WO2020116568A1 - Procédé de production d'article en céramique, et article en céramique - Google Patents

Procédé de production d'article en céramique, et article en céramique Download PDF

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Publication number
WO2020116568A1
WO2020116568A1 PCT/JP2019/047646 JP2019047646W WO2020116568A1 WO 2020116568 A1 WO2020116568 A1 WO 2020116568A1 JP 2019047646 W JP2019047646 W JP 2019047646W WO 2020116568 A1 WO2020116568 A1 WO 2020116568A1
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WIPO (PCT)
Prior art keywords
component
ceramic article
porous portion
zirconium
powder
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PCT/JP2019/047646
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English (en)
Japanese (ja)
Inventor
良太 大橋
安居　伸浩
齋藤　宏
香菜子 大志万
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キヤノン株式会社
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Priority claimed from JP2019219949A external-priority patent/JP2020093973A/ja
Application filed by キヤノン株式会社 filed Critical キヤノン株式会社
Priority to CN201980080468.7A priority Critical patent/CN113165207B/zh
Publication of WO2020116568A1 publication Critical patent/WO2020116568A1/fr
Priority to US17/331,906 priority patent/US20210309575A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
    • B28B11/04—Apparatus or processes for treating or working the shaped or preshaped articles for coating or applying engobing layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/111—Fine ceramics
    • C04B35/117—Composites
    • C04B35/119—Composites with zirconium oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof

Definitions

  • the present invention relates to a method for manufacturing a ceramics shaped article, and more particularly to a method for manufacturing a ceramics three-dimensional shaped article having a porous structure.
  • the modeling accuracy in the present invention refers to the difference (rate of change) between the dimension of the ceramic article that has undergone the firing process after modeling and the design dimension designated using CAD or the like.
  • a powder bed melting method is used to obtain dense and diverse shaped objects. The high density of the metal shaped article is realized by effectively melting and solidifying the metal powder.
  • porous ceramics are one of the important ceramic members used in various applications. Porous ceramics have excellent heat resistance, chemical resistance, strength characteristics, and light weight. Therefore, by utilizing the fluid (liquid, gas) passage function, various types of filters, separation columns, catalyst carriers, and lightweight structures are used. It is used for materials, heat insulating materials, vacuum chuck members, etc.
  • Non-Patent Document 1 discloses a method for producing a three-dimensional structure by a direct modeling method, in which ceramics having an Al 2 O 3 —ZrO 2 eutectic composition is used to lower the melting point and A technique for reducing the energy required for is disclosed.
  • Non-Patent Document 1 while heating ceramic material powder as a raw material with a heater (preliminary heating), laser light is irradiated to alleviate thermal stress and suppress cracking of the obtained modeled object. Is disclosed. According to this manufacturing method, there is an advantage that a dense ceramic structure can be obtained without shrinkage.
  • part of the ceramic material powder in the portion not irradiated with laser light is melted by preheating with a heater, and the accuracy of the surface boundary of the structure cannot be obtained. For example, to form a fine porous structure. Was difficult.
  • the preheating is stopped by giving priority to modeling accuracy, cracks are formed by rapid cooling after the process as described above, and there is a problem that a porous structure having high strength cannot be obtained. Therefore, it is difficult for such a technique to obtain a ceramics shaped article having a porous structure that achieves both shaping accuracy and mechanical strength.
  • the present invention has been made in view of the above problems, and a method for producing a ceramic article for improving the mechanical strength of a ceramic shaped article having a porous portion, which is produced with high shaping accuracy by making use of the features of the direct shaping method. , And a ceramic article.
  • One aspect of the present invention is a method for manufacturing a ceramic article, comprising: (i) a step of leveling a powder of a metal oxide containing aluminum oxide as a main component to form a powder layer, and (ii) the powder layer. Modeling having a porous portion formed by repeating a step of irradiating an energy beam based on molding data to melt and solidify or sinter the powder, and (iii) the steps (i) and (ii). A step of absorbing a liquid containing a zirconium component in the object, and (iv) heating the shaped article in which the liquid containing the zirconium component is absorbed. In the absorbing step, the porous portion is included. It is characterized in that the liquid is absorbed so that the ratio of the zirconium component in the metal component contained in is not less than 0.3 mol% and not more than 2.0 mol%.
  • Another aspect of the present invention is a method for producing a ceramic article, comprising: (i) irradiating a metal oxide powder containing aluminum oxide as a main component with an energy beam based on modeling data to melt the powder. And a step of solidifying or sintering to form a shaped article having a porous portion, (ii) a step of absorbing a liquid containing a zirconium component in the shaped article formed in the step (i), and (iii) A step of heating the shaped article that has absorbed the liquid containing the zirconium component, wherein the zirconium component in the metal component contained in the porous portion has a ratio of 0.3 mol% or more 2 It is characterized in that the liquid is absorbed so as to be 0.0 mol% or less.
  • Another aspect of the present invention is a ceramic article having a porous part made of a metal oxide containing aluminum oxide as a main component, wherein the zirconium component in the metal component is 0.3 mol in the porous part. % Or more and 2.0 mol% or less.
  • another aspect of the present invention is a ceramic article made of a metal oxide containing aluminum oxide as a main component and having a dense part and a porous part, wherein zirconium is a metal component contained in the porous part. It is characterized in that the proportion of the component is higher than the proportion of the zirconium component in the metal component contained in the dense portion.
  • the present invention it is possible to provide a method for manufacturing a ceramic article having a porous portion that achieves high mechanical strength by using a direct molding method, and a ceramic article.
