JP2021066177A - Ceramic article manufacturing method and ceramic article - Google Patents

Abstract

To provide a silica-based ceramic structure that is high in model accuracy and is excellent in mechanical strength.SOLUTION: The ceramic article manufacturing method is characterized by having: (i) a step in which a powder containing an absorber that absorbs light of the wavelength contained in the irradiating laser beam and containing silicon dioxide as the main component; (ii) a step in which, by irradiating the powder with a laser beam, the powder is sintered or melted and solidified; and (iii) a step in which the modeled product formed by repeating the steps (i) and (ii) is heat-treated at 1470°C or higher and lower than 1730°C.SELECTED DRAWING: Figure 1

Description

The present invention relates to a method for producing a silica-based ceramic article using an additional manufacturing technique, and a ceramic article produced by such a manufacturing method.

Addition manufacturing technology is becoming widespread, in which materials are added based on the three-dimensional data of the model to be manufactured to obtain a desired model in applications such as manufacturing prototypes or manufacturing a small number of articles in a short time. is there. In the manufacture of metal articles, a direct molding method is widely adopted in which a metal powder is solidified and shaped by irradiating the metal powder with a laser beam based on three-dimensional data of a model. According to this method, it is possible to obtain a dense and diverse article by effectively melting and solidifying the metal powder.

In recent years, efforts have been made to establish additional manufacturing technology using ceramic powder as a raw material. However, unlike metals, general-purpose ceramics such as aluminum oxide and zirconium oxide have a low ability to absorb laser light. Therefore, in order to melt the ceramic powder, it is necessary to input a large amount of energy, but it is difficult to obtain the required molding accuracy because the laser light is diffused and the melting becomes non-uniform.

Therefore, Patent Document 1 discloses a technique for producing a modeled object with high accuracy by suppressing the diffusion of light by adding an absorber that absorbs laser light to the raw material powder.

JP-A-2019-19051

Among ceramics, silica-based materials are widely used as materials for forming cores for casting. The casting core is a mold that fits into the cavity of the mold when making a casting with a cavity inside, and is finally removed from the cast article. Since the core is required to have excellent heat resistance without causing a chemical change with the molten metal to be cast and to be easily removed at the end of the casting process, it is a silica-based material that is soluble in an alkaline solution. The structure of is suitable as a core for casting. Here, "silica-based" means that silicon dioxide is the main component. In the present invention, the main component means a component (element or compound) contained most in terms of mass ratio.

If a core for casting can be produced by an additional manufacturing technique, it is possible to realize casting of a complicated shape at low cost. Since the dimensions or surface accuracy of the article to be cast are affected by the dimensions and surface condition of the core, the silica-based model used as the core has high modeling accuracy and high mechanical strength that can withstand the casting process. Is required.

Patent Document 1 describes a silica-based material as a modeling powder used in a direct modeling method. However, since the silica-based material has a high viscosity during the liquid phase, it tends to be spherical in a molten state by irradiation with laser light, and the solidified portion tends to be porous. Further, since the temperature of the molten portion after the passage of the laser beam is rapidly lowered and rapidly cooled, most of the solidified portion becomes amorphous. Even when liquid phase sintering occurs due to laser irradiation, the portion that has become a liquid phase is rapidly cooled after the laser beam has passed, and becomes amorphous. For these reasons, the silica-based model formed by the method disclosed in Patent Document 1 has excellent modeling accuracy, but has many amorphous parts, so that the mechanical strength may be insufficient depending on the application such as a casting core. There is.

The present invention has been made to solve such a problem, and provides a technique for manufacturing a silica-based ceramic article having high molding accuracy and excellent mechanical strength by using a direct molding method.

The method for producing a ceramic article according to the present invention is as follows.
(I) A step of arranging a powder containing an absorber that absorbs light of a predetermined wavelength and containing silicon dioxide as a main component, and
(Ii) A step of sintering, melting, and solidifying the powder by irradiating the powder with a laser containing light having a predetermined wavelength.
(Iii) A step of heating a modeled product formed by repeating the steps (i) and (ii) at 1470 ° C. or higher and lower than 1730 ° C.
It is characterized by having.

Further, the ceramic article according to the present invention is a ceramic article containing Tb or Pr and containing silicon dioxide as a main component, and the silicon content is more than 80% by mass, and 70% by mass or more of the silicon dioxide is cristobalite. It is characterized by being.

According to the present invention, it is possible to manufacture a silica-based ceramic structure having high molding accuracy and excellent mechanical strength by using a direct molding method.

It is schematic cross-sectional view which shows typically one Embodiment of the manufacturing method of the shaped object by the powder bed melt-bonding method. It is the schematic sectional drawing which shows one Embodiment of the manufacturing method of the modeled object by the cladding method schematically. It is a phase diagram which shows the relationship between the composition ratio and the state of A component and B component which can become eutectic. It is a figure which shows an example of the manufacturing flow of the ceramic article which concerns on this invention. It is a figure which shows another example of the manufacturing flow of the ceramic article which concerns on this invention. It is a schematic perspective view which shows the laser irradiation process in the Example of this invention.

The method for producing a ceramic article according to the present invention includes the following steps.
(I) A step of arranging a powder containing an absorber that absorbs light of a predetermined wavelength and containing silicon dioxide as a main component (ii) By irradiating the powder with a laser containing light of the predetermined wavelength, the said Step of sintering, melting and solidifying powder (iii) Step of heating a model formed by repeating the steps of (i) and (ii) at 1470 ° C. or higher and lower than 1730 ° C.

Hereinafter, embodiments of the present invention will be described with reference to the drawings with reference to specific examples, but the present invention is not limited to the following specific examples and drawings, and is modified within the scope of the technical idea of the present invention. Is possible.

Among the direct molding methods, the present invention is preferably used in a powder bed fusion bonding method and a directed energy lamination method (so-called cladding method) in which a molding material is deposited while being melted so as to build up. By applying the present invention, it is possible to greatly improve the mechanical strength of the obtained silica-based model while achieving good modeling accuracy.

In addition, silica means silicon dioxide. Silica has polymorphism, but it does not matter if it is amorphous, crystalline, or has a crystal structure. "Polymorph" means taking a plurality of different crystalline forms even though they have the same chemical composition.

The basic flow of modeling of the powder bed melt-bonding method will be described with reference to FIGS. 1 (a) to 1 (h).

First, the powder 101 is placed on the base 130 installed on the stage 151, and the powder (powder layer) 102 having a predetermined thickness is placed using the roller 152 (FIGS. 1 (a) and 1 (b)). The surface of the powder layer 102 is irradiated with a laser beam emitted from a laser beam source 180 while being scanned by the scanner unit 181 based on modeling data (slice data) generated from three-dimensional shape data of a model having a desired shape. To do. In the laser beam irradiation range 182, the powder is sintered, melted, and solidified to form the solidified portion 100 (FIG. 1 (c)). Subsequently, the stage 151 is lowered to form a new powder layer 102 on the solidified portion 100 (FIG. 1 (d)), and a laser beam is irradiated based on the modeling data. These series of steps are repeated to form a model 110 having a desired shape (FIGS. 1 (e) and 1 (f)). Finally, the uncured powder 103 is removed, and if necessary, unnecessary portions of the modeled object are removed and the modeled object and the base are separated to obtain a modeled object (FIGS. 1 (g) and 1 (h)).

Next, the cladding method will be described with reference to FIGS. 2A to 2C. Powder is ejected from a plurality of powder supply holes 202 in the cladding nozzle 201, and while irradiating the region where the powder is focused with the laser beam 203, the solidified portion 100 is additionally solidified at a desired location based on the modeling data. (Fig. 2 (a)). By continuously performing such steps, a model 110 having a desired shape is obtained (FIGS. 2 (b) and 2 (c)). Finally, if necessary, unnecessary parts of the modeled object are removed and the modeled object and the base are separated.

In the case of a direct molding method such as a powder bed direct molding method or a cladding method, the powder containing silicon dioxide as a main component melted by laser beam irradiation is rapidly cooled from the surroundings and solidified, and a solidified product mainly composed of amorphous silica is formed. It is formed. The shaped object mainly composed of amorphous silica formed by such a melting and solidifying process cannot obtain high mechanical strength due to its low density.

One of the crystalline forms that silica can take is cristobalite. Since cristobalite has a stable crystalline form at high temperatures, it can maintain a stable state at high temperatures exposed by casting. Furthermore, since it has a higher density than silica having an amorphous structure, it is also excellent in mechanical strength at high temperatures. In addition, cristobalite has a higher solubility in an alkaline solution than other crystal forms such as quartz, and is therefore suitable as a crystal form constituting a core for casting.

Therefore, in the present invention, the modeled product produced by repeating steps (i) and (ii) is heat-treated at a temperature of 1470 ° C. or higher and lower than 1730 ° C. By such heat treatment, a modeled object that is stable at high temperature and has excellent mechanical strength is realized. It is considered that this is because the modeled object, which was mainly amorphous silica immediately after modeling, is changed to cristobalite in which 70% by mass or more of silicon contained in the modeled object is bonded to oxygen by heat treatment.

