TW201504195A - Composite refractory and manufacturing method for composite refractory - Google Patents
Composite refractory and manufacturing method for composite refractory Download PDFInfo
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- TW201504195A TW201504195A TW103111185A TW103111185A TW201504195A TW 201504195 A TW201504195 A TW 201504195A TW 103111185 A TW103111185 A TW 103111185A TW 103111185 A TW103111185 A TW 103111185A TW 201504195 A TW201504195 A TW 201504195A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/0003—Linings or walls
- F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
- F27D1/1626—Making linings by compacting a refractory mass in the space defined by a backing mould or pattern and the furnace wall
Abstract
Description
本發明係適合用於作為陶瓷電子零件等的脫脂步驟、鍛燒步驟的承燒板等的用途的複合耐火物及其製造方法。 The present invention is suitable for use as a composite refractory for use in a degreasing step of a ceramic electronic component or the like, a setter for a calcining step, and the like, and a method for producing the same.
近幾年，由提升小型電子零件的鍛燒效率的觀點，需要可共用在脫脂步驟及鍛燒步驟兩者的承燒板。在用於脫脂步驟的承燒板，需要可迅速的排出膠合劑的通氣性，而用於鍛燒步驟的承燒板，於耐熱性及機械性強度之外，需要具備不與鍛燒的陶瓷電子零件反應的特性。 In recent years, from the viewpoint of improving the calcination efficiency of small electronic parts, it is necessary to share the setter in both the degreasing step and the calcining step. In the setter for the degreasing step, it is required to quickly discharge the air permeability of the adhesive, and the setter for the calcining step needs to have a ceramic which is not tempered except for heat resistance and mechanical strength. The characteristics of the reaction of electronic parts.
在於鍛燒步驟滿足上述要求的承燒板，已知於氧化鋁．莫來石系基材的表面，形成中間層，及耐反應性塗層之承燒板。此外，亦有取代上述氧化鋁．莫來石系基材，藉由使用Si-SiC燒結體作為基材，而耐熱性、耐蝕性較氧化鋁．二氧化矽質之燒結體優良，且具備高強度及高熱傳導率的特性，可圖謀承燒板的薄壁化而提升窯效率的同時，亦可圖謀能源效率的提升的技術之揭示(專利文獻1)。 In the calcining step, which meets the above requirements, is known in alumina. The surface of the mullite substrate forms an intermediate layer and a set of burn-resistant plates for the reactive coating. In addition, there is also a replacement for the above alumina. The mullite substrate is made of a Si-SiC sintered body as a substrate, and has higher heat resistance and corrosion resistance than alumina. The sintered body of cerium oxide is excellent, and it has the characteristics of high strength and high thermal conductivity, and it can be used to reduce the smelting efficiency of the kiln, and to improve the efficiency of the kiln. 1).
但是，專利文獻1的承燒板，由於缺乏通氣性，並不適於與脫脂步驟共用。具備通氣性的承燒板，有取代先前的陶瓷製的板材，而採用鐵絲網的技術之揭示(專利文獻2)。 However, the setter plate of Patent Document 1 is not suitable for use in the degreasing step because of lack of air permeability. A heat-insulating setter plate is used to replace the prior art ceramic plate, and the technique of using a wire mesh is disclosed (Patent Document 2).
但是，鐵絲網，在高溫的鍛燒步驟容易產生彎曲。 此外，與Si-SiC燒結體相比由於熱傳導性較低，故在於載置於鐵絲網的產品間發生溫度的逸散，而有產品品質不穩定的問題。 However, the wire mesh is prone to bending at the high temperature calcination step. Further, since the thermal conductivity is lower than that of the Si-SiC sintered body, the temperature is dissipated between the products placed on the wire mesh, and the product quality is unstable.
再者，關於具有通氣性的陶瓷構造體，已知藉由根據「施瓦茨瓦爾德(Schwarzwälder)法」製造連續氣孔發泡陶瓷之技術。對於先前的連續氣孔發泡陶瓷，容易由骨骼的氣孔部分發生龜裂，而有機械性強度差的問題，有藉由在SiC發泡陶瓷的骨骼的氣孔部分，將Si含浸，圖謀高強度化的技術之揭示(專利文獻3)。 Further, as a ceramic structure having air permeability, a technique of manufacturing a continuous pore-foamed ceramic according to the "Schwarzwälder method" is known. In the case of the conventional continuous-porous foamed ceramic, it is easy to be cracked by the pore portion of the skeleton, and there is a problem that the mechanical strength is poor. In the pore portion of the skeleton of the SiC foamed ceramic, Si is impregnated, and the strength is increased. Disclosure of technology (Patent Document 3).
但是，專利文獻3的技術，將陶瓷高強度化，則彈性膜數亦一體上升，而彈性模數的上升將關係到耐熱衝擊性(熱衝擊破壞阻抗係數R'=σ(1-ν)λ/(αE)，在此，σ：強度，E：彈性模數)的降低，而有無法適用在要求兼具有耐熱衝擊性能與高強度化之用途的問題。 However, in the technique of Patent Document 3, when the ceramic is increased in strength, the number of elastic films is also increased integrally, and the increase in the elastic modulus is related to thermal shock resistance (thermal shock damage coefficient R'=σ(1-ν)λ / (αE), here, σ: strength, E: elastic modulus) is lowered, and there is a problem that it cannot be applied to applications requiring both thermal shock resistance and high strength.
[專利文獻1]日本特開2012-56831號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-56831
[專利文獻2]日本特開2011-117669號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2011-117669
[專利文獻3]US6635339號公報 [Patent Document 3] US Pat. No. 6,635,339
本發明之目的係解決上述問題，提供高強度且高熱傳導率，耐熱衝擊性優良，且具備通氣性的同時，不會因為高溫條件下的使用而發生破裂或彎曲等的變形之複合耐火物 及其製造方法。 An object of the present invention is to provide a composite refractory which has high strength, high thermal conductivity, excellent thermal shock resistance, and air permeability without deformation due to cracking or bending due to use under high temperature conditions. And its manufacturing method.
為解決上述課題而實施之本發明之複合耐火物，以Si-SiC燒結體作為基材，其特徵在於：上述Si-SiC燒結體，具有以氣孔率1%以下的骨骼構成之三維網目狀構造，在於該骨骼之SiC含有比例為35~70質量%，金屬Si的含有比例為25~60質量%。 In the composite refractory of the present invention which is to be solved by the above-mentioned problem, the Si-SiC sintered body has a three-dimensional mesh structure composed of bone having a porosity of 1% or less. The SiC content ratio of the bone is 35 to 70% by mass, and the content ratio of the metal Si is 25 to 60% by mass.
申請專利範圍第2項之發明，係在於申請專利範圍第1項之複合耐火物，其中上述Si-SiC燒結體，在於該骨骼之SiC含有比例為40~65質量%，金屬Si的含有比例為30~55質量%。 The invention of claim 2 is the composite refractory of claim 1, wherein the Si-SiC sintered body has a SiC content of 40 to 65 mass%, and a metal Si content ratio is 30 to 55 mass%.
申請專利範圍第3項之發明，係在於申請專利範圍第1項之複合耐火物，其中在於上述三維網目狀構造，構成該三維網目狀構造之氣孔與骨骼之各個形狀，滿足(氣孔徑/骨骼徑)之平均值≧3。 The invention of claim 3 is the composite refractory of the first application of the patent scope, wherein the three-dimensional mesh structure constitutes the various shapes of the pores and bones of the three-dimensional mesh structure, satisfying (aperture/skeleton) The average value of the diameter is ≧3.
申請專利範圍第4項之發明，係在於申請專利範圍第1項之複合耐火物，其中上述骨骼，係由：以金屬Si作為主成分，於殘部包含C的芯部；及以SiC作為主成分，於殘部包含金屬Si的表層部所構成，在於上述芯部之C含量為5~20質量%，在於該表層部之C含量為15~50質量%。 The invention of claim 4 is the composite refractory of claim 1, wherein the skeleton is composed of a metal Si as a main component and a core of C in a residual portion; and SiC as a main component The surface portion including the metal Si in the residual portion is composed of a C content of the core portion of 5 to 20% by mass, and a C content of the surface layer portion of 15 to 50% by mass.
申請專利範圍第5項之發明，係在於申請專利範圍第1項之複合耐火物，其中構成上述三維網眼構造之骨骼密度於垂直剖面與水平剖面相異，在於垂直剖面之骨骼密度係在於水平剖面之骨骼密度之1.1~40倍。 The invention of claim 5 is the composite refractory of claim 1, wherein the bone density constituting the three-dimensional mesh structure is different from the horizontal section in the vertical section, and the bone density in the vertical section is horizontal. The bone density of the section is 1.1 to 40 times.
