KR20210015498A - Ceramic Materials with open-cell structures prepared by 3D printing and hydration-setting, and Manufacturing method of the same - Google Patents

Abstract

The present invention relates to a ceramic molded body obtained by water-curing an output of an open-cell structure manufactured by using 3D printing, and a method for manufacturing the same. More specifically, the present invention relates to a non-sintering method ceramic molded body, in which a tricalcium silicate powder is used as a 3D printing composition for printing, and the output has secured durability and strength by hydration reaction.

Description

Ceramic materials with open-cell structures prepared by 3D printing and hydration-setting, and Manufacturing method of the same}

The present invention relates to a ceramic molded body in which an output of an open-cell structure manufactured using 3D printing is hydro-cured and a method for manufacturing the same, and in more detail, a composition based on tricalcium silicate powder is used as a main component. The present invention relates to a non-sintering ceramic molded body and a method of manufacturing the same by outputting an open-cell structure output and securing durability and strength by hydrocuring the output.

Ceramics with open-cell structure or lattice structure have excellent light weight, internal fluidity, and shock energy absorption ability based on the intrinsic properties of ceramics such as thermal stability, high strength, and chemical resistance. In contrast, since it can express high specific surface area, light weight, and reflux function, it is used for separation, catalyst support, filter, electrode material, insulating material, scaffold, and the like.

Porous ceramics can be manufactured by using a template or by foaming, molding, or direct molding methods, among which 3D printing technology is an optimal process method capable of directly molding complex and fine shapes. Ceramic 3D printing technology has progressed relatively slowly due to factors such as drying, degreasing, and sintering processes and the need for post-processing, but attempts to overcome this have been started recently. Since ceramics based on powder materials are accompanied by deformations such as shrinkage in drying and sintering steps after molding, there is a need for technology development to solve this problem.

SiO₂, C3S)는 아래 식 1의 수화반응에 의해 경화되어 강도를 발현할 수 있어 포틀랜드 시멘트와 MTA 계 근관충전재의 주성분으로 사용되고 있다.Meanwhile, tricalcium silicate (3CaO)

SiO ₂ , C3S) can be hardened by the hydration reaction of Equation 1 below to develop strength, so it is used as a main component of Portland cement and MTA-based root canal filler.

[Equation 1]

SiO₂) + 6H₂O → 3CaO

2SiO

3H₂O + 3Ca(OH)₂ 2(3CaO

SiO ₂ ) + 6H ₂ O → 3CaO

2SiO

3H ₂ O + 3Ca(OH) ₂

However, while the C3S has a low heat of hydration, a long curing time is required, so the curing time should be shortened if necessary, and evaluation and supplementation of the deformation occurring according to the curing conditions are required.

Korean Patent Publication No. 2010-0037979 Korean Patent Publication No. 2015-0131319

SiO₂, C3S)의 수화반응에 의한 경화 속도를 향상시킬 수 있는 방법을 알아내고, 본 발명을 완성하게 되었다.In the present invention, as a result of intensive research and examination in order to solve the above problems, the deformation rate of the molded body formed of the powder-based ceramic is not large, and tricalcium silicate (3CaO)

SiO ₂ , C3S) found a method to improve the curing rate by the hydration reaction, and completed the present invention.

Therefore, it is an object of the present invention to exhibit excellent numerical stability because the deformation rate of the molded article is not large, and to secure high durability and high strength properties within a fast reaction time by improving the hydration reaction rate in preparing a composition for 3D printing based on C3S. It is to provide a ceramic molded body in which the output of an open cell structure manufactured by using 3D printing capable of being hydraulically cured.

On the one hand, the present invention

It provides a ceramic molded article obtained by hydro-curing the output of an open-cell structure prepared by 3D printing a composition containing tricalcium silicate powder.

On the other hand, the present invention

(i) preparing a composition for 3D printing comprising tricalcium silicate powder, a binder, and a medium; And

(ii) A step of producing a ceramic molded body by outputting the composition in an open-cell structure form using a 3D printer and hydrocuring the output output; including, manufacturing a hydrocurable ceramic molded body using 3D printing Provides a way.

