JPH0825181B2 - Method for producing three-dimensional fiber-reinforced ceramic matrix composite material - Google Patents
Method for producing three-dimensional fiber-reinforced ceramic matrix composite materialInfo
- Publication number
- JPH0825181B2 JPH0825181B2 JP5133852A JP13385293A JPH0825181B2 JP H0825181 B2 JPH0825181 B2 JP H0825181B2 JP 5133852 A JP5133852 A JP 5133852A JP 13385293 A JP13385293 A JP 13385293A JP H0825181 B2 JPH0825181 B2 JP H0825181B2
- Authority
- JP
- Japan
- Prior art keywords
- slurry
- dimensional fiber
- composite material
- fiber preform
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002131 composite material Substances 0.000 title claims description 24
- 239000011159 matrix material Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000011226 reinforced ceramic Substances 0.000 title claims description 7
- 239000000835 fiber Substances 0.000 claims description 44
- 239000002002 slurry Substances 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 17
- 239000012700 ceramic precursor Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000000945 filler Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229920001709 polysilazane Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003203 poly(dimethylsilylene-co-phenylmethyl- silylene) polymer Polymers 0.000 description 1
- 229920003257 polycarbosilane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Landscapes
- Producing Shaped Articles From Materials (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、３次元繊維強化セラミ
ックス基複合材料の製造法の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for producing a three-dimensional fiber-reinforced ceramic matrix composite material.
【０００２】[0002]
【従来の技術】繊維強化セラミックス基複合材料は、従
来の単体セラミックスがもっていた致命的な欠陥、即
ち、低靱性及び強度的な信頼性の低さ等を改善するもの
として注目を集めている。この種の繊維強化複合材料
は、それを構造材料として用いる場合、強化材繊維を直
交三方向に配置した３次元強化複合材料が、等方的な性
質をもつことから最も理想的であるが、１次元及び２次
元強化の場合に比して複合材料の作製が非常に難しく、
解決されなければならない幾つかの問題を含んでいる。2. Description of the Related Art Fiber-reinforced ceramic matrix composite materials have been attracting attention as a material for improving the fatal defects of conventional simple ceramics, that is, low toughness and low reliability in strength. This type of fiber-reinforced composite material is most ideal when it is used as a structural material because a three-dimensional reinforced composite material in which reinforcing material fibers are arranged in three orthogonal directions has isotropic properties. It is very difficult to fabricate composite materials compared to one-dimensional and two-dimensional reinforcement,
It contains some problems that must be resolved.
【０００３】即ち、３次元繊維強化セラミックス基複合
材料の製造法における問題点は、３次元的に構成された
繊維織成物（プリフォーム）の繊維間隙にマトリックス
となるセラミックスを高密に充填することにある。しか
し、３次元繊維プリフォームでは繊維が密に、しかも立
体的に織り上げられているため、各繊維が互いに強く接
触しあって繊維間隙が狭く、繊維間の空隙も全体的に大
きな流通路で連通していない。したがって、マトリック
ス物質の充填もそれだけ困難である。That is, a problem in the method for producing a three-dimensional fiber-reinforced ceramic matrix composite material is that the fiber gaps of the three-dimensional fiber woven (preform) are densely filled with the ceramic serving as a matrix. It is in. However, in the three-dimensional fiber preform, since the fibers are densely and three-dimensionally woven, the fibers are in close contact with each other and the fiber gaps are narrow, and the voids between the fibers communicate with each other through a large flow passage. I haven't. Therefore, the filling of the matrix material is so difficult.
