JP2008222500A - Porous molding, porous filled molding, method for producing porous molding and method for producing porous filled molding - Google Patents
Porous molding, porous filled molding, method for producing porous molding and method for producing porous filled molding Download PDFInfo
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本願発明は、前駆体ポリマーを成形して形成される多孔質成形体、多孔質充填成形体及びこれらの製造方法に関する。 The present invention relates to a porous molded body formed by molding a precursor polymer, a porous filling molded body, and a method for producing them.
有機珪素系ポリマーや炭化水素系ポリマーなどの有機物を前駆体として、これらを焼成してセラミックスやカーボン材料を合成する方法は前駆体法もしくはプレカーサ法と呼ばれ、その汎用性や制御性の面から繊維、粒子、薄膜の作製において広く用いられている。前駆体ポリマーを焼成するとその熱分解中にガス発生と体積収縮が起こり、これに起因して熱分解後の成形体に多数の気孔やクラック等の欠陥が形成される。また、ガス発生によって、熱分解物中の内圧が上昇し組織を破壊する。体積収縮は、ポリマーと熱分解成形体との密度の差により不可避であり、ポリマー硬化後の収縮で応力が発生して組織を破壊する。これらを軽減するための方策として、（１）前駆体ポリマーの熱分解後の収率を上げる、（２）前駆体ポリマーに粒子やウィスカなどを混合してスラリーとし見掛けの収率を上げる、（３）数ＭＰa 以上の外部圧力（一軸プレス圧力または静水圧）を成形力として付与するなどが行われている。 The method of synthesizing ceramics and carbon materials by firing organic substances such as organosilicon polymers and hydrocarbon polymers as precursors is called the precursor method or precursor method. From the viewpoint of versatility and controllability Widely used in the production of fibers, particles and thin films. When the precursor polymer is baked, gas generation and volume shrinkage occur during the thermal decomposition, and many defects such as pores and cracks are formed in the molded body after the thermal decomposition. In addition, due to gas generation, the internal pressure in the pyrolyzate rises and destroys the tissue. Volume shrinkage is unavoidable due to the difference in density between the polymer and the pyrolytic molded body, and stress is generated by the shrinkage after curing of the polymer to destroy the tissue. As measures to reduce these, (1) increase the yield after thermal decomposition of the precursor polymer, (2) mix particles and whiskers with the precursor polymer to increase the apparent yield, 3) An external pressure (uniaxial press pressure or hydrostatic pressure) of several MPa or more is applied as a forming force.
しかし、（１）および（２）の手法では、依然としてポリマーもしくはそのスラリーのみで成形体を得るまでの欠陥低減は実現できておらず、（３）についても強化材等の骨格構造が無いと圧力により潰れて成形できず、また適用性の面で大きな制約を生じさせる。これらの理由から、現状においては、強化プリフォーム等の骨格材料無しで前駆体ポリマーもしくはそのスラリーを焼成してセラミックスもしくはカーボンの成形体を得る製造方法は存在しない。前駆体ポリマーのみから成形体を得る方法は存在するが、そこでは一旦熱処理を行った中間物を加圧成形している。 However, in the methods (1) and (2), it is still impossible to reduce defects until a molded body is obtained only with a polymer or a slurry thereof. Therefore, it cannot be crushed and cannot be formed, and a great limitation is imposed on the applicability. For these reasons, there is currently no production method for obtaining a ceramic or carbon molded body by firing a precursor polymer or a slurry thereof without a skeletal material such as a reinforced preform. There is a method of obtaining a molded body only from a precursor polymer, but in this method, an intermediate once heat-treated is pressure-molded.
また、母相の原料として前駆体ポリマーを強化材に含浸、焼成して作製された複合材料においても、焼成プロセス中にガス発生と体積収縮が起こり母相に多数の欠陥が発生し、緻密度の低下と組織の不均質化を招いている。この改善のために前駆体ポリマーの含浸、焼成を繰り返す緻密化処理が行われるが、この後にも成形時の組織構造が残存する。このため、材料の強度、破壊抵抗など力学諸特性の低下とバラツキの増加を招き信頼性の低下につながっている。 In addition, even in composite materials made by impregnating and firing a precursor polymer as a raw material for the matrix phase, gas generation and volume shrinkage occur during the firing process, resulting in a large number of defects in the matrix phase. Has led to a decline in the organization and heterogeneity of the organization. In order to improve this, a densification treatment in which the precursor polymer is impregnated and fired repeatedly is performed, but the structure after molding remains. For this reason, the mechanical properties such as the strength and fracture resistance of the material are reduced and the variation is increased, leading to a decrease in reliability.
基材に溶融金属を含浸して互いに反応させてセラミックスを生成する反応焼結は、結晶性の高い強固なセラミックスを合成できる方法として広く用いられている。この方法で得られる材料の特性を向上させるには反応物同士をより効率的に反応させて目的とする成形体の純度を上げることが有効である。このためには基材をミクロンオーダの多孔質構造として比表面積の大きな組織とする必要がある。こうした組織を粉末原料から作製する場合には比較的良質のものができるが、複合材料の母相形成に適用する場合には強化繊維間の微小な隙間に充填することが極めて困難で含浸不良に起因した気孔が形成され特性の低下を招く。原料に液体の前駆体ポリマーを用いることで含浸性は改善されるが、従来の方法で焼成させて得られる熱分解成形体の比表面積は小さいため効率的な反応焼結が行われず特性の低い焼結体しか得られない。 Reaction sintering in which a base material is impregnated with molten metal and reacted with each other to produce ceramics is widely used as a method for synthesizing strong ceramics with high crystallinity. In order to improve the properties of the material obtained by this method, it is effective to react the reactants more efficiently to increase the purity of the desired molded article. For this purpose, it is necessary that the substrate has a micron-order porous structure with a large specific surface area. When such a structure is produced from a powder raw material, a relatively good quality can be produced. However, when applied to the formation of a matrix of a composite material, it is extremely difficult to fill a minute gap between reinforcing fibers, resulting in poor impregnation. The resulting pores are formed and the characteristics are degraded. Impregnation is improved by using a liquid precursor polymer as a raw material, but since the specific surface area of the pyrolysis molded body obtained by firing by a conventional method is small, efficient reaction sintering is not performed and the characteristics are low. Only a sintered body can be obtained.
上記特許文献には、メソポーラスシリカの細孔を利用して非常に比表面積の大きい炭化珪素系多孔質体を製造することができることが記載されている。上記比表面積を大きくすることにより、主としてフィルターや触媒担体として用いることができるとしている。 The above-mentioned patent document describes that a silicon carbide based porous material having a very large specific surface area can be produced by utilizing pores of mesoporous silica. By increasing the specific surface area, it can be used mainly as a filter or a catalyst carrier.