The ceramic molded body according to the present invention uses tricalcium silicate powder as a composition for 3D printing and is cured by a hydration reaction, so that a ceramic molded body capable of securing durability and strength without undergoing processes such as degreasing and sintering can be manufactured. .

In addition, since the manufacturing method according to the present invention uses a hydrocuring process, it does not require high temperatures required in the heat treatment process for degreasing and sintering, so it is not only economical, but also can be compared with the deformation problem occurring in the thermal curing process. The degree of deformation due to the curing process is small, and the numerical stability is excellent.

1 is a photograph showing a ceramic molded body obtained by hydro-curing the output of an open cell structure manufactured using 3D printing according to the present invention.
2 is a photograph showing a crack occurring on the surface of the ceramic formed body and the interlayer filament surface according to the comparative example of the present invention.
FIG. 3 is a graph showing the expansion strain generated when the ceramic formed body is hydraulically cured according to an embodiment and a comparison of the present invention.
4 is a photograph showing the degree of deformation occurring in the process of drying and sintering a ceramic formed body according to a comparative example of the present invention.
5 is a graph showing the compressive strength of a ceramic formed body according to an embodiment of the present invention.
6 is a graph showing compressive strength according to porosity according to an embodiment of the present invention.
7 is a photograph showing the output before hydrocuring (left) molded according to an embodiment of the present invention and the ceramic molded body (right) hydrocured under 80°C and 80% humidity conditions.

Hereinafter, the present invention will be described in more detail.

A method of manufacturing a hydrocurable ceramic molded body using 3D printing according to an embodiment of the present invention,

(i) preparing a composition for 3D printing comprising tricalcium silicate powder, a binder, and a medium; And

(ii) And producing a ceramic molded body by outputting the composition in an open-cell structure using a 3D printer, and hydrocuring the output.

In one embodiment of the present invention, instead of using the tricalcium silicate powder alone in step (i), a mixed powder obtained by mixing tricalcium silicate (C3S) and tricalcium aluminate (C3A) may be used.

SiO₂, C3S)를 주원료로 사용하여, 고온에서의 소결과정을 필요로 하지 않으므로 간단한 공정 단계 및 시간, 비용 감소 효과를 나타낼 수 있으며, 성형체의 변형률을 최소화할 수 있다.In the present invention, tricalcium silicate (3CaO), which can be cured by a hydration reaction to exhibit high strength properties.

SiO ₂ , C3S) is used as the main raw material, and since it does not require a sintering process at high temperature, it can show a simple process step, time and cost reduction effect, and can minimize the strain of the molded body.

Al₂O₃)를 혼합하여 사용하는 것을 특징으로 한다. 트리칼슘알루미네이트는 아래 식 2와 같이 수화반응 속도가 빨라 성형체의 내구성 유지에 기여할 수 있는 장점이 있으나, 강도 향상 효과는 없다.However, the tricalcium silicate takes a long time to cure, and in order to secure durability and shorten the total curing time in the initial curing step, tricalcium aluminate (3CaO)

Al ₂ O ₃ ) is characterized in that it is used by mixing. Tricalcium aluminate has the advantage of contributing to maintaining the durability of the molded body due to the fast hydration reaction rate as shown in Equation 2 below, but there is no effect of improving strength.

[Equation 2]

Al₂O₃)+6H₂O→ 3CaO

Al₂O₃

6H₂O2(3CaO

Al ₂ O ₃ )+6H ₂ O→ 3CaO

Al ₂ O ₃

6H ₂ O

Therefore, through the manufacturing method according to the present invention, a ceramic molded body capable of securing durability and strength within a fast reaction time can be manufactured by using a powder obtained by mixing tricalcium silicate and tricalcium aluminate as a 3D printing composition.

In one embodiment of the present invention, the tricalcium silicate (C3S) and tricalcium aluminate (C3A) are preferably mixed in a blending ratio of 50:50 to 70:30.

When the C3A is used in excess of 50% of the blending ratio, it is difficult to secure numerical stability due to a large expansion rate, and since it contains a relatively small amount of C3S, the ceramic molded body cannot exhibit high strength characteristics. In addition, when the C3A is used at a blending ratio of less than 30%, it is difficult to secure initial durability during the process of completing the hydro-curing step of the ceramic molded body, so that the shape cannot be maintained, and cracks may occur between the layers or the surface of the output due to the water function. have. Defects caused by an increase in the content of C3S can be corrected by the hydration method and design of the printout, but the C3S and C3A are preferably used in the above range.

