JPH0952776A - Fiber bonded ceramics and its production - Google Patents
Fiber bonded ceramics and its productionInfo
- Publication number
- JPH0952776A JPH0952776A JP7242262A JP24226295A JPH0952776A JP H0952776 A JPH0952776 A JP H0952776A JP 7242262 A JP7242262 A JP 7242262A JP 24226295 A JP24226295 A JP 24226295A JP H0952776 A JPH0952776 A JP H0952776A
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- Prior art keywords
- fiber
- inorganic
- substance
- crystalline
- amorphous
- 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.)
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- Ceramic Products (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高い強度及びきわめて高
い破壊靱性を有し、さらに１０００℃以上の空気中でも
優れた力学的特性を発現する繊維結合型セラミックス及
びその製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-bonded ceramic having high strength and extremely high fracture toughness, and further exhibiting excellent mechanical properties even in air at 1000 ° C. or higher, and a method for producing the same.
【０００２】[0002]
【従来の技術及びその課題】特開平７−６９７４７号公
報には、Ｓｉ、Ｃ、Ｔｉ又はＺｒ、及びＯを構成元素と
する無機質繊維と、この無機質繊維の間隙を充填するよ
うに存在する、ＳｉＴｉ又はＺｒ、及びＯを構成元素と
する無機物質とから構成され、無機質繊維と無機物質と
の境界層として１〜２００ｎｍの非晶質及び／又は結晶
質の炭素からなる層が存在する無機繊維焼結体が開示さ
れている。2. Description of the Related Art Japanese Unexamined Patent Publication (Kokai) No. 7-69747 discloses an inorganic fiber having Si, C, Ti or Zr and O as constituent elements, and an inorganic fiber so as to fill a gap between the inorganic fibers. Inorganic fiber composed of SiTi or Zr and an inorganic substance containing O as a constituent element, and having a layer of 1 to 200 nm of amorphous and / or crystalline carbon as a boundary layer between the inorganic fiber and the inorganic substance A sintered body is disclosed.
【０００３】また、上記公報には、Ｓｉ、Ｃ、Ｔｉ又は
Ｚｒ、及びＯを構成元素とする内面層と、Ｓｉ、Ｔｉ又
はＺｒ、及びＯを構成元素とする表面層とからなる無機
繊維の積層物を、不活性ガス中、５０〜１０００ｋｇ／
ｃｍ２の圧力下に、段階的に昇温して加熱焼結する無機
繊維焼結体の製法が開示されている。Further, the above publication discloses an inorganic fiber comprising an inner surface layer containing Si, C, Ti or Zr, and O as constituent elements and a surface layer containing Si, Ti or Zr, and O as constituent elements. 50-1000 kg / of the laminate in an inert gas
A method for producing an inorganic fiber sintered body is disclosed, in which the temperature is raised stepwise under a pressure of cm 2 to perform heat sintering.
【０００４】上記公報に記載の無機繊維焼結体は、高い
破壊エネルギー及び優れた力学的特性を示す一方で、１
３００℃を超える高温下では塑性変形的な挙動を示すこ
とがある。上記の無機繊維焼結体は構造材料として有望
なものであり、構造材料には高温下でも塑性変形的な挙
動を示さないことが望まれる。The inorganic fiber sintered body described in the above publication shows high breaking energy and excellent mechanical characteristics, while
At high temperatures exceeding 300 ° C., plastic deformation behavior may occur. The above-mentioned inorganic fiber sintered body is promising as a structural material, and it is desired that the structural material does not show plastic deformation behavior even at high temperatures.
【０００５】従って、上記公報の開示されている無機繊
維焼結体における高い破壊エネルギー及び優れた力学的
特性を保持しつつ、同時に、１３００℃を超えるような
きわめて高い温度においても塑性変形的な挙動を示さな
い材料の開発が望まれる。Therefore, while maintaining the high fracture energy and the excellent mechanical properties of the inorganic fiber sintered body disclosed in the above publication, at the same time, it is plastically deformable even at an extremely high temperature exceeding 1300 ° C. The development of materials that do not exhibit
【０００６】[0006]
【課題を解決する技術的手段】本発明の目的は、上記要
望を満足する繊維結合型セラミックス及びその製法を提
供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a fiber-bonded ceramic and a method for producing the same which satisfy the above demands.