  • a first aspect of the present invention is a method for producing a ceramic article having a porous portion, comprising: (i) leveling a powder of a metal oxide containing aluminum oxide (Al 2 O 3 ) as a main component to form a powder layer. And (ii) irradiating the powder layer with an energy beam based on modeling data to melt and solidify or sinter the powder, and (iii) the steps (i) and (). ii) Absorbing a liquid containing a zirconium (Zr) component in a shaped product having a porous portion formed by repeating step ii), and (iv) heating the shaped product absorbed with the liquid containing the zirconium component. And a step of absorbing the liquid such that the ratio of the zirconium component in the metal component contained in the porous portion is 0.3 mol% or more and 2.0 mol% or less in the absorbing step. And
  • the present invention is suitable for manufacturing an article using a direct molding method.
  • the mechanical strength of the porous ceramic article can be greatly improved by combining with a powder bed fusion bonding method or a directional energy lamination method (a so-called cladding method) in which a molding material is piled up.
  • FIGS. 1A to 1H A basic molding flow of the powder bed fusion bonding method will be described with reference to FIGS. 1A to 1H.
  • the powder 101 is placed on the base 130, and the roller 152 is used to form the powder layer 102 (FIGS. 1A and 1B).
  • the powder 101 is melted and then solidified to form the solidified portion 103. (FIG. 1C).
  • the stage 151 is lowered to newly form a powder layer 102 on the solidified portion 103 and the unsolidified powder (FIG. 1D).
  • the cladding method will be described with reference to FIGS. 2A to 2C.
  • powder is ejected from a plurality of powder supply holes 202 provided in a cladding nozzle 201, an area where the powder is focused is irradiated with an energy beam 203, and a solidification portion 103 is additionally added to a desired place. Is formed (FIG. 2A), and this step is repeated to obtain a molded article 110 having a desired shape (FIGS. 2B and 2C). Finally, unnecessary parts are removed and the molded object 110 and the base 130 are separated as necessary.
  • the modeled object 110 having various porous structures can be formed by inputting appropriate (three-dimensional) modeling data. it can.
  • a porous portion is formed and a ceramic article having the porous portion can be obtained.
  • the porous portion means a portion having a plurality of open pores having a porosity of 5 vol (volume)% or more, a thickness of the bridge portion of 1 mm or less, and a pore diameter of 50 ⁇ m or more and 1000 ⁇ m or less.
  • the dense portion in the present invention means a portion having a porosity of less than 5 vol (volume)% and a bridge portion having a thickness of 1 mm or more.
  • the porosity refers to the ratio of open pores to the volume of the ceramic article, and does not include closed pores.
  • An open pore is a hole in which a part of the pore is connected to the outside (also called an open pore). Closed pores are pores that are not connected to the outside.
  • the communication hole refers to a hole whose both ends are connected to the outside, and is included in the open pores.
  • the porosity can be measured by the mercury injection method.
  • the bridge portion refers to a structural portion that forms a hole in the porous portion, and the thickness of the bridge portion refers to the shortest distance between the hole and the hole adjacent thereto.
  • FIG. 3 shows an enlarged schematic view of a part of the surface of the porous ceramics 301, which is a ceramics article having a porous portion according to the present invention, in which the cross-sectional shape of the holes can be seen.
  • the cross-sectional shape means the shape of a surface perpendicular to the extending direction of the hole.
  • FIG. 3 shows an example, and the present invention is not limited to these.
  • FIG. 3 shows a hole having a circular cross-sectional shape
  • the hole may have a circular cross-sectional shape of any of a circle, a quadrangle, and a triangle, and holes having a plurality of shapes may be provided in combination.
  • the porosity is the open porosity measured by the mercury injection method as described above.
  • the porosity is the ratio of the volume of the openings 302 to the total volume including the pores of the porous ceramics 301.
  • the porous portion has a plurality of openings each having a pore diameter of 50 ⁇ m or more and 1000 ⁇ m or less.
  • the hole diameter 303 refers to an elliptical (including circular) minor axis diameter (2b) that approximates the contour of the hole. The method for approximating the contour of the hole to an elliptical shape is as follows.
  • the maximum distance (2a) between the contours in the contour of the hole and the area S in the contour of the hole are measured.
  • the major axis diameter 2a and the minor axis diameter 2b are introduced.
  • the pore diameter can be measured using an optical microscope, a scanning electron microscope (SEM), or the like in an arbitrary cross section that is substantially perpendicular to the openings of the ceramic article.
  • the opening period 304, shape, pore diameter 303, porosity, etc. of the porous part can be controlled independently by changing the input molding data.
  • the irradiation energy density by the energy beam is reduced, it is possible to form a porous portion having a random shape.
  • the average pore diameter is the average value of the pore diameters 303 of a plurality of pores in the porous part.
  • the open pores and the closed pores may be regarded as having substantially the same diameter, and the open pores and the closed pores may be measured and calculated without distinction.
  • the average pore diameter of the pores of the porous portion is preferably 50 ⁇ m or more and 1000 ⁇ m or less. The open pores and the closed pores cannot be distinguished only by observing an arbitrary cross section of the ceramic article with an optical microscope or SEM.
  • FIB focused ion beam
  • X-ray CT X-ray computed tomography
  • the hole diameter 303, the opening period 304, and the porosity of the openings 302 of the porous ceramics 301 shown in FIG. 3 will be described.
  • the opening period is 1, when the porosity (vol%) is 5, 10, 20, 30, 40, 50, 60, the pore diameters are 0.25, 0.36, 0.51 and 0.62, respectively. , 0.71, 0.80, 0.87, and the bridge portion thicknesses are 0.75, 0.64, 0.50, 0.38, 0.29, 0.20, and 0.13, respectively.
  • the pore size 303 of the porous part of the present invention may be constant in the direction in which the pores are stretched, or may change midway. Further, one hole may be divided into a plurality of holes on the way. A plurality of openings having different cross-sectional shapes may be combined. In any case, in order to complete the porous portion, it is necessary to remove the unsolidified powder remaining in the pores after the shaping is completed. Therefore, both ends of the hole communicate with the outside.