The tricalcium silicate (C3S) and tricalcium aluminate (C3A) are preferably powders having an average particle diameter of about 0.05 to 5 µm, but are not limited thereto.

In one embodiment of the present invention, the composition for 3D printing includes the mixed powder of C3S and C3A, a binder, and a media.

The mixed powder is preferably included in 45 to 80% by weight based on 100% by weight of the total composition, and the binder is preferably included in 5 to 30% by weight, and the medium is included in 10 to 30% by weight. It is desirable.

It is preferable to use a polyethylene glycol (PEG) series as the binder, and PEG 500, PEG 1000, PEG 4000, etc. may be used, but the present invention is not limited thereto.

The medium is preferably polyalkylene glycol, specifically, polypropylene glycol (PPG), and PPG 400, etc., but is not limited thereto.

In one embodiment of the present invention, it is preferable to use a filament extrusion method (FDM type) 3D printer as a 3D printer for molding the composition, but is not limited thereto.

In addition, it is preferable to output the composition in the form of a cube-type open-cell structure using such a 3D printer. In this case, the open cell structure may be a mesh type, a scaffold type, or the like, and the open-pore structure in which all holes are connected is not limited thereto.

The ceramic formed body according to the present invention is characterized in that it is non-sintered and hardened through a hydraulic hardening process. Therefore, since it does not require a high temperature such as a heat treatment process for degreasing and sintering, it is not only economical, but also has excellent numerical stability due to a small degree of deformation due to the water hardening process compared to the deformation problem occurring during the heat hardening process. In addition, the molded article according to the present invention uses C3S powder, but by using a mixed powder of C3A, it is possible to shorten the curing time of the molded article, and by securing durability in the initial curing process, it is possible to prevent the occurrence of cracks between layers or surfaces. .

In one embodiment of the present invention, the hydrocuring process may be performed by immersing or immersing the 3D printer output of the composition in distilled water, but is not limited thereto.

For example, the output may be cured by contacting moisture in the atmosphere, and a hydrocuring process may be performed under an atmosphere in which humidity is maintained (humid).

Since the ceramic molded body according to the manufacturing method of the present invention exhibits high strength characteristics and excellent numerical stability, it can be used as a scaffold, catalyst support, ceramic filter, dental, surgical implant, and the like.

A ceramic molded article obtained by hydrocuring the output of an open cell structure manufactured using 3D printing according to an embodiment of the present invention,

It is characterized in that it is a ceramic molded body in which the output of an open-cell structure manufactured by 3D printing a composition containing tricalcium silicate powder is hydro-cured.

In one embodiment of the present invention, the composition may be tricalcium silicate powder, or a mixed powder of tricalcium silicate and tricalcium aluminate may be used.

In addition, the composition may further include a binder, a medium, etc. in addition to the powder.

In one embodiment of the present invention, when the tricalcium silicate (C3S) and tricalcium aluminate (C3A) are mixed in a blending ratio of 50:50 to 70:30, the output filament has a diameter in the range of 400-550 μm. The hydraulic specimen of the output having a porosity of less than 50% is preferably characterized in that the compressive strength is 5 to 22 MPa, more preferably 12.6 to 19.3 MPa. The compression strength of the hydraulically cured specimen of the output having a porosity of 65% or more of the molded product having a diameter of the output filament in the range of 250-400 μm is 2 to 20 MPa.

Hereinafter, the present invention will be described in more detail by examples. These examples are for illustrative purposes only, and it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1: Preparation of 3D printing composition

Tricalcium silicate (C3S) powder having an average particle diameter of 3 µm is included in an amount of 50% by weight relative to 100% by weight of the total composition, and PEG1000 is included in 5 to 10% by weight as a binder, and PPG is 40 to 45% by weight as a medium. A composition for 3D printing was prepared, including %.