ところが、上記特許文献に記載されている炭化珪素系多孔質体は、３次元編目構造を構成するために、メソポーラスシリカの細孔を利用して多孔質体を製造している。このため、前駆体ポリマーは、上記メソポーラスシリカ内で焼成ないし無機化され、その後に上記シリカがエッチングにより除去される。このため、ロケット等の耐熱タイル等として用いることができる構造材として用いることができる強度の高い成形体を得ることは困難である。 However, the silicon carbide based porous material described in the above-mentioned patent document is manufactured using the pores of mesoporous silica in order to constitute a three-dimensional stitch structure. For this reason, the precursor polymer is calcined or mineralized in the mesoporous silica, and then the silica is removed by etching. For this reason, it is difficult to obtain a molded body having high strength that can be used as a structural material that can be used as a heat-resistant tile such as a rocket.
本願発明は、大きな比表面積を有するばかりでなく、前駆体ポリマーの熱分解中に起こるガス発生と体積収縮に起因して形成される欠陥を大幅に低減して、構造材としても利用することのできる多孔質体を提供することを課題とする。 The present invention not only has a large specific surface area, but also greatly reduces defects formed due to gas generation and volume shrinkage that occur during thermal decomposition of the precursor polymer, and can also be used as a structural material. It is an object to provide a porous body that can be formed.
本願の請求項１に記載した発明は、流動性のある前駆体ポリマーから得られる多孔質成形体であって、前駆体ポリマー成形体から互いに連通する気孔を有する前駆体硬化成形体を形成し、この前駆体硬化成形体を焼成することにより得られる多孔質成形体に関するものである。 The invention described in claim 1 of the present application is a porous molded body obtained from a fluid precursor polymer, and forms a precursor cured molded body having pores communicating with each other from the precursor polymer molded body, The present invention relates to a porous molded body obtained by firing this precursor cured molded body.
すなわち、本願発明に係る多孔質体は、流動性のある前駆体ポリマーを成形して所定形状を付与し、焼成する前に、この前駆体ポリマー成形体を硬化させるとともに多孔質化して前駆体硬化成形体を形成し、この前駆体硬化成形体を焼成して無機化することにより多孔質成形体を得るものである。 That is, the porous body according to the present invention forms a fluid precursor polymer to give a predetermined shape, and before firing, the precursor polymer molded body is cured and made porous to cure the precursor. A porous molded body is obtained by forming a molded body and firing the precursor cured molded body to make it inorganic.
たとえば、液状の炭化珪素前駆体は、１３０℃〜２００℃程度の温度に達すると、粘度が急激に増加して硬化し、その後の温度上昇範囲において形態変化の少ない状態が続く。上記硬化現象は、焼成による無機化とは異なり、ガスの発生及び体積の減少は少ない。本願発明は、上記硬化現象に着目し、上記硬化現象を生じさせるとともに多孔質化し、その後に焼成して多孔質成形体を得るものである。 For example, when the temperature of the liquid silicon carbide precursor reaches a temperature of about 130 ° C. to 200 ° C., the viscosity rapidly increases and cures, and the state with little form change continues in the subsequent temperature increase range. Unlike the mineralization by baking, the above-mentioned curing phenomenon is less likely to generate gas and decrease in volume. The present invention pays attention to the above-mentioned curing phenomenon, causes the above-mentioned curing phenomenon to be made porous, and then fires to obtain a porous molded body.
本願発明では、互いに連通する気孔を備える前駆体硬化成形体を焼成して多孔質体を得るものであるため、焼成時にガスによる欠陥が生じることはない。また、多孔質化した後に焼成できるため、気孔が体積収縮を吸収して、クラック等の欠陥の発生を有効に防止することができる。 In the present invention, since the precursor cured molded body having pores communicating with each other is fired to obtain a porous body, no defects due to gas occur during firing. In addition, since it can be fired after being made porous, the pores absorb volume shrinkage and can effectively prevent the occurrence of defects such as cracks.
本願発明は、液状等流動性のある前駆体ポリマーを焼成して形成される種々の多孔質体に適用することができる。流動性のある前駆体ポリマーを用いることにより、種々の形態の成形体を形成することが可能となる。たとえば、請求項４に記載した発明のように、炭化珪素、カーボン、アルミナ、窒化珪素、シリカから選ばれた１以上の材料から形成された多孔質体に適用できる。好ましくは、無機物質から形成される多孔質成形体、あるいは、非酸化物系の多孔質成形体に適用できる。 The present invention can be applied to various porous bodies formed by firing a precursor polymer having fluidity such as liquid. By using a flowable precursor polymer, it is possible to form molded bodies of various forms. For example, the present invention can be applied to a porous body formed of one or more materials selected from silicon carbide, carbon, alumina, silicon nitride, and silica as in the invention described in claim 4. Preferably, the present invention can be applied to a porous molded body formed from an inorganic substance or a non-oxide porous molded body.
上記前駆体硬化成形体を多孔質化するには、前駆体ポリマーの硬化後であって、熱分解開始前（焼成開始前）に分解して消失する気孔形成材を配合しておき（消失気孔形成材を用いる手法は、粉末焼結の分野において、一般にスペースホルダー法と呼ばれている。）、焼成温度に達するまでに上記気孔形成材を消失させて多孔質の前駆体成形体とし、その後、高温焼成して多孔質の熱分解生成物、すなわち多孔質成形体を得ることができる。この方法は、前駆体ポリマーを用いた成形物、複合材料、反応焼結基材の作製に適用することができる。この方法を用いることにより、使用する前駆体ポリマーの量を低下させて分解ガスの発生量と体積収縮を低減することができる。また、多孔質とすることで発生ガスによる内圧上昇を回避することもできる。さらに、多孔質構造とすることで体積収縮によって発生する応力を低減させることができるとともに、成形体の一部に応力が集中するのを低減させることもできる。 In order to make the precursor-cured molded body porous, a pore-forming material that is decomposed and disappears after curing of the precursor polymer and before thermal decomposition is started (before firing is started) (disappeared pores). The method using the forming material is generally called the space holder method in the field of powder sintering.), The pore forming material is eliminated by the time the temperature reaches the firing temperature, and then a porous precursor molded body is obtained. By baking at a high temperature, a porous pyrolysis product, that is, a porous molded body can be obtained. This method can be applied to the production of a molded article, a composite material, and a reaction sintered base material using a precursor polymer. By using this method, it is possible to reduce the amount of precursor polymer to be used and reduce the generation amount of cracked gas and volume shrinkage. Moreover, the increase in internal pressure by generated gas can also be avoided by setting it as porous. Furthermore, by using a porous structure, stress generated by volume shrinkage can be reduced, and concentration of stress on a part of the molded body can be reduced.
