KR20160049493A - Composite refractory and method for manufacturing the same - Google Patents

Abstract

The present invention provides a technology capable of obtaining a setter having excellent thermal shock resistance. A composite refractory material contains 35-70 wt% of SiC and 25-60 wt% of metal Si as a chemical composition, and is formed with a first Si-SiC sintered compact part (1) having a fibrous three-dimensional structure and a second Si-SiC sintered compact part (2) which is a matrix for supporting the fibrous three-dimensional structure, wherein the first Si-SiC sintered compact part (1) is covered with the second Si-SiC sintered compact part (2), and the first Si-SiC sintered compact part (1) and the second Si-SiC sintered compact part (2) both are formed of a dense substance having 1% of porosity or less.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a composite refractory,

The present invention relates to a composite refractory and a method of manufacturing the same.

The refractory (setter, etc.) used for the heat treatment of electronic components (ceramic capacitors, etc.) is required to have properties such as heat resistance and mechanical strength. Further, from the viewpoint of thermal energy efficiency and kiln filling efficiency, there has been a demand for a technology for reducing the setter thickness for the purpose of reducing the heat capacity. In addition, improvement of thermal shock resistance of the setter due to thinning is required.

With regard to thinning of the setter, a technique of producing a setter having a thickness of 0.2 to 2 mm by tape forming using a doctor blade apparatus is disclosed (Patent Document 1).

In Patent Document 1, ceramics such as alumina, silica, mullite, magnesia, zirconia, cordierite, silicon nitride, and silicon carbide are used as a setter material, or a material mainly composed of them is used.

However, in the prior art such as Patent Document 1, all of the setters have insufficient thermal shock resistance, and the setter tends to have cracks.

Patent Document 1: JP-A-11-79853

An object of the present invention is to solve the above-mentioned problems and to provide a technique capable of obtaining a refractory excellent in thermal shock resistance.

According to a first aspect of the present invention for achieving the above object, there is provided a method for manufacturing a semiconductor device, comprising the steps of: providing a silicon carbide film containing SiC in an amount of 35 to 70 mass% and metal Si in an amount of 25 to 60 mass% SiC sintered body portion and a second Si-SiC sintered body portion which is a matrix for supporting the fibrous three-dimensional structure, wherein the first Si-SiC sintered body portion is covered with the second Si-SiC sintered body portion And the first Si-SiC sintered body portion and the second Si-SiC sintered body portion are both dense with a porosity of 1% or less.

The invention recited in claim 2 is characterized in that the composite refractory according to claim 1 contains, as chemical components, SiC by 40 to 65 mass% and metal Si by 30 to 55 mass%.

According to a third aspect of the present invention, in the composite refractory according to the first aspect of the present invention, the first Si-SiC sintered body portion contains metal Si as a main component and SiC as the remainder, and the second Si- And the metallic Si is contained in the remaining part.

According to a fourth aspect of the present invention, in the composite refractory according to the first aspect, the content ratio of the C element in the first Si-SiC sintered body portion is 5 to 45 mass% and the content of C in the second Si- And the content of the element is 15 to 60% by mass.

The present invention according to claim 5 is characterized by having a structure in which two or more layers of the composite refractory according to claim 1 are laminated.

According to a sixth aspect of the present invention, in the composite refractory according to the fifth aspect, the first Si-SiC sintered body portion having the fiber-like three-dimensional structure in two adjacent layers has a center And has anisotropy.

The invention described in claim 7 is characterized in that the composite refractory according to claim 1 has a structure in which a porous layer having a three-dimensional mesh structure is laminated.

The present invention according to claim 8 is a setter using the complex refractory according to claim 1, wherein the setter is formed of a dense layer having a two-dimensional mesh-like framework structure, has a through-hole on a surface on which the object to be heated is placed, 10% or more.

According to a ninth aspect of the invention, there is provided a setter using the complex refractory according to the first aspect, characterized in that the surface on which the object to be heated is placed has a two-dimensional mesh-like concavo-convex portion.

The invention according to claim 10 relates to a process for producing a complex refractory according to claim 1, wherein the template is immersed in a molding slurry obtained by dispersing SiC powder in an organic solvent and further adding a gelling agent, and the slurry is cured And a sintering step of sintering the SiC compacted body by impregnating the SiC compacted body with the metal Si to form a Si-SiC sintered body. As a manufacturing method, a sheet-like fabric and / or a nonwoven fabric made of a flammable or thermosetting fiber and / or a flammable or thermosetting fiber is used as the template.

The composite refractory of the present invention (that is, as the component, contains SiC in an amount of 35 to 70 mass% and metal Si in an amount of 25 to 60 mass%, and the composite refractory is formed into a first Si- SiC sintered body portion and a second Si-SiC sintered body portion which is a matrix for supporting the fibrous three-dimensional structure, wherein the first Si-SiC sintered body portion and the second Si-SiC sintered body portion are both compact Has a high thermal conductivity and a low modulus of elasticity, and therefore has excellent thermal shock resistance. By using the composite refractory of the present invention having these properties as a setter, it is possible to realize a setter excellent in thermal shock resistance than the conventional one.

Further, by using the composite refractory of the present invention as a setter, it is possible to realize a setter having high thermal shock resistance and high reliability even when it is made thinner.