【０００４】このような問題に対処し、本発明者は、先
に、３次元繊維プリフォーム内の間隙に、マトリックス
として、セラミックス微粉末と有機結合剤又はその前駆
体物質（化学反応又は熱分解によってセラミックスとな
る有機または無機物質）を含むスラリーを高密に充填し
て、３次元繊維強化セラミックス基複合材料を製造する
方法を提案している（特願平５−７５２７０号）。この
既提案の方法において、セラミックスの前駆体物質を用
いて繊維強化セラミックス基複合材料を製造する場合に
は、その前駆体物質、セラミックス微粉末（通常結晶性
粒子）、焼結助剤及び溶媒（有機、無機液体）などによ
り構成されるスラリーを、３次元繊維プリフォーム内に
高圧で圧入すると同時に、３次元繊維プリフォームの反
対側からペーパーフィルタ及び多孔性焼結金属板を介し
て真空吸引し、このペーパーフィルタにおいてスラリー
中のセラミックス微粉末の通過を抑制しながら、溶媒部
分を通過させて排出して、３次元繊維プリフォーム中に
スラリーを高密に含浸させ、その後前駆体の熱分解過程
を経て焼結を行い、セラミックス基複合材料を得る。In order to deal with such a problem, the present inventor first found that the fine ceramic powder and the organic binder or its precursor substance (chemical reaction or thermal decomposition) as a matrix in the gap in the three-dimensional fiber preform. Proposes a method of manufacturing a three-dimensional fiber-reinforced ceramic matrix composite material by densely filling a slurry containing an organic or inorganic substance which becomes ceramics (Japanese Patent Application No. 5-75270). In the case of producing a fiber-reinforced ceramic matrix composite material by using a ceramic precursor substance in this already proposed method, the precursor substance, ceramic fine powder (usually crystalline particles), sintering aid and solvent ( A slurry composed of organic or inorganic liquid) is pressed into the three-dimensional fiber preform at high pressure, and at the same time, vacuum suction is performed from the opposite side of the three-dimensional fiber preform through a paper filter and a porous sintered metal plate. In this paper filter, while suppressing the passage of the ceramic fine powder in the slurry, the solvent portion is passed through and discharged, the slurry is densely impregnated into the three-dimensional fiber preform, and then the thermal decomposition process of the precursor is performed. After that, sintering is performed to obtain a ceramics-based composite material.
【０００５】上記方法における上記前駆体物質は、複合
体成形過程におけるバインダーとしての役割、及びその
後熱分解された前駆体（通常無定形物質）が焼結助剤と
相互作用して、スラリー中に添加したセラミックス微粉
末粒子を結合させて焼結させる効果を促進させる役割を
もっている。The above-mentioned precursor substance in the above-mentioned method serves as a binder in the process of molding the composite, and the precursor (usually amorphous substance) which is then pyrolyzed interacts with the sintering aid to form a slurry. It also has a role of promoting the effect of binding and sintering the added ceramic fine powder particles.
【０００６】しかるに、上記方法のように、前駆体物質
を含むスラリーを３次元繊維プリフォーム内へ高圧で圧
入すると同時に、反対側からペーパーフィルタを通して
真空吸引することによって含浸させる場合には、その含
浸の条件次第で、たとえ、目の細かなペーパーフィルタ
（０．１μｍ）を用いても、スラリー中の溶媒と共に溶
質部分である前駆体物質の可成りの量がこのフィルタを
通して系外へ出ることが確かめられたHowever, when the slurry containing the precursor substance is pressed into the three-dimensional fiber preform at a high pressure as in the above method, and at the same time, the slurry is impregnated by vacuum suction through the paper filter from the opposite side, the impregnation is performed. Depending on the conditions, even if a fine paper filter (0.1 μm) is used, a considerable amount of the precursor substance that is the solute part together with the solvent in the slurry can flow out of the system through this filter. Confirmed
【０００７】[0007]
【発明が解決しようとする課題】本発明の技術的課題
は、このような問題に対処し、前駆体物質を含むスラリ
ーを３次元繊維プリフォーム内へ高圧で圧入すると同時
に、反対側からペーパーフィルタを通して真空吸引する
ことによって、３次元繊維プリフォーム内の間隙にマト
リックス物質を充填するに際し、上記ペーパーフィルタ
を通してスラリー中の溶媒と共に溶質部分である前駆体
物質が系外へ排出されるのを可及的に抑制する手段を得
ることにある。SUMMARY OF THE INVENTION The technical problem of the present invention is to address such problems and to pressurize a slurry containing a precursor substance into a three-dimensional fiber preform at a high pressure, and at the same time, press the paper filter from the opposite side. When the matrix material is filled in the gaps in the three-dimensional fiber preform by vacuum suction through the through, the precursor material that is a solute portion together with the solvent in the slurry can be discharged to the outside of the system through the paper filter. To obtain a means to suppress it.