【０００７】本発明によれば、（ａ）Ｓｉ、Ｍ、Ｃ及び
Ｏからなる非晶質物質、（ｂ）β−ＳｉＣ、ＭＣ及びＣ
の結晶質超微粒子と、ＳｉＯ２及びＭＯ２の非晶質物質
との集合体（ＭはＴｉ又はＺｒを示す。）、又は（ｃ）
上記（ａ）の非晶質物質と上記（ｂ）の集合体との混合
物から構成される無機質繊維と、この無機質繊維の間隙
を充填するように存在する、（ｄ）Ｓｉ及びＯ、場合に
よりＭからなる非晶質物質、（ｅ）結晶質のＳｉＯ２及
び／又はＭＯ２からなる結晶質物質、又は（ｆ）上記
（ｄ）の非晶質物質と上記（ｅ）の結晶質物質との混合
物から構成され、かつ１００ｎｍ以下の粒径のＭＣから
なる結晶質微粒子が分散した無機物質とから構成され、
さらに、上記の無機質繊維と上記の無機物質との境界層
として１〜２００ｎｍの非晶質及び／又は結晶質の炭素
からなる層が存在することを特徴とする繊維結合型セラ
ミックスが提供される。According to the present invention, (a) an amorphous substance composed of Si, M, C and O, (b) β-SiC, MC and C
Of the crystalline ultrafine particles of SiO 2 and an amorphous substance of SiO 2 and MO 2 (M represents Ti or Zr), or (c).
Inorganic fibers composed of a mixture of the amorphous substance of (a) and the aggregate of (b), and (d) Si and O, which are present so as to fill the gaps between the inorganic fibers, optionally An amorphous substance made of M, (e) a crystalline substance made of crystalline SiO 2 and / or MO 2 , or (f) an amorphous substance of (d) above and a crystalline substance of (e) above. And an inorganic substance in which crystalline fine particles of MC having a particle diameter of 100 nm or less are dispersed,
Further, there is provided a fiber-bonded ceramics characterized in that a layer made of amorphous and / or crystalline carbon having a thickness of 1 to 200 nm is present as a boundary layer between the inorganic fiber and the inorganic substance.
【０００８】さらに、本発明によれば、内面層と表面層
とからなる無機繊維であって、内面層が（ａ）Ｓｉ、
Ｍ、Ｃ及びＯからなる非晶質物質、（ｂ）β−ＳｉＣ、
ＭＣ及びＣの結晶質超微粒子と、ＳｉＯ２及びＭＯ２の
非晶質物質との集合体（ＭはＴｉ又はＺｒを示す。）、
又は（ｃ）上記（ａ）の非晶質物質と上記（ｂ）の集合
体との混合物から構成される無機質物質で構成され、表
面層が、（ｄ）Ｓｉ及びＯ、場合によりＭからなる非晶
質物質、（ｅ）結晶質のＳｉＯ２及び／又はＭＯ２から
なる結晶質物質、又は（ｆ）上記（ｄ）の非晶質物質と
上記（ｅ）の結晶質物質との混合物からなる無機質物質
で構成され、かつ、表面層の厚さＴ（単位μｍ）がＴ＝
ａＤ（ここで、ａは０．０２３〜０．０５３の範囲内の
数値であり、Ｄは無機繊維の直径（単位μｍ）であ
る。）を満足する無機繊維の積層物を、不活性ガス中、
５０〜１０００ｋｇ／ｃｍ２の圧力下に１５５０〜１８
５０℃の範囲の温度でホットプレスすることを特徴とす
る繊維結合型セラミックスの製造方法が提供される。Further, according to the present invention, an inorganic fiber comprising an inner surface layer and a surface layer, wherein the inner surface layer is (a) Si,
An amorphous material composed of M, C and O, (b) β-SiC,
An aggregate of crystalline ultrafine particles of MC and C and an amorphous substance of SiO 2 and MO 2 (M represents Ti or Zr),
Or (c) an inorganic substance composed of a mixture of the amorphous substance of (a) above and the aggregate of (b) above, and the surface layer comprises (d) Si and O, and possibly M. From an amorphous substance, (e) a crystalline substance consisting of crystalline SiO 2 and / or MO 2 , or (f) a mixture of the amorphous substance of (d) above and the crystalline substance of (e) above And the surface layer has a thickness T (unit: μm) of T =
An inorganic fiber laminate satisfying aD (where a is a numerical value within the range of 0.023 to 0.053 and D is the diameter of the inorganic fiber (unit: μm)) is placed in an inert gas. ,
1550-18 under pressure of 50-1000 kg / cm 2.
There is provided a method for producing a fiber-bonded ceramic, which comprises hot pressing at a temperature in the range of 50 ° C.
【０００９】まず、本発明の繊維結合型セラミックスに
ついて説明する。無機質繊維は上記の（ａ）、（ｂ）又
は（ｃ）で構成される。（ｂ）におけるβ−ＳｉＣとＭ
Ｃとはそれらの固溶体として存在することもでき、また
ＭＣは炭素欠損状態であるＭＣ１−ｘ（ｘは０以上で１
未満の数である。）として存在することもできる。無機
質繊維を構成する各元素の割合は、通常、Ｓｉ：３０〜
６０重量％、Ｍ：０．５〜３５重量％、好ましくは１〜
１０重量％、Ｃ：２５〜４０重量％、Ｏ：０．０１〜３
０重量％である。無機質繊維の相当直径は一般に５〜２
０μｍである。First, the fiber-bonded ceramics of the present invention will be described. The inorganic fiber is composed of the above (a), (b) or (c). Β-SiC and M in (b)
C can also exist as a solid solution thereof, and MC is a carbon deficient state MC 1-x (x is 0 or more and 1
Less than. ) Can exist as well. The ratio of each element constituting the inorganic fiber is usually Si: 30 to
60% by weight, M: 0.5 to 35% by weight, preferably 1 to
10% by weight, C: 25-40% by weight, O: 0.01-3
0% by weight. The equivalent diameter of the inorganic fiber is generally 5 to 2
0 μm.