Further, depending on the conditions under which the steps (i) and (ii) are performed, the portion irradiated with the laser beam is exposed to the melting temperature and the solidification temperature in a short time, so that many of the shaped objects obtained by thermal stress are exposed. Cracks may be formed. The cracks are distributed throughout the model, i.e., on the surface and inside. When the cross section of the modeled object is confirmed with a scanning electron microscope or the like, most of the cracks have a width of several nm to several μm, and the length of the crack varies from several μm to several mm. If many such cracks are formed in the modeled object, the mechanical strength is lowered.

In the case of a modeled object in which there is a concern that the mechanical strength is lowered due to cracks, it is preferable to allow the cracks of the modeled object to absorb the metal component-containing liquid before the heat treatment in the step (iii). By heating, the amorphous silica contained in the modeled object is changed to cristobalite with higher mechanical strength, and at the same time, the vicinity of the crack is selectively melted by the action of the metal component-containing liquid to repair the crack and repair the crack in the modeled object. Cracks can be reduced. As a result, the mechanical strength of the modeled object can be remarkably improved.

The metal component-containing liquid to be absorbed by the cracks is preferably one capable of supplying a metal oxide to the cracks. For example, it is preferable that the metal component-containing liquid contains a metal oxide, or contains a component that produces a metal oxide by heat treatment performed after absorbing the metal component-containing liquid. The metal component-containing liquid is preferably a composition capable of supplying the metal oxide by itself, but the metal oxide is accompanied by compounding, solid solution, or diffusion with the component contained in the modeled product. It may be a composition that produces.

As the metal component-containing liquid, a solution, a sol liquid, a particle dispersion liquid, or the like containing a metal element can be used. When the metal component-containing liquid is absorbed by the modeled object in the step (iii), the metal component-containing liquid can be prepared by adjusting the characteristics such as the viscosity and concentration of the liquid so that the metal element spreads throughout the modeled object. It doesn't matter what it is. The metal element is contained in the metal component-containing liquid in the form of, for example, a metal salt, a metal alkoxide, particles containing the metal element, and the like. Examples of particles containing a metal element include particles such as metals, oxides, nitrides, carbides, borides, and hydroxides. The particle dispersion liquid contains a solvent, a dispersant, a stabilizer and the like in addition to the particles. Examples of the solvent include water, organic solvents and oils, and examples of the dispersant include a pH adjuster, a silane coupling agent, and a surfactant. Examples of the stabilizer include a pH adjuster, a surfactant, a chelating agent, an autolysis inhibitor and the like. However, it is not limited to these.

When a particle dispersion in which particles containing a metal element are dispersed in a solvent is used as the metal component-containing liquid, the particles have a diameter sufficiently smaller than the width of the crack in order to spread over the entire crack in the modeled object. It is preferable that the particles are used. It is considered that the strength of the modeled object is greatly affected by cracks having a width of 1 μm or more. In order to allow the particles to penetrate into a crack having a width of 1 μm or more, the average particle size of the particles is preferably 300 nm or less, more preferably 50 nm or less, still more preferably 30 nm or less. The metal component-containing liquid in which the particles are dispersed can easily adjust the concentration of the metal element by a method such as adjusting the composition of the particles and the content of the particles, and a liquid containing a high concentration of the metal element can be prepared. it can. When a liquid containing a high concentration of metal elements is used as the metal component-containing liquid, it is possible to shorten the time required for the step of absorbing the metal component-containing liquid into the modeled object and heat-treating it. That is, the crack can be repaired by a small number of absorption and heat treatment steps.

On the other hand, when a solution or sol solution containing a metal element is used, the metal element spreads to fine cracks, so that it is possible to repair finer cracks than when using a particle dispersion liquid. However, since it is difficult to prepare a liquid containing a high concentration of metal elements, the time required for repairing cracks tends to be longer than when a particle dispersion liquid is used.

The metal component-containing liquid is preferably one that produces a phase capable of forming an eutectic with the phase constituting the modeled object by heating. When the modeled object contains a plurality of phases, a phase capable of forming an eutectic with any of the phases contained in the modeled object may be formed. When the phase formed from the metal component-containing liquid by the heat treatment is a metal oxide and the phase of the metal oxide and the phase contained in the modeled product are in a relationship capable of forming a eutectic, the metal component invades. The vicinity of the crack melts at a temperature lower than the melting point of other parts of the shaped object. Then, as time goes by, the metal element or metal oxide diffuses into the modeled object, and as the heating is completed and the temperature drops, the crystal is recrystallized in the modeled object with a composition containing the metal element. As a result, while maintaining the shape of the modeled object, only the region near the crack is softened, and the effect of reducing or eliminating the crack can be obtained.

The fact that the component A and another component B can be eutectic may be expressed as "the component A and the component B are in a eutectic relationship". Eutectic is a mixture of two or more types of crystals that crystallize at the same time from a liquid phase containing two or more components. "Component A and component B can be eutectic" is synonymous with "component A and component B have a eutectic state". If it has a eutectic state, there is a eutectic point (also called a eutectic melting point). The eutectic point is the temperature at which eutectic occurs, and corresponds to the minimum value of the liquid phase curve in the state diagram represented by the temperature on the vertical axis and the component composition ratio on the horizontal axis. The composition corresponding to the eutectic point is called the eutectic composition (or eutectic composition). Therefore, the eutectic point of component A and component B is lower than the melting point of each of component A and component B.

The compound component contained in the modeled object that absorbs the metal component-containing liquid is the component A, the oxide of the metal element contained in the metal component-containing liquid is the component B, and the component A and the component B have a eutectic state. Suppose there is. At this time, the local melting caused by the crack is presumed to be due to the following phenomenon.

When the modeled object absorbs the metal component-containing liquid, the metal oxide or metal element contained in the liquid is present on the surface of the modeled object forming the crack. When heating is performed in this state, the metal element changes to a metal oxide. Then, regardless of whether the metal component-containing liquid contains the metal oxide or the metal element, the component B is present on the surface of the modeled object forming the crack. When further heat is applied in this state, in the vicinity of the region where the component B exists on the surface of the modeled object, the amount of the component B and the amount of the component A having a eutectic composition or a composition close to the eutectic composition become the melting point of the modeled object. It is thought that it melts at a lower temperature and recrystallizes, contributing to the repair of cracks. That is, since the amount of component A corresponding to the amount of component B present in the crack is melted, only the region near the crack is softened, and the effect of reducing or eliminating the crack while maintaining the shape of the modeled object can be obtained. I think.

The amount of component B on the surface of the modeled object that constitutes the crack of the modeled object is controlled by adjusting the number of times the metal component-containing liquid is absorbed by the crack and the concentration of the metal element contained in the metal component-containing liquid. Can be done. In the vicinity of the region where the component B exists, the amount of the component A having a eutectic composition or a composition ratio close to the eutectic composition is melted at a temperature lower than the melting point of the modeled object. The larger the amount of component B, the wider the crack can be repaired.

In order to melt the vicinity of the crack, the temperature of the heat treatment performed after the metal component-containing liquid is absorbed by the crack of the modeled object is also important. FIG. 3 shows a phase diagram in the case where the component A, which is a compound contained in the modeled object, and the component B (metal oxide) formed from the metal component-containing liquid are a combination capable of forming a eutectic. The horizontal axis represents the composition ratio of the component A and the component B, and the vertical axis represents the state in each composition.

The melting point of component A _{T m,} the melting point of component B _{T i,} the eutectic temperature of the components A and B and _{T E,} each _temperature, T _E <T _m, the relationship of T E _{<T i} Meet. In this case, the maximum temperature T _S reaching the molded product by heat treatment performed after imbibed with the metal component-containing liquid, it is preferable to set such that _{T E ≦ T S <T m} . More _{preferably, T E ≦ T S <T} m - (T m -T E) is / 2. As a result, _{the vicinity of the crack can be selectively melted at a temperature lower than the melting point T m} of the modeled object to reduce or eliminate the crack, and the shape of the modeled object can be easily maintained.

The technical idea of the present invention is to generate cristobalite in a modeled object to improve mechanical strength. Accordingly, the maximum temperature T _S at the time of heating for repairing cracks is required to be less 1470 ° C. or higher 1730 ° C. which is the temperature range to produce cristobalite shaped object. For this purpose, it is important to appropriately select the combination of the component A contained in the modeled object and the metal component-containing liquid.

Depending on the composition of the metal component-containing liquid used, cracks can be further reduced or eliminated by repeatedly performing the treatment of absorbing the metal component-containing liquid and then heating the metal component-containing liquid a plurality of times. Component A, the respective melting points B selects a combination which satisfies the relationship T _{m <T i,} it is possible to obtain a high effect with a relatively small number of times. This is because, as shown in FIG. 3, T m _<because the components A and B with high composition ratio of the components A in the case of T _i to form a eutectic, of component B contained in the metal component-containing liquid This is because the vicinity of the crack can be melted at the eutectic temperature in a state where the ratio is small. In _{addition, T} m <T _i is not an essential condition.