【０００８】[0008]
【課題を解決するための手段、作用】上記課題を解決す
るための本発明の複合材料製造法は、３次元繊維プリフ
ォーム内の間隙にセラミックスの前駆体物質を含むスラ
リーを高圧で圧入すると同時に、３次元繊維プリフォー
ムの反対側からペーパーフィルタを介して真空吸引し、
このペーパーフィルタを通して溶媒部分を排出させるこ
とにより、３次元繊維プリフォーム中にスラリーを高密
に含浸させるに際し、上記スラリーとして、セラミック
スの前駆体物質、それを予め熱分解して得られたものの
粉末、セラミックス微粉末（これをフィラー粉末と呼
ぶ。）及び溶媒を含んだものを用いることを特徴とする
ものである。The composite material manufacturing method of the present invention for solving the above problems is such that a slurry containing a ceramics precursor substance is pressed into a gap in a three-dimensional fiber preform at a high pressure. Vacuum suction through the paper filter from the opposite side of the 3D fiber preform,
When the three-dimensional fiber preform is highly densely impregnated with the slurry by discharging the solvent portion through the paper filter, a ceramic precursor substance, a powder obtained by previously thermally decomposing it as the slurry, It is characterized by using a ceramic fine powder (this is called a filler powder) and a solvent.
【０００９】さらに具体的に説明すると、本発明の複合
材料製造法においては、マトリックス物質として、溶融
前駆体物質、溶融前駆体物質とフィラー粉末、溶媒に溶
かされた前駆体物質、若しくは溶媒に溶かされた前駆体
物質とフィラー粉末からなる液体状前駆体物質に、それ
らの前駆体物質をあらかじめ熱分解して得られたもの
（無定形無機質）を粉末にして加え、さらに、セラミッ
クス微粉末及び溶媒などを加えたスラリーが充填され
る。即ち、この場合のスラリー構成は、上記前駆体物
質、セラミックス微粉末、前駆体物質を熱分解して得ら
れた粉末、及び溶媒などを含むものである。More specifically, in the composite material manufacturing method of the present invention, as the matrix substance, the molten precursor substance, the molten precursor substance and the filler powder, the precursor substance dissolved in the solvent, or the solvent dissolved in the solvent. To the liquid precursor substance consisting of the obtained precursor substance and filler powder, powder obtained by previously thermally decomposing these precursor substances (amorphous inorganic substance) is added, and further, ceramic fine powder and solvent are added. And the like are added. That is, the slurry composition in this case includes the precursor substance, the ceramic fine powder, the powder obtained by thermally decomposing the precursor substance, the solvent, and the like.
【００１０】上記フィラー粉末としては、マトリックス
となる各種セラミックスの微粉末を用い得るが、例え
ば、ＳｉＣをマトリックスとする場合には、β−ＳｉＣ
微粉末（０．３μｍ）が適している。スラリー中の前駆
体物質や有機結合剤は、セラミックス複合材料作製時の
焼成過程において、熱分解を起こして揮発成分が離脱す
るが、それをできるだけ除去しないと、複合材料のマト
リックス部分に気孔を生ずることになるが、スラリー中
に上記フィラー粉末を加えることは、この気孔の発生を
抑制し、高密度化された複合材料を作製するために有効
なものである。本発明において用いる溶融前駆体物質と
しては、ポリシラスチレン、ポリカルボシラン、ポリシ
ラザン及びポリヒドロシラザンなどが適している。これ
らの前駆体物質は、焼成過程において熱分解してセラミ
ックス化するが、その割合は、７０％以下が一般的であ
る。また、必要に応じて添加する有機結合剤としては、
ポリビニールアルコール、炭化水素系ワックスなどが適
している。As the above-mentioned filler powder, fine powders of various ceramics which serve as a matrix can be used. For example, when SiC is used as a matrix, β-SiC is used.