By stacking the composite refractory of the present invention on a porous layer having a three-dimensional mesh-like structure as in the invention described in claim 7, it is possible to realize an air permeable setter having a highly dense layer with high thermal shock resistance and high reliability.

1 is a flowchart showing a manufacturing process of the first embodiment.
2 is a graph showing the composition of the setter in the vertical section in the setting plane of the setter (template made of polyurethane fiber fabric) of Embodiment 1 (photographed using a scanning electron microscope JSM-5600 manufactured by JEOL) ].
3 is a graph showing the composition of the setter in the vertical cross section (taken using a scanning electron microscope JSM-5600 manufactured by Nihon Denshi Co., Ltd. (JEOL)) on the loading surface of the setter of the first embodiment (using a pulp fiber nonwoven fabric as a template) .
4 is a flowchart showing the manufacturing process of the second embodiment.
5 is a schematic explanatory view of an SiC compact using urethane foam as a template.
6 is a schematic explanatory diagram of a setter according to the second embodiment.
7 is a schematic explanatory view of the porous layer.
8 is a schematic cross-sectional view of the setter of the first to seventh embodiments and the center line of the filter of the eighth embodiment.

Hereinafter, preferred embodiments of the present invention will be described.

(Embodiment 1: compactness setter)

The composite refractory of this embodiment is a dense quality setter.

Hereinafter, a method of manufacturing the setter of the present embodiment will be described in detail. The setter of the present embodiment is manufactured by the gel-casting method by the steps (ST1) to (ST7) shown in Fig. The gel casting method refers to a powder forming method related to the present invention of the present applicant, wherein a gelation agent (gelling agent) is added to a slurry prepared by dispersing at least one powder selected from ceramics, glass or metal in a dispersion medium And then the slurry is cured to obtain a shaped body having an arbitrary shape.

(ST1):

Since the setter of the present embodiment is formed by a gel casting method, a slurry for molding is first produced. The molding slurry of the present embodiment can be obtained by dispersing an SiC powder having an average particle diameter of 1 mu m or less in an organic solvent and then adding a gelling agent or by adding an SiC powder having an average particle diameter of 1 mu m or less and a gelling agent And then dispersing the mixture.

In addition to SiC powder, powders of carbon, boron carbide and the like may be appropriately mixed and used. The particle diameters of the above-mentioned ceramic powders are not particularly limited as long as the slurry can be produced, and are appropriately selected according to the intended molded article.

Examples of the organic solvent used as the dispersion medium include polyhydric alcohols such as diols such as ethylene glycol and triols such as glycerin, polybasic acids such as dicarboxylic acid, polybasic acid esters such as dimethyl glutarate and dimethyl malonate, triacetin, And the like.

The gelling agent may be an organic compound having a reactive functional group for curing the slurry. Examples of such an organic compound include a urethane resin, an acrylic resin, an epoxy resin, and a phenol resin, such as a prepolymer which is three-dimensionally crosslinked by interposing a crosslinking agent. The gelling agent is preferably selected to have a suitable reactive functional group in consideration of the reactivity with the organic compound in the dispersion medium. For example, when an ester having a relatively low reactivity is used as the dispersion medium, the organic compound having a reactive functional group constituting the gelling agent is preferably an isocyanate group (-N═C═O) having high reactivity and / or an isothiocyanate group (-N = C = S). In this embodiment, since the molding slurry is impregnated into the sheet-form template as described in ST2 below, it is preferable to use a resin having high rubber elasticity so as to prevent breakage of the SiC formed body due to deformation Is preferably used.

It is preferable that the molding slurry is not cured at the time of impregnation of the sheet-form template but hardened quickly after molding. Therefore, in the production of the slurry, it is preferable to take into consideration the kind and content of the gelling agent. In consideration of workability, the slurry viscosity at 20 캜 is preferably 50 dPa s or less, and more preferably 20 dPa 쨌 s or less.

In the production step of the slurry for molding, the ceramics powder and the dispersion medium are combined and mixed. Thereafter, a gelling agent is added and mixed, and this is defoamed prior to impregnation molding with the sheet-form template.

Mixing of the molding slurry is carried out using a pot mill, a ball mill or the like and is carried out at a temperature of 15 ° C to 35 ° C for 12 hours or more, preferably 72 hours or more, using a jade stone. The degassing of the slurry is carried out by stirring in a vacuum atmosphere. The degree of vacuum is -0.090 MPa or less, preferably -0.095 MPa or less, the stirring speed is preferably 100 rpm to 500 rpm, the stirring time is preferably 5 minutes to 30 Min.

(ST2) to (ST4):

A sheet (fabric, nonwoven fabric, paper, mesh, etc.) made of flammable or thermosetting fibers is immersed as a sheet-form template in the molding slurry prepared in ST1, and the excess slurry is removed. And is left at room temperature to 40 DEG C for several hours to several hours. As a result, the molding slurry is cured by gelation and becomes an SiC compact having an SiC layer formed on the surface of the sheet-like template. As the sheet type template, for example, a sheet made of chemical fiber such as polyurethane or polyester or a sheet made of natural fiber such as cotton, hemp, wool, wool or cashmere can be used.

(ST5):

Subsequently, the molded body is dried at 40 ° C to 200 ° C for 3 to 24 hours.