上記気孔の形態及び大きさは特に限定されることはないが、本願の請求項２に記載した発明のように、上記各気孔が壁部で互いに連通する略球形状に形成されているのが好ましい。 The shape and size of the pores are not particularly limited. However, as in the invention described in claim 2 of the present application, the pores are formed in a substantially spherical shape communicating with each other at the wall portion. preferable.
球状の気孔は、上記液状の前駆体ポリマーに球状の気孔形成材を配合して成形し、硬化後に消失させることにより容易に形成することができる。また、気孔形成材の大きさや配合割合を変更することにより、種々の形態の多孔質成形体を形成することができる。また、連通する気孔を形成するには、上記気孔形成材の大きさ、形状、配合割合等を調整すればよい。 Spherical pores can be easily formed by blending the above liquid precursor polymer with a spherical pore-forming material, molding it, and eliminating it after curing. Moreover, the porous molded body of various forms can be formed by changing the size and blending ratio of the pore forming material. Moreover, what is necessary is just to adjust the magnitude | size of the said pore formation material, a shape, a mixture ratio, etc., in order to form the communicating pore.
また、上記気孔を略球状に形成することにより、気孔内面からのガスの放出を円滑に行えるとともに、焼成時の収縮を吸収して応力の発生を有効に防止できる。また、各方向へ均等に収縮できるため、成形体の寸法精度が向上する。さらに、均一な力学的特性を有する多孔質成形体を得ることもできる。 Further, by forming the pores into a substantially spherical shape, the gas can be smoothly released from the inner surface of the pores, and the shrinkage during firing can be absorbed to effectively prevent the generation of stress. Moreover, since it can shrink | contract uniformly in each direction, the dimensional accuracy of a molded object improves. Furthermore, a porous molded body having uniform mechanical properties can be obtained.
請求項３に記載した発明は、上記多孔質成形体が、繊維状無機質補強材を含んで形成されたものである。 According to a third aspect of the present invention, the porous molded body is formed including a fibrous inorganic reinforcing material.
上記補強材を含むことにより、力学的特性を飛躍的に向上させることができる。また、熱膨張を局所的に吸収させることができるため、成形体全体の熱膨張係数を低減させることもできる。 By including the reinforcing material, the mechanical characteristics can be dramatically improved. Moreover, since thermal expansion can be absorbed locally, the thermal expansion coefficient of the whole molded article can also be reduced.
上記繊維状無機質補強材を構成する材料も特に限定されることはなく、たとえば、請求項５に記載した発明のように、炭化珪素、カーボン、タングステン、アラミド、ガラスから形成された無機質補強繊維を含む補強材を採用することができる。 The material constituting the fibrous inorganic reinforcing material is not particularly limited. For example, as in the invention described in claim 5, an inorganic reinforcing fiber formed from silicon carbide, carbon, tungsten, aramid, glass is used. Including reinforcing material can be employed.
また、上記補強材の形態も特に限定されることはない。例えば、編み物状、織物状、不織布状の補強材を採用することができる。また、短繊維状の補強繊維を液状前駆体ポリマー段階から配合しておくこともできる。 Further, the form of the reinforcing material is not particularly limited. For example, a knitted, woven, or non-woven reinforcing material can be used. Short fiber-like reinforcing fibers can also be blended from the liquid precursor polymer stage.
請求項６に記載した発明は、請求項１から請求項５のいずれかに記載の多孔質成形体の上記気孔に、前駆体ポリマーを充填するとともに再焼成して得られる多孔質充填成形体に係るものである。 The invention described in claim 6 is a porous filled molded body obtained by filling the pores of the porous molded body according to any one of claims 1 to 5 with a precursor polymer and re-firing. It is concerned.
請求項１から請求項５に記載された発明によって得られる多孔質成形体自体も種々の用途に用いることができるが、請求項６に記載された発明に係る多孔質充填成形体は、上記多孔質成形体を利用して中実の緻密組織を有する成形体を製造するものである。 Although the porous molded body itself obtained by the invention described in claims 1 to 5 can also be used for various applications, the porous filled molded body according to the invention described in claim 6 has the above porous structure. A molded product having a solid dense structure is produced using a molded product.
請求項１から請求項５に記載した発明に係る多孔質成形体においては、焼成時のガス発生や収縮による欠陥を防止するため、互いに連通する気孔を形成した多孔質の前駆体硬化物を焼成して成形体を得た。上記気孔は連通状に形成されているため、前駆体ポリマーを容易に充填することができる。充填手法は特に限定されることはなく、浸漬、真空引き等を利用できる。 In the porous molded body according to the first to fifth aspects of the present invention, in order to prevent defects due to gas generation or shrinkage during firing, the porous precursor cured product having pores communicating with each other is fired. Thus, a molded body was obtained. Since the pores are formed in a continuous shape, the precursor polymer can be easily filled. The filling method is not particularly limited, and immersion, evacuation, or the like can be used.
上記焼成工程は、多孔質成形体を得る手法と同様の手法を用いて行うことができる。焼成時にガスの発生や収縮が生じるが、上記気孔が連通して形成されているため、ガスを円滑に成形体の外部へ放出でき、また、すでに焼成された多孔質体内部で焼成されるため、成形体にクラックやひずみが生じることはない。これにより、緻密構造の成形体を得ることができる。 The said baking process can be performed using the method similar to the method of obtaining a porous molded object. Gas generation and shrinkage occur during firing, but the pores are formed in communication, so the gas can be smoothly discharged to the outside of the molded body, and because it is fired inside the already fired porous body The molded body is not cracked or distorted. Thereby, a compact having a dense structure can be obtained.
請求項７に記載した発明のように、多孔質成形体を生成した前駆体ポリマーと同一の前駆体ポリマーを上記気孔に充填して多孔質充填成形体を得ることもできるし、異なる前駆体ポリマーを充填して多孔質充填成形体を得ることもできる。 As in the invention described in claim 7, the porous polymer can be obtained by filling the pores with the same precursor polymer as the precursor polymer that has produced the porous molding, or a different precursor polymer. It is also possible to obtain a porous filled molded body by filling with.
