.
X: The shape cannot be maintained.

  From the results shown in Table 1, in the case of Experimental Examples 2 to 5, the shape could be maintained even when fired at 600 ° C. These experimental examples were confirmed to be suitable for the production of a sintered body by an additive manufacturing method. From this result, it was found that when an inorganic binder is used, the shape can be maintained even if the molded body is sintered.

2. Examination of Density of Molded Body <Experimental Examples 6 to 11>
5 parts by mass of an inorganic binder (sodium silicate) was added to a raw material preparation system of 50 parts by mass of molocite and 50 parts by mass of Masui feldspar, and a molded body (5 cm square, 1 cm thick) was modeled using a simple additive manufacturing apparatus. . The bulk density of these molded bodies was measured. And these molded objects were baked at 600 degreeC and it was confirmed whether the shape maintenance of a molded object was possible.
The conditions and results of Experimental Examples 6 to 11 are shown in Table 2. The evaluation is as follows. Experimental examples 6 to 11 are examples.
A: The shape can be maintained. The handleability of the molded body is also very good.
○: The shape can be maintained. The handleability of the molded product is slightly poor.
Δ: Shape maintenance is slightly difficult.

  The conditions and results of Experimental Examples 6 to 11 are shown in Table 2.

From the results shown in Table 2, it was confirmed that in the case of Experimental Examples 7 to 11, the shape can be maintained and is suitable for the additive manufacturing method. In Experimental Example 6, it was confirmed that it was suitable for the additive manufacturing method depending on the application.
Further, from this result, it was confirmed that the sintered state at 600 ° C. was particularly good when the bulk density of the compact was 1.2 g / cm ³ or more. Furthermore, when the bulk density of the compact was 1.5 g / cm ³ or more, it was confirmed that the sintered state at 600 ° C. was very good.

3. Examination of curing accelerator <Experimental Examples 12 to 16>
5 parts by mass of sodium silicate and 5 parts by mass of various curing accelerators are added to a raw material blending system of 50 parts by mass of molocite and 50 parts by mass of Masui feldspar, and a commercial 3D printer ProJet160 (manufactured by 3D Systems) 5 cm square, 1 cm thick The molded body hardness was measured with a TYPE A rubber hardness meter in accordance with JIS K6253A ISO 7619A.

  The conditions and results of Experimental Examples 12 to 16 are shown in Table 3. Experimental examples 12 to 16 are examples.

  From the results in Table 3, it was confirmed that the hardness of the molded bodies of Experimental Examples 12 to 16 was practical as a molded body of the additive manufacturing method. It was confirmed that Experimental Examples 13 to 16 using the curing accelerator were particularly excellent in shape retention. From these results, it was confirmed that aluminum tripolyphosphate, zinc oxide, aluminum hydroxide, and alum are extremely effective as a curing accelerator.

4). Appearance observation after glazing <Experimental Examples 17-18>
5 parts by mass of sodium silicate or 5 parts by mass of polyvinyl alcohol (PVA) are added to a raw material preparation system of 50 parts by mass of molocite and 50 parts by mass of Masui feldspar, and 5 cm square by a commercially available 3D printer ProJet160 (manufactured by 3D Systems), A shaped body having a thickness of 1 cm was shaped, and after shaping, the surface of the shaped body was glazed. And the external appearance was confirmed visually.

The conditions and results of Experimental Examples 17 to 18 are shown in Table 4. The evaluation is as follows. Experimental example 18 is an example. Experimental example 17 is a comparative example.
○: Appearance is good.
X: Appearance is poor.

  From the results in Table 4, the appearance of Experimental Example 18 using sodium silicate was good. On the other hand, the appearance of Experimental Example 17 using PVA was poor, and it was confirmed that a separate degreasing step was required to use PVA. Thus, it was confirmed that the use of an inorganic binder was also more effective than the case of using an organic binder for glazing.