  • the accuracy in modeling is about several tens of ⁇ m, so if the hole diameter of the holes formed in the porous portion is 50 ⁇ m or less, the uniform hole diameter is Since 303 cannot be obtained and the opening 302 is filled up on the contrary, the porosity may decrease. Further, when the average pore diameter is larger than 1000 ⁇ m, the porous portion does not function as fine pores capable of controlling the flow of gas or liquid, so that it is preferably 1000 ⁇ m or less. Therefore, it is preferable that the average diameter of the openings 302 is 50 ⁇ m or more and 1000 ⁇ m or less. When the porous portion is formed for the purpose of reducing the weight, the preferable pore diameter is not limited to this as long as the desired mechanical strength can be obtained.
  • the microcracks can be reduced and the mechanical strength of the molded article can be improved by absorbing and heating the liquid containing the zirconium component in the microcracks of the ceramic shaped article having a porous structure.
  • the zirconium component adhered to the porous surface was solid-phase diffused over a wide area within the crystal forming the shaped article by heating, and the crystal was recrystallized with the composition containing the zirconium component. It is considered that such a structure enhances the bonding force between the crystal structures of the resulting ceramic article and improves the mechanical strength.
  • the present invention is characterized in that the zirconium component is introduced into the shaped article formed by melting and solidifying the powder with the energy beam. Even if the powder contains a zirconium component in advance, it is not possible to suppress the occurrence of cracks during modeling, so the bond strength between crystal structures is not sufficient, and the effect of the present invention (improvement of mechanical strength ) Cannot be obtained.
  • the porous part and the dense part have different porosities, and the porosity of the porous part is 5% by volume or more, and the porosity of the dense part is less than 5% by volume. is there.
  • the porosity of the porous portion is 5% by volume or more, it is possible to obtain the functions required as a porous material such as heat resistance, light weight, and use as a flow channel.
  • the zirconium component spreads inside the porous portion of the shaped article, and sufficient strength can be obtained.
  • the porosity of the porous portion is preferably 5% by volume or more and 60% by volume or less.
  • the closed pores included in the porous portion do not contribute much to the function improvement of the porous portion. Further, it does not have a function of spreading the zirconium component inside the shaped article. Therefore, from the viewpoint of obtaining sufficient strength, the proportion of closed pores contained in the porous portion is preferably 1% by volume or less. More preferably, it is 0.5% by volume or less.
  • the zirconium component-containing liquid permeates into the shaped article through the openings.
  • the surface area is large, a large amount of zirconium component penetrates as compared with the dense portion.
  • the bridge portion forming the holes in the porous portion is fine and thin, the zirconium concentration has a great influence on the forming accuracy and the mechanical strength.
  • the modeling accuracy and the mechanical strength have a correlation with the Zr content rate, and it has been found that setting the Zr content rate to an appropriate value is preferable in terms of achieving both the modeling accuracy and the mechanical strength.
  • the mechanical strength if the Zr content is low, the degree of improvement in mechanical strength is small, and the possibility that the porous part will be damaged during processing or in the operating environment increases.
  • the ratio of the zirconium component in the metal component forming the metal oxide in the porous portion is 0.3 mol% or more, the mechanical strength practically usable as a ceramic article can be obtained.
  • the modeling accuracy If the content of the zirconium component added to the aluminum oxide as the main component becomes excessive, the melting point of the porous part lowers, so that a portion where the crystal melts occurs when the shaped article in which zirconium is absorbed is heated. As a result, in particular, in the porous body, the fine bridge portion is easily deformed and the modeling accuracy is lost, the opening is blocked, and the porous body does not function as a porous body. Therefore, from the viewpoint of modeling accuracy, it is necessary to control the Zr content in the porous portion more finely than in the dense portion. In the present invention, by setting the ratio of the zirconium component in the metal component forming the metal oxide in the porous portion to 2.0 mol% or less, the shape of the bridge portion can be maintained and sufficient modeling accuracy can be obtained.
  • the ratio of the zirconium component in the metal component constituting the metal oxide in the porous portion is 0.3 mol% or more.2. It should be 0 mol% or less. Further, the ratio of the zirconium component in the metal component forming the metal oxide in the porous portion is preferably 0.3 mol% or more and 1.5 mol% or less.
  • the zirconium component becomes a metal oxide compounded with another metal component to form a zirconia region having an average circle equivalent diameter of 5 ⁇ m or more on the surface or inside of the bridge part.
  • the other metal component for example, a gadolinium component is preferable, the gadolinium component is preferably the same mol or more as the zirconium component, and the zirconia region is preferably a composite metal oxide of zirconium and gadolinium.
  • the method for producing a ceramic article according to the present invention is characterized by having the following four steps (i) to (iv).
  • a powder of a metal oxide containing aluminum oxide as a main component is leveled to form a powder layer.
  • the powder layer is irradiated with an energy beam based on modeling data to melt, solidify, or sinter the powder.
  • a liquid containing a zirconium component is absorbed in a shaped article having a porous portion, which is formed by repeating the above step (i) and the above step (ii).
  • the above-mentioned shaped object that has absorbed the liquid containing the above-mentioned zirconium component is heated.
  • the liquid is absorbed in the absorption step so that the ratio of the zirconium component in the metal component contained in the porous part is 0.3 mol% or more and 2.0 mol% or less.
  • the ratio of the zirconium component in the metal component contained in the porous portion is preferably 0.3 mol% or more and 1.5 mol% or less.
  • the method for producing a shaped article according to the present invention includes a step (i) of forming a powder layer by leveling a powder of a metal oxide containing aluminum oxide as a main component.
  • Aluminum oxide is a general-purpose structural ceramic, and by appropriately sintering or melting and solidifying it, a shaped article with high mechanical strength can be obtained.
  • the metal oxide powder according to the present invention preferably has a zirconium oxide content of less than 0.1 mol %. Further, the ratio of the zirconium component in the metal component contained in the powder of the metal oxide is preferably less than 0.15 mol%.