請求項８に記載した発明は、請求項１から請求項５のいずれかに記載の多孔質成形体の上記気孔に、上記多孔質成形体と反応焼結する材料を充填して得られる、多孔質充填成形体に関するものである。 The invention described in claim 8 is a porous material obtained by filling the pores of the porous molded body according to any one of claims 1 to 5 with a material that undergoes reactive sintering with the porous molded body. It relates to a quality-filled molded body.
すなわち、本願発明における反応焼結は、多孔質成形体の気孔に反応焼結しうる材料を充填して、上記気孔内で上記多孔質体成形体と反応焼結させるものである。 That is, the reactive sintering in the present invention is a method in which the pores of the porous molded body are filled with a material that can be reactively sintered, and the porous molded body is reacted and sintered in the pores.
上記充填材料として種々のものを採用できるが、溶融金属等の液相の材料を採用するのが好ましい。この場合、充填するととともに反応焼結が進行して、多孔質充填成形体を容易に形成することができる。 Although various materials can be used as the filling material, it is preferable to use a liquid phase material such as molten metal. In this case, the reaction sintering proceeds with filling, and a porous filling molded body can be easily formed.
たとえば、請求項９に記載した発明のように、上記多孔質成形体をカーボンから形する一方、上記充填材料に溶融珪素を採用できる。溶融珪素をカーボンの気孔に充填すると、反応焼結によって多孔質成形体のほぼ全体が炭化珪素に変化する。これにより、緻密な中実構造の炭化珪素成形体を得ることができる。 For example, as in the invention described in claim 9, while the porous molded body is formed from carbon, molten silicon can be adopted as the filling material. When molten silicon is filled into the pores of carbon, almost the entire porous molded body is changed to silicon carbide by reaction sintering. Thereby, a silicon carbide compact with a dense solid structure can be obtained.
請求項１０に記載した発明は、繊維状無機質補強材を含む多孔質成形体に反応焼結する材料を充填して多孔質充填成形体を得るものである。 In the tenth aspect of the present invention, a porous molded body containing a fibrous inorganic reinforcing material is filled with a material to be reactively sintered to obtain a porous filled molded body.
繊維状無機質補強材を含む多孔質成形体に適用することにより、より強度の高い多孔質充填成形体を得ることができる。 By applying to a porous molded body containing a fibrous inorganic reinforcing material, a porous filled molded body with higher strength can be obtained.
請求項１１に記載した発明は、液状前駆体ポリマーと、気孔形成材とを含む成形材料を調整する成形材料調整工程と、上記成形材料を所定形状に成形する成形工程と、上記前駆体ポリマーを硬化させて前駆体硬化成形体を得る前駆体硬化工程と、上記気孔形成材を消失させて、隣接する気孔が互いに連通する多孔質の前駆体硬化成形体を形成する気孔形成材消失工程と、上記前駆体硬化成形体を無機化する焼成工程とを含む多孔質成形体の製造方法に係るものである。 The invention described in claim 11 includes a molding material adjusting step for adjusting a molding material including a liquid precursor polymer and a pore forming material, a molding step for molding the molding material into a predetermined shape, and the precursor polymer. A precursor curing step for curing to obtain a precursor cured molded body, and a pore forming material disappearing step for forming a porous precursor cured molded body in which adjacent pores communicate with each other by erasing the pore forming material; The present invention relates to a method for producing a porous molded body including a firing step for mineralizing the precursor cured molded body.
上記成形材料調整工程は、目的とする多孔質体の特性や、種々の成形手法に応じた成形材料を調整する工程である。すなわち、押し出し成形等に適用する場合には、粘度の高い粘土状の成形材料が調整される。粘度を高く設定するには、気孔形成材料の配合割合を高く設定すればよい。 The molding material adjustment step is a step of adjusting the molding material according to the characteristics of the target porous body and various molding techniques. That is, when applied to extrusion molding or the like, a clay-like molding material having a high viscosity is adjusted. In order to set the viscosity high, the blending ratio of the pore forming material may be set high.
上記成形工程を行う手法も特に限定されることはない。たとえば、射出成形、押し出し成形のみならず、単に型容器に液状の成形材料を充填することにより行われるものも含まれる。また、粘土質の成形材料を造形する手法により行うこともできる。 The method for performing the molding step is not particularly limited. For example, not only injection molding and extrusion molding, but also those performed simply by filling a mold container with a liquid molding material. Moreover, it can also carry out by the method of modeling a clay-like molding material.
上記前駆体硬化工程は、前駆体ポリマーと気孔形成材とを含む成形体を硬化させるものである。上記工程は、前駆体を無機化する焼成工程とは異なり、前駆体からのガスの発生や収縮はそれほど生じない。また、気孔形成材がそのままの形態で保持された状態で前駆体ポリマーが硬化させられるため、成形体に欠陥等を生じさせることなく前駆体ポリマーを硬化させることができる。なお、前駆体ポリマーは、次に行われる気孔形成材消失工程及び焼成工程における保形性を確保できる程度に硬化させればよい。一般に、前駆体硬化工程は、成形体を所定温度に加熱することにより行われる。上記前駆体硬化工程は、空気中で行うこともできるが、精度を高めるため、不活性雰囲気下又は真空下で行うのが好ましい。 In the precursor curing step, a molded body including the precursor polymer and the pore forming material is cured. Unlike the baking process which mineralizes a precursor, the said process does not generate | occur | produce and shrink | contract so much gas from a precursor. Moreover, since the precursor polymer is cured in a state where the pore forming material is held as it is, the precursor polymer can be cured without causing defects or the like in the molded body. In addition, what is necessary is just to harden a precursor polymer to such an extent that the shape retention property in the pore formation material disappearance process and baking process which are performed next can be ensured. Generally, a precursor hardening process is performed by heating a molded object to predetermined temperature. The precursor curing step can be performed in air, but is preferably performed in an inert atmosphere or in vacuum in order to improve accuracy.
上記気孔形成材消失工程は、成形体を上記気孔形成材が消失する温度まで上昇させることにより行われる。上記前駆体を硬化させた後に、気孔形成材を消失させるとともに、少なくとも上記前駆体硬化成形体の無機質化が始まるまでに終了させるのが好ましい。これにより、成形体に欠陥等を生じさせることなく、焼成前の成形体を多孔質化することができる。 The pore forming material disappearing step is performed by raising the molded body to a temperature at which the pore forming material disappears. After curing the precursor, it is preferable that the pore-forming material is disappeared and at least before the mineralization of the precursor-cured molded body starts. Thereby, the molded object before baking can be made porous, without producing a defect etc. in a molded object.