申請專利範圍第6項之發明，係在於申請專利範圍第1項之複合耐火物，其中上述Si-SiC燒結體的氣孔率為50~98%。 The invention of claim 6 is the composite refractory of claim 1, wherein the Si-SiC sintered body has a porosity of 50 to 98%.
申請專利範圍第7項之發明，係在於申請專利範圍第1項之複合耐火物，其中於上述基材的表層，具有對被處理體具備耐反應性的表面塗層。 The invention of claim 7 is the composite refractory of claim 1, wherein the surface layer of the substrate has a surface coating having reactivity with respect to the object to be treated.
申請專利範圍第8項之發明，係在於申請專利範圍第1項之複合耐火物，其中於上述基材的表層，具有由氣孔率為0.1~2%的Si-SiC燒結體所構成之緻密質層。 The invention of claim 8 is the composite refractory of claim 1, wherein the surface layer of the substrate has a dense structure composed of a Si-SiC sintered body having a porosity of 0.1 to 2%. Floor.
申請專利範圍第9項之發明，係在於申請專利範圍第1項之複合耐火物，其中上述基材，具有層積氣孔率不同的上述Si-SiC燒結體之構造。 The invention of claim 9 is the composite refractory according to the first aspect of the invention, wherein the substrate has a structure in which the Si-SiC sintered body having a different porosity is laminated.
申請專利範圍第10項之發明，係在於申請專利範圍第9項之複合耐火物，其中上述層積構造之內，最表層，係氣孔率為0.1~2%的緻密層。 The invention of claim 10 is the composite refractory of claim 9 in which the outermost layer is a dense layer having a porosity of 0.1 to 2%.
申請專利範圍第11項之發明，係在於申請專利範圍第1項之複合耐火物，其中於上述基材的邊緣部，形成由氣孔率為0.1~2%的緻密層所構成的框部。 The invention of claim 11 is the composite refractory according to the first aspect of the invention, wherein a frame portion composed of a dense layer having a porosity of 0.1 to 2% is formed at an edge portion of the base material.
申請專利範圍第12項之發明，係在於申請專利範圍第1項之複合耐火物，其中具備以鎳合金構成之支持上述基材之框構件。 The invention of claim 12 is the composite refractory of claim 1, which comprises a frame member made of a nickel alloy and supporting the substrate.
申請專利範圍第13項之發明，係製造申請專利範圍第1項之複合耐火物，其特徵在於：將具有由三維網目構造構成之骨骼之尿烷發泡體浸漬在將SiC粉末分散於有機溶劑，進一步，對添加凝膠化劑而得之成形用漿料，使漿料硬化之成 形步驟；使上述成形步驟所得成形體乾燥之乾燥步驟；及將金屬Si載置在經由上述乾燥步驟之乾燥成形體，於減壓且還原氣氛中進行鍛燒，使金屬Si含浸於上述乾燥成形體的骨骼之鍛燒步驟。 The invention of claim 13 is the composite refractory of claim 1 which is characterized in that a urethane foam having a skeleton composed of a three-dimensional mesh structure is immersed in dispersing SiC powder in an organic solvent. Further, the slurry for molding obtained by adding a gelling agent hardens the slurry a drying step of drying the formed body obtained in the forming step; and placing the metal Si on the dried formed body through the drying step, and calcining in a reduced pressure and reducing atmosphere to impregnate the metal Si in the dry forming The calcination step of the body's bones.
使用具備高強度且高熱傳導率的特性的Si-SiC，使氣孔率為1%以下的骨骼，作成三維網目狀構造，且在於骨骼之SiC的含有比例為35~70質量%，Si的含有比例為25~60質量%，更佳的是藉由使SiC的含有比例為40~65質量%，Si的含有比例為30~55質量%，可實現高強度且高熱傳導率、耐熱衝擊性優良，且具備通氣性的同時，並不會因高溫條件下的使用而破裂或彎曲等的變形之複合耐火物。 By using Si-SiC having high strength and high thermal conductivity, a skeleton having a porosity of 1% or less is formed into a three-dimensional mesh structure, and the content ratio of SiC in the bone is 35 to 70% by mass, and the content ratio of Si is It is preferably 25 to 60% by mass, and more preferably, the content of Si is 40 to 65 mass%, and the content ratio of Si is 30 to 55 mass%, thereby achieving high strength, high thermal conductivity, and excellent thermal shock resistance. Further, it is provided with a composite refractory which is ventilated and which is not deformed by bending or bending due to use under high temperature conditions.
1‧‧‧Si-SiC骨骼的芯部 1‧‧‧Si-SiC bone core
2‧‧‧氣孔部 2‧‧‧ stomata
3‧‧‧Si-SiC骨骼的表層部 3‧‧‧Surface of the Si-SiC skeleton
4‧‧‧尿烷發泡體的骨骼部 4‧‧‧Bone parts of urethane foam
5‧‧‧空隙部 5‧‧‧Voids
7‧‧‧金屬Si 7‧‧‧Metal Si
8‧‧‧第1層 8‧‧‧1st floor
9‧‧‧第2層 9‧‧‧2nd floor
10‧‧‧SiC漿料成形體 10‧‧‧SiC paste molded body
第1圖(a)係實施形態1之承燒板的全體立體圖。(b)係實施形態1之承燒板之骨骼放大圖。 Fig. 1(a) is a perspective view of the whole of a setter according to the first embodiment. (b) is an enlarged view of the skeleton of the setter plate of the first embodiment.
第2圖係表示本實施形態之承燒板的Si-SiC骨骼的長邊方向的剖面及垂直剖面之組成影像(使用日本電子股份有限公司(JEOL)製，掃描式電子顯微鏡JSM-5600拍攝)。 Fig. 2 is a view showing a composition of a cross section and a vertical cross section of a Si-SiC skeleton of a setter according to the present embodiment (using a scanning electron microscope JSM-5600 manufactured by JEOL Co., Ltd.) .
第3圖係說明實施形態1之製造步驟之流程圖。 Fig. 3 is a flow chart showing the manufacturing steps of the first embodiment.
第4圖係說明實施形態1之製造步驟之圖。 Fig. 4 is a view showing the manufacturing steps of the first embodiment.
第5圖係將金屬Si載置於經由尿烷形狀的燒付步驟之尿烷發泡體上之圖。 Fig. 5 is a view in which metal Si is placed on a urethane foam which is subjected to a burning step of a urethane shape.
第6圖係說明實施形態1之製造步驟之流程圖。 Fig. 6 is a flow chart showing the manufacturing steps of the first embodiment.
第7圖(a)係實施形態2的承燒板的全體立體圖。(b)係實施形態2之承燒板之骨骼放大圖。 Fig. 7(a) is a perspective view of the whole of the setter according to the second embodiment. (b) is an enlarged view of the skeleton of the setter according to the second embodiment.
第8圖係表示實施形態2之承燒板的垂直剖面與水平剖面之放大影像(使用日本電子股份有限公司(JEOL)製，掃描式電子顯微鏡JSM-5600拍攝)。 Fig. 8 is an enlarged view showing a vertical cross section and a horizontal cross section of a setter according to the second embodiment (photographed by a Japanese electronic company (JEOL), scanning electron microscope JSM-5600).
第9圖係說明實施形態3之製造步驟之流程圖。 Fig. 9 is a flow chart showing the manufacturing steps of the third embodiment.
第10圖(a)係實施形態3的承燒板的全體立體圖。(b)係實施形態3之承燒板之骨骼放大圖。 Fig. 10 (a) is a perspective view of the whole of the setter according to the third embodiment. (b) is an enlarged view of the skeleton of the setter plate of the third embodiment.
將本發明之較佳的實施形態表示如下。 Preferred embodiments of the present invention are shown below.
(實施形態1：單層、無壓縮) (Embodiment 1: Single layer, no compression)
本實施形態之複合耐火物，係如第1圖(a)所示，以Si-SiC燒結體作為基材之單層構造的承燒板。承燒板，係如第1圖(b)所示，將骨骼作成三維網目狀之構造所構成。骨骼的氣孔率為1%以下。 The composite refractory of the present embodiment is a single-layer structure setter having a Si-SiC sintered body as a base material as shown in Fig. 1(a). The setter is composed of a three-dimensional mesh structure as shown in Fig. 1(b). The porosity of the bone is 1% or less.