Example 2: Preparation of 3D printing composition

A mixed powder was prepared by using tricalcium silicate (C3S) having an average particle diameter of 3 μm and tricalcium aluminate (C3A) having an average particle diameter of 3 μm at a powder mixing ratio of 50:50. At this time, the mixed powder contained 50% by weight relative to 100% by weight of the total composition. In addition, a composition for 3D printing was prepared by including 5 to 10% by weight of PEG1000 as a binder and 40 to 45% by weight of PPG as a medium relative to 100% by weight of the total composition.

Example 3: Preparation of 3D printing composition

A composition for 3D printing was prepared in the same manner as in Example 2, except that the powder mixing ratio of C3S and C3A was 65:35 instead of 50:50.

Example 4: Preparation of 3D printing composition

A composition for 3D printing was prepared in the same manner as in Example 2, except that the powder mixing ratio of C3S and C3A was set to 70:30 instead of 50:50.

Example 5: Preparation of open-cell structured hydraulic ceramic molded body using 3D printing

The composition for 3D printing prepared in Example 1 was output in the form of a 10×10×9mm cube-type mesh using a filament extrusion method (FDM type) 3D printer, and the output was immersed in distilled water to cure. A ceramic molded body having an open cell structure was prepared (output conditions: nozzle size 0.4 mm, interlayer thickness 0.4 mm, extrusion amount 2.5%, molding speed 25 mm/sec). At this time, the total curing time took about 18 hours.

Example 6: Preparation of open-cell structured hydraulic ceramic molded body using 3D printing

The composition for 3D printing prepared in Example 2 was output in the form of a 10×10×9mm cube-type mesh using a filament extrusion method (FDM type) 3D printer, and the output was immersed in distilled water and cured to open cell A ceramic molded body having a structure was prepared (output condition: nozzle size 0.4 mm, interlayer thickness 0.4 mm, extrusion amount 2.5%, molding speed 25 mm/sec). At this time, the initial curing time took about 15 minutes, but finally, the curing step was maintained for 18 hours.

Example 7: Preparation of open-cell structured hydraulic ceramic molded body using 3D printing

A ceramic molded body having an open cell structure was manufactured by performing the same method as in Example 6, except that the composition prepared in Example 3 was used instead of the composition prepared in Example 2. At this time, the curing time took about 15 minutes, but finally, the curing step was maintained for 18 hours.

Example 8: Preparation of a hydrocurable ceramic molded body having an open cell structure using 3D printing

A ceramic molded body having an open cell structure was manufactured by performing the same method as in Example 6, except that the composition prepared in Example 4 was used instead of the composition prepared in Example 2. At this time, the curing time took about 15 minutes, but finally, the curing step was maintained for 18 hours.

Comparative Example 1: Preparation of 3D printing composition

A composition for 3D printing was prepared in the same manner as in Example 2, except that the powder mixing ratio of C3S and C3A was set to 80:20 instead of 50:50.

Comparative Example 2: Preparation of 3D printing composition

Contains 50% by weight of tricalcium aluminate (C3A) having an average particle diameter of 3 μm compared to 100% by weight of the total composition, 5 to 10% by weight of PEG1000 as a binder, and 40 to 45% by weight of PPG as a medium A composition for 3D printing was prepared, including %.

Comparative Example 3: Preparation of a hydrocurable ceramic molded body having an open cell structure using 3D printing

A ceramic molded body having an open cell structure was manufactured by performing the same method as in Example 6, except that the composition prepared in Comparative Example 1 was used instead of the composition prepared in Example 1. At this time, it was confirmed that cracks appeared on the surface within 3 minutes during curing.

Comparative Example 4: Preparation of open-cell structured hydraulic ceramic molded body using 3D printing

A ceramic molded body having an open cell structure was manufactured in the same manner as in Example 6, except that the composition prepared in Comparative Example 2 was used instead of the composition prepared in Example 1. At this time, it was confirmed that cracks appeared on the surface within 3 minutes during curing.

Comparative Example 5: Preparation of a ceramic molded body having an open cell structure using 3D printing

Aqueous composition for 3D printing including 50% by weight of alumina paste, 0.8 to 2% by weight of PVA as a binder, 1 to 5% by weight of PEG400 as a medium, and distilled water based on 100% by weight of the total composition Was prepared.