上記焼成工程は前駆体硬化成形体を焼成して無機化する工程であり、通常、１０００℃以上に加熱することにより行われる。上記前駆体硬化成形体は、連通する気孔を有する多孔質体であるため、焼成により生じるガスを、成形体内部から円滑に放出することができる。また、上記気孔が形成されているため、収縮も円滑に進行し、収縮による応力等の発生を防止できる。したがって、均質な多孔質体を形成することができる。 The said baking process is a process of baking and mineralizing a precursor hardening molded object, and is normally performed by heating at 1000 degreeC or more. Since the precursor-cured molded body is a porous body having pores that communicate with each other, the gas generated by firing can be smoothly released from the inside of the molded body. Further, since the pores are formed, the contraction also proceeds smoothly, and generation of stress or the like due to the contraction can be prevented. Therefore, a homogeneous porous body can be formed.
本願の請求項１２に記載した発明は、上記成形材料に、無機質補強繊維を含ませたものである。無機質補強繊維を含ませることにより、成形体の強度を大幅に向上させることができる。また、気孔形成材消失工程及び焼成工程における保形性が向上し、寸法精度の高い多孔質成形体を得ることもできる。 The invention described in claim 12 of the present application is one in which an inorganic reinforcing fiber is included in the molding material. By including inorganic reinforcing fibers, the strength of the molded body can be greatly improved. Moreover, the shape retention in the pore forming material disappearing step and the firing step is improved, and a porous molded body with high dimensional accuracy can be obtained.
上記無機質補強繊維の材質及び形態は特に限定されることはない。たとえば、成形材料の成形性に悪影響を与えることがない程度の短繊維を補強繊維として含ませることができる。 The material and form of the inorganic reinforcing fiber are not particularly limited. For example, short fibers that do not adversely affect the moldability of the molding material can be included as reinforcing fibers.
本願の請求項１３に記載した発明は、上記成形工程が、無機質繊維から形成された補強材に上記成形材料を充填することにより行われるものである。 In the invention described in claim 13 of the present application, the molding step is performed by filling the molding material into a reinforcing material formed from inorganic fibers.
たとえば、ＦＲＰ成形体を製造するのと同様に、織物状の補強材に成形材料を含浸充填することにより行うことができる。また、成形型内に補強材を配置して、成形材料を流し込むことにより行うこともできる。 For example, it can be carried out by impregnating and filling a woven reinforcing material with a molding material, in the same manner as manufacturing an FRP molded body. Moreover, it can also carry out by arrange | positioning a reinforcing material in a shaping | molding die, and pouring a molding material.
本願の請求項１４に記載した発明は、上記成形材料に溶剤を添加して粘度及び補強材に対する濡れ性を調整する成形特性調整工程と、成形後に、上記溶剤を除去する溶剤除去工程とを含むものである。 The invention described in claim 14 of the present application includes a molding characteristic adjusting step of adjusting the viscosity and wettability to the reinforcing material by adding a solvent to the molding material, and a solvent removing step of removing the solvent after molding. It is a waste.
溶剤を添加して粘度及び濡れ性を改善することにより、成形性を高めることができる。特に、補強材を構成する織物体等の繊維間へ補強材を容易に充填することができるため、均一な多孔質成形体を得ることができるとともに、均質な機械的強度を備える多孔質体を形成することができる。 By adding a solvent to improve viscosity and wettability, moldability can be enhanced. In particular, since a reinforcing material can be easily filled between fibers such as a woven fabric constituting the reinforcing material, a uniform porous molded body can be obtained and a porous material having a uniform mechanical strength can be obtained. Can be formed.
請求項１５に記載した発明は、上記成形工程が成形型を用いて行われる一方、上記気孔形成材消失工程及び上記焼成工程が、成形体を上記成形型から取り出して行われるものである。 In the invention described in claim 15, while the molding step is performed using a mold, the pore forming material disappearing step and the firing step are performed by removing the molded body from the mold.
型を用いて成形工程を行う場合、型に入れたまま気孔形成材消失工程及び焼成工程を行うと、上記型ガスの放出を阻害する場合が考えられる。成形体を型から取り出して上記工程を行うことにより、ガスの放出が促進されるとともに、収縮を均一に生じさせて精度の高い多孔質成形体を得ることができる。 When performing a shaping | molding process using a type | mold, when the pore formation material disappearance process and a baking process are performed in the type | mold, the case where the discharge | release of the said type | mold gas is inhibited is considered. By taking out the molded body from the mold and carrying out the above steps, the release of gas is promoted and the shrinkage is uniformly caused to obtain a highly accurate porous molded body.
請求項１６に記載した発明は、請求項１１から請求項１５のいずれかに記載された上記気孔形成材消失工程の後に、形成された多孔質前駆体硬化成形体の上記気孔に前駆体ポリマーを充填する前駆体ポリマー充填工程を含むものである。上記前駆体硬化工程において前駆体ポリマーが硬化させられているため、液状の前駆体ポリマーを、上記連通する気孔の毛細管現象を利用して充填することができるため、前駆ポリマーの充填作業を容易に行うこともできる。 According to a sixteenth aspect of the present invention, a precursor polymer is added to the pores of the formed porous precursor cured molded body after the pore forming material disappearing step according to any one of the eleventh to fifteenth aspects. It includes a precursor polymer filling step of filling. Since the precursor polymer is cured in the precursor curing step, the liquid precursor polymer can be filled using the capillary phenomenon of the communicating pores, so that the precursor polymer can be easily filled. It can also be done.
これにより、中実成形体を形成することができる。また、多孔質成形体と同一の前駆体ポリマーを充填することにより、単一材料から形成された緻密度の高い成形体を形成することも可能となる。 Thereby, a solid molded body can be formed. Further, by filling the same precursor polymer as the porous molded body, it is possible to form a molded body having a high density formed from a single material.
請求項１７に記載した発明は、請求項１１から請求項１５に記載の製造方法によって製造された多孔質成形体の気孔に、前駆体ポリマーを充填する前駆体ポリマー充填工程と、上記前駆体ポリマーが充填された多孔質成形体を再焼成する再焼成工程とを含む、多孔質充填成形体の製造方法に係るものである。 According to a seventeenth aspect of the present invention, there is provided a precursor polymer filling step of filling the pores of the porous molded body produced by the production method according to the eleventh to fifteenth aspects with a precursor polymer, and the precursor polymer. And a re-firing step of re-firing the porous molded body filled with slag.