In view of the above, in the case of a modeled product containing silicon dioxide (SiO ₂ ; melting point T _m = 1730 ° C.) as a main component, a liquid containing aluminum (aluminum component-containing liquid) is preferable as the metal component-containing liquid. .. Many aluminum element contained in the aluminum component-containing liquid is alumina by heating; a _{(Al 2 O} 3 mp _T i = 2070 ℃). The eutectic temperature _{T E} of SiO ₂ and _Al 2 _{O 3} is 1595 ° C.. Since SiO ₂ is component A, the _Al 2 _{O 3} corresponding to the component _B, the relationship T m _{<T i} is satisfied. Then, within the temperature T _S of the heat treatment performed after imbibed with aluminum component-containing liquid into shaped mainly composed of silicon dioxide, of 1730 less than ° C. 1595 ° C. or higher which is capable of generating a cristobalite in the shaped object It can be set with. T _S is more preferably set in a range of higher 1663 ° C. or higher 1595 ° C..

In the case of a modeled product whose main component is silicon dioxide, the cracks are not reduced even if the cracks are heat-treated at a temperature 100 ° C. or higher lower than the melting point of _{SiO 2 by absorbing the aluminum component-containing liquid.} It can be extinguished. _{As described above, by heat treatment at a temperature sufficiently lower than the melting point of SiO 2} , which is the main component of the modeled object, it is possible to obtain a modeled object having improved mechanical strength while suppressing the shape change of the modeled object. ..

The metal component-containing liquid, even when using a liquid (zirconium component-containing liquid) containing zirconium element, component A SiO ₂ (melting point _T mi = 1730 ° C.), component B is ZrO ₂ (melting point _T i = 2715 ° C.) becomes , T _m <T _i .

As described above, it is excellent to absorb the metal component that forms a co-crystal with silica into the cracks of the modeled object mainly composed of amorphous silica produced by the direct modeling method and to heat-treat it at an appropriate temperature. A silica-based ceramic article having mechanical strength can be obtained.

Even if the powder itself contains a metal element used for repairing cracks, the effect of reducing cracks in the modeled object cannot be obtained. If the powder used for modeling contains a certain amount or more of the metal element used for repairing cracks, the entire modeled object will contain the metal element used for repairing cracks, and the melting point near the crack will be locally determined. It cannot be lowered. Then, the entire modeled object is melted by heating, and the modeled object may be deformed. In other words, in order to repair cracks without lowering the molding accuracy of the model, it is important to perform heat treatment with the concentration of metal elements in the vicinity of the cracks generated in the produced model locally increased. Is.

In order for the crack to absorb the metal component-containing liquid after molding and locally melt only the vicinity of the crack, the powder must not contain 3.0% by mass or more of the metal element oxide contained in the metal component-containing liquid. Is preferable. That is, when the modeling powder contains a metal element contained in the metal component-containing liquid, the content is preferably less than 3.0% by mass, more preferably less than 2.0% by mass of the entire powder. is there. By using such a powder in combination with a liquid containing a metal component, it is possible to realize an article having high molding accuracy and improved mechanical strength.

Next, three steps included in the method for producing a ceramic article according to the present invention will be described in detail.

<Step (i)>
A powder containing silicon dioxide as a main component, which contains an absorber that absorbs light having a wavelength contained in the irradiating laser, is placed on a base. The absorber can be selected depending on the type of laser used, but terbium oxide or praseodymium oxide is particularly preferable.

Silicon dioxide (silica) is represented by the _{chemical formula as SiO 2. The bonding state between the atoms of SiO 2} contained in the powder is not particularly limited, and may be amorphous, crystalline such as cristobalite or quartz, or a mixed state thereof. Among them, a powder containing cristobalite as a main component having high thermal conductivity is particularly preferable because the powder is easily melted by laser irradiation. _{Since the SiO 2 particles constituting the SiO 2} powder as the main component are densely arranged in the step (i), the shape is preferably close to a sphere where high fluidity can be obtained, and the average particle size is 5 μm or more and 200 μm or less. It is preferable to have it. A more preferable average particle size is 10 μm or more and 150 μm or less. In the present invention, the average particle size is not that of individual particles, but is the median diameter of a group of particles having the same composition, that is, the particle size (D ₅₀ ) at which the cumulative frequency is 50%. And. The method for measuring the average particle size is not particularly limited, but it can be calculated as the equivalent circle diameter of the projected image from the micrograph of the powder powder, or can be obtained by using the dynamic light scattering method.

The powder containing silicon dioxide as a main component contains an absorber as a sub-component. The term "absorber" as used herein refers to a component (element or compound) that exhibits a higher absorption capacity than silicon dioxide with respect to light having a wavelength contained in a laser used for modeling. The absorptive capacity of the absorber is preferably 10% or more, more preferably 40% or more, and further more preferably 60% or more with respect to the light of the wavelength contained in the laser beam used. preferable. The absorption rate of the absorber alone can be measured using a general spectroscope. Specifically, using an integrating sphere, a single absorber filled in a sample dish is irradiated with an assumed wavelength (near the laser wavelength used in manufacturing) for measurement. Then, it is advisable to calculate the absorption rate from the ratio using the case where there is no sample as reference data.

Such an absorber efficiently absorbs the laser light used in manufacturing, and by raising the temperature by itself, it spreads to other compositions existing in the region corresponding to the focal size of the laser light and the temperature rises. Bring. As a result, effective local heating is realized, the interface between the process region (the region irradiated with the laser beam) and the non-process region (the region not irradiated with the laser beam) can be clarified, and the molding accuracy is improved.

The absorber preferably changes to another composition having relatively low absorption, at least in part, by irradiation with a laser. For example, there is a composition in which the valence of a metal element changes due to the withdrawal of oxygen due to a temperature rise, and the composition changes to another metal oxide having a relatively low absorption to laser light. In addition, due to decomposition such as binding with other compositions contained in gas or powder in the atmosphere or release of oxygen, the composition changes to a composition different from that in the powder state and is incorporated into the modeled product. The composition may be the same. Specific examples of the absorber, oxides, transition metal carbide, transition metal _nitride, Si ₃ N 4, AlN, borides, and silicides. Suitable compositions as absorbers are Tb ₄ O ₇ , Pr ₆ O ₁₁ , Ti ₂ O ₃ , TiO, SiO, ZnO, antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , Cu ₂ O, CuO, Cr ₂ O ₃ , CrO ₃ , NiO, V ₂ O ₃ , VO ₂ , V ₂ O ₅ , V ₂ O ₄ , Co ₃ O ₄ , CoO, transition metal carbides, transition metal nitrides, Si ₃ N ₄ , AlN, borides, silicates. The transition metal carbide is preferably TiC or ZrC. The transition metal nitride is preferably TiN or ZrN. The boride is preferably TiB ₂ , ZrB ₂ , and LaB ₆ . The silicide is preferably TiSi ₂ , ZrSi ₂ , and MoSi ₂ . From these, a composition having a high affinity with other compositions constituting the powder may be selected as an absorber. Since the powder is silicon dioxide, a metal oxide is preferable as the absorber. From the viewpoint of having the highest affinity with silicon dioxide, SiO is preferable as an absorber. The absorber may be one kind of composition or a combination of a plurality of kinds of compositions.

It is preferable that the absorber showing good energy absorption with respect to the laser beam is finely and uniformly dispersed in the powder. As a result, the reaction that occurs in the powder when irradiated with the laser beam becomes uniform, and the molding accuracy is further improved. From such a viewpoint, the average particle size of the absorber contained in the powder is preferably 1 μm or more and less than 10 μm, and more preferably 1 μm or more and less than 5 μm.

The amount of the absorber contained in the powder is preferably 0.5 vol% or more and 10 vol% or less. By containing 0.5 vol% or more, in a general laser beam usage situation, one or more absorber particles are stochastically present in the laser beam irradiation portion, and the function as an absorber can be sufficiently obtained. it can. Further, by setting it to 10 vol% or less, it is possible to suppress a rapid temperature rise of the powder due to laser beam irradiation, and it is possible to suppress scattering of the molten material around, that is, a decrease in molding accuracy.

When using an Nd: YAG laser or a fiber laser as the laser used for modeling, the absorber may be terbium oxide (Tb ₄ O ₇ ) or placeodymium oxide, which can form a co-crystal with silicon dioxide, for the following two reasons. (Pr ₆ O ₁₁ ) is particularly preferable. The first reason is that terbium oxide and placeodymium oxide show good energy absorption for Nd: YAG laser (wavelength: 1064 nm) and fiber laser (wavelength: 1030 to 1100 nm). Since the powder used for modeling contains an absorber that has sufficient energy absorption in the powder that irradiates the laser beam, the spread of heat in the powder is further suppressed and becomes local, and the effect of heat on the non-modeled portion. Is reduced, so that the molding accuracy is further improved.

The second reason is that when the powder contains terbium oxide or praseodymium oxide, a phase-separated structure in which two or more kinds of phases are intricately intertwined with each other is formed in a network formed of silica. As described above, since the silica-based material has high viscosity in the liquid phase, the liquid silica melted by the laser beam becomes spherical, and the solidified portion has a structure in which spheres are connected in a network shape, that is, porous. Easy to get quality. However, when the powder contains terbium oxide or praseodymium oxide, the silica phase network and the phase containing terbium oxide or praseodymium oxide form a complicated phase separation structure, crack extension is suppressed, and the mechanical strength of the modeled product is suppressed. Is improved. In order to obtain a fine phase-separated structure, the particle size of terbium oxide and praseodymium oxide is preferably 1 μm or more and less than 10 μm. More preferably, it is 1 μm or more and less than 5 μm. As a result, a modeled object having higher mechanical strength can be obtained.