The composition was printed in a mesh form of 30×30×1.5mm using a filament extrusion method (FDM type) 3D printer, dried, and sintered by heat treatment at about 1,450°C (output conditions were the same as in Example 6). Did).

Experimental Example 1: Molding and curing test

The ceramic molded articles of the open cell structure prepared in Examples 4 to 6 and Comparative Examples 3 to 4 are summarized in Table 1 below.

C3S:C3A 100:0
(Example 5) 80:20
(Comparative Example 3) 70:30
(Example 4) 50:50
(Example 6) 0:100
(Comparative Example 4) Printout -

Luggage
(Hardened)

Cured state
(Minutes, min) 18 hours of final curing 18 hours of final curing Initial hardening 15 minutes
(Last 18 hours) Initial hardening 15 minutes
(Last 18 hours) Initial hardening 15 minutes
(Last 18 hours) crack Crack within 1 minute Within 3 minutes
Surface crack - - -

Referring to Table 1, when C3A is included in an amount of 30% or more compared to 100% of the total mixed powder, it is confirmed that curing is performed within 15 minutes of initial curing to 18 hours of final curing through Examples 4, 6 and Comparative Example 4. I did. In the present invention, initial curing is defined as a state in which the output printed by the 3D printer has a degree of durability that can be moved without damage. Due to the nature of the hydrocuring material, the longer the hydration time, the higher the strength is. need. In the present invention, a curing time of 12 hours or more is required in order to exhibit a compressive strength of 3 MPa or more of a molded filament having a diameter of 350 μm and a porosity of 70%. Accordingly, a more preferable range is 12 hours to 18 hours.

In addition, when containing 80% or more of C3S compared to 100% of the total mixed powder and 30% or less of C3A compared to the total mixed powder, it was confirmed that cracks occurred on the surface of the interlayer filament (a) and the surface of the molded body (b) during water curing. (See Fig. 2). In addition, as the water curing time continued, it was difficult to maintain the shape of the filament (see FIG. 2 (c)).

Through this, it was found that it is preferable to include C3A in an amount of less than 30% compared to 100% of the total mixed powder.

Experimental Example 2: Strain (numerical stability) test

Three samples of ceramic molded bodies prepared by the methods of Examples 6 to 8 and Comparative Example 4 were prepared, respectively, to check whether they were deformed after hydrocuring, and the average value results are shown in Tables 2 and 3 below.

division Sample shaft x y z Example 6 #One 10.78 10.82 9.12 #2 10.87 10.86 9.09 #3 10.82 10.80 9.13 Average 10.82(±0.04) 10.83(±0.06) 9.12(±0.02) Example 7 #One 10.64 10.61 9.56 #2 10.59 10.72 9.19 #3 10.58 10.64 9.21 Average 10.66(±0.03) 10.66(±0.06) 9.32(±0.21) Example 8 #One 11.0 11.01 9.11 #2 11.1 11.09 9.12 #3 11.08 11.09 9.11 Average 11.06(±0.05) 11.06(±0.04) 9.11(±0.00) Comparative Example 4 #One 11.90 11.87 9.23 #2 11.97 11.96 9.30 #3 11.94 11.95 8.92 Average 11.93(±0.04) 11.93(±0.05) 9.15(±0.20)

3 and Table 2, expansion and deformation occurred during the hydrocuring process, and in particular, the x and y axes of the molded body of Comparative Example 4 were deformed by about 20%, whereas the molded bodies of Examples 6 to 8 were x and y axes. It was confirmed that the strain was relatively low with less than about 10% and less than about 5% of the z-axis (see FIG. 3 and Table 2). Among them, in the case of Example 7, the x- and y-axis strain was less than 7%, showing the lowest expansion strain.

In addition, in order to compare the degree of deformation due to hydrocuring and the degree of deformation due to the sintering process, the deformation rates of the molded articles of Example 6 and Comparative Example 5 were compared (see FIG. 4).

Referring to FIG. 4, the x and y-axis lengths of the molded body of Example 6 are about 31 mm, whereas the x and y-axis lengths of the molded body of Comparative Example 5 that have undergone the sintering step are about 27 mm, compared to the hydraulic process. It was confirmed that the shrinkage deformation of 25% occurred. Therefore, by using the mixed powder of C3S and C3A according to the present invention and hydraulically curing it, the degree of shrinkage deformation is small compared to sintering by heat treatment, so that numerical stability can be expected.