在於電子零件等的鍛燒步驟，承燒板係使用於接近Si的熔點(1400℃附近)的1300℃前後的高溫。因此，上述骨骼僅以Si構成時，在於高溫的鍛燒步驟，有容易發生潛變變形的問題，或容易氧化而在表層上產生SiO2的問題，對爐內的氧攜入量多的問題。對此，於本發明，藉由將耐氧化性及耐熱性高，並且高強度的SiC複合構成Si-SiC，可實現迴避該等問題。 In the calcination step of an electronic component or the like, the setter is used at a high temperature around 1300 ° C which is close to the melting point of Si (near 1400 ° C). Therefore, when the above-mentioned skeleton is composed only of Si, the calcination step at a high temperature causes a problem that creep deformation easily occurs, or SiO 2 is easily oxidized to cause SiO 2 on the surface layer, and the amount of oxygen carried in the furnace is large. . On the other hand, in the present invention, Si-SiC is formed by SiC composite having high oxidation resistance and heat resistance and high strength, thereby avoiding such problems.
此外，於具備通氣性的承燒板，用於通氣性而形成的氣孔部容易成為隔熱層，使用熱傳導率低的不銹鋼或Ni 等的鐵絲網作為「具備通氣性的承燒板」時，在於加熱．冷卻時，容易在承燒板發生溫度分佈，載置於承燒板的產品之間發生溫度的離散，而有成為產品品質不穩定的問題，或在於高溫的鍛燒步驟，容易產生起因於溫度分佈，即熱膨脹差之承燒板的彎曲變形的問題。對此，於本發明，將熱傳導性較不銹鋼或Ni等的鐵絲網優良的Si-SiC的燒結體，作成三維網眼構造構成「具備通氣性的承燒板」，可實現迴避該等問題。 In addition, in a heat-insulating setter, the pore portion formed for air permeability is likely to be a heat insulating layer, and stainless steel or Ni having a low thermal conductivity is used. When the barbed wire is used as a "ventilated setter", it is heated. When cooling, the temperature distribution in the setter is easy to occur, and the temperature dispersion between the products placed on the setter is caused by the problem that the quality of the product is unstable, or the calcination step at a high temperature is likely to cause temperature. Distribution, that is, the problem of bending deformation of the setter plate with poor thermal expansion. On the other hand, in the present invention, a sintered body of Si-SiC having a thermal conductivity higher than that of a wire mesh such as stainless steel or Ni is formed into a three-dimensional mesh structure to form a "heat-stable set plate", thereby avoiding such problems.
於本發明，調整各成分量，使在於骨骼之SiC的含有比例為35~70質量%，Si的含有比例為25~60質量%。在此，化學成分，可藉由JIS R 2011(含有碳及碳化矽之耐火物之化學分析方法)測定。在於骨骼之SiC的含有比例較70質量%多時，由於氣孔容易殘存於SiC粒子間而有降低強度之問題，較35質量%少時，由於耐熱性會降低，在於高溫的鍛燒步驟，有容易發生潛變變形的問題。此外，Si的含有比例較60質量%多時，由於耐熱性會降低，故在於高溫的鍛燒步驟，有容易發生潛變變形的問題，較25質量%少時，由於氣孔容易殘存於SiC粒子間而有降低強度之問題。 In the present invention, the amount of each component is adjusted so that the content ratio of SiC in the bone is 35 to 70% by mass, and the content ratio of Si is 25 to 60% by mass. Here, the chemical composition can be measured by JIS R 2011 (chemical analysis method of refractory containing carbon and niobium carbide). When the content ratio of the SiC of the skeleton is more than 70% by mass, the pores tend to remain between the SiC particles and the strength is lowered. When the amount is less than 35% by mass, the heat resistance is lowered, and the high temperature calcination step is used. It is prone to the problem of latent deformation. In addition, when the content ratio of Si is more than 60% by mass, the heat resistance is lowered. Therefore, the calcination step at a high temperature causes a problem that creep deformation easily occurs. When the content is less than 25% by mass, the pores tend to remain in the SiC particles. There is a problem of reducing the intensity.
再者，在於骨骼之Si含有比例較55質量%多時，容易發生Si氧化於表層上產生SiO2，較30質量%少時，氣孔容易殘存於SiC粒子間，容易發生SiC氧化於表層上產生SiO2，均起因於產生於表層之SiO2，而容易因耐熱衝擊性及耐熱性的降低而破裂及彎曲變形，對爐內的氧攜入量的增加，與被處理體發生反應等的問題，由產品的長壽命化的觀點，調整各成分量，使SiC的含有比例為40~65質量%，Si的含有比例 為30~55質量%更佳。 In addition, when the content of Si in the bone is more than 55% by mass, SiO 2 is likely to occur in the surface layer due to oxidation of Si, and when it is less than 30% by mass, pores easily remain between the SiC particles, and SiC is easily generated on the surface layer. SiO 2 is caused by SiO 2 generated in the surface layer, and is easily broken and bent due to a decrease in thermal shock resistance and heat resistance, and an increase in the amount of oxygen carried in the furnace and a reaction with the object to be processed From the viewpoint of the long life of the product, the amount of each component is adjusted so that the content ratio of SiC is 40 to 65 mass%, and the content ratio of Si is preferably 30 to 55 mass%.
於本發明，如此地，將彈性模數高的SiC(彈性模數：400GPa程度)，與彈性模數低的Si(彈性模數：100GPa程度)，調整SiC的含有比例為35~70質量%，Si的含有比例為25~60質量%，更佳的是使SiC的含有比例為40~65質量%，Si的含有比例為30~55質量%，形成骨骼，圖謀減低Si-SiC燒結體的彈性模數。由於彈性模數的降低關係到耐熱衝擊性(熱衝擊破壞阻抗係數R'=σ(1-ν)λ/(αE)，在此，σ：強度，E：彈性模數)的上升，根據該構成，則加上高強度及高熱傳導率的特性，可實現具備耐熱衝擊性優良的特性的複合耐火物。 In the present invention, SiC (elastic modulus: about 400 GPa) having a high modulus of elasticity and Si (elastic modulus: about 100 GPa) having a low modulus of elasticity are adjusted to have a content ratio of SiC of 35 to 70% by mass. The content ratio of Si is 25 to 60% by mass, and more preferably, the content ratio of SiC is 40 to 65 mass%, and the content ratio of Si is 30 to 55 mass%, forming bones, and the Si-SiC sintered body is reduced. Elastic modulus. The decrease in the elastic modulus is related to the thermal shock resistance (the thermal shock damage resistance coefficient R'=σ(1-ν)λ/(αE), here, σ: strength, E: elastic modulus) rises, according to In addition, it is possible to realize a composite refractory having characteristics excellent in thermal shock resistance by adding characteristics of high strength and high thermal conductivity.
於本實施形態，係以圖謀降低Si-SiC燒結體的彈性模數為目標，作為另一個構成，採用構成上述三維網眼構造的氣孔與骨骼的各個形狀係滿足(氣孔徑/骨骼徑)的平均值≧3者。藉由作成滿足(氣孔徑/骨骼徑)平均值≧3者，可實現維持產品強度及降低彈性模數的並存。再者，承燒板的氣孔率，以50~98%為佳。於氣孔率49%以下，則無法得到充分的通氣性，以99%以上，則因強度顯著降低而變得容易破損，故均不佳。 In the present embodiment, it is intended to reduce the elastic modulus of the Si-SiC sintered body. As another configuration, each of the pores and bones constituting the three-dimensional network structure satisfy the (pore diameter/bones diameter). The average value is ≧3. By making the average value of the (pore diameter/bones diameter) ≧3, it is possible to maintain the strength of the product and reduce the modulus of elasticity. Furthermore, the porosity of the setter is preferably 50 to 98%. When the porosity is 49% or less, sufficient air permeability cannot be obtained, and when it is 99% or more, the strength is remarkably lowered to cause breakage, which is not preferable.
上述骨骼，係如第1圖(b)、第2圖所示，由芯部1、面於氣孔部2之表層部3所構成。 The skeleton is composed of the core portion 1 and the surface layer portion 3 of the air hole portion 2 as shown in Fig. 1 (b) and Fig. 2 .