In order to adjust the physical characteristics of the ceramic article to be produced, the powder may contain a composition other than silicon dioxide and an absorber in a proportion of less than 10% by mass.

In the present specification, _{the material may be expressed by using a chemical formula such as SiO 2} and Tb ₄ O ₇ described above, but if the gist of the present invention is satisfied, the composition ratio of the elements of the actual material is satisfied. Does not have to be exactly the same as the ratio in the chemical formula. That is, the valences of the metal elements constituting a certain material may be slightly different from the valences assumed from the chemical formula. For example, when the absorber is SiO, the constituent element ratio of the absorber is Si: O = 1. : Even if it is 1.30, it is included in the present invention. From the viewpoint of obtaining sufficient light absorption capacity, a more preferable element composition ratio is within ± 15% of the deviation from the stoichiometric ratio.

The modeling is carried out on the base. As the base material, it can be appropriately selected and used from materials such as ceramics, metal, and glass that are generally used in the production of the modeled object in consideration of the intended use and manufacturing conditions of the modeled object. When the modeled object is heated together with the base in the step (iii), it is preferable to use heat-resistant ceramics as the base.

In the powder bed melt-bonding method, as shown in FIG. 1, powder is arranged with a predetermined thickness on the entire base with a roller, a blade, or the like. In the cladding method, as shown in FIG. 2, the powder is jetted and supplied from the nozzle to the irradiation position of the laser beam, and the powder is overlaid on the base or the modeled object arranged on the base. Deploy.

<Step (ii)>
In the subsequent step (ii), the powder arranged in the step (i) is sintered or melted by irradiating the powder with a laser based on the modeling data generated from the three-dimensional shape data of the model to be produced. Solidify.

In the case of the powder bed melt-bonding method, as shown in FIG. 1, a predetermined region of the powder layer arranged on the base with a predetermined thickness in the step (i) is irradiated while scanning a laser beam to irradiate the powder. Sinter, or melt and solidify. In the case of the cladding method, as shown in FIG. 2, the powder is selectively placed in the area to be formed at the same time by injecting and supplying the powder in the step (i) and overlaying it on the base. , Irradiate a laser beam to melt and solidify the powder.

When the powder is irradiated with a laser beam, the absorber contained in the powder absorbs energy, and the energy is converted into heat to melt the powder. When the powder is sintered, some of the particles melt. When the laser beam passes and the irradiation is completed, the heat of the molten portion escapes to the atmosphere and the surroundings to be cooled, and the solidified portion is formed. Due to the rapid temperature change in the process of melting and solidification, most of the shaped objects formed are amorphous silica. In addition, due to rapid temperature changes, stress is generated in the surface layer and inside of the modeled object, and cracks are often formed. When cracks are formed, the cracks may be reduced by a subsequent heating step. Further, by introducing a step of absorbing the metal component-containing liquid described in detail later, cracks can be further reduced or eliminated.

As mentioned above, when the silicon dioxide-based powder contains terbium oxide or praseodymium oxide, two or more types of phases are intricately intertwined with each other in a network in which spherical silica formed by melting the powder is connected. It has a phase-separated structure. When heat treatment is performed on such a structure in the step (iii), silica crystallizes to become cristobalite, and the mechanical strength of the modeled object is improved.

The type of laser beam is not particularly limited, but a YAG laser having a wavelength band of 1 μm, a fiber laser, a CO2 laser having a wavelength band of 10 μm, and the like are suitable. In particular, a YAG laser or a fiber laser in the 1 μm wavelength band is preferable because terbium oxide and praseodymium oxide show high absorption.

<Process (iii)>
As shown in the flow chart of FIG. 4, in the step (iii), the shaped object formed by repeating the step (i) and the step (ii) a plurality of times is heated at 1470 ° C. or higher and lower than 1730 ° C. The number of repetitions corresponds to the number of slices n of the slice data generated from the three-dimensional shape data of the three-dimensional object to be manufactured.

In the modeled object, a powder layer is newly arranged by the step (i) on the solidified portion formed in the step (i) and the step (ii). When the arranged powder is irradiated while scanning the laser beam based on the modeling data generated from the three-dimensional shape data of the modeling model, the powder in the region irradiated with the laser beam melts and solidifies. At this time, since the surface layer of the solidified portion formed earlier is also melted, it becomes one with the solidified portion formed later. By alternately repeating the step (i) and the step (ii), it is possible to obtain a modeled object having a desired shape according to the three-dimensional shape data of the modeling model.

When a large number of cracks are contained in the modeled object formed by repeating the steps (i) and the step (ii), as shown in the flow chart of FIG. 5, the modeled object is subjected to the heat treatment before the heat treatment. It is preferable to perform a treatment for absorbing the metal component-containing liquid.

As long as the metal component-containing liquid in an amount required for the crack can be supplied over the entire crack contained in the modeled object, the method for causing the modeled object to absorb the metal component-containing liquid is not particularly limited. The modeled object may be impregnated by immersing the modeled object in the metal component-containing liquid, or the metal component-containing solution may be atomized and sprayed onto the modeled object, or may be applied to the surface with a brush or the like to be absorbed. Further, a plurality of these methods may be combined, or the same method may be repeated a plurality of times.

As described above, an aluminum component-containing liquid, a zirconium component-containing liquid (a liquid containing zirconium), or the like can be used as the metal component-containing liquid in the modeled product containing silica as a main component, but the aluminum component-containing liquid is particularly preferable. preferable. Hereinafter, a case where an aluminum component-containing liquid is used as the metal component-containing liquid will be described in detail.

The aluminum component-containing liquid is preferably composed of, for example, a raw material containing an aluminum element, a solvent, and a stabilizer. Various aluminum compounds can be used as the raw material containing the aluminum element, and aluminum metal alkoxides and chlorides can be used.

In the case of an aluminum component-containing liquid containing aluminum as a metal alkoxide, it is preferable to contain the aluminum alkoxide, an organic solvent, and a stabilizer. For example, first, aluminum alkoxide is dissolved in an organic solvent to prepare a solution of aluminum alkoxide. Specific examples of the aluminum alkoxide include aluminum sec-butoxide, aluminum ethoxydo, aluminum n-butoxide, aluminum tert-butoxide, aluminum isopropoxide and the like. The amount of the organic solvent added to the aluminum 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. In the present invention, the addition amount of M being 5 in molar ratio with respect to N means that the molar amount of M to be added is 5 times the molar amount of N. If the concentration of aluminum alkoxide in the solution is too low, a sufficient amount of aluminum component cannot be absorbed by the model. On the other hand, if the concentration of the aluminum alkoxide in the solution is too high, the aluminum component in the solution agglomerates, and the aluminum component cannot be uniformly arranged in the crack portion of the modeled object.

Examples of the organic solvent for dissolving the aluminum alkoxide include alcohols, carboxylic acids, aliphatic or alicyclic hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers, or a mixture of two or more thereof. A solvent is used. Examples of alcohols include methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propanol-2 propanol. 4-Methyl-2-pentanol, 2-ethylbutanol, 3-methoxy-3-methylbutanol, ethylene glycol, diethylene glycol, glycerin and the like are preferable. As the aliphatic or alicyclic hydrocarbons, n-hexane, n-octane, cyclohexane, cyclopentane, cyclooctane and the like are preferable. As the aromatic hydrocarbons, toluene, xylene, ethylbenzene and the like are preferable. As the esters, 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 are preferable. As the ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like are preferable. Examples of ethers include dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether and the like. In preparing the aluminum component-containing liquid, it is preferable to use alcohols among the various solvents described above from the viewpoint of solution stability.

Since aluminum alkoxide is highly reactive with water, it is rapidly hydrolyzed by the addition of moisture or water in the air, causing the solution to become cloudy or precipitate. In order to prevent these, it is preferable to add a stabilizer to stabilize the solution. Stabilizers include β-diketone compounds such as, for example, acetylacetone, 3-methyl-2,4-pentandione, 3-ethyl-2,4-pentandione, trifluoroacetylacetone; methyl acetoacetate, ethyl acetoacetate. , Butyl acetoacetate, allyl acetoacetate, benzyl acetoacetate, isopropyl acetoacetone, tert-butyl acetoacetate, isobutyl acetoacetate, ethyl 3-oxohexanate, ethyl 2-methylacetoacetate, ethyl 2-fluoroacetoacetone, acetoacetate 2 Β-ketoester compounds such as −methoxyethyl; further, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and the like can be mentioned. The amount of the stabilizer added is preferably 0.1 or more and 3 or less in terms of molar ratio with respect to the aluminum alkoxide. More preferably, it is 0.5 or more and 2 or less.

The solution may be prepared by reacting at room temperature or refluxing.