(ST6) to (ST7):

Subsequently, the SiC formed body is fired in an inert gas atmosphere at 1400 ° C to 1500 ° C for 1 to 3 hours in a state of being in contact with the metal Si. A sheet-like template made of a flammable or thermosetting fiber disappears or pyrolyzes at around 500 DEG C, but the space formed by the disappearance or thermal decomposition of the sheet-like template is impregnated with metal Si, , A first Si-SiC sintered body portion 1 having a fiber-like three-dimensional structure is formed as shown in Fig. 3 (using a pulp fiber nonwoven fabric as a sheet-shaped template). The second Si-SiC sintered body portion 2 having a function of supporting the fiber-like three-dimensional structure is formed by impregnating the pores of the SiC layer of the SiC compact with metal Si. Accordingly, the first Si-SiC sintered body portion and the second Si-SiC sintered body portion are both made of a compact having a porosity of 1% or less.

The setter manufactured through each of the steps described above is a dense setter of Si-SiC having a porosity of 1% or less. In the present invention, the term "porosity" means the apparent porosity obtained by the "method of measuring the apparent porosity, absorption and specific gravity of JIS R 2205 refractory bricks".

In the present invention, the chemical composition of the molding slurry is adjusted so that the content ratio of SiC in the complex refractory (in this embodiment, the dense setter) is 35 to 70 mass% and the Si content is 25 to 60 mass% have. Here, the chemical composition of the complex refractory material can be measured by JIS R 2011 (chemical analysis method of carbon and silicon carbide refractory). When the content ratio of SiC is more than 70% by mass, there is a problem that the strength is lowered because the SiC particles tend to remain in the pores. When the content is less than 35% by mass, the heat resistance is lowered. There is a problem that deformation easily occurs. When the content of Si is more than 60 mass%, the heat resistance is lowered. Therefore, creep deformation tends to occur in a high-temperature firing step. When the content is less than 25 mass%, pores remain in the SiC particles There is a problem that strength is lowered because it is easy. The remainder is an antioxidant such as carbon or boron carbide.

When the content of Si is more than 55 mass%, Si is easily oxidized to generate SiO ₂ in the surface layer. When the Si content is less than 30 mass%, pores are likely to remain between the SiC particles, It is easy to generate SiO ₂ in the surface layer and all of them cause problems such as crack and bending deformation due to deterioration of thermal shock resistance and heat resistance due to generated SiO ₂ , increase in oxygen loading amount in the furnace, and reaction with the object to be treated It is more preferable to adjust each component amount so that the content ratio of SiC is 40 to 65 mass% and the content ratio of Si is 30 to 55 mass% from the viewpoint of improving the reliability of the setter and prolonging the service life.

In the present invention, SiC having a high modulus of elasticity (about 400 GPa) and metallic Si having a low modulus of elasticity (elastic modulus: about 100 GPa) are contained in an amount of 35 to 70 mass% To 60% by mass, more preferably, the content ratio of SiC is set to 40 to 65% by mass and the content of Si is adjusted to 30% to 55% by mass to form a composite refractory material, thereby reducing the modulus of elasticity of the Si- . The thermal shock resistance is generally expressed by the following formula: R '= σ (1-ν) λ / (αE where σ is the strength, E is the modulus of elasticity, ν is the friction coefficient, λ is the thermal conductivity, , And reduction of the modulus of elasticity leads to improvement of thermal shock resistance. According to the above configuration, a composite refractory having excellent thermal shock resistance can be realized by reducing the elastic modulus in addition to the characteristics of high strength and high thermal conductivity.

In the present embodiment, as shown in Figs. 2 and 3, the composite refractory comprises a first Si-SiC sintered compact portion 1 having a fiber-like three-dimensional structure, and a second Si- And a second Si-SiC sintered body portion 2 serving as a matrix for forming a second Si-SiC sintered body.

Table 1 shows the results of EDS analysis at two arbitrary measurement points on the composition of FIG. 2 and FIG. As shown in Table 1, each of these Si-SiC sintered body portions has a different constituent element ratio. In the first Si-SiC sintered body portion 1, the content of C element is 5 to 45 mass%, the content of Si element In the second Si-SiC sintered compact portion 2, the content of the C element is 15 to 60 mass% and the content of the Si element is 35 to 85 mass%. The content of free carbon (F.C) in the complex refractory is 0.1% or less, and the C element in the complex refractory is present almost as SiC. Therefore, in the first Si-SiC sintered compact portion 1 composed of the above element-containing ratios, the main component is metal Si and the remaining portion contains a small amount of SiC. The second Si-SiC sintered body portion 2 has a structure in which SiC is the main component and the pores thereof are filled with metal Si.

When the content ratio of the C element in the first Si-SiC sintered compact portion 1 is more than 45 mass%, the pores are liable to remain in the first Si-SiC sintered compact portion 1, and the strength is lowered. On the other hand, if it is less than 5% by mass, the heat resistance deteriorates. Therefore, the content ratio of the C element in the first Si-SiC sintered body portion 1 is preferably set within the above-mentioned range.

When the content ratio of the C element in the second Si-SiC sintered compact portion 2 is more than 60% by mass, pores easily remain between the SiC particles and the strength is lowered. On the other hand, if it is less than 15% by mass, the heat resistance is lowered. Therefore, the content ratio of the C element in the second Si-SiC sintered body portion 2 is preferably set within the above-mentioned range.