本願発明は、多孔質成形体を形成した後に、上記気孔に前駆体ポリマーを充填して再焼成させるものである。したがって、再焼成工程において、成形体が変形等する恐れはなく、寸法精度の高い中実成形体を得ることができる。なお、上記前駆体ポリマー充填工程及び再焼成工程は、気孔が完全に充填されるまで複数回行うこともできる。 In the present invention, after forming a porous molded body, the pores are filled with a precursor polymer and re-fired. Therefore, in the refiring step, there is no fear that the molded body is deformed, and a solid molded body with high dimensional accuracy can be obtained. The precursor polymer filling step and the refiring step can be performed a plurality of times until the pores are completely filled.
請求項１８に記載した発明は、請求項１１から請求項１５に記載の製造方法によって製造された多孔質成形体の気孔に、上記多孔質成形体と反応焼結する溶融金属を上記気孔に充填して反応焼結生成物を生成させる反応焼結物生成工程を含む、多孔質充填成形体の製造方法に係るものである。 According to an eighteenth aspect of the present invention, the pores of the porous molded body manufactured by the manufacturing method according to the eleventh to fifteenth aspects are filled into the pores with molten metal that undergoes reactive sintering with the porous molded body. Thus, the present invention relates to a method for producing a porous filled molded body, which includes a reaction sintered product generation step of generating a reaction sintered product.
たとえば、カーボン前駆体ポリマーから多孔質カーボン成形体を形成し、このカーボン成形体の気孔に溶融珪素を充填すると、気孔内部で反応焼結が生じて炭化珪素が生成される。本願発明では、内部の気孔が連通するとともに、大きな比表面積を有するため、上記反応焼結を多孔質体全体に生じさせて、成形体全体を中実の炭化珪素にすることもできる。 For example, if a porous carbon molded body is formed from a carbon precursor polymer and molten silicon is filled in the pores of the carbon molded body, reactive sintering occurs inside the pores to generate silicon carbide. In the present invention, since the internal pores communicate with each other and have a large specific surface area, the above-mentioned reaction sintering can be caused in the entire porous body, and the entire compact can be made into solid silicon carbide.
前駆体ポリマーを原料として、強度の高いセラミックスおよびカーボンの多孔質成形体を得ることができる。また、上記気孔形成材等の配合割合や作業条件を変更することにより、多孔質構造から緻密構造まで種々の形態の成形体を得ることができる。また、比表面積の高い熱分解生成成形体を基材に用いることにより、より純度の高い反応焼結複合材料を得ることもできる。 By using the precursor polymer as a raw material, a ceramic and carbon porous molded body having high strength can be obtained. In addition, by changing the blending ratio of the pore forming material or the like and the working conditions, it is possible to obtain molded bodies having various forms from a porous structure to a dense structure. Moreover, the reaction sintered composite material with higher purity can also be obtained by using as a base material the thermal decomposition production | generation molded object with a high specific surface area.
（実施例１）
炭化珪素（ＳｉＣ）の液状前駆体ポリマーとしてアリルハイドライドポリカルボシラン（ＡＨＰＣＳ, Ｓｔａｒｆｉｒｅ Ｓｙｓｔｅｍｓ Ｉｎｃ.,アメリカ）、気孔形成材としてポリメタクリル酸メチル（ＰＭＭＡ）の球状粒子を用い、ＡＨＰＣＳ にＰＭＭＡ粒子を添加して数分以上攪拌した後、アルミナ製容器内でアルゴン中、２５℃／ｈｒ（室温−２５０℃）、５０℃／ｈｒ（２５０℃−５００℃）、１５０℃／ｈｒ（５００℃−９００℃）の条件で９００℃まで昇温した後、９００℃にて２ｈｒ保持することにより、多孔質の炭化珪素成形体を作製した。ＰＭＭＡ粒子の混合条件は以下のとおりである。
(Example 1)
Allyl hydride polycarbosilane (AHPCS, Starfire Systems Inc., USA) is used as a liquid precursor polymer of silicon carbide (SiC), and polymethyl methacrylate (PMMA) is used as a pore-forming material, and PMMA particles are added to AHPCS. After stirring for several minutes or more, in an alumina container, in argon, 25 ° C./hr (room temperature-250 ° C.), 50 ° C./hr (250 ° C.-500 ° C.), 150 ° C./hr (500 ° C.-900 ° C.) The temperature was raised to 900 ° C. under the conditions of (2), and then held at 900 ° C. for 2 hours to produce a porous silicon carbide molded body. The mixing conditions for the PMMA particles are as follows.
まず作製条件を設定するために、熱重量分析装置にてＡＨＰＣＳおよびＰＭＭＡ粒子の熱分解中の重量変化を、粘弾性測定装置にてＡＨＰＣＳの熱分解中の粘度変化と硬化温度を調査した。それぞれの結果を図１および図２に示す。これらの結果から以下のメカニズムが推定される。ＡＨＰＣＳが１３０℃付近で硬化した後、ＰＭＭＡが１９０℃から４２０℃の範囲で分解消失し多孔質のＡＨＰＣＳ硬化物となり、同温度の４２０℃付近からＡＨＰＣＳの主熱分解が開始して１０００℃以上で多孔質の炭化珪素組織となる。 First, in order to set production conditions, the weight change during thermal decomposition of AHPCS and PMMA particles was examined with a thermogravimetric analyzer, and the viscosity change during curing of AHPCS and the curing temperature were examined with a viscoelasticity measuring apparatus. Each result is shown in FIG. 1 and FIG. The following mechanism is estimated from these results. After AHPCS is cured at around 130 ° C., PMMA decomposes and disappears in the range of 190 ° C. to 420 ° C. to become a porous AHPCS cured product, and the main thermal decomposition of AHPCS starts from around 420 ° C. at the same temperature and above 1000 ° C. It becomes a porous silicon carbide structure.
図３に推定される組織変化の模式図を示す。図３に示すように、前駆体硬化工程（図３の（２））において、ＰＭＭＡ粒子の周囲のＡＨＰＣＳ（前駆体ポリマー）が硬化させられる。次に（図３の（３））に示されるように、上記ＰＭＭＡ粒子が消失させられる。上記ＰＭＭＡ粒子は、消失後に隣接する気孔が連通するほど近接して配置されるように配合されているため、消失ガスの通り道が確保される。 FIG. 3 shows a schematic diagram of the estimated tissue change. As shown in FIG. 3, in the precursor curing step ((2) in FIG. 3), AHPCS (precursor polymer) around the PMMA particles is cured. Next, as shown in (3) of FIG. 3, the PMMA particles are lost. Since the PMMA particles are blended so that adjacent pores communicate with each other after disappearance, the passage of the disappearing gas is secured.