In the case of an aluminum component-containing liquid containing aluminum as a chloride, it is preferable to contain an aluminum salt and water. The aluminum salt is not particularly limited as long as it is water-soluble. Nitrate, sulfate, acetate, chloride and the like are particularly preferred. Depending on the type of aluminum salt, the aqueous solution may become unstable. In that case, it is advisable to add a stabilizer to stabilize the liquid. The stabilizer preferably contains at least one of an organic acid, a surfactant and a chelating agent. Examples of the organic acid include acrylic acid, 2-hydroxyethyl acrylate, 2-acryloxyethyl succinic acid, 2-acryloxyethyl hexahydrophthalic acid, 2-acryloxyethyl phthalic acid, 2-methylhexane acid, 2-. Ethylhexanic acid, 3-methylhexanelic acid, 3-ethylhexanenic acid and the like are preferable. Examples of the surfactant include ionic surfactants such as sodium oleate, potassium fatty acid, sodium alkylphosphate, alkylmethylammonium chloride, and alkylaminocarboxylate, polyoxyethylene laurin fatty acid ester, and polyoxyethylene alkylphenyl. Nonionic surfactants such as ethers are preferred. Examples of the chelating agent include glycolic acid, ascorbic acid, citric acid, malonic acid, gluconic acid, oxalic acid, succinic acid, malic acid, tartaric acid, hydroxy acids such as lactic acid, glycine, alanine, glycine, glutamic acid, and aspartic acid. Amino acids such as histidine, phenylalanine, asparagine, arginine, glutamine, cystine, leucine, lysine, proline, serine, tryptophan, valine, tyrosine, diethylenetriamine-5 acid acid (DTPA), hydroxyethylethylenediamine 3acetic acid (HEDTA), triethylenetetraamine 6 Acetic acid (TTHA), 1,3-propanediamine 4 acetic acid (PDTA), 1,3-diamino-6-hydroxypropane 4 acetic acid (DPTA-OH), hydroxyethylimino diacetic acid (HIDA), dihydroxyethylglycine (DHEG) , Aminocarboxylic acids such as glycol etherdiamine tetraacetic acid (GEDTA), dicarboxymethyl glutamate (CMGA), and (S, S) -ethylenediamine disuccinic acid (EDDS), 1-hydroxyethylidene-1,1-diphosphonic acid ( HEDP), 2-phosphobutanone-1,2,4-tricarboxylic acid (PBTC), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), phosphonic acid such as nitrilotris (methylenephosphonic acid), salicylic acid, etc. Aromatic acids are preferred.

The method for producing the aluminum component-containing liquid does not matter. It is preferably prepared by mixing an aluminum salt, water and a stabilizer, but it may be prepared by mixing all at once. Alternatively, the metal salt and the stabilizer may be mixed and then water may be added and mixed, or the metal salt and water may be mixed and then the stabilizer may be added and mixed, or the mixture may be stabilized. It may be prepared by mixing the agent and water and then mixing the metal salt.

Further, as the aluminum component-containing liquid, it is also preferable to use a particle dispersion liquid composed of particles containing an aluminum element, a dispersant and a solvent.

As the particles containing an aluminum element, aluminum particles and alumina particles can be used. Aluminum particles or alumina particles may be produced by crushing each material by a top-down method, or by a bottom-up method such as a hydrothermal reaction from metal salts, hydrates, hydroxides, carbonates, etc. May be synthesized using, or a commercially available product may be used.

The size of the particles is 300 nm or less, more preferably 50 nm or less, still more preferably 30 nm or less in order to penetrate the cracks.

The shape of the fine particles is not particularly limited, and may be spherical, granular, columnar, elliptical spherical, cubic, rectangular parallelepiped, needle-shaped, columnar, plate-shaped, scaly, or pyramid-shaped.

The dispersant preferably contains at least one of an organic acid, a silane coupling agent, and a surfactant. Examples of the organic acid include acrylic acid, 2-hydroxyethyl acrylate, 2-acryloxyethyl succinic acid, 2-acryloxyethyl hexahydrophthalic acid, 2-acryloxyethyl phthalic acid, 2-methylhexane acid, 2-. Ethylhexanic acid, 3-methylhexanelic acid, 3-ethylhexanenic acid and the like are preferable. As the silane coupling agent, for example, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane and the like are preferable. Examples of the surfactant include ionic surfactants such as sodium oleate, potassium fatty acid, sodium alkylphosphate, alkylmethylammonium chloride, and alkylaminocarboxylate, polyoxyethylene laurin fatty acid ester, and polyoxyethylene alkylphenyl. Nonionic surfactants such as ethers are preferred.

As the solvent, alcohols, ketones, esters, ethers, ester-modified ethers, hydrocarbons, halogenated hydrocarbons, amides, water, oils, or a mixed solvent of two or more of these is used. As the alcohols, for example, methanol, ethanol, 2-propanol, isopropanol, 1-butanol, ethylene glycol and the like are preferable. As the ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like are preferable. As the esters, for example, ethyl acetate, propyl acetate, butyl acetate, 4-butyrolactone, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate and the like are preferable. As the ethers, for example, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, butyl carbitol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-butoxyethanol and the like are preferable. As the modified ethers, for example, propylene glycol monomethyl ether acetate is preferable. As the hydrocarbons, for example, benzene, toluene, xylene, ethylbenzene, trimethylbenzene, hexane, cyclohexane, methylcyclohexane and the like are preferable. As the halogenated hydrocarbons, for example, dichloromethane, dichloroethane, and chloroform are preferable. As the amides, for example, dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are preferable. As the oils, for example, mineral oil, vegetable oil, wax oil, and silicone oil are preferable.

The particle dispersion may be prepared by simultaneously mixing aluminum particles or alumina particles with a dispersant and a solvent, or may be prepared by mixing aluminum particles or alumina particles with a dispersant and then mixing the solvent. Alternatively, the dispersant may be mixed after mixing the fine particles of aluminum or alumina with the solvent, or the fine particles of aluminum or alumina may be mixed after mixing the dispersant and the solvent. You may.

In the above step (iii), in order to absorb the aluminum component-containing liquid in the cracks formed in the modeled object and locally melt the vicinity of the portion where the aluminum element is present, the heating temperature and the amount of the aluminum element in the crack are adjusted. You should adjust it. The amount of the aluminum element in the crack can be adjusted by the concentration of the aluminum element in the aluminum component-containing liquid, the method of allowing the crack to absorb the aluminum component-containing liquid, the number of times, and the like. It is also possible to adjust by repeating the steps of absorbing and heating the aluminum component-containing liquid in order. In particular, by increasing the amount of the aluminum element present in the crack, the vicinity of the crack becomes more likely to melt. By adjusting the amount of aluminum elements present in the cracks in this way, the complex shape and precise shape formed by the direct modeling method are maintained without the shape of the modeled object being deformed, and the modeled object is approximately as designed. A shape can be obtained, and modeling with high modeling accuracy can be realized.

The silica model having absorbed the aluminum content liquid is heated at a temperature equal to or higher than the eutectic point of the eutectic phase formed of silica and aluminum oxide and lower than the melting point of silica (1710 ° C.). Then, the amount of aluminum oxide generated from the aluminum component-containing liquid existing in the surface layer and internal cracks of the silica-based modeled material, or the amount having a eutectic composition according to the amount of aluminum oxide contained in the aluminum component-containing liquid from the beginning. Silica melts. That is, since more aluminum oxide is present on the surface of the modeled object in contact with the aluminum-containing liquid than in the portion away from the cracks, the vicinity of the cracks approaches the eutectic composition, and it is possible to selectively melt the mixture. By heat-treating the silica in the vicinity of the cracks, which has undergone the step of absorbing the aluminum component-containing liquid, so that the maximum temperature near the cracks is 1595 ° C. or higher and lower than 1730 ° C., the silica is changed to cristobalite, and at the same time, the cracks are reduced or eliminated. be able to.

The heating time does not matter as long as the vicinity of the crack reaches the above maximum temperature. Specifically, it is preferable to heat the modeled object at a temperature of 1595 ° C. or higher and lower than 1730 ° C., which is the temperature at which the vicinity of the crack is desired to reach.

The heating method is not particularly limited. The modeled object that has absorbed the aluminum component-containing liquid may be heated by irradiating it with an energy beam, or it may be placed in an electric furnace and heated. When heating with an energy beam, it is advisable to grasp in advance the relationship between the amount of heat input of the energy beam and the temperature of the modeled object by a thermoelectric pair or the like so that the modeled object is heated to the above-mentioned preferable temperature.

In the heat treatment step, the surface layer of the modeled object or the vicinity of cracks may melt and stick to the setter. Therefore, when the modeled object is placed on the setter in the heat treatment step, the setter is preferably inert. As the inert setter, for example, platinum or the like can be applied in an atmospheric atmosphere, and iridium or the like can be applied in a low oxygen atmosphere.

By the step (iii), a phase containing silicon dioxide, terbium or praseodymium (crystal grains) and a phase containing an aluminum element (crystal grains) are formed in the modeled product, and their particle sizes (for example, average particle size) are formed. ) Are very different. It is considered that this is because the crack portion and its vicinity melt and move in the direction in which the surface energy decreases, so that the crack decreases or disappears. Then, as the heating progresses further, the aluminum component distributed in the crack portion diffuses into the crystalline and non-crystalline inside of the modeled product, and the crystal of the modeled product recrystallizes in a state containing the aluminum component. It is thought that. In addition to reducing or eliminating cracks in the modeled object in this way, the machinability of the modeled object is improved by forming a phase-separated structure composed of a plurality of phases having different average particle sizes of crystal grains. However, precise finishing with few chips is possible.