第1表，表示在於第2圖之組成影像之任意2點之EDS分析結果。如第1表所示，各部位(芯部1與表層部3)，構成元素比例不同，於芯部1，C元素的含有比例為5~20質量%，Si元素的含有比例為80~95質量%，於表層部3，C元素的含有比例為15~50質量%，Si元素的含有比例為50~85質量%。骨骼中的游離碳(F.C)為0.1%以下，C元素，由於在骨骼中幾乎以SiC存在，故在由上述元素含有率所組成的芯部1，係金屬Si成為主要構成成分，在此，含有少量的SiC。表層部3，係與先前的Si-SiC燒結體同樣地，具有以SiC作為主成分，於其氣孔填充Si的構造。 The first table shows the EDS analysis results at any two points of the composition image of Fig. 2. As shown in the first table, the ratio of the constituent elements in the respective portions (the core portion 1 and the surface layer portion 3) is different, and the content ratio of the C element in the core portion 1 is 5 to 20% by mass, and the content ratio of the Si element is 80 to 95. The mass % is in the surface layer portion 3, the content ratio of the C element is 15 to 50% by mass, and the content ratio of the Si element is 50 to 85% by mass. The free carbon (FC) in the bone is 0.1% or less, and the C element is almost SiC in the bone. Therefore, the metal portion Si composed of the element content is the main constituent component. Contains a small amount of SiC. The surface layer portion 3 has a structure in which SiC is used as a main component and Si is filled in pores, similarly to the conventional Si-SiC sintered body.
芯部1的C元素的含有比例較20質量%多時，氣孔容易殘存於芯部1，而強度會降低。另一方面，較5質量%少時，由於耐熱性會下降，在於高溫的鍛燒步驟，容易發生潛變變形，故芯部1的C元素的含有比例以上述範圍為佳。 When the content ratio of the C element in the core portion 1 is more than 20% by mass, the pores tend to remain in the core portion 1 and the strength is lowered. On the other hand, when the amount is less than 5% by mass, the heat resistance is lowered, and the calcination step at a high temperature tends to cause creep deformation. Therefore, the content of the C element in the core portion 1 is preferably in the above range.
表層部3的C元素的含有比例較50質量%多時，氣孔容易殘存於SiC粒子間，而強度會降低。另一方面，較15質量%少時，由於耐熱性會下降，在於高溫的鍛燒步驟，容易發生潛變變形，故表層部3的C元素的含有比例以上述範圍為佳。 When the content ratio of the C element in the surface layer portion 3 is more than 50% by mass, the pores tend to remain between the SiC particles, and the strength is lowered. On the other hand, when the amount is less than 15% by mass, the heat resistance is lowered, and the calcination step at a high temperature is likely to cause creep deformation. Therefore, the content ratio of the C element in the surface layer portion 3 is preferably in the above range.
以下，詳述關於本實施形態之承燒板的製造方法。本實施形態的承燒板，係藉由凝膠注模法，以第3圖所示各步驟(ST1)~(ST8)製作。凝膠注模法，係關於本案申請人之發明之粉體成形方法，將選自由陶瓷、玻璃、或金屬之一種以上的粉體，藉由對使用分散劑分散於分散媒所製作的漿料，添加具有凝膠化能的物質(凝膠化劑)，使漿料硬化，得到任意形狀 的成形體的方法。 Hereinafter, a method of manufacturing the setter according to the embodiment will be described in detail. The setter plate of the present embodiment is produced by the gel injection molding method in steps (ST1) to (ST8) shown in Fig. 3 . The gel injection molding method relates to a powder molding method according to the invention of the present applicant, which is selected from the group consisting of ceramics, glass, or metal powders, which are prepared by dispersing a dispersing agent in a dispersion medium. Adding a gelling energy substance (gelling agent) to harden the slurry to obtain an arbitrary shape The method of forming a body.
(ST1)：本實施形態的承燒板，由於係藉由凝膠注模法成形，首先製作成形用漿料。本實施形態的成形用漿料，係將SiC粉末分散於有機溶劑作成漿料之後，藉由添加凝膠化劑，或者，藉由將SiC粉末與凝膠化劑同時添加分散於有機溶劑而製作。 (ST1): The set substrate of the present embodiment is first formed into a slurry for molding by a gel injection molding method. The molding slurry of the present embodiment is prepared by dispersing SiC powder in an organic solvent as a slurry, adding a gelling agent, or dispersing the SiC powder and the gelling agent in an organic solvent. .
於SiC粉末之外，亦可適宜混合碳、碳化硼等的粉體使用。再者，上述各陶瓷粉體的粒徑，只要可製作漿料，並無特別限定，可按照製造目的之成形體適宜選定。 In addition to the SiC powder, a powder such as carbon or boron carbide may be suitably used. In addition, the particle diameter of each of the ceramic powders is not particularly limited as long as the slurry can be produced, and can be suitably selected according to the molded article for the purpose of production.
用於作為分散媒的有機溶劑，可舉乙二醇等的二醇類，或甘油等的三醇類等的多元醇、二羧酸等的多元酸、谷胺酸二甲酯、丙二酸二甲酯等的多元酸酯、三乙酸甘油酯等的多元醇之酯等之酯類。 Examples of the organic solvent to be used as the dispersing medium include glycols such as ethylene glycol, polyhydric alcohols such as triols such as glycerin, polybasic acids such as dicarboxylic acids, dimethyl glutamate, and malonic acid. An ester such as a polyvalent acid ester such as a dimethyl ester or a polyhydric alcohol ester such as triacetin.
凝膠化劑，只要是具有可使陶瓷漿料硬化之反應性官能基之有機化合物即可。如此之有機化合物，可舉藉由架橋劑的介入三維架橋之預聚合物等，例如，尿烷樹脂、丙烯酸樹脂、環氧樹脂、酚樹脂等。凝膠化劑，考慮分散媒中的有機化合物的反應性，選定具有適合的反應性官能基者為佳。例如，使用反應性相對較低的酯類作為有機溶劑時，具有構成凝膠化劑之反應性官能基之有機化合物，選擇具有反應性高的異氰酸酯基(-N=C=O)及/或異硫代氰酸酯基(-N=C=S)之有機化合物為佳。於本實施形態，由於係如下述ST2所記載，將成形用漿料含浸於尿烷發泡體形而成形，故為防止SiC漿料成形體伴隨尿烷發泡體的彈性變形(繞曲)而破壞，使用橡膠軟性高的尿 烷樹脂為佳。 The gelling agent may be any organic compound having a reactive functional group capable of hardening the ceramic slurry. Examples of such an organic compound include a three-dimensional bridge prepolymer or the like by a bridging agent, for example, a urethane resin, an acrylic resin, an epoxy resin, a phenol resin, or the like. The gelling agent preferably takes into consideration the reactivity of the organic compound in the dispersion medium, and it is preferred to select a suitable reactive functional group. For example, when an ester having a relatively low reactivity is used as the organic solvent, the organic compound having a reactive functional group constituting the gelling agent is selected to have a highly reactive isocyanate group (-N=C=O) and/or An organic compound of an isothiocyanate group (-N=C=S) is preferred. In the present embodiment, since the slurry for molding is formed by impregnating a slurry of urethane with a shape as described in the following ST2, the SiC slurry molded body is prevented from being elastically deformed (curved) by the urethane foam. Destroy, use rubber with high soft urine An alkane resin is preferred.
成形用漿料含浸於尿烷發泡體時不會硬化，而於成形後迅速硬化為佳。因此，在於陶瓷漿料的製作時，考慮漿料的溫度、分散媒的種類或含量、凝膠化劑的種類或含量、有無涉及凝膠化反應之觸媒、觸媒的種類或含量等為佳。考慮作業性，則在於20℃的漿料黏性以50dPa．s以下為佳，進一步，在於20℃的漿料黏性以20dPa．s以下更佳。 When the slurry for molding is impregnated into the urethane foam, it does not harden, and it is preferably hardened immediately after molding. Therefore, in the production of the ceramic slurry, the temperature of the slurry, the type or content of the dispersion medium, the type or content of the gelling agent, the presence or absence of a catalyst involved in the gelation reaction, and the type or content of the catalyst are considered. good. Considering workability, the viscosity of the slurry at 20 ° C is 50dPa. The following is better, further, the viscosity of the slurry at 20 ° C is 20dPa. s is better below.
於成形用漿料的製作步驟，進行陶瓷粉體、分散劑及分散媒的調配、混合。之後，添加凝膠化劑及觸媒等進行漿料的最後調配，將此在對尿烷發泡體含漬成形之前，進行脫泡。 In the production step of the slurry for molding, the ceramic powder, the dispersant, and the dispersion medium are blended and mixed. Thereafter, a gelling agent, a catalyst, or the like is added to carry out final formulation of the slurry, and defoaming is performed before the formation of the urethane foam.