Fine powder (0.3 μm) is suitable. Precursor substances and organic binders in the slurry undergo thermal decomposition during the firing process during ceramic composite material production to release volatile components, but if these are not removed as much as possible, pores will form in the matrix portion of the composite material. However, adding the filler powder to the slurry is effective for suppressing the generation of pores and producing a densified composite material. As the molten precursor substance used in the present invention, polysilastyrene, polycarbosilane, polysilazane, polyhydrosilazane and the like are suitable. These precursor substances are thermally decomposed into ceramics during the firing process, but the ratio thereof is generally 70% or less. Further, as the organic binder to be added as necessary,
Polyvinyl alcohol and hydrocarbon wax are suitable.
【００１１】これらのスラリーは、炭素繊維、ガラス繊
維、その他適宜材料の強化用繊維で３次元的に織成され
た繊維プリフォーム中に高圧で圧入して含浸させるが、
その圧入と同時に、３次元繊維プリフォームの反対側か
らペーパーフィルタを介して真空吸引し、溶媒部分を積
極的に排出させる。この場合に、フィラー粉末ばかりで
なく、溶質部分である前駆体物質の通過を抑制する必要
があり、そのため、前駆体物質を予め熱分解して得られ
た無定形無機質材料を粉末にしてスラリー成分として加
える。これは溶媒に溶けないので、フィラー粉末と同様
にペーパーフィルタを通過せず、プリフォーム間隙に残
って、その後の焼結過程においてマトリックス緻密化の
役割をはたす。These slurries are pressed and impregnated at a high pressure into a fiber preform three-dimensionally woven with carbon fibers, glass fibers, and other appropriate reinforcing fibers to impregnate them.
Simultaneously with the press-fitting, vacuum suction is performed from the opposite side of the three-dimensional fiber preform through a paper filter, and the solvent portion is positively discharged. In this case, it is necessary to suppress the passage of not only the filler powder but also the precursor substance that is the solute portion, and therefore, the amorphous inorganic material obtained by thermally decomposing the precursor substance in advance is made into powder and the slurry component Add as. Since it does not dissolve in the solvent, it does not pass through the paper filter like the filler powder, remains in the preform gap, and plays a role of matrix densification in the subsequent sintering process.
【００１２】また、本発明において用いる前駆体物質や
有機結合剤の役割の一つは、スラリーを３次元繊維プリ
フォームに含浸させ、乾燥状態にして作製されたグリー
ン成形体中での繊維／充填物質間の強度をある程度に保
ち、その後の作業を行い易くすることである。このよう
な目的のために、前駆体物質や有機結合剤の量は、経験
的に、媒質液体の５〜１００％が必要である。また、媒
質液体はフィラー粉末量の０．５倍以上必要である。な
お、複合材成形用としての有機結合剤の含有量はフィラ
ー粉末の１０％以下であることが特に望ましい。Further, one of the roles of the precursor substance and the organic binder used in the present invention is to impregnate the slurry into the three-dimensional fiber preform and dry the fiber / filling material in the green molded product. It is to maintain the strength between substances to a certain degree and facilitate the subsequent work. For such purposes, the amount of precursor material and organic binder is empirically required to be 5-100% of the medium liquid. Further, the medium liquid needs to be 0.5 times or more the amount of the filler powder. The content of the organic binder for molding the composite material is particularly preferably 10% or less of the filler powder.
【００１３】図１は、上述したような液体状のマトリッ
クス物質を３次元繊維プリフォームの繊維間隙に充填す
るための複合材料製造装置の構成例を模式的に示すもの
である。この製造装置は、内部に吸引室１２を凹設した
基台１１と、その基台１１の上部に設置され、上記吸引
室１２と連通するシリンダ孔１４をもったシリンダ１３
とを備えている。上記基台１１は、内部の吸引室１２
を、その内底に開口する吸引路１５を介して真空ポンプ
に接続するようにしたもので、吸引室１２内の段部には
Ｏリング１７を介して多孔のステンレス製底板１６を載
置し、その底板１６上には多孔性焼結金属板（ポーラス
トン）１８を装着し、更に、その焼結金属板１８上には
ペーパーフィルタ１９を敷き、このペーパーフィルタ１
９と上記シリンダ１３との間にＯリング２０を介装し
て、ペーパーフィルタ１９の周囲からの高圧のスラリー
の漏洩を防止している。FIG. 1 schematically shows a structural example of a composite material manufacturing apparatus for filling the liquid matrix material as described above into the fiber gaps of a three-dimensional fiber preform. This manufacturing apparatus has a base 11 in which a suction chamber 12 is recessed, and a cylinder 13 having a cylinder hole 14 which is installed above the base 11 and communicates with the suction chamber 12.