Experimental Example 3: Compressive Strength Test

In order to check the degree of deformation of the strength according to the mixing powder ratio of the ceramic formed body according to the present invention, the compressive strength of the ceramic formed bodies prepared in Examples 6 to 8 and Comparative Example 4 was tested, and the results are shown in FIG. .

Referring to FIG. 5, the ceramic compact of Comparative Example 4 composed of only C3A powder has a compressive strength of 5.6 MPa, whereas the ceramic compact of Examples 6 to 8 composed of a mixed powder of C3S and C3A each has a compressive strength of 12.6 MPa. , 19.3 MPa, 14.2 MPa was confirmed to be excellent.

Through this, the higher the mixing ratio of C3A, the shorter the curing time, but the strength is very weak, so it is preferable to use a mixed powder of C3S and C3A. In this case, it was found that the mixing ratio of C3S and C3A is preferably 70:30 to 50:50 because it is difficult to maintain the shape in the curing step (see Table 1).

Experimental Example 4: Compressive strength test according to porosity

In order to check the compressive strength according to the filament thickness and pore size of the ceramic molded body according to the present invention, a composition of 65:35 of C3S and C3A was tested for the compressive strength of the ceramic molded body by adjusting the pore size. Is shown in FIG. 6.

In order to control the pore size of the 10x10x10 porous body to which the 50%-Infill mode was applied, the order (stacking direction) of the filaments was adjusted to 1x1, 2x2, and 1x3. The diameter of the output filament is determined by the amount of extrusion (the “top” of the printed image), and the smaller the layer spacing, the larger the lamination line width and the line spacing occurred.

By changing the lamination direction (or lamination order), the pore size could be adjusted to ~700 μm, and the porosity could be adjusted to ~70% by reducing the diameter of the filament (adjusting the extrusion amount). It was confirmed that the compressive strength of the molded body having an open-cell structure was different depending on the porosity (see Table 3).

Lamination condition 1x1 2x2 1x3 design

Printout

(Top)

(section)

Output condition Nozzle inner diameter (mm) 0.4 0.4 0.4 Extrusion amount (%) 2 1.5 1.5 Stacking interval (μm) 400 350 350 Hydrogenated specimen Output diameter (μm) 500 400 400 Lamination line width (μm) 500 400 400 Interlayer spacing (μm) 250 450 700 hole size 250x250 400x450 400x700 Porosity (%) 48.1 70.7 69.7

Experimental Example 5: Filament diameter and layer spacing control test

In order to confirm the change in pore size due to the adjustment of the filament diameter and the layer spacing of the ceramic molded body according to the present invention, a 65:35 composition of C3S and C3A was tested by adjusting the diameter and the layer spacing.

By controlling the amount of extrusion, it was possible to control the diameter of the output filament, and since the lower the lamination interval, the linear line width and line spacing were affected, so it was possible to control the pore size. By adjusting the output thickness and the lamination interval, printing with a porosity of ~73% was possible (see Table 4).

Extrusion conditions (change of extrusion amount) 1.5 1.2 1.0 Top

section

Output condition Nozzle inner diameter (mm) 0.4 0.4 0.4 Extrusion amount (%) 1.5 1.2 1.0 Stacking interval (μm) 350 340 300 Hydrogenated specimen Output diameter (μm) 390 380 360 Lamination line width (μm) 410 450 480 Line spacing (μm) 470 330 270 Interlayer spacing (μm) 430 500 450 hole size 470x430 330x500 270x450 Porosity (%) 70.7 71.6 73.2

Experimental Example 6: Pore size control test using the filling function

In order to confirm the change in pore size using the filling function of the ceramic formed body according to the present invention, the change in pore size was tested through the filling function of a composition of 65:35 of C3S and C3A.

The line spacing was adjusted by lowering the infill amount for pore molding of 400 μm or less.

Regardless of the output diameter, if the stacking interval is excessively reduced, the precision of the molded product itself is deteriorated due to interlayer deformation, so the difference between the output diameter and the interlayer thickness was considered not to be large.