In the step (ST2) of immersing the sheet-form template in the molding slurry, if necessary, the excess slurry is removed so as to prevent the scale interval portion from being filled with the slurry, fixed with a jig so as to have a predetermined thickness and shape, And then dried at 40 ° C to 200 ° C for 3 to 24 hours. Thereafter, the SiC compact is contacted with metallic Si in an inert gas atmosphere at 1400 ° C to 1500 ° C for 1 to 3 hours By carrying out the sintering, an air-permeable setter having a two-dimensional mesh-like structure formed of a Si-SiC dense framework having a porosity of 1% or less can be produced. The superior thermal shock resistance is the same as described above.

Further, in the step (ST2) of immersing the sheet-form template in the slurry for molding, if necessary, two or more sheets made of the above-mentioned flammable or thermosetting fibers are used in a superposed state, A setter having a laminated structure may be produced by fixing the substrate with a jig so as to have a shape.

Further, a sheet made of the adjacent flammable or thermosetting fibers is joined and rotated around an axis perpendicular to the lamination surface (1 DEG or more), and after the excess slurry is removed, a jig SiC sintered body having the fibrous three-dimensional structure in the adjacent two layers is set to have a laminate structure having a laminate structure having anisotropy (at least 1 DEG) around an axis perpendicular to the laminate surface You may. The superior thermal shock resistance is the same as described above.

Thus, by forming a laminate structure in which the first Si-SiC sintered body having the fibrous three-dimensional structure in the adjacent two layers has anisotropy (about 1 DEG or more) about an axis perpendicular to the laminate surface, Cracks are less likely to propagate between the layers, so that cracks are more likely to occur.

(Embodiment 2: Setter in which a dense layer and a porous layer are laminated)

The composite refractory of the present embodiment has a Si-SiC dense layer having a porosity of 1% or less and a Si-SiC porous layer having a 3-dimensional mesh structure having a porosity of 50 to 98% formed of a Si-SiC dense framework having a porosity of 1% Are stacked.

Hereinafter, a method of manufacturing the setter of the present embodiment will be described in detail. The setter of the present embodiment is manufactured by the gel casting method by the steps ST1 to ST7 shown in Fig. The gel casting method refers to a powder forming method related to the present invention of the present applicant, wherein a gelation agent (gelling agent) is added to a slurry prepared by dispersing at least one powder selected from ceramics, glass or metal in a dispersion medium And then the slurry is cured to obtain a shaped body having an arbitrary shape.

(ST1):

Since the setter of the present embodiment is formed by a gel casting method, a slurry for molding is first produced. The raw materials and the manufacturing procedure of the molding slurry are the same as those in the first embodiment.

(ST2) to (ST3):

A sheet (fabric, nonwoven fabric, paper, mesh, etc.) made of flammable or thermosetting fibers is immersed as a sheet-form template in the molding slurry prepared in ST1, and the excess slurry is removed. And is left at room temperature to 40 DEG C for several hours to several hours. Thus, the molding slurry is cured by gelation, and becomes an SiC compact (hereinafter referred to as a pre-compact) having a SiC layer formed on the surface of the sheet-like template.

(ST2 ') to (ST3') to (ST3 '') to (ST4):

Subsequently, a plate-like urethane foam is immersed in the slurry for forming, and the excess slurry is removed. Thereafter, on any surface of the urethane foam (for example, the upper surface or side surface when laid flat) The preform bodies are joined and integrated, fixed with a jig so as to have a predetermined thickness and shape, and allowed to stand at room temperature to 40 deg. C for several hours to several hours to cure the molding slurry, SiC < / RTI >

5, the urethane foam is constituted by a skeleton portion 3 and a void portion 4, and in the SiC formed body having the above, the urethane foam portion is formed on the surface of the skeleton portion 3 with the SiC layer 5 ) Is formed.

(ST5):

Subsequently, the molded body is dried at 40 ° C to 200 ° C for 3 to 24 hours.

(ST6) to (ST7):

Subsequently, the SiC compact is sintered in an inert gas atmosphere at 1400 ° C to 1500 ° C for 1 to 3 hours while being in contact with the metal Si. The sheet-like template made of the urethane foam and the combustible or thermosetting fiber is disappeared or pyrolyzed at around 500 캜, but the space formed by the disappearance or pyrolysis of the urethane foam and the sheet-like template is impregnated with the metal Si and at the same time, By impregnating the pores of the SiC layer with the metal Si, as shown in Fig. 6, the porous layer 6 having a three-dimensional mesh structure with a porosity of 50 to 98% formed of a Si-SiC dense framework having a porosity of 1% SiC material having a structure in which a Si-SiC dense layer 7 having a porosity of 1% or less (= a layer formed by using a sheet-shaped template made of a combustible or thermosetting fiber) Can be produced. By using the porous layer 6 having a three-dimensional mesh structure as the surface on which the object to be heated is placed, it is possible to obtain an effect of efficiently exhausting the combustion gas generated from the object in the heat treatment process of the electronic component. On the other hand, the porous layer 6 composed of only the three-dimensional mesh structure is insufficient in strength, abrasion resistance and the like. However, according to the air permeable setter of the present invention, the porous layer 6 having a porosity of 50 to 98% By providing a laminated structure of the porous layer 6 having a three-dimensional mesh structure and the Si-SiC dense layer 7 having a porosity of 1% or less, excellent air permeability, strength and abrasion resistance can be realized.