成形用漿料的混合，係以罐磨和球磨等進行，使用尼龍製的磨球，以溫度15℃~35℃進行12小時以上，進行72小時以上為佳。此外，漿料的脫泡，係將漿料在真空氣氛下進行攪拌，真空度為-0.090MPa以下，以-0.095MPa以下為佳，攪拌速度以100rpm~500rpm為佳，攪拌時間進行5分鐘~30分鐘為佳。 The mixing of the slurry for molding is carried out by pot grinding, ball milling, or the like, and it is preferably carried out at a temperature of 15 ° C to 35 ° C for 12 hours or more using a grinding ball made of nylon. Further, in the defoaming of the slurry, the slurry is stirred 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, and the stirring time is 5 minutes. 30 minutes is better.
(ST2)~(ST4)：將於ST1製作的成形用漿料含浸於尿烷發泡體之後，使漿料不阻塞尿烷發泡體的氣孔的程度去除多餘的漿料，載置於固定用夾具上，以常溫~40℃，放置數小時~數十小時。藉此，成形用漿料，藉由凝膠化硬化而成為成形體。 (ST2) to (ST4): After the slurry for molding prepared in ST1 is impregnated with the urethane foam, the slurry is removed to the extent that the pores of the urethane foam are not blocked, and the slurry is placed and fixed. Use a jig to hold the temperature at ~40 ° C for several hours to tens of hours. Thereby, the slurry for molding is formed into a molded body by gelation and hardening.
如第4圖(A)所示，尿烷發泡體，係由骨骼部4與空隙部5構成，於(ST2)，如第4圖(B)所示，面於空隙部5形 成SiC漿料成形體10。 As shown in Fig. 4(A), the urethane foam is composed of the skeleton portion 4 and the void portion 5, and as shown in Fig. 4(B), the surface of the void portion is formed as shown in Fig. 4(B). The SiC slurry molded body 10 is formed.
(ST5)~(ST6)：接著，以40℃~100℃進行乾燥3~12小時，進一步，以100℃~200℃，加熱3~12小時，進行尿烷形狀的燒付，即，進行去除尿烷發泡體之彈性的處理。 (ST5) to (ST6): Next, drying is carried out at 40 ° C to 100 ° C for 3 to 12 hours, and further, heating at 100 ° C to 200 ° C for 3 to 12 hours to perform urethane-shaped burning, that is, removal The treatment of the elasticity of the urethane foam.
再者，SiC漿料成形體10會伴隨乾燥而收縮。使用水作為分散媒的水系漿料時，由於在含浸成形用漿料時不會發生尿烷發泡體的膨潤，故無法確保在於乾燥時之SiC漿料成形體10的收縮餘白，有容易使SiC漿料成形體10發生裂紋的問題。對此，於本實施形態，由於使用含浸成形用漿料時會發生尿烷發泡體的膨潤之有機溶劑作為分散媒，故可確保在於乾燥時之SiC漿料成形體10的收縮餘白，可避免SiC漿料成形體10伴隨乾燥而發生裂紋。 Further, the SiC slurry molded body 10 shrinks accompanying drying. When the water-based slurry is used as the dispersion medium, the urethane foam does not swell when the slurry for molding is impregnated. Therefore, it is not easy to ensure the shrinkage of the SiC slurry molded body 10 during drying. The SiC slurry molded body 10 has a problem of cracking. On the other hand, in the present embodiment, since the organic solvent which swells the urethane foam when the slurry for impregnation is used is used as the dispersion medium, the shrinkage of the SiC slurry molded body 10 during drying can be ensured. It is possible to prevent cracks from occurring in the SiC slurry molded body 10 with drying.
(ST7)~(ST8)：如第4圖(C)及第5圖所示，將金屬Si7載置於去除彈性的尿烷發泡體的上面，以惰性氣體氣氛，以1400℃~1500℃，進行加熱1~3小時。尿烷發泡體的骨骼部4，會在500℃附近燒去，但如第4圖(D)所示，藉由金屬Si7含浸於燒去骨骼部4所形成的空間，可得由三維網目構造構成之具有緻密的SiC-Si骨骼之新穎複合耐火物(氣孔率50~98%)。由於根據該方法，可使金屬Si7，遞過SiC漿料成形體10所構成的骨骼而含浸，故可不使金屬Si7阻塞空隙部5，而進行均勻的含浸。 (ST7)~(ST8): As shown in Fig. 4(C) and Fig. 5, the metal Si7 is placed on top of the elastic urethane foam, and is 1400 ° C to 1500 ° C in an inert gas atmosphere. , heat for 1 to 3 hours. The skeletal portion 4 of the urethane foam is burned at around 500 ° C, but as shown in Fig. 4 (D), the metal Si7 is impregnated into the space formed by burning the bone portion 4, and the three-dimensional mesh can be obtained. Constructed a novel composite refractory with a dense SiC-Si skeleton (porosity 50~98%). According to this method, the metal Si7 can be impregnated with the skeleton formed by the SiC slurry molded body 10, so that the metal Si7 can be uniformly impregnated without blocking the void portion 5.
再者，亦可按照必要，如第6圖所示，接著上述ST8，設耐反應性塗層燒付步驟(ST9)，於被處理體與成為接觸 面之基材的上層側，形成對被處理體具備耐反應性之表面塗層。表面塗層，係與被處理體反應性低的材質形成，材質按照被處理體的種類而異。例如，以鈦酸鋇構成之陶瓷電容器之情形，選擇與此反應性低的氧化鋯化合物為佳。氧化鋯化合物，可由選自由氧化鈣(CaO)或氧化釔(Y2O3)安定化之安定化氧化鋯、BaZrO3、及CaZrO3之中之至少一種所組成之氧化鋯化合物，考慮已述之反應性適宜選擇最佳的氧化鋯即可。再者，根據電子零件的種類，亦可使用包含氧化鋁與氧化鋯的共晶物之熔射披膜作為表面塗層。表面塗層的形成方法，並無特別限定，可採用例如，熔射或噴灑塗層法等，適宜的最佳手法。 Further, as shown in Fig. 6, as shown in Fig. 6, next to the above-mentioned ST8, a reactive-resistance coating baking step (ST9) is provided to form a pair on the upper layer side of the substrate to be treated and the substrate to be contacted. The treatment body is provided with a surface coating resistant to reactivity. The surface coating layer is formed of a material having low reactivity with the object to be processed, and the material varies depending on the type of the object to be processed. For example, in the case of a ceramic capacitor composed of barium titanate, it is preferred to select a zirconia compound having low reactivity. The zirconia compound may be a zirconia compound composed of at least one selected from the group consisting of stabilized zirconia stabilized by calcium oxide (CaO) or yttrium oxide (Y 2 O 3 ), BaZrO 3 , and CaZrO 3 . The reactivity is suitable for selecting the best zirconia. Further, depending on the type of the electronic component, a spray coating comprising a eutectic of alumina and zirconia may be used as the surface coating. The method for forming the surface coating layer is not particularly limited, and a suitable optimum method such as a spray coating or a spray coating method can be employed.
此外，亦可按照必要，將於ST1所製作的成形用漿料含浸於基材的邊緣部，將氣孔堵塞之後，使之硬化，藉由進行ST5~8所記載的乾燥，Si含浸步驟，於基材的邊緣部，形成氣孔率為0.1~2%的Si-SiC緻密層所構成的框部。 In addition, the molding slurry prepared in ST1 may be impregnated into the edge portion of the substrate as needed, and then the pores may be clogged, and then cured, and the Si impregnation step described in ST5 to 8 may be performed. The edge portion of the substrate forms a frame portion composed of a Si-SiC dense layer having a porosity of 0.1 to 2%.
此外，亦可按照必要，使用支持基材之框構件。框構件，以鎳合金等構成為佳。此時，為吸收由Si-SiC燒結體所構成的基材與鎳合金的熱膨脹差，並不將基材與框構件固定，於框構件與基材之間設既定的間隙為佳。 Further, a frame member supporting the substrate may be used as necessary. The frame member is preferably made of a nickel alloy or the like. At this time, in order to absorb the difference in thermal expansion between the base material composed of the Si—SiC sintered body and the nickel alloy, the base material and the frame member are not fixed, and a predetermined gap is preferably provided between the frame member and the base material.