  • a modeled object having a porous structure that absorbs a zirconium-containing liquid there is a large difference in the zirconium concentration between the crystal part of the modeled object and the microcrack part of the modeled object, so only the microcrack vicinity is selected. Can be melted. As a result, it is possible to suppress the deformation of the modeled object due to the heating process.
  • the powder in the present invention more preferably contains at least one selected from gadolinium oxide, terbium oxide and praseodymium oxide as an accessory component. Since the powder contains gadolinium oxide, it has a lower melting point than aluminum oxide alone in the vicinity of the Al 2 O 3 —Gd 2 O 3 eutectic composition. As a result, the powder can be melted with a small amount of heat, and the diffusion of energy in the powder is suppressed, so that the modeling accuracy is improved. Further, by including gadolinium oxide, the shaped article has a phase separation structure composed of two or more phases. This suppresses the extension of cracks and improves the mechanical strength of the modeled object.
  • gadolinium oxide is replaced with an oxide of another rare earth element (except terbium and praseodymium), the same effect as gadolinium oxide can be obtained.
  • the energy beam is a laser beam, because the powder has sufficient energy absorption, the spread of heat in the powder is suppressed and becomes local, and the influence of heat on the non-printing part is reduced, so that the shaping accuracy is reduced. Is improved.
  • terbium oxide (Tb 4 O 7 ) or praseodymium oxide (Pr 6 O 11 ) exhibits good energy absorption, and thus may be contained in the powder as an accessory component. More preferable.
  • the composition ratio of the rare earth oxide material consisting of gadolinium oxide, terbium oxide and praseodymium oxide, which is an accessory component, and aluminum oxide is 46:54 (mol %)
  • the composition ratio of the rare earth oxide material and aluminum oxide is Is preferably within the range of ⁇ 5 mol% from the above eutectic composition ratio, that is, 41:59 to 51:49 (mol %). Within this range, it is possible to obtain the effect of lowering the melting point by using ceramics having a eutectic composition.
  • more preferable powders include Al 2 O 3 —Gd 2 O 3 , Al 2 O 3 —Tb 4 O 7 , Al 2 O 3 —Gd 2 O 3 —Tb 4 O 7 , and Al 2 O.
  • 3- Pr 6 O 11 , Al 2 O 3 -Gd 2 O 3 -Pr 6 O 11 , Al 2 O 3 -Gd 2 O 3 -Tb 4 O 7 -Pr 6 O 11 and the like can be mentioned.
  • the base material used in the present invention may be appropriately selected and used from materials such as ceramics, metal, and glass that are usually used in the production of three-dimensional shaped objects, in consideration of the use and manufacturing conditions of the shaped object. it can.
  • the step (iv) when heating the shaped article integrated with the base, it is preferable to use heat-resistant ceramics for the base.
  • the method of arranging the powder on the base is not particularly limited.
  • the powders are arranged in layers on the base with rollers, blades, or the like.
  • the cladding method as shown in FIG. 2A to FIG. 2C, the powder is jetted and supplied from the nozzle to the irradiation position of the energy beam, and the powder is overlaid on the base or the shaped object arranged on the base.
  • the powder is melted and solidified by irradiation with an energy beam to produce a shaped article.
  • the method for producing a shaped article according to the present invention includes a step (ii) of irradiating the powder layer formed in the step (i) with an energy beam based on shaping data to melt, solidify, or sinter the powder. ..
  • this step will be described based on a preferred embodiment.
  • a predetermined region on the surface of the powder placed on the base in step (i) is irradiated with an energy beam to melt the powder and then solidify.
  • the powder in the case of the cladding method, as shown in FIGS. 2A to 2C, the powder is jet-supplied and the powder is placed on the base so as to be built up, and at the same time, The whole is irradiated with an energy beam to melt and solidify the powder.
  • the powder absorbs energy, the energy is converted into heat, and the powder is melted.
  • the melted powder is cooled and solidified by the atmosphere and the adjacent peripheral portion thereof, and a shaped object is formed. Due to the rapid cooling during the melting and solidifying process, stress is generated in the surface layer and inside of the shaped article, and innumerable microcracks are formed.
  • the shaped object may be formed by irradiating the powder layer with an energy beam and sintering it.
  • a light source having an appropriate wavelength is selected in view of the absorption characteristics of the powder.
  • a laser beam or electron beam having a narrow beam diameter and high directivity examples include a YAG laser in the 1 ⁇ m wavelength band, a fiber laser, and a CO 2 laser in the 10 ⁇ m wavelength band.
  • a YAG laser having a wavelength band of 1 ⁇ m is suitable.
  • the method for producing a molded article according to the present invention comprises a step of absorbing a liquid containing a zirconium component (sometimes referred to as a zirconium component-containing liquid) in a molded article formed by repeating the step (i) and the step (ii). Have.
  • a zirconium component sometimes referred to as a zirconium component-containing liquid
  • step (ii) On the shaped article obtained in step (ii), a new powder is placed in step (i).
  • the powder in the energy beam irradiation portion is melted and solidified to form a new modeled object integrated with the original modeled object.
  • a liquid containing a zirconium component (sometimes referred to as a zirconium component-containing liquid) is absorbed in the obtained shaped product.
  • a zirconium component-containing liquid composed of a zirconium component raw material, an organic solvent, and a stabilizer is a preferable example.
  • Various zirconium compounds can be used as raw materials for the zirconium component.
  • a raw material containing no metal element other than zirconium is preferable.
  • a raw material for the zirconium component a metal alkoxide of zirconium or a salt compound such as chloride or nitrate can be used.
  • the use of metal alkoxide is preferable because the liquid containing the zirconium component can be uniformly absorbed in the microcracks of the shaped article.
  • zirconium alkoxide examples include zirconium tetraethoxide, zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, zirconium tetra t-butoxide and the like.
  • a zirconium alkoxide solution is prepared by dissolving zirconium alkoxide in an organic solvent.