As described above, in the present invention, the content ratio of SiC in the complex refractory material (in this embodiment, the setter in which the dense layer and the porous layer are laminated) is 35 to 70 mass%, the Si content is 25 to 60 mass% The chemical composition of the slurry for molding is adjusted.

In the present embodiment, the dense layer includes a first Si-SiC sintered compact portion 1 having a fiber-like three-dimensional structure and a function as a matrix for supporting the fibrous three-dimensional structure And a second Si-SiC sintered body portion 2 having a second Si-

In this embodiment, the skeleton of the porous layer 6 is composed of a core portion 8, a surface layer portion 9 and a punched portion 10 as shown in Fig. The core portion 8 and the surface layer portion 9 have different constituent elements and the content of the C element is 5 to 20 mass% and the content of the Si element is 80 to 95 mass% in the core portion 8 In the surface layer portion 9, the content of the C element is 15 to 50 mass% and the content of the Si element is 50 to 85 mass%. The content of free carbon (F.C) in the skeleton is 0.1% or less, and the element C in the skeleton substantially exists as SiC. Therefore, in the core portion 8 made of the above element content, the main component is metal Si and the remaining portion contains a small amount of SiC. The surface layer portion 9 has a structure in which SiC is the main component and the pores thereof are filled with metal Si.

When the content ratio of the C element in the core portion 8 is more than 20 mass%, the pores are liable to remain in the core portion 8, and the strength is lowered. On the other hand, when the content is less than 5% by mass, the heat resistance is lowered, and therefore creep deformation tends to occur in a high-temperature firing step. Therefore, the content ratio of the C element in the core portion 8 is preferably within the above-

When the content ratio of the C element in the surface layer portion 9 is more than 50 mass%, pores are likely to remain between the SiC grains and the strength is lowered. On the other hand, if it is less than 15% by mass, the heat resistance is lowered, so that creep deformation tends to occur in the high-temperature firing step, so that the content ratio of the C element in the surface layer portion 9 is preferably set within the above-

(Embodiment 3: a filter in which a dense layer and a porous layer are laminated)

It is also possible to use, for example, a cylindrical urethane foam in place of the plate-like urethane foam used in the second embodiment, and to apply the preformed product prepared in ST3 on any surface of the urethane foam (for example, SiC compacted layer having a porosity of 1% or less and a Si-SiC dense layer on the side of the Si-SiC porous layer having a three-dimensional mesh structure with a porosity of 50 to 98% It is possible.

Example

[Example A]

The setter produced by the method of the following Examples 1 to 7, the filter prepared by the method of Example 8 and the setter produced by the method of Comparative Example 1 were subjected to a heating test, As a result of investigating the occurrence, "cracks" were not confirmed in all of Examples 1 to 8, while "cracks" in Comparative Example 1 were confirmed. The outline of the filter fabricated by the method of Examples 1 to 7 below and the filter fabricated by the method of Example 8 is shown in Fig.

(Example 1: dense setter)

SiC slurry having an average particle diameter of 1 mu m dispersed in an organic solvent and having a urethane resin (isocyanate) mixed therein was coated with a polyurethane fiber cloth having a size of 150 x 150 x 0.4 mm (10% polyurethane fiber and A cloth in which a fiber bundle having a thickness of about 10 占 퐉 and having a thickness of about 200 占 퐉 is knitted in a three-dimensionally woven fabric) is dipped in a polyester textile 90% And the slurry was cured to form a SiC (-C, -B4C) layer on the surface of the polyurethane fiber. The formed body was dried at 40 to 110 deg. C to produce an SiC compact having a thickness of 0.5 mm. Next, the SiC formed body was fired at 1500 캜 in an inert gas atmosphere with a metal Si of 110% by weight in contact with the SiC formed body to prepare a setter of Si-SiC having a size of 150 x 150 x 0.5 mm in thickness . The porosity of the prepared setter was 1% or less.

(Example 2: dense setter)

A pulp nonwoven fabric (a cloth formed of pulp fibers) having a size of 150 x 150 x 0.05 mm in thickness was applied to an SiC slurry in which SiC (-C, -B4C) having an average particle size of 1 mu m was dispersed in an organic solvent and a urethane resin (isocyanate) The slurry is immersed and removed with a jig, and the slurry is cured to form a SiC (-C, -B4C) layer on the surface of the pulp fiber. The formed body is then dried at 40 to 110 deg. A 0.1 mm SiC compact was produced. Next, the SiC formed body was fired at 1500 캜 in an inert gas atmosphere in a state in which metal Si of 90% by weight was in contact with the SiC formed body to prepare a setter of Si-SiC having a size of 150 × 150 × 0.1 mm in thickness . The porosity of the prepared setter was 1% or less.