上記焼成工程（図３の（４））においては、気孔及び連通孔を介してガスが円滑に外部に放出されるため、機械的特性及び寸法精度の高い多孔質成形体が形成される。 In the firing step ((4) in FIG. 3), the gas is smoothly discharged to the outside through the pores and the communication holes, so that a porous molded body having high mechanical characteristics and high dimensional accuracy is formed.
以上の熱分解に関する情報を基に、ＡＨＰＣＳに添加するＰＭＭＡ粒子の粒径と配合割合を変化させてサンプルを作製し、欠陥の少ない多孔質組織が得られる条件を検討した。この結果、以下のことが判明した。 Based on the above information on thermal decomposition, samples were prepared by changing the particle size and blending ratio of PMMA particles added to AHPCS, and conditions for obtaining a porous structure with few defects were examined. As a result, the following was found.
ＰＭＭＡ粒子の粒径と配合割合が、得られる組織に大きな影響を及ぼすとともに、
（ａ）気孔形成材の分解ガスの排気のための通路としての連続気孔が形成される必要がある。
（ｂ）ＡＨＰＣＳの主熱分解に欠陥形成を抑制するに有効な微細多孔構造が必要である。
（ｃ）熱分解後に生成物の連続構造が形成されている必要がある。
（ｄ）気孔形成材がスラリー全体に均一分布していることが必要である。
The particle size and blending ratio of PMMA particles have a great influence on the resulting structure,
(A) It is necessary to form continuous pores as a passage for exhausting the decomposition gas of the pore forming material.
(B) A microporous structure effective for suppressing the formation of defects in the main thermal decomposition of AHPCS is required.
(C) The product must have a continuous structure after pyrolysis.
(D) It is necessary that the pore forming material is uniformly distributed throughout the slurry.
以上の検討を経て、ＡＨＰＣＳに平均粒径９０μｍのＰＭＭＡ粒子を６８ｖｏｌ．％を混合して図４及び図５に示す直径７３ｍｍ、厚さ１１ｍｍの炭化珪素のの多孔質成形体（ＰＭＭＡ粒径９０μｍ）を得た。図５に示されているように、略球状の気孔が形成されているとともに、隣接する気孔間に連通孔が形成されている。図６に示す組織分析結果によると、従来法で生成される熱分解物と異なり、比表面積が非常に大きく均質な連続気孔を有した多孔質材料である。 As a result of the above examination, 68 vol. % And a porous molded body (PMMA particle size 90 μm) of silicon carbide having a diameter of 73 mm and a thickness of 11 mm shown in FIGS. As shown in FIG. 5, substantially spherical pores are formed, and communication holes are formed between adjacent pores. According to the result of the structural analysis shown in FIG. 6, unlike the thermal decomposition product produced by the conventional method, the porous material has a very large specific surface area and uniform continuous pores.
（実施例２）
カーボン（Ｃ）の液状前駆体ポリマーとしてフェノール樹脂のフェノライト（商品名，大日本インキ化学工業（株））に気孔形成材としての平均粒径１０μｍのＰＭＭＡ粒子を添加し、数分以上攪拌後、アルミナ製容器内でアルゴン中、２５℃／ｈｒ（室温−２５０℃）、５０℃／ｈｒ（２５０℃−５００℃）、１５０℃／ｈｒ（５００℃−９００℃）の条件で９００℃まで昇温した後、９００℃にて２ｈｒ保持することにより、多孔質カーボン成形体を作製した。
(Example 2)
After adding PMMA particles with an average particle size of 10 μm as pore forming material to phenolic phenolic (trade name, Dainippon Ink & Chemicals, Inc.) as a liquid precursor polymer of carbon (C) and stirring for several minutes or more In an alumina container, the temperature was increased to 900 ° C. in argon at 25 ° C./hr (room temperature-250 ° C.), 50 ° C./hr (250 ° C.-500 ° C.), 150 ° C./hr (500 ° C.-900 ° C.). After heating, the porous carbon molded body was produced by holding at 900 ° C. for 2 hours.
作製条件は実施例１と同様の手順で、フェノライトとＰＭＭＡ粒子の熱重量分析を実施して、フェノライトの熱分解挙動（図７）が実施例１の図１において示したＡＨＰＣＳのそれと同様であることを確認した上で、実施例１と同様の工程でフェノライトに平均粒径９０μｍのＰＭＭＡ粒子を６８ｖｏｌ．％を混合して図８に示す直径１８ｍｍ、厚さ３ｍｍの多孔質カーボン成形体を得た。 The production conditions were the same as in Example 1 and thermogravimetric analysis of phenolite and PMMA particles was performed. The thermal decomposition behavior of phenolite (FIG. 7) was the same as that of AHPCS shown in FIG. After confirming that the PMMA particles having an average particle size of 90 μm were added to phenolite in the same process as in Example 1, 68 vol. % Was mixed to obtain a porous carbon molded body having a diameter of 18 mm and a thickness of 3 mm shown in FIG.
図９に示すように、隣接する気孔との間に連通孔を有する球状の気孔が形成されていることが判る。 As shown in FIG. 9, it can be seen that spherical pores having communication holes are formed between adjacent pores.
（実施例３）
実施例１で多孔質炭化珪素成形体を作製した条件を適用し、ＡＨＰＣＳに平均粒径１０μｍのＰＭＭＡ粒子を６８ｖｏｌ．％混合したスラリーに、炭化珪素長繊維（チラノＺＭＩ，宇部興産（株））を一方向に配向させたものに化学気相蒸着法（ＣＶＩ法）により１００ｎｍおよび３００ｎｍ厚さのカーボン層を形成した一方向炭化珪素繊維プリフォームを浸積した後、含浸を促進する目的で周囲をシートとシーリングテープで密閉し、シート内を真空引きしながら１３０℃まで加熱してＡＨＰＣＳを硬化させて成形し（バンキング成形）、これをアルゴン中、２５℃／ｈｒ（室温−２５０℃）、５０℃／ｈｒ（２５０℃−５００℃）、１５０℃／ｈｒ（５００℃−９００℃）の条件で９００℃まで昇温した後、９００℃にて２ｈｒ保持することにより成形体を得、それにＡＨＰＣＳのみを真空含浸させ、同様の条件での焼成を７回繰り返すことにより、一方向炭化珪素繊維強化炭化珪素基複合材料を得た。
(Example 3)
The conditions under which the porous silicon carbide molded body was prepared in Example 1 were applied, and PMMA particles having an average particle diameter of 10 μm were added to 68 vol. A carbon layer having a thickness of 100 nm and 300 nm was formed by chemical vapor deposition (CVI method) on a slurry in which silicon carbide long fibers (Tyranno ZMI, Ube Industries, Ltd.) were oriented in one direction. After immersing the unidirectional silicon carbide fiber preform, the periphery is sealed with a sheet and a sealing tape for the purpose of promoting impregnation, and AHPCS is cured by heating to 130 ° C. while evacuating the inside of the sheet ( Banking molding), and the temperature was increased to 900 ° C. under argon at 25 ° C./hr (room temperature-250 ° C.), 50 ° C./hr (250 ° C.-500 ° C.), 150 ° C./hr (500 ° C.-900 ° C.). After heating, the molded body is obtained by holding at 900 ° C. for 2 hours, and only AHPCS is vacuum impregnated therein, and firing under the same conditions is repeated 7 times to obtain a unidirectional carbon. To obtain a silicon carbide fiber-reinforced silicon carbide matrix composite.