5. Examination of bending strength of fired body <Experimental Examples 19 to 22>
5 parts by mass of sodium silicate is added to a raw material preparation system of 50 parts by mass of molocite and 50 parts by mass of Masui feldspar, and a molded product of 1 cm × 10 cm and 1 cm in thickness is formed with a commercially available 3D printer ProJet160 (manufactured by 3D Systems). After shaping, it was fired at 1220 ° C. And the relationship between the bulk density and bending strength of the fired body was examined.

  The conditions and results of Experimental Examples 19 to 22 are shown in Table 5. Experimental examples 19 to 22 are examples.

From the results shown in Table 5, it was confirmed that when the bulk density of the fired body was 1.1 g / cm ³ or more, the bending strength of the fired body was sufficient when used as a practical product.

6). Examination of stacking pitch <Experimental Examples 23 to 26>
5 parts by mass of sodium silicate is added to a raw material preparation system of 50 parts by mass of molocite and 50 parts by mass of Masui feldspar, and a molded product of 1 cm × 10 cm and 1 cm in thickness is formed with a commercially available 3D printer ProJet160 (manufactured by 3D Systems). After shaping, it was fired at 1220 ° C. Then, the dimensional accuracy and appearance of the fired body were confirmed. In the production of the molded body, the stacking pitch was 0.1 mm (Experimental Example 23), 0.5 mm (Experimental Example 24), 1.0 mm (Experimental Example 25), and 5 mm (Experimental Example 26), respectively. Experimental examples 23 to 26 are examples.

  As a result, as the stacking pitch decreases, that is, in the order of 5 mm (Experimental example 26), 1.0 mm (Experimental example 25), 0.5 mm (Experimental example 24), 0.1 mm (Experimental example 23), It was confirmed that the dimensional accuracy was improved. Further, as the stacking pitch becomes smaller, that is, in the order of 5 mm (Experimental example 26), 1.0 mm (Experimental example 25), 0.5 mm (Experimental example 24), and 0.1 mm (Experimental example 23), It was confirmed that it would improve.

7). Effects of Examples When the ceramic raw materials of this example are used, practical ceramics and ceramic products can be obtained without causing shape collapse even by firing at 600 ° C. or higher.
Moreover, according to the manufacturing method of the present embodiment, a ceramic or ceramic product having a high degree of freedom in shape using the additional manufacturing method can be obtained.
The fired body of this example is useful as a ceramic or ceramic product.
In addition, this invention is not limited to the Example demonstrated with the said description and drawing.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used for three-dimensional modeling by an additive manufacturing technique (3D printer) using ceramic materials.

DESCRIPTION OF SYMBOLS 1 ... Powder layer 3 ... Base 5 ... Head 7 ... Liquid (modeling liquid)
9 ... Molded body 11 ... Hot layer

Claims (7)

  A ceramic raw material for producing a fired body by an additive production method, characterized by containing an inorganic binder.   The ceramic raw material according to claim 1, further comprising a curing accelerator that accelerates the curing of the inorganic binder.   The ceramic raw material according to claim 1 or 2, wherein the inorganic binder contains silicate. (1) A powder layer forming step of forming a powder layer having a predetermined thickness using ceramic raw materials, and (2) a spraying step of spraying a liquid on a predetermined region of the powder layer are sequentially repeated and laminated to form a compact. A method for producing a fired body that is formed and fires the molded body,
The method for producing a fired body, wherein the ceramic raw material and / or the liquid contains an inorganic binder. (1) A powder layer forming step of forming a powder layer having a predetermined thickness using ceramic raw materials, and (2) a spraying step of spraying a liquid on a predetermined region of the powder layer are sequentially repeated and laminated to form a compact. A method for producing a fired body that is formed and fires the molded body,
A fired body obtained by a method for producing a fired body in which the ceramic raw material and / or the liquid contains an inorganic binder. The sintered body according to claim 5, wherein the bulk density is 1.0 g / cm ³ or more.   The fired body according to claim 5 or 6, wherein a stacking trace remains in a cross section, and a stacking pitch is 5 mm or less.

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