It has and. The base 11 has an internal suction chamber 12
Is connected to a vacuum pump through a suction passage 15 that opens to the inner bottom thereof, and a porous stainless bottom plate 16 is placed on the step inside the suction chamber 12 through an O-ring 17. A porous sintered metal plate (Poraston) 18 is mounted on the bottom plate 16, and a paper filter 19 is laid on the sintered metal plate 18.
An O-ring 20 is provided between the cylinder 9 and the cylinder 13 to prevent leakage of high-pressure slurry from around the paper filter 19.
【００１４】また、上記シリンダ１３内のシリンダ孔１
４の下部においては、上記ペーパーフィルタ１９の上方
に位置させて、３次元繊維プリフォーム５及びスラリー
６を収容する空間を設け、この空間を介してシリンダ孔
１４内にピストン２１を嵌装し、このピストン２１を加
圧装置（図示省略）のラム２２によって圧下できるよう
に構成している。そして、上記ピストン２１の周囲に
は、シリンダ１３内面との間の間隙よりスラリー６が逆
流出しないように、Ｏリング２３及び必要数のテフロン
（商品名）製ピストンリング２４を装着している。The cylinder hole 1 in the cylinder 13
In the lower part of 4, a space for accommodating the three-dimensional fiber preform 5 and the slurry 6 is provided above the paper filter 19, and a piston 21 is fitted into the cylinder hole 14 through this space, The piston 21 is configured so that it can be pressed down by a ram 22 of a pressurizing device (not shown). Then, around the piston 21, an O-ring 23 and a necessary number of Teflon (trade name) piston rings 24 are mounted so that the slurry 6 does not flow backward from the gap between the piston 21 and the inner surface of the cylinder 13.
【００１５】このようなピストン２１により、３次元繊
維プリフォーム５及びスラリー６を収容した部分を上方
から閉鎖すると、スラリー６の上方の空間に空気が封じ
込められる。この空気を排出するため、上記ピストン２
１には、空気抜き孔２６を穿設し、その内端に該孔２６
を閉鎖する鋼球栓２７を嵌入し、この鋼球栓２７を空気
抜き穴２６に螺挿した供給固定ねじ２８により閉鎖位置
に保持できるようにしている。When such a piston 21 closes the portion containing the three-dimensional fiber preform 5 and the slurry 6 from above, air is enclosed in the space above the slurry 6. In order to discharge this air, the piston 2
1 is provided with an air vent hole 26, and the hole 26 is provided at the inner end thereof.
A steel ball plug 27 for closing the above is inserted, and the steel ball plug 27 can be held in the closed position by a supply fixing screw 28 screwed into the air vent hole 26.
【００１６】上記ステンレス製の底板１６は、直径１mm
φ程度の穴径をもつ多数の穴を穿設したものである。ま
た、ペーパーフィルタ１９は、スラリー６中のフィラー
粉末（通常１μm 以下の粒径）や溶質部分である前駆体
物質、その前駆体物質を予め熱分解して得られた無定形
無機質材料の粉末などの通過をくい止め、溶媒部分のみ
を通過させるため、０．１μｍあるいはそれ以下の穴径
を有するものを使用する。The stainless steel bottom plate 16 has a diameter of 1 mm.
A large number of holes having a hole diameter of about φ are drilled. The paper filter 19 includes filler powder (usually having a particle size of 1 μm or less) in the slurry 6, a precursor substance that is a solute portion, and an amorphous inorganic material powder obtained by previously thermally decomposing the precursor substance. In order to block the passage of the solvent and allow only the solvent portion to pass, a hole diameter of 0.1 μm or less is used.