(Example 3: dense setter having a laminated structure)

A SiC slurry having an average particle diameter of 1 占 퐉 of an average particle size of 1 占 퐉 and dispersed in an urethane resin (isocyanate) was dispersed in an organic solvent, and a 150 占 150 占 0.4 mm polyurethane fiber cloth (polyurethane fiber 10% A cloth in which a fiber bundle is three-dimensionally woven by bundling fibers having a thickness of about 10 占 퐉 in a thickness of about 200 占 퐉 per one ol of an ester fiber of 90% of an ester fiber), and an adjacent polyurethane fiber cloth has an axis perpendicular to the lamination surface The slurry was immersed in water by 45 ° centrally, and the excess slurry was removed. Thereafter, the slurry was fixed in a state of being pressurized with a jig to a total thickness of 2 mm, and the slurry was directly cured, (-C, -B4C) layer was dried at 40 to 110 deg. C to produce an SiC compact having a laminated structure with a total thickness of 2 mm. Next, the same procedure as in Example 1 was carried out to obtain a Si-SiC made of a 150 × 150 × 2 mm total thickness having a structure in which four Si-SiC dense layers having substantially the same composition as the composition shown in FIG. Setter. The porosity of the prepared setter was 1% or less.

(Example 4: air permeable setter in which a dense quality layer and a porous layer were laminated)

A polyurethane fiber cloth (10% polyurethane fiber and 90% polyester fiber) having a size of 150 x 150 x 0.4 mm in thickness was prepared by dispersing SiC (-C, -B4C) in an organic solvent and mixing SiC slurry containing urethane resin (isocyanate) A fabric in which a bundle of fibers each having a thickness of about 10 占 퐉 and having a thickness of about 200 占 퐉 is three-dimensionally woven) is immersed in the cloth, and the surplus slurry is removed and fixed with a jig, To obtain an SiC formed body (preform 1) having a thickness of 0.5 mm in which a SiC (-C, -B4C) layer was formed on the surface of the polyurethane fiber. Next, a urethane foam having a size of 150 × 150 × 1.5 mm was immersed in the SiC slurry, and a surplus slurry was removed. Thereafter, a SiC (-C, -B4C) layer having a thickness of 1.5 mm was formed on the surface of the urethane foam Thereby obtaining a molded article (preformed article 2). The preform 1 is bonded to one surface (upper surface or lower surface when placed flat) of the preform 2, integrated with a jig so as to have a total thickness of 2 mm, and the slurry is directly cured, And dried at 110 DEG C to produce a SiC compact having a total thickness of 2 mm. Next, the same procedure as in Example 1 was carried out to obtain a 150 x 150 x gun having a structure in which a Si-SiC dense layer having a thickness of 0.5 mm and a Si-SiC porous layer having a thickness of 1.5 mm having a three- A setter of Si-SiC having a thickness of 2 mm was produced. The porosity of the Si-SiC dense layer in the prepared setter was 1% or less, and the porosity of the Si-SiC porous layer was 80%.

(Example 5: air permeable setter in which a dense layer was laminated on the edge portion of the porous layer)

A urethane foam having a size of 150 x 150 x 5 mm in thickness was immersed in a SiC slurry in which SiC (-C, -B4C) was dispersed in an organic solvent and a urethane resin (isocyanate) was mixed. After the excess slurry was removed, And the slurry was cured to form a SiC (-C, -B4C) layer on the surface of the urethane foam to obtain a SiC formed body (preformed body 3) having a thickness of 5 mm and having a three-dimensional mesh structure. Next, after pulp nonwoven fabric (cloth formed of pulp fiber) having a size of 150 x 15 x 0.05 mm in thickness was immersed in the SiC slurry and the excess slurry was removed, the edge portions of the four sides of the preformed body 3 Side surface), integrated with each other, fixed with a jig so that the total thickness was 5 mm, the slurry was directly cured, and dried at 40 to 110 deg. C to produce a SiC compact having a total thickness of 5 mm. Next, firing was carried out in the same manner as in Example 1, and Si-SiC porous layers each having a three-dimensional mesh structure with a thickness of 5 mm were coated with Si (thickness: 0.1 mm) -SiC dense layer was laminated on the Si-SiC substrate to obtain a setter of Si-SiC of 150 mm x 150 mm total thickness of 5 mm. The porosity of the Si-SiC dense layer (edge portion) in the produced setter was 1% or less and the porosity of the Si-SiC porous layer was 80%.

(Example 6: air-permeable setter having a two-dimensional mesh structure)

A SiC slurry in which SiC (-C, -B4C) having an average particle size of 1 占 퐉 was dispersed in an organic solvent and a urethane resin (isocyanate) mixed therein was coated with a polyester net having a size of 150 占 150 占 0.8 mm Three-dimensionally or substantially two-dimensionally woven webs are immersed so that the fibers having a thickness of 400 占 퐉 per one per 100 占 퐉 are spaced apart by 600 占 퐉 so that the intervals of the scales are not filled with the slurry After the excess slurry is removed, it is fixed with a jig and the slurry is cured to form a SiC (-C, -B4C) layer on the surface of the polyester fiber, and the resulting molded body is dried at 40 to 110 DEG C, A SiC compact having a thickness of 1 mm and a two-dimensional mesh structure of 500 mu m and a scale interval of 500 mu m was produced. Next, the same set as in Example 1 was fired to produce a setter made of Si-SiC having a two-dimensional mesh structure with a skeleton diameter of 500 mu m and a scale interval of 500 mu m and having a size of 150 x 150 x 1 mm thick. The porosity of the skeleton of the Si-SiC dense layer forming the two-dimensional mesh structure in the produced setter was 1% or less.