By narrowing the lamination interval, the pore size was prevented from being excessively expanded, and it was confirmed that moldings having different pore sizes but similar porosity could be manufactured (see Tables 5 and 6).

Infill Mode
55 50 48 45 Top

section

Output condition Nozzle inner diameter (mm) 0.4 0.4 0.4 0.4 Extrusion amount (%) 1.0 1.0 1.0 1.0 Stacking interval (μm) 325 275 275 250 Hydrogenated specimen Output diameter (μm) 350 350 350 350 Lamination line width (μm) 420 450 430 400 Line spacing (μm) 260 330 400 430 Interlayer spacing (μm) 420 400 400 300 hole size 260x420 330x400 400x400 430x300 Porosity (%) 67.5 70.3 70.3 70.2

Nozzle: 0.4, extrusion volume 1.5%
Output diameter: 390
Interlayer thickness 0.35 Nozzle: 0.4, extrusion volume 1.0%
Output diameter: 350
Interlayer thickness 0.275 Nozzle: 0.4, extrusion volume 1.0%
Output diameter: 350
Interlayer thickness 0.25 [Output shape indicated by the difference in print diameter-thickness between layers]

Experimental Example 7: Pore size control test by changing the output thickness of the filling function

In order to confirm the change in pore size due to the change in the output thickness of the filling function of the ceramic molded body according to the present invention, the composition of the 65:35 ratio of C3S and C3A was tested for the change in pore size by changing the output thickness.

The nozzle was replaced with 320 μm to reduce the filament molding diameter to 300 μm to secure pore volume.

Through this, it was confirmed that the smaller the infill value, the wider the line spacing, and showed a change in porosity (see Table 7).

Infill Mode
48 45 45 42 Top

section

Output condition Nozzle inner diameter (mm) 0.32 0.32 0.32 0.32 Extrusion amount (%) 1.0 1.0 1.0 1.0 Stacking interval (μm) 250 250 275 250 Hydrogenated specimen Output diameter (μm) 300 300 300 300 Lamination line width (μm) 350 360 360 350 Line spacing (μm) 290 290 320 400 Interlayer spacing (μm) 330 390 410 400 hole size 290x330 290x390 320x410 400x400 Porosity (%) 66.8 67.1 69.6 69.1

As described above, specific parts of the present invention have been described in detail, and it is obvious that these specific techniques are only preferred embodiments and are not intended to limit the scope of the present invention for those of ordinary skill in the art to which the present invention belongs. Do. Those of ordinary skill in the art to which the present invention belongs will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

Therefore, it will be said that the substantial scope of the present invention is defined by the appended claims and their equivalents.

Claims (8)

A ceramic molded article obtained by hydro-curing the output of an open-cell structure manufactured using 3D printing with a composition containing tricalcium silicate powder. The ceramic molded article according to claim 1, wherein the composition comprises a mixed powder of tricalcium silicate and tricalcium aluminate, and the output of an open-cell structure manufactured using 3D printing is hydrocured. The method of claim 2, wherein the tricalcium silicate and tricalcium aluminate powder are mixed at a blending ratio of 50:50 to 70:30, and the output of an open-cell structure manufactured using 3D printing is hydrocured. Ceramic molded body (i) preparing a composition for 3D printing comprising tricalcium silicate powder, a binder, and a medium; And
(ii) outputting the composition in the form of an open-cell structure using a 3D printer, and hydrocuring the output to produce a ceramic molded body; including, hydrocurable ceramic using 3D printing Method of manufacturing a molded article. The method of claim 4, wherein a mixed powder obtained by mixing tricalcium silicate and tricalcium aluminate at a blending ratio of 50:50 to 70:30 in step (i) is used, using 3D printing. The method of claim 4, wherein the binder is polyethylene glycol (PEG), and the medium is polypropylene glycol (PPG). The method of claim 4, wherein the open-cell structure is in a mesh form or a scaffold form, using 3D printing. The method of claim 5, wherein the composition containing the mixed powder of tricalcium silicate and tricalcium aluminate is cured within 18 hours through a water curing process, and thus exhibits high strength properties without surface cracking, hydrocuring using 3D printing. Method for producing a ceramic molded body.

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