(實施形態2：單層、有尿烷發泡體的壓縮) (Embodiment 2: Single layer, compression with urethane foam)
第3圖及第6圖中，在於ST3的「固定於既定厚度．形狀」的步驟，亦可將尿烷發泡體壓縮固定。 In the third and sixth figures, in the step of "fixing to a predetermined thickness and shape" of ST3, the urethane foam may be compression-fixed.
如此地，先於成形用漿料的硬化(ST4)，藉由將尿烷發泡體壓縮，提高上述「具有三維網目構造之新穎複合耐火物」的骨骼密度，得到強度。此外，如第7圖(a)所示，可圖謀 承燒板的薄壁化。 In this way, the strength of the bone density of the "new composite refractory having a three-dimensional mesh structure" is improved by compressing the urethane foam prior to the curing of the slurry for molding (ST4). In addition, as shown in Figure 7 (a), it can be plotted The wall of the setter is thinned.
將尿烷發泡體壓縮而可得之本實施形態之複合耐火物，係如第7圖(b)所示，具有扁平的骨骼構造，如第8圖所示，於垂直剖面與水平剖面具有不同的骨骼密度。垂直剖面與水平剖面的骨骼密度比較40倍大時，在於側面(垂直剖面)無法得到充分的通氣性。此外，在於使用面(水平剖面)因產生漿料的阻塞，而無法得到充分的通氣性，故以40倍以下為佳。此外，垂直剖面與水平剖面的骨骼密度比較1.1倍小時，在於承燒板的高強度化無法得到充分的效果，故以1.1倍以上為佳。 The composite refractory of the present embodiment obtained by compressing the urethane foam has a flat skeleton structure as shown in Fig. 7(b), and has a vertical cross section and a horizontal cross section as shown in Fig. 8. Different bone density. When the bone density of the vertical section and the horizontal section is 40 times larger, the side surface (vertical section) cannot be sufficiently ventilated. Further, since the surface (horizontal cross section) is used to cause clogging of the slurry, sufficient air permeability cannot be obtained, so that it is preferably 40 times or less. Further, the bone density of the vertical section and the horizontal section is 1.1 times smaller than that of the horizontal section, and the strength of the setter is not sufficient, so that it is 1.1 times or more.
在此，各骨骼密度係以下述方法測定。首先，將上述複合耐火物埋設於酚樹脂等，將複合耐火物向垂直方向及水平方向切斷．研磨製作測定用試料。接著，使用日本電子股份有限公司(JEOL)製，掃描式電子顯微鏡JSM-5600得到測定用試料在於垂直剖面及水平剖面之視野範圍0.1cm2的組成影像。根據利用每個元素的亮度差的組成影像，可明確的表示Si-SiC骨骼部與空隙部。接著，將所得組成影像使用影像處理軟體，以一定的亮度條件2值化成黑白，計測在於組成影像之骨骼部與空隙部的各總像素數。影像處理軟體，可使用例如，免費軟體的lmageNos(ver1.04)。如此地以骨骼部的總像素數對視野範圍的總像素數之比例作為骨骼密度(骨骼密度=骨骼部的總像素數/骨骼部及空隙部的總像素數)。可如此算出在於垂直剖面及水平剖面方面之骨骼密度比(骨骼密度比=在於垂直剖面之骨骼密度/在於水平剖面之骨骼密度)。惟，在於三維網目構造，由於骨骼構造係隨機配置，故無法以1視野的剖面組 成影像算出骨骼密度。需要以垂直剖面及水平剖面之至少各個5視野以上，以10視野以上的剖面組成影像算出骨骼密度更佳。 Here, each bone density was measured by the following method. First, the composite refractory is embedded in a phenol resin or the like, and the composite refractory is cut in the vertical direction and the horizontal direction. The measurement sample was prepared by polishing. Next, a scanning electron microscope JSM-5600 manufactured by JEOL Co., Ltd. was used to obtain a composition image in which the sample for measurement was 0.1 cm 2 in the field of view of the vertical cross section and the horizontal cross section. The Si-SiC skeleton and the void portion can be clearly expressed based on the composition image using the luminance difference of each element. Next, the obtained component image is image-processed using the image processing software, and is converted into black and white under a constant luminance condition, and the total number of pixels of the skeleton portion and the space portion constituting the image is measured. For image processing software, for example, lmageNos (ver1.04) of free software can be used. In this way, the ratio of the total number of pixels of the skeleton to the total number of pixels in the field of view is taken as the bone density (bone density = total number of pixels in the bone portion / total number of pixels in the bone portion and the gap portion). The bone density ratio in the vertical section and the horizontal section can be calculated as such (bone density ratio = bone density in the vertical section / bone density in the horizontal section). However, in the three-dimensional mesh structure, since the skeleton structure is randomly arranged, the bone density cannot be calculated from the image of the cross-sectional view of one field of view. It is necessary to calculate the bone density by using at least five fields of view of the vertical section and the horizontal section and the profile of the profile of 10 or more fields.
再者，於第3圖及第6圖中，在於ST3的「固定於既定厚度．形狀」的步驟，亦可使用既定形狀的模具將尿烷發泡體壓縮固定。如此地，先於成形用漿料的硬化(ST4)，將尿烷發泡體固定於既定形狀，可提高上述「具有三維網目構造之新穎複合耐火物」之形狀自由度，可製作複雜形狀的承燒板。複雜形狀的承燒板，可製作例如，匣缽(saggers)，具有堆疊腳之承燒板(setter with legs for stacking)。 Further, in the third and sixth figures, in the step of "fixing to a predetermined thickness and shape" of ST3, the urethane foam may be compression-fixed using a mold having a predetermined shape. In this way, the urethane foam is fixed to a predetermined shape in advance of the curing of the slurry for molding (ST4), and the degree of freedom of the above-mentioned "new composite refractory having a three-dimensional mesh structure" can be improved, and a complicated shape can be produced. Burning board. A complex shaped set of burnt plates can be made, for example, saggers with setter with legs for stacking.
(實施形態3：多層) (Embodiment 3: Multilayer)
如第9圖所示，亦可先於成形用漿料的硬化(ST4)，設重疊尿烷發泡體的壓縮率不同的層一體化的步驟(ST10)。 As shown in Fig. 9, the step of integrating the layers having different compression ratios of the urethane foams may be preceded by the step of curing the molding slurry (ST4) (ST10).
本實施形態的複合耐火物，如第10圖所示，具有層積骨骼密度不同的層之層積構造。可例如，假設在於輥道窯之輥輪輸送，使第1層8為高密度緻密層，第2層9為通氣性高的層等，按照使用形狀作成最佳的層積構造。此時，第1層8即使是緻密層，由於第2層9具有三維網目構造，故在於第2層9的上面及側面可得高的通氣性。其他，亦可將最表面，作成氣孔率0.1~2%的緻密層。 As shown in Fig. 10, the composite refractory of the present embodiment has a laminated structure in which layers having different skeletal densities are laminated. For example, it is assumed that the roller conveyor of the roller kiln conveys the first layer 8 as a high-density dense layer, and the second layer 9 is a layer having high air permeability, and an optimum laminated structure is formed according to the shape to be used. At this time, even if the first layer 8 is a dense layer, since the second layer 9 has a three-dimensional mesh structure, high air permeability can be obtained on the upper surface and the side surface of the second layer 9. Others, the outermost surface can also be made into a dense layer with a porosity of 0.1 to 2%.
[實施例A] [Example A]
使用下述實施例1~6及比較例1~2之承燒板，調查在加熱時之「破裂」及「彎曲變形」的發生的結果，於實施例1~6，均沒有確認到「破裂」及「彎曲變形」，而於比較例 1~2均確認到「破裂」及「彎曲變形」。 Using the setter sheets of the following Examples 1 to 6 and Comparative Examples 1 and 2, the results of the occurrence of "cracking" and "bending deformation" during heating were examined. In Examples 1 to 6, no "rupture" was observed. And "bending deformation", and in the comparative example "Broken" and "bending deformation" were confirmed in 1~2.