<Ceramics article>
The ceramic article of the present invention preferably has a phase-separated structure containing two or more types of phases, particularly three or more types. A preferable combination of the three types of phases _{is a phase containing SiO 2} as a main component, a phase containing a rare earth silicate containing terbium or praseodymium as a main component, and Al, which is an oxide of a metal element contained in the metal component-containing liquid. It is a phase containing ₂ O _{3 as a main component.} SiO ₂ , rare earth silicate, and Al ₂ O ₃ are in a relationship of forming eutectics with each other, and a complicated phase separation structure composed of three types of phases can be stably formed.

The _{phase containing SiO 2} as a main component is a phase in which amorphous silica is changed to cristobalite by the heating step of the step (iii). Specifically, the phase containing a rare earth silicate containing terbium or praseodymium as a main component is preferably a _{Si 2} Tb ₂ O ₇ phase or a Si ₂ Pr ₂ O _{7 phase.} Each phase can be identified by, for example, X-ray diffraction, electron diffraction, or structural analysis by EBSD (Electron Backscattering Diffraction). The crystal structure of each phase varies slightly depending on the production process, but it is preferable that the three types of eutectic phases have the above-mentioned crystal structure.

Cristobalite includes α-cristobalite and β-cristobalite, and their phase transition temperature is about 240 ° C. Cristobalite has been regarded as a vulnerable material to temperature changes because the volume change of cristobalite occurs rapidly at this phase transition temperature. However, in the present invention, even if silica is changed to cristobalite, excellent mechanical strength against temperature change is obtained. It is considered that this is because the silica-based structure has a phase-separated structure composed of a plurality of phases such as _{Tb 2} Si ₂ O ₇ phase and Pr ₂ Si ₂ O _{7 phase in addition to cristobalite.} It is considered that when the silica-based structure has a phase-separated structure composed of a plurality of phases, the volume change due to thermal expansion at the phase transition temperature becomes gentle and the sudden volume change due to the temperature change is suppressed. ..

When used as a core for casting, the amount of Si contained in the ceramic article of the present invention is preferably more than 80% by mass in terms of _{oxide (converted to SiO 2).} If Si is 80% by mass or less, the solubility in an alkaline solution required as a casting core cannot be obtained. Examples of the alkaline solution include an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide.

The Tb or Pr contained in the ceramic article of the present invention is preferably 1.0% by mass or more and 20% by mass or less in _{terms of oxides (Tb 2} O ₃ and Pr ₂ O _{3 conversion), preferably 3.0% by mass.} More preferably 15% by mass or less. If Tb or Pr is less than 1.0% by mass, the amount of laser energy absorbed is small, so that a highly accurate model may not be obtained. If Tb or Pr is larger than 20% by mass, the solubility in an alkaline aqueous solution required as a casting core cannot be obtained.

More than 70% by mass of silicon dioxide in the ceramic article of the present invention is cristobalite bonded to oxygen. If cristobalite is less than 70% by mass, the strength required for a casting core may not be obtained. Preferably, 90% by mass or more, more preferably 95% by mass or more of silicon dioxide is cristobalite.

The porosity of the ceramic article of the present invention is preferably 10% or more and 40% or less. If the porosity is less than 10%, the bending strength becomes too strong, and the casting may crack when used as a casting core. If the porosity is greater than 40%, the strength required for the structure cannot be obtained. As will be described in detail later, the porosity in the present invention indicates the open porosity.

Boron (B) contained in the ceramic article in the present invention is preferably less than 1000 ppm. If B is more than 1000 ppm, the softening point is lowered, and the heat resistance required for a casting core may not be obtained.

<Evaluation method of physical property value>
(Mechanical strength)
The mechanical strength of the modeled object was evaluated by a three-point bending test based on R1601, which is a JIS standard for a room temperature bending strength test of fine ceramics. For each of the 10 test pieces, the 3-point bending strength is P [N] for the maximum load when broken, L [mm] for the distance between external fulcrums, w [mm] for the width of the test piece, and the test piece. When the thickness is t [mm]
3 × P × L / (2 × w × t2) (Equation 1)
Was calculated using, and the values were averaged.

(Porosity)
The porosity of the modeled object was evaluated by a method based on R1634, which is a JIS standard for measuring the sintered body density and open porosity of fine ceramics. Specifically, for three ceramic articles similar to the sample used for measuring the mechanical strength, when the dry mass of the modeled object is W1, the mass in water is W2, and the mass of saturated water is W3, {(W3-W1). ) / (W3-W2)} × 100, and averaged them.

(Relative density)
The relative density [%] was calculated by dividing the bulk density (mass divided by volume) of the modeled object by the theoretical density. The theoretical density was calculated from the crystal structure. The crystal structure was identified by performing X-ray diffraction measurements and performing Rietveld analysis.

(Crystal structure)
The phase contained in the ceramic article was identified by X-ray diffraction measurement by polishing the cross section of the central portion of the object to be measured to form a measurement surface.

The content of each phase contained in the object to be measured was calculated by the following method. Simultaneous analysis of SEM-EDX and EBSD was performed at 10 different locations with a visual field size of 100 μm × 100 μm on the measurement surface, and mapping was performed for the composition and crystal phase. For the created 10 maps, the area ratio occupied by each phase was obtained, and the ratio of each phase contained in the sample was calculated from the average value of them. When a small phase is included, the composition and crystal structure can be analyzed in the same manner by using a transmission electron microscope (TEM).

For the particle size of the crystal grains constituting the phase, use EBSD to observe 300 or more crystal grains in the same phase observed on the measurement surface, and calculate the average value of the equivalent circle diameters of each crystal grain. I calculated that.

(Composition analysis)
The content of Si, Tb, Pr, Al and Zr contained in powders, shaped objects or ceramic articles is measured by inductively coupled plasma atomic emission spectrometry (ICP-AES), and the content of other elements including B is GDMS. Alternatively, it was measured by ICP-MS.

(Example 1)
_{Prepare SiO 2} powder with an average particle size of about 38 _{μm and Tb 4} O ₇ powder with an average particle size of 4 μm, Si is 90.0% by mass in oxide conversion (SiO ₂ conversion), and Tb is oxide conversion (Tb). was weighed powders in ₄ O ₇ terms) such that the 10.0 wt% (Table 1). The _{main component of SiO 2} powder is cristobalite. Each weighing powder was mixed in a dry ball mill for 30 minutes to obtain a mixed powder. The average particle size in the present invention is the median diameter (also referred to as the median value), and is the particle size (D50) at which the cumulative frequency is 50%. When the composition of the mixed powder was analyzed by ICP emission spectroscopic analysis, the content of aluminum oxide was less than 1% by mass.

Next, the modeled product of Example 1 was produced in the same manner as in the process shown in FIG. The shape of the produced modeled object is a rectangular parallelepiped of 5 mm × 42 mm × 6 mm. A ProXDMP 100 (trade name) manufactured by 3D SYSTEMS, which is equipped with a 50 W fiber laser (beam diameter 65 μm), was used to form the modeled object.

First, a 20 μm-thick first-layer powder layer made of the powder was formed on an alumina base 130 using a roller (FIGS. 1 (a) and 1 (b)).

Next, the powder layer was irradiated while scanning a 47.5 W laser beam to melt and solidify the material powder in a rectangular region of 5 mm × 42 mm to form a solidified portion 100 (FIG. 1 (c)). At this time, the drawing speed was 60 mm / s and the drawing pitch was 80 μm. As shown in FIG. 6A, the drawing line is set to be at an angle of 45 degrees with respect to each side of the rectangle.

Next, a 20 μm-thick powder layer is newly formed by a roller so as to cover the solidified portion 100, the powder layer is irradiated while scanning the laser beam, and the material powder in the rectangular region of 5 mm × 42 mm is melted and formed. It was solidified to form a solidified portion 100 (FIGS. 1 (d) and 1 (e)). At this time, as shown in FIG. 6B, the laser was scanned in a direction orthogonal to the drawing line of the first layer to melt and solidify the powder. Such a process was repeated until the height of the solidified portion became 6 mm, and 14 42 mm × 5 mm × 6 mm shaped objects were produced.

When the surface of the modeled object was observed with an optical microscope, the Ra of the surface of the modeled object measured while avoiding the pores was 30 μm or less.

Each of the produced shaped objects was separated from an alumina base, and 13 of them were polished to obtain a 40 mm × 4 mm × 3 mm shaped object as a test piece for a three-point bending strength test and a porosity measurement.

When the porosity was evaluated for the test piece prepared for the porosity measurement, the porosity was 18.4%. Moreover, when the X-ray diffraction of the polished surface was measured, it was found that the crystal phase in the ceramic article was substantially amorphous.

The modeled object excluding the test piece for porosity measurement was placed in an electric furnace and heat-treated. Specifically, the temperature was raised to 1610 ° C. in an air atmosphere for 2.5 hours, held at 1610 ° C. for 50 minutes, and then energization was terminated to cool the temperature to 200 ° C. or lower in 5.0 hours.

When the composition of the obtained ceramic article was measured by ICP-AES, Si was 90.3% by mass in terms of _{SiO 2} and Tb was 9.7% by mass in terms of _{Tb 2} O _3. Moreover, when GDMS analysis was performed, B was 0.4 ppm.