  • the amount of the organic solvent added to the zirconium alkoxide is preferably 5 or more and 30 or less in terms of molar ratio with respect to the compound. More preferably, it is 10 or more and 25 or less.
  • that the addition amount of A is 5 with respect to B in a molar ratio means that the addition amount of A is 5 times that of B. If the concentration of zirconium alkoxide in the solution is too low, a sufficient amount of zirconium component cannot be absorbed by the shaped article. On the other hand, if the concentration of zirconium alkoxide in the solution is too high, the zirconium component in the solution aggregates, and the zirconium component cannot be uniformly arranged in the microcrack portion of the modeled object.
  • alcohol carboxylic acid, aliphatic or alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, or a mixed solvent of two or more thereof is used.
  • alcohols include methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 4-Methyl-2-pentanol, 2-ethylbutanol, 3-methoxy-3-methylbutanol, ethylene glycol, diethylene glycol, glycerin and the like are preferable.
  • esters are ethyl formate, ethyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and the like.
  • ketones acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like are preferable.
  • ethers include dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether and the like.
  • zirconium alkoxide Since zirconium alkoxide has high reactivity with water, it is rapidly hydrolyzed by the addition of water in the air or water to cause cloudiness or precipitation of the solution. In order to prevent these, it is preferable to add a stabilizer to stabilize the solution.
  • the stabilizer include ⁇ -diketone compounds such as acetylacetone, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione and trifluoroacetylacetone; methyl acetoacetate and ethyl acetoacetate.
  • the addition amount of the stabilizer is preferably 0.1 or more and 3 or less in molar ratio with respect to the zirconium alkoxide. More preferably, it is 0.5 or more and 2 or less.
  • Another preferred example is a zirconium component-containing liquid composed of zirconium component particles, a dispersant, and a solvent.
  • zirconium particles or zirconia particles that are oxides can be used.
  • Zirconium particles or zirconia particles may be prepared by crushing each material by the top-down method, or by a bottom-up method from metal salts, hydrates, hydroxides, carbonates, etc., such as hydrothermal reaction. Or a commercially available product may be used.
  • the size of the particles is 300 nm or less, more preferably 50 nm or less in order to penetrate into the microcracks.
  • the shape of the fine particles is not particularly limited, and may be spherical, granular, columnar, elliptic spherical, cubical, rectangular parallelepiped, needle-shaped, columnar, plate-shaped, scale-shaped, or pyramid-shaped.
  • the dispersant preferably contains at least one of an organic acid, a silane coupling agent, and a surfactant.
  • organic acid include acrylic acid, 2-hydroxyethyl acrylate, 2-acryloxyethyl succinic acid, 2-acryloxyethyl hexahydrophthalic acid, 2-acryloxyethyl phthalic acid, 2-methylhexanoic acid, 2- Ethylhexanoic acid, 3-methylhexanoic acid, 3-ethylhexanoic acid and the like are preferable.
  • the silane coupling agent include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, and decyltrimethoxysilane.
  • the surfactant include ionic surfactants such as sodium oleate, potassium fatty acid, sodium alkyl phosphate, alkylmethyl ammonium chloride, and alkylaminocarboxylate, polyoxyethylene laurin fatty acid ester, polyoxyethylene alkylphenyl.
  • Nonionic surfactants such as ether are preferred.
  • alcohols As the solvent, alcohols, ketones, esters, ethers, ester-modified ethers, hydrocarbons, halogenated hydrocarbons, amides, water, oils, or a mixed solvent of two or more thereof is used.
  • Preferred alcohols are, for example, methanol, ethanol, 2-propanol, isopropanol, 1-butanol, ethylene glycol and the like.
  • ketones for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like are preferable.
  • Preferred esters are, for example, ethyl acetate, propyl acetate, butyl acetate, 4-butyrolactone, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and the like.
  • Preferred ethers are, for example, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, butyl carbitol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-butoxyethanol and the like.
  • the modified ethers for example, propylene glycol monomethyl ether acetate is preferable.
  • hydrocarbons for example, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, hexane, cyclohexane, methylcyclohexane and the like are preferable.
  • Preferred halogenated hydrocarbons are, for example, dichloromethane, dichloroethane and chloroform.
  • Preferred amides are, for example, dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.
  • oils for example, mineral oil, vegetable oil, wax oil and silicone oil are preferable.
  • the zirconium component-containing liquid may be prepared by simultaneously mixing zirconium particles or zirconia particles with a dispersant and a solvent, or may be mixed with zirconium particles or zirconia particles and a dispersant and then mixed with a solvent. .. Alternatively, the zirconium or zirconia fine particles may be mixed with the solvent and then the dispersant may be mixed, or the dispersant and the solvent may be mixed and then the zirconium or zirconia fine particles may be mixed. You may.
  • the solution may be prepared by reacting at room temperature or refluxing.
  • the solid concentration of the zirconia component is determined by the above molar ratio of zirconium alkoxide, organic solvent, and stabilizer.
  • the weight percentage of the zirconia solids is preferably in the range of 3% to 20%, more preferably 8% to 15%. If the concentration is low, it becomes difficult to obtain the effect of filling the microcracks. If the weight% is 3% or more, a certain effect is obtained, and if it is 8% or more, the effect is further enhanced. When the weight% is high, the viscosity becomes too high, and the liquid is difficult to be absorbed even in the microcracks, and it becomes difficult to obtain the effect. When the weight% is 20% or less, a certain effect is obtained. If it is 15% or less, the effect is further enhanced.
  • the powder melted by the energy beam irradiation in the above step (ii) is cooled by the surroundings and solidifies to form an intermediate shaped object.
  • the difference in melting/solidifying temperature is large, many microcracks occur in the intermediate shaped product.
  • the zirconium component-containing liquid penetrates not only on the surface layer of the modeled object but also along the microcracks to be distributed inside the modeled object.