【００１７】複合材料の製造装置をこのように構成する
と、ピストン２１に最大圧力４００kgf/cm2 を印加して
も、シリンダ孔１４内のスラリーが外部へ滲み出すこと
がないことを実験的に確かめている。また、３次元繊維
プリフォーム５内にスラリー６中の各成分を均質かつ高
密に充填するためには、加圧装置において、加圧速度を
０．０５〜５０ mm/min の間で任意に設定することがで
き、さらに加圧速度の精密制御（等速制御の場合：５０
mm/min ±０．２％以内、定荷重制御の場合：１．００
〜２０．００ tf ±１％以内）ができることが望まし
い。When the apparatus for producing a composite material is configured in this way, it is experimentally confirmed that the slurry in the cylinder hole 14 does not exude to the outside even when the maximum pressure of 400 kgf / cm 2 is applied to the piston 21. ing. Moreover, in order to uniformly and densely fill the respective components in the slurry 6 into the three-dimensional fiber preform 5, the pressurizing speed is arbitrarily set within the range of 0.05 to 50 mm / min in the pressurizing device. Precision control of pressurization speed (in case of constant speed control: 50
mm / min ± 0.2% or less, for constant load control: 1.00
~ 20.00 tf ± 1%) is desirable.
【００１８】上記構成を有する製造装置により３次元繊
維強化複合材料を製造するに際しては、まず、シリンダ
孔１４の内底に繊維プリフォーム５を入れ、その上に上
記スラリー６、即ち、液状のマトリックス物質を繊維プ
リフォーム５の嵩体積よりも多量に入れ、ピストン２１
における鋼球固定ねじ２８を一旦ゆるめて鋼球栓２７を
開き、スラリー６液面上の空気を排出した後、再び鋼球
栓２７を閉じてピストン２１によりスラリー６を上から
押し、それと同時に下方から吸引室１２を真空ポンプで
吸引することにより、スラリー６が繊維プリフォーム５
の繊維間隙に高密に充填される。ペーパーフィルタ１９
を通過した溶媒部分は、ペーパーフィルタ１９の下の多
孔性焼結金属板１８及び底板１６の穴を通して吸引室１
２に排出される。When the three-dimensional fiber reinforced composite material is manufactured by the manufacturing apparatus having the above structure, first, the fiber preform 5 is put in the inner bottom of the cylinder hole 14, and the slurry 6, that is, the liquid matrix is placed on the fiber preform 5. The substance is put in a larger amount than the bulk volume of the fiber preform 5, and the piston 21
After loosening the steel ball fixing screw 28 in 1 to open the steel ball stopper 27 and discharging the air on the liquid surface of the slurry 6, the steel ball stopper 27 is closed again and the slurry 21 is pushed from above by the piston 21, and at the same time, downward. The slurry 6 is sucked into the fiber preform 5 by sucking the suction chamber 12 with a vacuum pump.
It is densely packed in the fiber gaps. Paper filter 19
The solvent portion that has passed through the suction chamber 1 passes through the holes in the porous sintered metal plate 18 and the bottom plate 16 below the paper filter 19.
It is discharged to 2.
【００１９】加圧操作以前に投入されたスラリー６は、
繊維プリフォーム５の間隙への含浸を容易にするため低
粘性状態にしている（媒質液体中での有機結合剤または
前駆体物質の濃度が低い。）が、図１の装置による加圧
−吸引操作のうち、特に吸引操作によって、スラリー６
中での溶媒成分を多く離脱させることができ、結果とし
て、溶質（有機結合剤または前駆体物質）の濃度の高い
状態として、フィラー粉末と共に繊維プリフォーム５の
間隙に充填可能になる。なお、この効果は、図１のシリ
ンダ１３の底部にあるペーパーフィルタ１９の穴径によ
って調節可能である。通常、小さな穴径（例えば、０．
３または０．１μｍ）のペーパーフィルタを用いると、
かなりの量の溶質部分を残すことが可能である。）The slurry 6 charged before the pressurizing operation is
In order to facilitate the impregnation of the fiber preform 5 into the gap, a low viscosity state (low concentration of organic binder or precursor substance in the medium liquid) is used, but pressure-suction by the device of FIG. Among the operations, especially the suction operation, the slurry 6
A large amount of the solvent component therein can be released, and as a result, it becomes possible to fill the gaps of the fiber preform 5 together with the filler powder in a state where the concentration of the solute (organic binder or precursor substance) is high. This effect can be adjusted by the hole diameter of the paper filter 19 at the bottom of the cylinder 13 in FIG. Usually a small hole diameter (eg.