Next, in order to analyze the crystal structure of the ceramic article, the ceramic article was cut and polished. First, both sides were cut with a wire saw so that the central portion of the unpolished ceramic article remained, and a test piece of 10 mm × 4 mm × 3 mm was obtained. Then, by polishing about 1.5 mm in the H direction and further polishing in a mirror shape, an observation surface of 10 mm × 4 mm was obtained.

From the X-ray diffraction of the observation surface, it was found that the crystal phase in the ceramic article was composed of cristobalite (SiO ₂ ) and Tb ₂ Si ₂ O _{7 phase.}

Furthermore, simultaneous analysis of SEM-EDX and EBSD on the observation surface was performed. 10 different locations were analyzed with a field size of 100 μm × 100 μm to obtain a mapping between composition and crystal phase. As a result, _{most of the SiO 2} portion was cristobalite, and the ratio was 97 [mass%]. The rest was amorphous silica in which the Kikuchi pattern was not detected by EBSD. The ratio of cristobalite to amorphous silica is based on the respective areas obtained by SEM-EDX and EBSD mapping, the general cristobalite density of 2.3 g / cc, and the general amorphous silica density of 2.2 g / cc. Calculated. The Tb ₂ Si ₂ O ₇ phases were scattered throughout the visual field, and the average circle equivalent diameter calculated from the area obtained by mapping was 2.3 μm.

When a three-point bending test was performed on the test piece for the strength test, it was 7.2 [MPa].

The Si, Tb, Al, Zr, and B contents, porosity, and three-point bending strength of the ceramic article were evaluated. The results are shown in Table 2. The following examples and comparative examples were also evaluated in the same manner, and the results are shown in Table 2.

In Table 1, which shows the weighed values of the powder, the contents of Si, Al, and Tb, Pr, and Si of the absorber are set to SiO ₂ , Al ₂ O ₃ , Tb ₄ O ₇ , Pr ₆ O ₁₁ , and SiO, respectively. It is expressed as a converted value. On the other hand, Table 2 showing the evaluation results of the ceramic articles shows that the contents of Si, Tb, Pr, Al, and Zr are set to SiO ₂ , Tb ₂ O ₃ , Pr ₂ O ₃ , Al ₂ O ₃ , and ZrO ₂ , respectively. It is expressed as a converted value.

(Example 2)
A ceramic article was produced in the same manner as in Example 1 except that the produced model was impregnated with an aluminum component-containing liquid before being heat-treated.

The aluminum component-containing liquid was prepared as follows. Aluminum sec-butoxide was dissolved in 2-propanol (IPA) and ethyl acetoacetate (EAcAc) was added as a stabilizer. The molar ratio of each component was aluminum sec-butoxide: IPA: EAcAc = 1.04: 5: 2. Then, the aluminum component-containing liquid was prepared by stirring at room temperature for about 3 hours.

In Example 2, the W40 mm × D4 mm × H3 mm model processed for the test was immersed in the adjusted aluminum component-containing liquid, degassed under reduced pressure for 1 minute, and then the liquid was absorbed into the model, and then 1 Allowed to air dry for hours.

Subsequently, the modeled object that had absorbed the aluminum component-containing liquid was placed in an electric furnace and heated. The temperature was raised to 1610 ° C. in the air atmosphere for 2.5 hours, held at 1610 ° C. for 50 minutes, and then energization was terminated and the temperature was cooled to 200 ° C. or lower in 5.0 hours.

As a result of polishing the surface of the obtained ceramic article and analyzing the crystal structure by X-ray diffraction and EBSD, SiO ₂ was cristobalite, and the proportion thereof was 97% by mass. Furthermore, Si ₂ Tb ₂ O ₇ phase was also observed.

(Example 3)
Example 3 is different from Example 2 in that the step of absorbing the aluminum component-containing liquid and the step of heat-treating the produced modeled object are alternately repeated twice.

Three ceramic articles for a three-point bending strength test of W40 mm × D4 mm × H3 mm and one ceramic article for composition and structure evaluation same as those for the strength test were prepared.

The surface of the obtained ceramic article was polished, and the crystal structure was analyzed by X-ray diffraction and EBSD. As a result, SiO ₂ was cristobalite, and its proportion was 98% by mass. Furthermore, Si ₂ Tb ₂ O ₇ phase was also observed.

(Example 4)
A ceramic article was produced in the same manner as in Example 1 except that the zirconium component-containing liquid was impregnated before the heat treatment and the heat treatment temperature was set to 1670 ° C.

The zirconium component-containing liquid was prepared as follows. A solution prepared by dissolving 85% by mass of zirconium butoxide (zirconium (IV) butoxide (hereinafter referred to as Zr (On-Bu) 4)) in 1-butanol was prepared. The solution of Zr (On-Bu) 4 was dissolved in 2-propanol (IPA), and ethyl acetoacetate (EAcAc) was added as a stabilizer. The molar ratio of each component was Zr (On-Bu) 4: IPA: EAcAc = 1: 15: 2. Then, the zirconium component-containing liquid was prepared by stirring at room temperature for about 3 hours.

In Example 4, the modeled product processed for the test was immersed in the zirconium component-containing liquid, degassed under reduced pressure for 1 minute, impregnated with the liquid to the inside of the modeled product, and then naturally dried for 1 hour. Then, the modeled product impregnated with the zirconium component-containing liquid was placed in an electric furnace and heated. The temperature was raised to 1670 ° C. in the air atmosphere for 2.5 hours, held at 1670 ° C. for 50 minutes, and then the energization was terminated and the temperature was cooled to 200 ° C. or lower in 1.5 hours.

Next, the surface of the obtained ceramic article was polished, and the crystal structure was analyzed by X-ray diffraction and EBSD. As a result, SiO ₂ was cristobalite, and its proportion was 98% by mass. Furthermore, Si ₂ Tb ₂ O ₇ phase was also observed.

(Example 5)
Example 5 is different from Example 4 in that the step of impregnating the modeled object with the zirconium component-containing liquid and the step of heat-treating the modeled object are alternately repeated twice.

The produced ceramic articles consist of three W40 mm x D4 mm x H3 mm cubes for a three-point bending strength test, one cube for composition and structure evaluation, which is the same as for the strength test, and a wear resistance test of W5 mm x D5 mm x H5 mm. There is one cube for use.

As a result of evaluating the produced silica-based structure, SiO ₂ was cristobalite, and the proportion thereof was 99% by mass. Furthermore, Si ₂ Tb ₂ O ₇ phase was also observed.

(Examples 6 to 9)
Similar to Example 3, the steps of impregnating the aluminum component-containing liquid and the step of heat treatment were alternately repeated twice each, except that the mass ratios of the SiO ₂ powder and the Tb ₄ O _{7 powder were changed.} 6 to 9 ceramic articles were prepared. The mass ratio of the mixed powder of each example is shown in Table 1.

(Example 10 and Example 11)
Ceramic articles of Example 10 and Example 11 were prepared in the same manner as in Example 1 except that the mass ratios of the SiO ₂ powder and the Tb ₄ O _{7 powder were changed.} The mass ratio of the mixed powder of each example is shown in Table 1.

(Examples 12 to 14)
Examples 12 to 14 were carried out in the same steps as in Example 1 except that the heat treatment temperature was changed by using a powder obtained by mixing _{SiO 2} powder and Tb ₄ O ₇ powder in the mass ratio shown in Table 1. A ceramic article was produced. Table 2 shows the respective heat treatment temperatures.

(Example 15 and Example 16)
_{SiO 2} powder and Tb ₄ O ₇ powder were weighed at the mass ratios shown in Table 1, and a powder obtained by adding a very small amount of _{B 2} O _{3 powder and mixing them was used.} The ceramic articles of Example 15 and Example 16 were produced in the same steps as in Example 1 except that the heat treatment temperature was set to 1470 ° C.

(Example 17)
As an absorbent, _{the same steps as in Example 1 were carried out except that the Tb 4} O ₇ powder was changed to Pr ₆ O ₁₁ powder and the powder mixed at the mass ratio shown in Table 1 was used. Obtained a ceramic article.

(Example 18)
The ceramic structure of Example 18 was obtained in the same process as in Example 2 except that the aluminum component-containing liquid used was different. Table 1 shows the mass ratios of the weighed SiO ₂ powder and Tb ₄ O _{7 powder.}

The aluminum component-containing liquid was prepared as follows using alumina particles. Alumina particles with an average particle size of 24 nm (manufactured by Kanto Chemical Co., Inc.), 2-hydroxyethyl acrylate and 3-acryloxypropyltrimethoxysilane as dispersants, and methyl ethyl ketone as a solvent are used as a dispersion, and the concentration of alumina in the dispersion is 70% by mass. The mixture was uniformly stirred to obtain an alumina particle dispersion.

(Example 19)
A ceramic article was produced in the same manner as in Example 3 except that SiO powder was used as an absorber at the mass ratio shown in Table 1. The SiO powder used had an average particle size of 5 μm.

Three silica-based structures for a three-point bending strength test of W40 mm × D4 mm × H3 mm and one silica-based structure for strength test were prepared for composition and structural evaluation.

The surface of the obtained silica-based structure was polished, and the crystal structure was analyzed by X-ray diffraction and EBSD. As a result, SiO ₂ was cristobalite, and its proportion was 98% by mass.