  • the method for absorbing the zirconium component-containing liquid in the shaped product is not particularly limited as long as a sufficient amount of the zirconia component can be present in a sufficient range of the microcracks of the shaped product.
  • the shaped product may be impregnated in the zirconium component-containing liquid, the zirconium component-containing liquid may be atomized and sprayed onto the intermediate shaped product, or may be applied with a brush or the like. Further, a plurality of these methods may be combined, or the same method may be repeated a plurality of times.
  • the zirconium component-containing liquid When the zirconium component-containing liquid is sprayed and when the zirconium component-containing liquid is applied, 5% by volume or more and 20% by volume or less of the zirconium component-containing liquid of the shaped article not absorbing the zirconium component-containing liquid is sprayed or applied. Preferably. If it is less than 5% by volume, the amount of zirconium component arranged in the microcrack portion of the molded article may be insufficient, and the microcrack portion may not melt. When it is more than 20% by volume, when the step (i) is carried out after the present step (iii), it may be difficult to uniformly dispose the powder on the shaped article due to the influence of the zirconium component-containing liquid.
  • the molded article is immersed in a zirconium component-containing liquid and degassed under reduced pressure.
  • the method of impregnating and then impregnating is preferable.
  • the steps (i) and (ii) are repeated to form a shaped article having a porous portion, it is preferable that the zirconium component-containing liquid be sprayed in a mist state to be absorbed by the shaped article at each stage.
  • step (iv) of the method for producing a shaped article according to the present invention the shaped article having the zirconium component-containing liquid absorbed therein is heated.
  • the zirconium component-containing liquid is distributed in the surface layer of the shaped article and the microcracks inside the shaped article.
  • the zirconium component has a relationship of forming a eutectic with aluminum oxide
  • melting starts at the eutectic point in the portion where these components are present.
  • the eutectic point of aluminum oxide and zirconium oxide is about 1900° C., which is lower than the melting point of each component alone (Al 2 O 3 is 2070° C. and ZrO 2 is 2715° C.). That is, melting starts at a temperature lower than the melting temperature of the modeled product containing aluminum oxide as the main component.
  • the melting point at the location where zirconium is present can be greatly reduced locally, and by utilizing this difference in melting point, heating is performed at a temperature equal to or higher than the eutectic point and lower than the melting point of the shaped article, and only the vicinity of the microcracks is heated. It can be selectively locally melted. Specifically, the shaped article that has undergone the step (iv) is heated so that the maximum temperature becomes 1600° C. or higher and 1710° C. or lower.
  • the microcracks containing the zirconium component melt. Therefore, the heating time does not matter. In the molten state, the diffusion of atoms proceeds in the direction in which the surface energy decreases, and eventually microcracks decrease or disappear.
  • the heating temperature By controlling the heating temperature, only the vicinity of the portion where the zirconium component is present can be melted, so that the shape of the modeled object is not destroyed and the advantage of the direct modeling method is secured. Therefore, the shape of the modeled object is maintained even if it is heated for a long time.
  • the mechanical strength of the molded article solidified and recrystallized after melting is greatly improved by the reduction and disappearance of microcracks.
  • the vicinity of the microcracks is melted as described above, and the microcracks are reduced or eliminated.
  • the vicinity of the microcracks approaches the eutectic composition in which zirconium oxide is in the vicinity of 22 mol% with respect to the molded product containing aluminum oxide as the main component in an amount of 78 mol%, the vicinity of the microcracks is more easily melted.
  • the method of heating the shaped object is not particularly limited.
  • the shaped article that has absorbed the zirconium component-containing liquid may be heated again by irradiating it with an energy beam, or may be placed in an electric furnace and heated.
  • the molded product may stick to the setter (firing shelf, shelf board, floor board, etc.) due to melting near the surface layer and microcracks. Therefore, when the shaped object is placed on the setter in the heating step, the setter is preferably inert.
  • the inert setter for example, platinum or the like can be applied in the air atmosphere, and iridium or the like can be applied in the low oxygen atmosphere.
  • the basic flow is basically a flow of executing each step in the order of step (i) ⁇ step (ii) ⁇ step (iii) ⁇ step (iv), but step (iii) and step (iv) are repeated. You may execute.
  • the eutectic composition in which the vicinity of the microcracks of the modeled object is about 22 mol% of zirconium oxide with respect to 78 mol% of the modeled object containing aluminum oxide as the main component It is preferable to bring them closer. This facilitates melting in the vicinity of the microcracks and improves the effect of reducing and eliminating the microcracks.
  • the liquid is absorbed in the absorbing step such that the ratio of the zirconium component to the metal component contained in the porous portion is 0.3 mol% or more and 2.0 mol% or less.
  • FIG. 7 shows a schematic view of an example of a piece of composite ceramic component 403 including a porous portion 401 and a dense portion 402 for holding the porous portion 401.
  • the porous portion 401 is surrounded by the dense portion 402 and integrated.
  • These composite ceramic parts 403 can be used as a suction plate by connecting intake and exhaust members.
  • the example of FIG. 7 is merely an example, and a plurality of porous parts 401 may be independently arranged in the dense part 402, or the dense part 402 is arranged inside the porous part 401. Good.
  • the dense part 402 constituting the composite ceramic part 403 is made of a metal oxide containing aluminum and zirconium, and the ratio of the zirconium component in the metal component constituting the metal oxide is the porous part. It is smaller than 401.
  • Example 1 In this example, a porous portion having a grid pattern was produced. This roughly corresponds to the case where the lattice pattern has a hole period of 175 ⁇ m.
  • the respective weighing powders were mixed by a dry ball mill for 30 minutes to obtain a mixed powder (material powder).
  • the composition of the material powder was analyzed by ICP emission spectroscopy, the content of zirconium oxide was less than 0.1 mol %.
  • Example 1 was formed through steps basically similar to the steps shown in FIGS. 1A to 1H described above.