3 or 0.1 μm) paper filter,
It is possible to leave a significant amount of solute fraction. )
【００２０】[0020]
【実施例】次に、本発明の複合材料製造方法の実施例を
示す。前駆体物質としてのポリシラザン２３．１ｇを、
Ｎ2 雰囲気中で８５０℃に加熱して熱分解したものを粉
砕し、微粉末とする。次に、この微粉末１５ｇ、α−Ｓ
ｉ3 Ｎ4 フィラー粉末（焼結助剤としてＡｌ2 Ｏ3 、Ｙ
2 Ｏ3 を含んでいる）８０ｇ及びポリシラザン７ｇをト
ルエン中に入れ、ボールミル混合機でよく混合してスラ
リーを作製した。このスラリーを、炭素繊維で織製され
た平板状３次元繊維プリフォーム（繊維含有率：５４
％、４５ｍｍ×６０ｍｍ×６ｍｍｔ）とともに、図１で
示される複合材料製造装置のシリンダ内に入れ、圧力３
０ＭＰａでプリフォーム中へスラリーを含浸させ、繊維
／マトリックス複合体グリーンボディーを作製した。EXAMPLES Examples of the composite material manufacturing method of the present invention will be described below. 23.1 g of polysilazane as a precursor substance,
What was pyrolyzed by heating to 850 ° C. in an N 2 atmosphere is pulverized into a fine powder. Next, 15 g of this fine powder, α-S
i 3 N 4 filler powder (Al 2 O 3 as a sintering aid, Y
80 g (containing 2 O 3 ) and 7 g of polysilazane were placed in toluene and mixed well with a ball mill mixer to prepare a slurry. A flat plate-shaped three-dimensional fiber preform woven of carbon fibers (fiber content: 54
%, 45 mm × 60 mm × 6 mmt) into the cylinder of the composite material manufacturing apparatus shown in FIG.
The preform was impregnated with the slurry at 0 MPa to produce a fiber / matrix composite green body.
【００２１】その後、このボディーをＮ2 雰囲気中８５
０℃で加熱してポリシラザンを熱分解させた後、更に同
雰囲気中で１６５０℃で焼結させて複合材料を作製し
た。この複合材料のかさ密度は１．５５ｇ／ｃｍ3 の値
を示し、マトリックスは主相としてのβ−Ｓｉ3 Ｎ4 と
少量のα−Ｓｉ3 Ｎ4 相より構成されていた。上記工程
により３次元繊維プリフォーム内の間隙にマトリックス
物質を充填した際、ペーパーフィルタを通して前駆体物
質が系外へ排出されるのを十分に抑制することができ
た。Then, this body is subjected to 85 in N 2 atmosphere.
After heating at 0 ° C. to thermally decompose the polysilazane, it was further sintered at 1650 ° C. in the same atmosphere to produce a composite material. The bulk density of this composite material was 1.55 g / cm 3 , and the matrix was composed of β-Si 3 N 4 as the main phase and a small amount of α-Si 3 N 4 phase. When the matrix substance was filled in the gaps in the three-dimensional fiber preform by the above process, it was possible to sufficiently suppress the precursor substance from being discharged out of the system through the paper filter.
【００２２】[0022]
【発明の効果】このような本発明の方法及び装置によれ
ば、前駆体物質を含むスラリーを３次元繊維プリフォー
ム内へ高圧で圧入すると同時に、反対側からペーパーフ
ィルタを通して真空吸引することによって、３次元繊維
プリフォーム内の間隙にマトリックス物質を充填するに
際し、上記ペーパーフィルタを通してスラリー中の溶媒
と共に溶質部分である前駆体物質が系外へ排出されるの
を可及的に抑制することができる。According to the method and apparatus of the present invention as described above, the slurry containing the precursor substance is pressed into the three-dimensional fiber preform at a high pressure, and at the same time, vacuum suction is performed through the paper filter from the opposite side. When the matrix substance is filled in the gaps in the three-dimensional fiber preform, the precursor substance which is a solute portion together with the solvent in the slurry can be prevented from being discharged out of the system through the paper filter. .