The setter of the present embodiment is formed of a dense layer having a two-dimensional mesh-like framework structure, and has a through-hole on the surface on which the object to be heated is placed. For example, the diameter of the through-holes in this setter was 500 μm and the interval was 500 μm. The ratio of the aperture ratio of the through-holes on the surface on which the object to be heated was placed (the ratio of the total area of the through-holes to the area of the surface on which the object to be heated was placed (150 × 150 mm ² in this embodiment)] was 16%.

(Example 7: air-permeable setter having a two-dimensional mesh-type concave-convex portion on the surface layer)

A SiC slurry in which SiC (-C, -B4C) having an average particle size of 1 占 퐉 was dispersed in an organic solvent and a urethane resin (isocyanate) mixed therein was coated with a polyester net having a size of 150 占 150 占 0.8 mm Three-dimensionally or substantially two-dimensionally woven webs are immersed so that the fibers having a thickness of 400 占 퐉 per one per 100 占 퐉 are spaced apart by 600 占 퐉 so that the intervals of the scales are not filled with the slurry After removing the surplus slurry, it was fixed with a jig and the slurry was cured to form a SiC (-C, -B4C) layer on the surface of the polyester fiber. The skeleton diameter was 500 mu m and the scale interval was 500 mu m An SiC formed body (preformed body 4) having a thickness of 1 mm and having a two-dimensional mesh structure was obtained. Next, the above-mentioned SiC slurry was coated with a polyurethane fiber cloth (150% by weight x 0.4 mm thick) having 10% polyurethane fibers and 90% polyester fibers, each having a thickness of about 10 mu m per 100 mu m (--C, -B4C) layer is formed on the surface of the polyurethane fiber by immersing the bundle of bundles of fibers in a three-dimensionally woven fabric, removing the excess slurry, fixing the bundle using a jig, and curing the slurry Thereby obtaining an SiC formed body (preformed body 5) having a thickness of 0.5 mm formed. The preforms 4 were bonded to one surface (upper surface or lower surface when laid flat) of the preforms 5 by using a molded body slurry, integrated with a jig so as to have a total thickness of 2 mm, Cured, and dried at 40 ° C to 110 ° C to produce an SiC compact having a total thickness of 2 mm. Next, the same procedure as in Example 1 was carried out to form a two-dimensional mesh-shaped layer formed of Si-SiC dense skeleton having a thickness of 1 mm on the surface layer of the Si-SiC dense layer having a thickness of 1 mm, A setter made of Si-SiC having a size of 150 x 150 x total thickness of 2 mm was produced. The Si-SiC compactness skeleton and the Si-SiC dense layer forming the two-dimensional mesh type layer in the produced setter had a porosity of 1% or less.

The setter of the present embodiment has a two-dimensional mesh-shaped concavo-convex portion on the surface on which the non-heated object is placed. For example, the width of the convex portion (skeleton) in the setter was 500 μm, the depth was 500 μm, and the interval was 500 μm. In other words, the depth of the concave portion was 500 mu m and the interval was 500 mu m. (The ratio of the total area of the concave portion to the area of the surface on which the object to be heated is placed (in this embodiment, 150 x 150 mm ² )) on the surface on which the object to be heated is placed, Was 16%.

(Example 8: filter obtained by laminating a dense layer on the side wall of the porous layer)

A cylindrical urethane foam having a diameter of 99 mm and a length of 100 mm was immersed in an SiC slurry in which SiC (-C, -B4C) was dispersed in an organic solvent and a urethane resin (isocyanate) was mixed. After removing a surplus slurry, Shaped SiC formed body having a diameter of 99 mm and a length of 100 mm and having a three-dimensional mesh structure in which a SiC (-C, -B4C) layer was formed on the surface of the urethane foam by fixing using a jig Free preform 8). Next, the above-mentioned SiC slurry was coated with a polyurethane fiber cloth of 310 x 100 x 0.4 mm thickness (10% of polyurethane fibers and 90% of polyester fibers), and fibers having a thickness of about 10 mu m per one- After the excess slurry was removed, the slurry was bonded to the side surface (the side surface of the cylinder) of the preformed body 8 and integrated. Then, a cylindrical body having a diameter of 100 mm and a length of 100 mm The slurry was directly cured and dried at 40 to 110 DEG C to prepare a cylindrical SiC compact having a diameter of 100 mm and a length of 100 mm. Next, firing was carried out in the same manner as in Example 1 to laminate Si-SiC dense layers having a thickness of 0.5 mm on side walls of a cylindrical Si-SiC porous layer having a diameter of 99 mm and a length of 100 mm and having a three- A cylindrical Si-SiC filter having a structure of 100 mm in diameter and 100 mm in length was produced. The porosity of the Si-SiC dense layer in the fabricated filter was 1% or less, and the porosity of the Si-SiC porous layer was 80%.

(Comparative Example 1)

Specifically, a SiC-C molded article is obtained by using a raw material for molding kneaded by adding an appropriate amount of an organic binder and water to SiC powder and C powder, and a known method (for example, the method described in Japanese Patent Laid- Then, this SiC-C molded body is fired in an inert gas atmosphere at a temperature of 1400 ° C. to 1500 ° C. for 1 to 3 hours in a state of being in contact with metallic Si to impregnate metallic Si with pores of the Si- SiC sintered body) having a thickness of 2 mm, which has a monolithic structure (a structure which does not have the first Si-SiC sintered body portion but only the second Si-SiC sintered body portion) A setter made of Si-SiC was produced.