  • a ProX DMP 100 (trade name) manufactured by 3D SYSTEMS Co., which is equipped with a 50 W Nd:YAG laser (beam diameter: 65 ⁇ m) was used for forming the modeled object.
  • a 20 ⁇ m-thick first powder layer of the above material powder was formed on a pure alumina base using a roller (step (i)). Then, the powder layer was irradiated with a 30 W laser beam to melt and solidify the material powder in a square region of 10 mm ⁇ 10 mm in a mesh shape. The drawing speed was 180 mm/s and the drawing pitch was 175 ⁇ m (step (ii)). The drawing line was inclined at 45 degrees with respect to each side of the square. Next, a 20 ⁇ m-thick powder layer was newly formed with a roller so as to cover the melting/solidifying portion (step (i)). The powder layer directly above the square region was irradiated with a laser in a state of being orthogonal to the drawing line of the first layer, and the powder in the region of 10 mm ⁇ 10 mm was melted and solidified (step (ii)).
  • a modeled object having a bottom surface of 10 mm ⁇ 10 mm and a height of 3 mm was formed.
  • the obtained shaped product contained unsolidified powder, and the unsolidified powder was removed to obtain a shaped product having a porous structure.
  • the above-described shaped product processed for the test was immersed in the zirconium component-containing liquid, degassed under reduced pressure for 1 minute to permeate (impregnate) the liquid into the inside of the shaped product, and then naturally dried for 1 hour.
  • the shaped article impregnated (absorbed) with the zirconium component-containing liquid as described above was provided with a platinum wire on an alumina plate, placed on the platinum wire, and placed in an electric furnace for heating. Specifically, the temperature was raised to 1670° C. in 2.5 hours in the air atmosphere, kept at 1670° C. for 50 minutes, then turned off, and cooled to 200° C. or less in 1.5 hours (step (iv)). ).
  • Example 1 the step of absorbing the zirconium component-containing liquid (step (iii)) and the step of heating (step (iv)) were alternately repeated 5 times to obtain a ceramic article having a porous portion. It was
  • the average pore size was evaluated by the following method.
  • a scanning electron microscope (SEM) is used to acquire an SEM image of the polished surface of the shaped article provided with the porous portion.
  • the average value of the minor axis diameters of the ellipse having the major axis diameter 2a and the minor axis diameter 2b thus obtained is defined as the average pore diameter.
  • the average pore size described in this specification is synonymous with this.
  • the porosity in the present invention refers to the ratio of open pores to the volume of the ceramic article, and does not include closed pores.
  • the Zr content and the average particle size in the Zr region were evaluated by the following methods.
  • SEM-EDX analysis composition analysis of the porous portion was performed in an area of 2 mm ⁇ 2 mm, and the ratio of Zr component in all metal elements was defined as Zr content.
  • the composition distribution of the porous part is mapped in the same area, the continuous area containing the Zr component as the main component is regarded as one zirconia area, and the area is calculated.
  • the diameter (equivalent circle diameter) was calculated.
  • the equivalent circle diameter was calculated for a plurality of zirconia regions, and the average value was used as the average equivalent circle diameter of the zirconia regions.
  • the modeling accuracy refers to the difference between the dimension and the design dimension of the ceramic article that has undergone the firing process after modeling.
  • the maximum change rates on the upper surfaces of the modeled objects in step (iii) and step (iv) are compared, and A, B, and C are in descending order of the rate of change. write. That is, if the rate of change is 3% or less, the modeling accuracy A is 3% and 5% or less is the modeling accuracy B, and if the variation rate is 5% or more, the modeling accuracy C is generated.
  • Those that do not exist are referred to as modeling accuracy D.
  • the molding accuracy A has an upper surface dent of 0.3 mm or less
  • the molding accuracy B has an upper surface dent of more than 0.3 and is 0.5 mm or less.
  • the dent on the upper surface was larger than 0.5 mm.
  • FIG. 4A An optical microscope image of the porous portion of the produced ceramic article is shown in FIG. 4A.
  • An SEM image is shown in FIG. 5A, and a mapping image of the composition distribution of the Zr component by SEM-EDX in the same region is shown in FIG. 5B.
  • the obtained porous portion had pores communicating from one surface to the opposite surface.
  • the average pore diameter in the porous portion was 115 ⁇ m, and the porosity was 31% by volume.
  • the closed pores were 0.4% by volume.
  • the Zr content was 1.56 mol %.
  • the average equivalent circle diameter of the zirconia region was 20 ⁇ m, and the zirconia region was distributed so as to extend from the bridge portion to the outside of the bridge portion.
  • the forming accuracy was B and the mechanical strength was A.
  • Example 2 The present example is an example in which the content of the zirconium component in the porous portion is different.
  • a porous ceramic was produced under the same conditions as in Example 1 except that the step of immersing in the zirconium component-containing liquid (step (iii)) and the step of heating (step (iv)) were alternately repeated twice each.
  • the produced porous ceramics article was evaluated in the same manner as in Example 1.
  • Example 3 The present example is an example in which the arrangement of the openings in the porous portion is random.
  • a porous ceramic article was produced under the same conditions as in Example 1 except that the drawing speed was 220 mm/s and the drawing pitch was 125 ⁇ m in order to obtain a porous portion having randomly arranged openings.
  • An optical microscope image of the porous portion is shown in FIG. 4B. The produced porous ceramics were evaluated in the same manner as in Example 1.
  • Example 4 The present example is an example of producing a composite ceramic component including a porous portion made of ceramics and a dense portion made of ceramics for holding the porous portion.
  • a composite ceramic component including a porous portion made of ceramics and a dense portion made of ceramics for holding the porous portion.
  • FIG. 7 this corresponds to the case where the porous portion has a lattice-like pattern with a period of 175 ⁇ m and the dense portion surrounds and is integrated.
  • the porous part was produced under the same laser irradiation conditions as in Example 1.