(Example 20 and Example 21)
The same steps as in Example 4 were carried out to prepare ceramic articles of Example 20 and Example 21. However, at the mass ratio shown in Table 1, SiO ₂ powder, Al ₂ O ₃ powder, and SiO powder as an absorber were weighed, a zirconium component-containing liquid was used as the metal component-containing liquid, and the heat treatment temperature was set to 1680 ° C. Is different from Example 4. The Al ₂ O ₃ powder used had an average particle size of 20 μm. As the zirconium component-containing liquid, an aqueous zirconium acetate solution prepared so that the zirconia content was 30% by mass was used.

The ceramic articles of Examples other than Example 15 had a smaller amount of B and a higher mechanical strength of 5.0 MPa or more as compared with the structures of other Examples 15. Further, when the ceramic articles of Examples 15 and 16 were heated at 1600 ° C., the corners of the structure of Example 15 were slightly deformed. Example 15 containing a large amount of B had lower heat resistance than other examples.

_Si 2 _Tb 2 _{O 7} phase in the ceramic article from Example 1 16 and Example 18, _Si 2 _Pr 2 _{O 7} phase in the ceramic article of Example 17 was observed. As a result, a phase-separated structure is formed inside the structure, and it is considered that the mechanical strength is improved. It is presumed that these structures also have the effect of suppressing the temperature change of the coefficient of thermal expansion and relaxing the thermal stress.

Metal component-containing liquid Example 21 from Example 2 to 9 and Example 18 in which the heat treatment after imbibed with the reduction or elimination of cracks, and even higher strength by the formation of the Al ₂ O ₃ phase obtained Was done.

Further, when the surface of the ceramic article was observed with a microscope, the Ra of the structure surface measured while avoiding the pores was 30 μm or less in the ceramic article of all the examples.

(Comparative Example 1)
As shown in Table 1, a _{powder obtained by increasing the Tb 4} O ₇ powder mixed with the _{SiO 2} powder to about 27.0% by mass was used, except that the drawing pitch of the irradiated laser beam was 170 μm. The ceramic article of Comparative Example 1 was produced in the same manner as in 1. The porosity of the obtained ceramic article was as large as 45.0%, and the three-point bending strength was as small as 1.2 MPa.

(Comparative Example 2)
As shown in Table 1, when modeling was performed in the same manner as in Example 1 except that the mass ratio of the powder _{Tb 4} O _{7 powder used for modeling was increased to about 27.0% by mass, Tb 2 occupying the modeled object.} The amount of Si ₂ O _{7 has increased.} The amount of Si contained in the ceramic article was 80% by mass or less in terms of oxide. 0.1 g of the modeled product of Comparative Example 2 was placed in 20 ml of an aqueous sodium hydroxide solution having a concentration of 20% by mass, and the container was sealed and kept heated to 100 ° C. for 450 minutes. 0.02 g of was left undissolved.

Therefore, it is considered that the ceramic article of Comparative Example 2 has insufficient solubility in sodium hydroxide for use as a casting core.

(Comparative Example 3)
A ceramic article was produced in the same manner as in Example 1 except that the heating temperature after modeling was 1440 ° C. When the crystal structure of the ceramic article was evaluated in the same manner as in Example 1, most of the ceramic articles were amorphous silica, and the three-point bending strength evaluated in the same manner as in Example 1 was as small as 2.0 MPa.

(Comparative Example 4)
When a ceramic article was produced in the same manner as in Example 1 except that the heating temperature after modeling was set to 1740 ° C., the corners and rhombuses were blunted and deformed.

In Comparative Example 4, since the modeled product was heat-treated at 1740 ° C., which exceeds the melting point of silicon dioxide (1730 ° C.), it is probable that the silicon dioxide became a liquid phase and the shape could not be maintained.

According to the present invention, there is provided a method for manufacturing a ceramic article capable of further improving the mechanical strength of a modeled object while making the best use of the characteristics of the direct modeling method for obtaining a modeled object having a complicated shape in a silica-based material. can do. Further, it is possible to provide a ceramic article having improved mechanical strength while maintaining shape accuracy. Further, the ceramic article of the present invention, which suppresses a rapid change in shape due to thermal expansion, can be used as a core for metal casting.

100 Solidified part 101 Powder 102 Powder layer 103 Unsolidified powder 110 Modeled object 130 Base 151 Stage 152 Roller 180 Laser beam source 181 Scanner part 190 Liquid injection nozzle 201 Cladding nozzle 202 Powder supply hole 203 Laser beam

Claims (27)

(I) A step of arranging a powder containing silicon dioxide as a main component and containing an absorber that absorbs light having a wavelength contained in the irradiated laser beam.
(Ii) A step of sintering, melting and solidifying the powder by irradiating the powder with a laser beam.
(Iii) A step of heat-treating a modeled product formed by repeating the above steps (i) and (ii) at 1470 ° C. or higher and lower than 1730 ° C.
A method for producing a ceramic article, which comprises. A method for producing a ceramic structure, wherein the absorber has a higher absorption capacity than silicon dioxide with respect to light having a wavelength contained in the laser beam. The method for producing a ceramic article according to claim 1 or 2, wherein the absorber has an absorptive capacity of 10% or more with respect to light having a wavelength contained in the laser beam. The method for producing a ceramic article according to any one of claims 1 to 3, wherein the absorber is Tb ₄ O ₇ or Pr ₆ O _11. The absorbers are Ti ₂ O ₃ , TiO, SiO, ZnO, antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), MnO, MnO ₂ , Mn ₂ O ₃ , Mn ₃ O ₄ , FeO, Fe. _{From 2} O ₃ , Fe ₃ O ₄ , Cu ₂ O, CuO, Cr ₂ O ₃ , CrO ₃ , NiO, V ₂ O ₃ , VO ₂ , V ₂ O ₅ , V ₂ O ₄ , Co ₃ O ₄ , CoO The method for producing a ceramic article according to any one of claims 1 to 3, wherein the method comprises at least one selected from the group. The absorber is a transition metal carbide, transition metal nitride, Si 3 N _{4, AlN,} borides, claim 1, characterized in that it comprises at least one selected from the group consisting of silicide of 3 The method for producing a ceramic article according to any one of the items. The ceramic article according to any one of claims 1 to 6, wherein the silicon dioxide has an average particle size of 5 μm or more and 200 μm or less, and the absorber has an average particle size of 1 μm or more and less than 10 μm. Production method. The method for producing a ceramic article according to any one of claims 1 to 7, wherein the absorber is contained in the powder in an amount of 0.5 vol% or more and 10 vol% or less. The method for producing a ceramic article according to any one of claims 1 to 8, wherein the silicon dioxide is cristobalite. The ceramics according to any one of claims 1 to 9, wherein the step (iii) includes a step of allowing the modeled object to absorb a metal component-containing liquid containing a metal element before the heat treatment. Manufacturing method of goods. The method for producing a ceramic article according to claim 10, wherein the metal component-containing liquid contains aluminum or zirconium as the metal element. The method for producing a ceramic article according to claim 10, wherein the metal component-containing liquid contains particles of an oxide of the metal element. The method for producing a ceramic article according to claim 10 or 11, wherein the metal component-containing liquid produces an oxide of the metal element by the heat treatment. The method for producing a ceramic article according to claim 13, wherein the metal element contained in the metal component-containing liquid is contained as a metal alkoxide or chloride. The method for producing a ceramic article according to claim 14, wherein the metal component-containing liquid further contains a solvent and a stabilizer. The method for producing a ceramic structure according to claim 15, wherein the metal component-containing liquid contains an aluminum alkoxide, an organic solvent, and a stabilizer. The method for producing a ceramic structure according to claim 15, wherein the metal component-containing liquid contains an aluminum salt, water, and a stabilizer. The method for producing a ceramic article according to any one of claims 12 to 17, wherein the oxide of the metal element can form a eutectic with silicon dioxide. The melting point of silicon dioxide T _m, when the eutectic temperature of the metal oxide and silicon dioxide and T _E, the maximum temperature T _S of the molded object is reached in the heat treatment of the step (iii) is, T _E ≦ method of manufacturing a ceramic article according to claim 18, characterized in that to satisfy the relation T S _{<T m.} The melting point of silicon dioxide T _m, when the melting point T _i of the metal oxide, method for producing a ceramic article according to claim 18 or 19, characterized in that to satisfy the relation T m _{<T i.} The method for producing a ceramic article according to any one of claims 12 to 20, wherein the content of the metal oxide in the powder is less than 3.0% by mass. A ceramic article containing Tb or Pr and containing silicon dioxide as a main component.
A ceramic article characterized in that the content of Si is more than 80% by mass in terms of oxide, and 70% by mass or more of the silicon dioxide is cristobalite. The ceramic article according to claim 22, wherein Tb or Pr is contained in a range of 1.0% by mass or more and 20% by mass or less in terms of oxide. The ceramic article according to claim 22 or 23, which comprises a Tb ₂ Si ₂ O ₇ phase or a Pr ₂ Si ₂ O _{7 phase.} The ceramic article according to any one of claims 22 to 24, wherein the ceramic article has a porosity of 10% or more and 40% or less. The ceramic article according to any one of claims 22 to 25, wherein the ceramic article contains aluminum oxide or zirconium oxide. The ceramic article according to any one of claims 22 to 26, which is a core for casting.

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