【図１】本発明の方法を実施する複合材料製造装置の構
成を示す側断面図である。FIG. 1 is a side sectional view showing a configuration of a composite material manufacturing apparatus for carrying out the method of the present invention.
５ 繊維プリフォーム、 ６ スラリー、 １９ ペーパーフィルタ。 5 fiber preform, 6 slurry, 19 paper filter.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２８Ｂ 3/02 Ｓ Ｃ０４Ｂ 35/80 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B28B 3/02 S C04B 35/80
Claims (1)
ックスの前駆体物質を含むスラリーを高圧で圧入すると
同時に、３次元繊維プリフォームの反対側からペーパー
フィルタを介して真空吸引し、このペーパーフィルタを
通して溶媒部分を排出させることにより、３次元繊維プ
リフォーム中にスラリーを高密に含浸させるに際し、上
記スラリーとして、セラミックスの前駆体物質、それを
予め熱分解して得られたものの粉末、セラミックス微粉
末及び溶媒を含んだものを用いることを特徴とする３次
元繊維強化セラミックス基複合材料の製造法。1. A slurry containing a ceramic precursor substance is press-fitted into a gap in a three-dimensional fiber preform at a high pressure, and at the same time, vacuum suction is performed from a side opposite to the three-dimensional fiber preform through a paper filter. When the slurry is highly densely impregnated into the three-dimensional fiber preform by discharging the solvent portion through the above, as the slurry, a precursor substance of ceramics, a powder obtained by previously thermally decomposing it, a ceramic fine powder A method for producing a three-dimensional fiber-reinforced ceramic matrix composite material, which comprises using a solvent and a solvent.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5133852A JPH0825181B2 (en) | 1993-05-11 | 1993-05-11 | Method for producing three-dimensional fiber-reinforced ceramic matrix composite material |
| US08/205,405 US5489408A (en) | 1993-03-08 | 1994-03-03 | Method for producing ceramics reinforced with three-dimensional fibers |
| FR9402593A FR2702475B1 (en) | 1993-03-08 | 1994-03-07 | Method for manufacturing ceramics reinforced by fibers arranged in three dimensions, and apparatus for carrying out this method. |
| US08/767,413 US5660863A (en) | 1993-03-08 | 1996-12-16 | Apparatus for production of ceramics reinforced with three-dimensional fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5133852A JPH0825181B2 (en) | 1993-05-11 | 1993-05-11 | Method for producing three-dimensional fiber-reinforced ceramic matrix composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06320516A JPH06320516A (en) | 1994-11-22 |
| JPH0825181B2 true JPH0825181B2 (en) | 1996-03-13 |
Family
ID=15114543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5133852A Expired - Lifetime JPH0825181B2 (en) | 1993-03-08 | 1993-05-11 | Method for producing three-dimensional fiber-reinforced ceramic matrix composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0825181B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100816371B1 (en) * | 2006-12-20 | 2008-03-24 | (주) 제하 | Hot Pressure Sintering Device |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10230509A (en) * | 1997-02-19 | 1998-09-02 | Nichiha Corp | Production of tiled building panel |
| WO2000010685A1 (en) * | 1998-08-24 | 2000-03-02 | Pall Corporation | Porous structures and methods and apparatus for forming porous structures |
| JP3723830B2 (en) * | 2001-03-30 | 2005-12-07 | 川崎重工業株式会社 | Method for producing highly airtight ceramic composite material |
| JP2007165432A (en) * | 2005-12-12 | 2007-06-28 | Taiyo Yuden Co Ltd | Manufacturing method and manufacturing apparatus of multilayer electronic component |
| FR3071245B1 (en) * | 2017-09-21 | 2019-09-20 | Safran Ceramics | METHOD FOR INJECTING A BARBOTIN CHARGED WITH FIBROUS TEXTURE |
| US20230257309A1 (en) * | 2022-02-11 | 2023-08-17 | The Florida State University Research Foundation, Inc. | Composite Materials Including Nanofibers and Ceramics and Methods |
-
1993
- 1993-05-11 JP JP5133852A patent/JPH0825181B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100816371B1 (en) * | 2006-12-20 | 2008-03-24 | (주) 제하 | Hot Pressure Sintering Device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06320516A (en) | 1994-11-22 |
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