  • the dense portion was irradiated with a laser beam of 30 W, the drawing speed was 100 mm/s to 140 mm/s, and the drawing pitch was 100 ⁇ m.
  • the SEM image of the boundary between the porous part and the dense part of the obtained composite ceramic part is shown in FIG. 6A.
  • 6B and 6C show mapping images of the composition distribution of the Zr component by SEM-EDX in the regions corresponding to the part 601 of the porous part and the part 602 of the dense part shown in FIG. 6A, respectively.
  • the porous part and the dense part of the produced ceramic article were evaluated in the same manner as in Example 1.
  • Example 5 The present example is an example in which the content of the zirconium component in the lattice-shaped porous portion is different.
  • the conditions are the same as in Example 1 except that the step of immersing in the zirconium component-containing liquid was repeated 3, 4, 6, and 8 times, respectively.
  • Example 9 to 14 The present example is an example in which the content of the zirconium component in the porous portion having random openings is different.
  • the conditions are the same as in Example 3 except that the step of immersing in the zirconium component-containing liquid is repeated 2, 3, 4, 6, 7, and 8 times, respectively.
  • Example 15 and 16 The present example is an example in which the content of the zirconium component in the composite ceramic component including the porous portion made of ceramics and the dense portion made of ceramics for holding the porous portion is different.
  • the conditions are the same as in Example 4 except that the step of immersing in the zirconium component-containing liquid is repeated 4 and 6 times, respectively.
  • Comparative Example 1 does not include the step of immersing the intermediate shaped article in the zirconium component-containing liquid (step (iii)) and the step of heating the intermediate shaped article absorbed with the zirconium component-containing liquid (step (iv)).
  • a porous ceramic was obtained in the same manner as in Example 1 except for the steps of Comparative Example 2 once and Comparative Example 3 8 times. The produced ceramic article having a porous portion was evaluated in the same manner as in Example 1.
  • Comparative example 4 This comparative example is an example in which the content of the zirconium component in the porous portion having random openings is different. The conditions are the same as in Example 3 except that the step of immersing in the zirconium component-containing liquid was performed once.
  • Example 17 The present example is an example in which the content of the zirconium component in the composite ceramic component including the porous portion and the dense portion for holding the porous portion is different.
  • the conditions are the same as in Example 4 except that the step of immersing in the zirconium component-containing liquid is repeated 2, 3, and 7 times, respectively.
  • Comparative example 5 This comparative example is an example in which the content of the zirconium component in the composite ceramic component including the porous portion and the dense portion for holding the porous portion is different. The conditions are the same as in Example 4 except that the step of immersing in the zirconium component-containing liquid was repeated 9 times.
  • Table 1 collectively shows the above evaluation results of the examples and the comparative examples.
  • the porous part is more dense than the dense part. Became higher. This is because in the porous portion, the zirconium component-containing liquid permeates through the pores to the inside of the shaped article, and since the surface area is large, a large amount of the zirconium component permeates into the dense portion. it is conceivable that.
  • the ceramic articles having modeling accuracy of A, B, and C had no damage and were practically usable as ceramic articles.
  • the ceramic articles having modeling accuracy of A and B have good modeling accuracy and were suitable as an example for obtaining a ceramic article having a complicated shape or a fine shape.
  • the comparative ceramic article having a molding accuracy of D had a poor molding accuracy, a large difference from the design dimension, and damage such as cracks was observed, so that a practical specification could not be obtained.
  • the mechanical strength will improve as the Zr content increases.
  • the mechanical strength is weak and the defect ratio is more than 20% (mechanical strength C).
  • the defect ratio decreased (more than 10% and 20% or less), and sufficient mechanical strength was obtained (mechanical strength B).
  • the defect ratio was 10% or less and the mechanical strength was further improved (mechanical strength A).
  • the ratio of the zirconium component in the metal component forming the metal oxide is 0. It was found that it is necessary to be 3 mol% or more and 2.0 mol% or less. Further, it was found that the zirconium component under this condition forms a crystal grain having an average particle size of 10 ⁇ m or more as a metal oxide compounded with another metal component, and the crystal grains are connected to each other to have a network structure.
  • the crystal grains containing zirconium as a main component form a crystal complexed with Gd and form a network that permeates intricately inside the eutectic structure.
  • the ratio of the zirconium component in the metal component forming the metal oxide is 0.7 mol% or more and 1.5 mol% or less. I found it necessary to be.

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Abstract

L'invention concerne : un procédé de production d'un article en céramique ayant une partie poreuse et permettant une amélioration de la résistance mécanique d'un article moulé tout en obtenant une précision de moulage élevée ; et un article en céramique. Le procédé de production selon l'invention comprend : (i) une étape de formation d'une couche de poudre par étalement uniforme d'une poudre d'oxyde métallique qui contient de l'oxyde d'aluminium en tant que composant principal ; (ii) une étape de fusion et de solidification ou de frittage de la poudre par irradiation de la couche de poudre avec un faisceau d'énergie sur la base de données de mise en forme ; (iii) une étape pour amener un liquide qui contient un composant de zirconium à être absorbé par un article moulé ayant une partie poreuse et étant formé par répétition des étapes (i) et (ii) ; et (iv) une étape de chauffage de l'article moulé qui a absorbé le liquide contenant le composant de zirconium, dans l'étape d'absorption, le liquide étant absorbé de telle sorte que la proportion du composant de zirconium parmi les composants métalliques contenus dans la partie poreuse devienne de 0,3 à 2,0 % en moles.
PCT/JP2019/047646 2018-12-06 2019-12-05 Procédé de production d'article en céramique, et article en céramique WO2020116568A1 (fr)

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WO2022080318A1 (fr) * 2020-10-16 2022-04-21 キヤノン株式会社 Procédé de production d'un article en céramique, liquide contenant des ions métalliques utilisé dans celui-ci et kit de production d'un article en céramique

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