(實施例1) (Example 1)
將SiC(-C、-B4C)分散於有機溶劑，將150×150×5mm的尿烷發泡體浸漬於混合尿烷樹脂(異氰酸酯及觸媒)之SiC漿料，去除多餘漿料後，藉由使漿料硬化於尿烷發泡體的骨骼表面上形成SiC(-C、-B4C)層之成形體，以120℃乾燥，製作SiC成形體。對SiC成形體，將重量比90%的金屬Si載置於SiC成形體，於減壓且還原氣氛中以1500℃鍛燒，製作由具有三維網目構造之Si-SiC所構成之厚度5mm之通氣性承燒板。製作之通氣性承燒板之氣孔率為95%。 SiC (-C, -B 4 C) was dispersed in an organic solvent, and a 150 × 150 × 5 mm urethane foam was immersed in a SiC slurry of a mixed urethane resin (isocyanate and catalyst) to remove excess slurry. The SiC (-C, -B 4 C) layer was formed by curing the slurry on the bone surface of the urethane foam, and dried at 120 ° C to prepare a SiC molded body. In the SiC formed body, 90% by weight of metal Si was placed on the SiC formed body, and calcined at 1500 ° C in a reduced pressure and reducing atmosphere to prepare a 5 mm-thickness ventilating layer composed of Si-SiC having a three-dimensional mesh structure. Sex-bearing board. The porosity of the ventilated setter plate produced was 95%.
(實施例2) (Example 2)
將SiC(-C、-B4C)分散於有機溶劑，將150×150×5mm的尿烷發泡體浸漬於混合尿烷樹脂(異氰酸酯及觸媒)之SiC漿料，去除多餘漿料後，藉由使用固定用夾具，加壓．壓縮使尿烷發泡體的厚度成1mm，藉由直接將漿料硬化，製作厚度1mm的SiC成形體。以與實施例1同樣的進行鍛燒，製作厚度1mm的通氣性承燒板。製作之通氣性承燒板的氣孔率為60%。藉由段落【0055】所記載的方法算出之骨骼密度比為1.4倍。 SiC (-C, -B 4 C) was dispersed in an organic solvent, and a 150 × 150 × 5 mm urethane foam was immersed in a SiC slurry of a mixed urethane resin (isocyanate and catalyst) to remove excess slurry. , by using a fixing fixture, pressurizing. The urethane foam was compressed to a thickness of 1 mm, and the slurry was directly cured to prepare a SiC molded body having a thickness of 1 mm. The calcination was carried out in the same manner as in Example 1 to produce a ventilated setter having a thickness of 1 mm. The ventilated setter plate produced was made to have a porosity of 60%. The bone density ratio calculated by the method described in paragraph [0055] was 1.4 times.
(實施例3) (Example 3)
將SiC(-C、-B4C)分散於有機溶劑，將180×180×5mm的尿烷發泡體浸漬於混合尿烷樹脂(異氰酸酯及觸媒)之SiC漿料，去除多餘漿料後，使用箱型的固定用夾具，使尿烷發泡體成為匣缽形狀地固定，直接使漿料硬化，製作厚度5mm的箱型的SiC成形體。以與實施例1同樣的進行鍛燒，製作厚度5mm的 通氣性匣缽。製作的通氣性匣缽的氣孔率為95%。 SiC (-C, -B 4 C) was dispersed in an organic solvent, and a 180×180×5 mm urethane foam was immersed in a SiC slurry of a mixed urethane resin (isocyanate and catalyst) to remove excess slurry. Using a box-shaped fixing jig, the urethane foam was fixed in a crucible shape, and the slurry was directly cured to prepare a box-shaped SiC molded body having a thickness of 5 mm. The calcination was carried out in the same manner as in Example 1 to produce a gas permeable crucible having a thickness of 5 mm. The porosity of the produced ventilated sputum was 95%.
(實施例4) (Example 4)
於實施例1所得之SiC成形體之一面或兩面，黏貼實施例2所得SiC成形體，將一體化之SiC成形體以與實施例1同樣的進行鍛燒，製作具有多層構造之厚度6~7mm的通氣性承燒板。 The SiC formed body obtained in Example 2 was adhered to one surface or both surfaces of the SiC formed body obtained in Example 1, and the integrated SiC formed body was calcined in the same manner as in Example 1 to have a multilayer structure having a thickness of 6 to 7 mm. Ventilation set board.
(實施例5) (Example 5)
於實施例2所得之SiC成形體的單面，黏貼不使用尿烷發泡體，使SiC漿料硬化，形成厚度1mm的板片狀之SiC成形體，將使之一體化之SiC成形體，以與實施例1同樣的進行鍛燒，製作具有包含高強度的緻密質層之多層構造之厚度2mm的通氣性承燒板。 On the one surface of the SiC formed body obtained in Example 2, the SiC paste was cured without using a urethane foam, and a SiC molded body having a thickness of 1 mm was formed, and the SiC formed body was integrated. The calcination was carried out in the same manner as in Example 1 to prepare a ventilated setter having a thickness of 2 mm having a multilayer structure including a high-strength dense layer.
(實施例6) (Example 6)
於實施例2所得SiC成形體的邊緣部，將SiC漿料含浸至寬5mm，阻塞氣孔之後，將使之硬化並一體化之SiC成形體，以與實施例1同樣的進行鍛燒，製作具有寬5mm的高強度緻密質層之邊緣部之厚度1mm的通氣性承燒板。 In the edge portion of the SiC molded body obtained in Example 2, the SiC slurry was impregnated to a width of 5 mm, and the pores were blocked, and then the SiC molded body which was cured and integrated was calcined in the same manner as in Example 1. A ventilated setter having a thickness of 1 mm at the edge of the high-strength dense layer having a width of 5 mm.
(實施例7) (Example 7)
於實施例2所得Si-SiC鍛燒體的單面或雙面，將ZrO2及/或Al2O3-SiO2所組成的漿料，噴灑塗佈之後，以1350℃鍛燒，形成由ZrO2及/或Al2O3-SiO2所組成之層。 On one or both sides of the Si-SiC calcined body obtained in Example 2, a slurry composed of ZrO 2 and/or Al 2 O 3 -SiO 2 was spray-coated, and then calcined at 1350 ° C to form a slurry. A layer composed of ZrO 2 and/or Al 2 O 3 -SiO 2 .
(比較例1) (Comparative Example 1)
製作由Ni鐵絲網構成的承燒板。 A setter plate made of Ni wire mesh was produced.
(比較例2) (Comparative Example 2)
以專利文獻1所記載的手法製作厚度1mm的承燒板。 A setter plate having a thickness of 1 mm was produced by the method described in Patent Document 1.
[實施例B] [Example B]
(實施例8) (Example 8)
將SiC(-C、-B4C)分散於有機溶劑，將150×150×5mm的尿烷發泡體浸漬於混合尿烷樹脂(異氰酸酯及觸媒)之SiC漿料，去除多餘漿料後，使用固定夾將尿烷發泡體加壓成厚度1mm，直接將漿料硬化，製作厚度1mm的SiC成形體。以與實施例1同樣地進行鍛燒，製作厚度1mm的通氣性承燒板。製作的通氣性承燒板的氣孔率為60%。骨骼全體的SiC的含有比例為46.5質量%，Si的含有比例為48.4質量%，在於該骨骼的芯部的C含量為19.8質量%，在於表層部之C含量為46.8質量%。此外，(氣孔徑/骨骼徑)的比例為4.9。 SiC (-C, -B 4 C) was dispersed in an organic solvent, and a 150 × 150 × 5 mm urethane foam was immersed in a SiC slurry of a mixed urethane resin (isocyanate and catalyst) to remove excess slurry. The urethane foam was pressed to a thickness of 1 mm using a fixing clip, and the slurry was directly cured to prepare a SiC molded body having a thickness of 1 mm. The calcination was carried out in the same manner as in Example 1 to prepare a ventilated setter having a thickness of 1 mm. The ventilated setter plate produced had a porosity of 60%. The content ratio of SiC in the entire skeleton was 46.5 mass%, and the content ratio of Si was 48.4 mass%, and the C content in the core portion of the skeleton was 19.8% by mass, and the C content in the surface layer portion was 46.8 mass%. In addition, the ratio of (pore diameter/bones diameter) was 4.9.
(實施例9) (Example 9)
使用150×150×3mm的尿烷發泡體，以與實施例8同樣的方法製作厚度1mm的通氣性承燒板。製作之通氣性承燒板的氣孔率為70%。骨骼全體的SiC的含有比例為54.1質量%，Si的含有比例為40.0質量%，在於該骨骼的芯部之C含量為11.1質量%，在於表層部之C含量為33.6質量%。此外，(氣孔徑/骨骼徑)的比例為4.6。 An air-through setter having a thickness of 1 mm was produced in the same manner as in Example 8 using a 150 × 150 × 3 mm urethane foam. The ventilated setter plate produced has a porosity of 70%. The content ratio of SiC in the entire skeleton was 54.1% by mass, and the content ratio of Si was 40.0% by mass, and the C content in the core portion of the skeleton was 11.1% by mass, and the C content in the surface layer portion was 33.6% by mass. In addition, the ratio of (pore diameter/bones diameter) was 4.6.