[Example B]

The chemical components of the SiC slurry were respectively changed by the method of Example 1 to prepare the setters shown in Examples 9 to 11 and Comparative Examples 2 and 3 set forth in Table 2 below, A setter shown in Comparative Example 4 described in Table 2 below was prepared by the method of Example 1. Each of the setters of the compositions shown in Examples 9 to 11 and Comparative Examples 2 to 4 described in Table 2 was subjected to a heating test to investigate occurrence of " cracking " by thermal shock, In Example 11, improvement in thermal shock resistance was confirmed as compared with Comparative Examples 2 to 4.

[Example C]

Using the SiC slurry prepared by changing the chemical components to the compositions of Examples 9 to 11 and Comparative Examples 2 and 3 by the method of Example 4, the SiC slurry having a size of 150 x 150 x 0.5 mm To obtain an SiC compact (preform 1: compacted layer) and a 150 占 150 占 1.5 mm SiC compact (preform 2: porous layer). The preform 1 was bonded to one surface (upper surface or lower surface when laid flat) of the preform 2 and integrated, followed by drying and firing in the same manner as in Example 4, 12 to Example 14 and Comparative Example 5 and Comparative Example 6 were produced. In addition, by the method of Comparative Example 1, a SiC compact (150 mm x 150 mm thick 0.5 mm thick) of the composition of Comparative Example 4 (preform 1: dense layer) was obtained. Subsequently, an SiC compact (a preform 2: porous layer) having a composition of the composition of Example 14 and having a size of 150 mm x 150 mm and a thickness of 1.5 mm was obtained. The preform 1 was bonded to one surface (upper surface or lower surface when laid flat) of the preform 2 and integrated, followed by drying and firing in the same manner as in Example 4 to obtain Comparative Example 7 Was prepared. All of these are breathable setters made of Si-SiC having a total thickness of 2 mm, having a structure in which a Si-SiC dense layer having a thickness of 0.5 mm and a Si-SiC porous layer having a thickness of 1.5 mm having a three-dimensional mesh structure are laminated. The porosity of the Si-SiC dense layer in each of the manufactured breathable setters was 1% or less, and the porosity of the Si-SiC porous layer was 80%. Each of the setters of the compositions shown in Examples 12 to 14 and Comparative Examples 5 to 7 shown in Table 3 was subjected to a heating test to investigate occurrence of " cracking " In Example 14, improvement in thermal shock resistance was confirmed as compared with Comparative Examples 5 to 7. [

1: SiC sintered body part, 2: SiC sintered body part, 3: skeleton part, 4: void part, 5: SiC layer, 6: porous layer, 7: dense layer, 9: surface layer, 10:

Claims (10)

As a chemical component, SiC is contained in an amount of 35 to 70 mass% and metal Si is contained in an amount of 25 to 60 mass%
A first Si-SiC sintered body portion having a fiber-like three-dimensional structure and a second Si-SiC sintered body portion serving as a matrix for supporting the fibrous three-dimensional structure,
The first Si-SiC sintered body portion is covered with a second Si-SiC sintered body portion,
Wherein the first Si-SiC sintered body portion and the second Si-SiC sintered body portion are both dense with a porosity of 1% or less. The composite refractory according to claim 1, wherein as the chemical component, SiC is contained by 40 to 65 mass% and metal Si is contained by 30 to 55 mass%. The semiconductor device according to claim 1, wherein the first Si-SiC sintered body portion comprises metal Si as a main component and SiC as a remainder,
Wherein the second Si-SiC sintered body portion comprises SiC as a main component and metallic Si as a remainder. The method according to claim 1, wherein the content ratio of element C in the first Si-SiC sintered body portion is 5 to 45 mass%
And the content ratio of element C in the second Si-SiC sintered body portion is 15 to 60 mass%. A composite refractory characterized by having a structure in which two or more layers of the composite refractory according to claim 1 are laminated. The composite refractory according to claim 5, wherein the first Si-SiC sintered body having the fibrous three-dimensional structure in the adjacent two layers has an anisotropy of 1 DEG or more around an axis perpendicular to the laminated surface. A composite refractory characterized by having a structure in which a porous layer having a three-dimensional mesh structure is laminated on the complex refractory according to claim 1. A setter using the complex refractory according to claim 1, characterized in that it is formed of a dense layer having a two-dimensional mesh-like framework structure, has a through-hole on a surface on which the object to be heated is placed, and has a total opening ratio of 10% Setter. A setter using the complex refractory according to claim 1, wherein the setter has a two-dimensional mesh-shaped concavo-convex portion on the surface on which the object to be heated is placed. A forming step of forming a SiC compact by immersing a template in a slurry obtained by dispersing SiC powder in an organic solvent and further adding a gelling agent and curing the slurry; A method for producing a composite refractory material having a sintering step in which an SiC compact is impregnated with a metal Si to form a Si-SiC sintered compact by firing in an inert gas atmosphere, wherein the template is a combustible or thermosetting fiber and / And a non-woven fabric is used as the non-woven fabric.

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