図１０に、上記一方向炭化珪素繊維強化炭化珪素基複合材料の破断面顕微鏡写真を示す。また、図１１に模式構造を示す。これらの図から明らかなように、多孔質成形体が強化繊維によって強化されている状態が判る。 FIG. 10 shows a fracture surface micrograph of the unidirectional silicon carbide fiber reinforced silicon carbide based composite material. FIG. 11 shows a schematic structure. As is clear from these figures, it can be seen that the porous molded body is reinforced by the reinforcing fibers.
得られた複合材の強化繊維の配向方向に対して実施した引張試験と破壊靭性試験の結果を図１２及び図１３に示す。ＰＳＨ−ＰＩＰ法−１は強化材表面に厚み３００ｎｍのカーボン層が形成されたプリフォームに対しＰＭＭＡ粒子を配合した原料で作製したもので、同じプリフォームに対して気孔形成材を混合しない従来ＰＩＰ法にて作製したものと比較して、引張強度が約1 割上昇し、破壊靭性値が約１．５倍上昇すると共に、誤差棒の長さで表されるバラつきが減少した。ＰＳＨ−ＰＩＰ法−２は繊維上へのカーボン層厚みを１００ｎｍに低減させたプリフォームに対しＰＭＭＡ粒子を配合した原料で作製したもので、こちらも同様に引張強度が向上しバラつきが低減した。 12 and 13 show the results of the tensile test and the fracture toughness test performed on the orientation direction of the reinforcing fiber of the obtained composite material. The PSH-PIP method-1 is made of a raw material in which PMMA particles are blended with a preform having a carbon layer having a thickness of 300 nm formed on the surface of a reinforcing material, and does not mix a pore-forming material with the same preform. The tensile strength increased by about 10%, the fracture toughness value increased by about 1.5 times, and the variation represented by the length of the error bar decreased. The PSH-PIP method-2 was prepared from a raw material in which PMMA particles were blended with a preform whose carbon layer thickness on the fiber was reduced to 100 nm. This also improved the tensile strength and reduced the variation.
なお、上記実施例では、多孔質硬化体ないし多孔質成形体の気孔に、前駆体ポリマーあるいは反応焼結しうる材料を充填したが、上記多孔質成形体の気孔内に種々の材料を充填して、複合材料を形成することができる。たとえば、カーボン多孔質成形体の気孔に溶融アルミを充填した複合材料を構成することもできる。 In the above embodiment, the pores of the porous cured body or porous molded body are filled with a precursor polymer or a material that can be reactively sintered, but various materials are filled into the pores of the porous molded body. Thus, a composite material can be formed. For example, a composite material in which molten aluminum is filled in the pores of the carbon porous molded body can also be configured.
本願発明に係る多孔質成形体は、航空宇宙輸送機の機体、エンジン、ガスタービン、ディーゼル排ガスフィルタ、燃料電池電極、熱交換器等に利用することができる。 The porous molded body according to the present invention can be used for aerospace transport aircraft bodies, engines, gas turbines, diesel exhaust gas filters, fuel cell electrodes, heat exchangers, and the like.
Claims (18)
前駆体ポリマー成形体から互いに連通する気孔を有する前駆体硬化成形体を形成し、この前駆体硬化成形体を焼成することにより得られる、多孔質成形体。 A porous molded body obtained from a flowable precursor polymer,
A porous molded body obtained by forming a precursor cured molded body having pores communicating with each other from a precursor polymer molded body, and firing the precursor cured molded body.
上記充填材料が溶融珪素である、請求項８に記載の多孔質充填成形体。 While the porous molded body is formed from carbon,
The porous filling molding according to claim 8, wherein the filling material is molten silicon.
上記成形材料を所定形状に成形する成形工程と、
上記前駆体ポリマーを硬化させて前駆体硬化成形体を得る前駆体硬化工程と、
上記気孔形成材を消失させて、隣接する気孔が互いに連通する多孔質の前駆体硬化成形体を形成する気孔形成材消失工程と、
上記前駆体硬化成形体を無機化する焼成工程とを含む、多孔質成形体の製造方法。 A molding material adjustment step of adjusting a molding material containing a liquid precursor polymer and a pore-forming material;
A molding step of molding the molding material into a predetermined shape;
A precursor curing step for curing the precursor polymer to obtain a precursor cured molded body;
A pore-forming material disappearing step of forming a porous precursor cured molded body in which the pore-forming material disappears and adjacent pores communicate with each other;
The manufacturing method of a porous molded object including the baking process which mineralizes the said precursor hardening molded object.
成形後に、上記溶剤を除去する溶剤除去工程とを含む、請求項１１から請求項１３のいずれかに記載の多孔質成形体の製造方法。 A molding property adjusting step of adjusting the viscosity and wettability to the reinforcing material by adding a solvent to the molding material;
The manufacturing method of the porous molded object in any one of Claims 11-13 including the solvent removal process of removing the said solvent after shaping | molding.
上記気孔形成材消失工程及び上記焼成工程は、成形体を上記成形型から取り出して行われる、請求項１１から請求項１４のいずれかに記載の多孔質成形体の製造方法。 While the molding process is performed using a mold,
The method for producing a porous molded body according to any one of claims 11 to 14, wherein the pore forming material disappearance step and the firing step are performed by removing the molded body from the mold.
上記前駆体ポリマーが充填された多孔質成形体を再焼成する再焼成工程とを含む、多孔質充填成形体の製造方法。 A precursor polymer filling step of filling the pores of the porous molded body produced by the production method according to claim 11 with a precursor polymer,
And a re-firing step of re-firing the porous molded body filled with the precursor polymer.
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