(實施例10) (Embodiment 10)
使用150×150×2mm的尿烷發泡體，以與實施例8同樣的方法製作厚度1mm的通氣性承燒板。製作之通氣性承燒板的氣孔率為80%。骨骼全體的SiC的含有比例為58.8質量%，Si的含有比例為35.8質量%，在於該骨骼的芯部之C含量為6.0 質量%，在於表層部之C含量為16.0質量%。此外，(氣孔徑/骨骼徑)的比例為3.9。 An air-permeable setter having a thickness of 1 mm was produced in the same manner as in Example 8 using a 150 × 150 × 2 mm urethane foam. The ventilated setter plate produced had a porosity of 80%. The content ratio of SiC in the entire skeleton is 58.8% by mass, and the content ratio of Si is 35.8 mass%, and the C content in the core of the skeleton is 6.0. The % by mass is that the C content in the surface layer portion is 16.0% by mass. In addition, the ratio of (pore diameter/bones diameter) was 3.9.
(比較例3) (Comparative Example 3)
將SiC(-C、-B4C)分散於有機溶劑，將150×150×5mm的尿烷發泡體浸漬於混合尿烷樹脂(異氰酸酯及觸媒)之SiC漿料，去除多餘漿料後，使用固定夾將尿烷發泡體加壓成厚度1mm，直接將漿料硬化，製作厚度1mm的SiC成形體。其次，對SiC成形體，將重量比60%的金屬Si載置於SiC成形體，於減壓且還原氣氛中以1500℃鍛燒，製作厚度1mm的通氣性承燒板。製作的通氣性承燒板的氣孔率為60%。骨骼全體的SiC的含有比例為73.3質量%，Si的含有比例為21.6質量%，在於該骨骼的芯部的C含量為10.1質量%，在於表層部之C含量為55.7質量%。此外，(氣孔徑/骨骼徑)的比例為3.6。 SiC (-C, -B 4 C) was dispersed in an organic solvent, and a 150 × 150 × 5 mm urethane foam was immersed in a SiC slurry of a mixed urethane resin (isocyanate and catalyst) to remove excess slurry. The urethane foam was pressed to a thickness of 1 mm using a fixing clip, and the slurry was directly cured to prepare a SiC molded body having a thickness of 1 mm. Next, in the SiC formed body, 60% by weight of metal Si was placed on the SiC formed body, and calcined at 1500 ° C in a reduced pressure and reducing atmosphere to prepare a ventilated setter having a thickness of 1 mm. The ventilated setter plate produced had a porosity of 60%. The content ratio of SiC in the entire skeleton was 73.3 mass%, and the content ratio of Si was 21.6% by mass. The C content in the core of the skeleton was 10.1% by mass, and the C content in the surface layer portion was 55.7 mass%. In addition, the ratio of (pore diameter/bones diameter) is 3.6.
(比較例4) (Comparative Example 4)
以與比較例3同樣的方法，製作厚度1mm的SiC成形體。其次，對SiC成形體，將重量比120%的金屬Si載置於SiC成形體，於減壓且還原氣氛中以1500℃鍛燒，製作厚度1mm的通氣性承燒板。製作的通氣性承燒板的氣孔率為60%。骨骼全體的SiC的含有比例為28.4質量%，Si的含有比例為66.2質量%，在於該骨骼的芯部的C含量為11.4質量%，在於表層部之C含量為13.6質量%。此外，(氣孔徑/骨骼徑)的比例為4.2。 A SiC formed body having a thickness of 1 mm was produced in the same manner as in Comparative Example 3. Next, a SiC molded body was placed on a SiC molded body at a weight ratio of 120%, and calcined at 1500 ° C in a reduced pressure and reducing atmosphere to prepare an air-permeable setter having a thickness of 1 mm. The ventilated setter plate produced had a porosity of 60%. The content ratio of SiC in the entire skeleton was 28.4% by mass, and the content ratio of Si was 66.2% by mass, and the C content in the core portion of the skeleton was 11.4% by mass, and the C content in the surface layer portion was 13.6% by mass. In addition, the ratio of (pore diameter/bones diameter) is 4.2.
(比較例5) (Comparative Example 5)
將SiC(-C、-B4C)分散於有機溶劑，將150×150×5mm的尿烷發泡體浸漬於混合尿烷樹脂(異氰酸酯及觸媒)之SiC漿料， 不充分去除多餘漿料，使用固定夾將尿烷發泡體加壓成厚度1mm，直接將漿料硬化，製作厚度1mm的SiC成形體。其次，對SiC成形體，將重量比60%的金屬Si載置於SiC成形體，於減壓且還原氣氛中以1500℃鍛燒，製作厚度1mm的通氣性承燒板。製作的通氣性承燒板的氣孔率為40%。骨骼全體的SiC的含有比例為68.8質量%，Si的含有比例為23.8質量%，在於該骨骼的芯部的C含量為11.1質量%，在於表層部之C含量為55.4質量%。此外，(氣孔徑/骨骼徑)的比例為1.3。 SiC (-C, -B 4 C) was dispersed in an organic solvent, and a 150 × 150 × 5 mm urethane foam was immersed in a SiC slurry of a mixed urethane resin (isocyanate and catalyst), and the excess slurry was not sufficiently removed. The urethane foam was pressed to a thickness of 1 mm using a fixing clip, and the slurry was directly cured to prepare a SiC molded body having a thickness of 1 mm. Next, in the SiC formed body, 60% by weight of metal Si was placed on the SiC formed body, and calcined at 1500 ° C in a reduced pressure and reducing atmosphere to prepare a ventilated setter having a thickness of 1 mm. The ventilated setter plate produced had a porosity of 40%. The content ratio of SiC in the entire skeleton was 68.8% by mass, and the content ratio of Si was 23.8% by mass. The C content in the core of the skeleton was 11.1% by mass, and the C content in the surface layer portion was 55.4% by mass. In addition, the ratio of (pore diameter/bones diameter) is 1.3.
製作上述實施例8~10及比較例3~5之承燒板，調查耐熱衝擊性及耐熱性的結果，確認實施例8~10，耐熱衝擊性及耐熱性均有較比較例3~5提升。 The test plates of the above Examples 8 to 10 and Comparative Examples 3 to 5 were prepared, and the results of thermal shock resistance and heat resistance were examined. It was confirmed that Examples 8 to 10, the thermal shock resistance and the heat resistance were improved in Comparative Examples 3 to 5. .
1‧‧‧Si-SiC骨骼的芯部 1‧‧‧Si-SiC bone core
2‧‧‧氣孔部 2‧‧‧ stomata
3‧‧‧Si-SiC骨骼的表層部 3‧‧‧Surface of the Si-SiC skeleton
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| TWI811283B (en) * | 2018-01-10 | 2023-08-11 | 日商日本碍子股份有限公司 | setter for firing |
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| JP6670153B2 (en) * | 2016-03-31 | 2020-03-18 | 日本碍子株式会社 | Heat storage material |
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| JP7307578B2 (en) * | 2019-03-29 | 2023-07-12 | 日本碍子株式会社 | Firing jig |
| CN114945787A (en) * | 2020-01-06 | 2022-08-26 | 日本碍子株式会社 | Burning bearing plate for burning |
| JP7390272B2 (en) | 2020-09-30 | 2023-12-01 | 日本碍子株式会社 | Setter for firing |
| JP2023136805A (en) * | 2022-03-17 | 2023-09-29 | 日本碍子株式会社 | PRODUCTION METHOD OF Si-SiC-BASED COMPOSITE STRUCTURE |
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Family Cites Families (13)
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| JP2007044674A (en) * | 2005-08-12 | 2007-02-22 | National Institute Of Advanced Industrial & Technology | Porous structure filter and its production method |
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| JP2010163293A (en) * | 2009-01-13 | 2010-07-29 | Bridgestone Corp | Method for producing silicon carbide porous body, and silicon carbide porous body |
| JP5431891B2 (en) * | 2009-12-03 | 2014-03-05 | 株式会社モトヤマ | Sheath sheath and method of manufacturing ceramic electronic component using the same |
| JP2011236070A (en) * | 2010-05-07 | 2011-11-24 | National Institute Of Advanced Industrial Science & Technology | Filter for warming fluid and method for manufacturing the same |
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| CN102976785A (en) * | 2012-12-12 | 2013-03-20 | 武汉科技大学 | Light Al2O3-SiC-C refractory brick and preparation method thereof |
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