【００１０】無機質繊維は、本発明の繊維結合型セラミ
ックス中に、８０体積％以上、好ましくは８５〜９１体
積％存在する。それぞれの無機質繊維の表面には、非晶
質及び結晶質の炭素が、１〜２００μｍの範囲の境界層
として層状に偏析している。そして、この無機質繊維の
間隙を充填するように、上記の（ｄ）、（ｅ）又は
（ｆ）の無機質物質が存在している。また、場所によっ
ては、無機質繊維と無機質物質とが、前記の炭素を境界
層として相互に接触していてもよい。The inorganic fiber is present in the fiber-bonded ceramic of the present invention in an amount of 80% by volume or more, preferably 85 to 91% by volume. Amorphous and crystalline carbon is segregated in layers as a boundary layer in the range of 1 to 200 μm on the surface of each inorganic fiber. The inorganic substance (d), (e) or (f) described above is present so as to fill the gaps between the inorganic fibers. In some places, the inorganic fiber and the inorganic substance may be in contact with each other with the carbon as the boundary layer.
【００１１】本発明の繊維結合型セラミックスにおいて
重要なことは、無機質繊維が円柱形最密構造にきわめて
近い状態で充填されるに十分な量で存在していること、
それぞれの無機質繊維の間隙には１００ｎｍ以下のＭＣ
からなる結晶質微粒子が分散したＳｉＯ２を主体とする
酸化物が充填されていること、及び無機質繊維の表面に
は１〜２００μｍの範囲の非晶質及び／又は結晶質の炭
素が存在していることである。前述した特開平７−６９
７４７号公報には、本発明の繊維結合型セラミックスの
特徴である、上記の（ｄ）〜（ｆ）の酸化物中にＭＣの
超微粒子が存在することについての記載がないことが理
解される。What is important in the fiber-bonded ceramics of the present invention is that the inorganic fibers are present in an amount sufficient to be packed in a state very close to a columnar close-packed structure,
MC of 100 nm or less in the gap between each inorganic fiber
Is filled with an oxide having SiO 2 as a main component in which crystalline fine particles are dispersed, and the surface of the inorganic fiber has amorphous and / or crystalline carbon in the range of 1 to 200 μm. It is that you are. JP-A-7-69 mentioned above
It is understood that the publication No. 747 does not describe the presence of ultrafine particles of MC in the oxides (d) to (f), which is a feature of the fiber-bonded ceramics of the present invention. .
【００１２】上記の無機質繊維と酸化物との境界に存在
する炭素層及び酸化物中のＭＣは、後述する製法におけ
るホットプレスの過程で生成するが、こららの生成機構
について説明する。本発明の製法においては、前記
（ｄ）〜（ｆ）の酸化物を有する無機繊維が使用される
が、ホットプレスの過程で無機繊維内部から移動してき
た炭素が、酸化物に含有されているＭと結合することに
よりＭＣが生成すると同時に、内面層の回りに偏析する
ことによって炭素層が生成する。The carbon layer existing at the boundary between the inorganic fiber and the oxide and the MC in the oxide are generated in the process of hot pressing in the manufacturing method described later. The mechanism of generation of these will be described. In the production method of the present invention, the inorganic fibers having the oxides (d) to (f) are used, but the carbon that has moved from the inside of the inorganic fibers during the hot pressing is contained in the oxides. At the same time as MC is formed by combining with M, a carbon layer is formed by segregating around the inner surface layer.
【００１３】本発明の繊維結合型セラミックスにおける
無機物質中に存在するＭＣは結晶径が１００ｎｍ以下と
微細であるため、無機物質の分散強化に重要な役割を果
たしており、無機物質内部に進展してくる亀裂に伴った
転位を抑制して破壊に対する抵抗力を増大する作用を有
する。また、上記の炭素層は、化学気相蒸着法又は化学
気相含浸法によって形成される炭素層とは異なってい
る。この炭素層は無機質繊維の内部に向かって濃度が減
少する傾斜した組成分布を有しており、繊維結合型セラ
ミックスが破壊する際の滑り層として作用し、直線的な
亀裂の進行を阻止する作用を有する。Since MC existing in the inorganic substance in the fiber-bonded ceramics of the present invention has a fine crystal diameter of 100 nm or less, it plays an important role in strengthening the dispersion of the inorganic substance and progresses inside the inorganic substance. It has the effect of suppressing dislocations associated with cracks and increasing the resistance to fracture. Further, the carbon layer is different from the carbon layer formed by the chemical vapor deposition method or the chemical vapor impregnation method. This carbon layer has an inclined composition distribution in which the concentration decreases toward the inside of the inorganic fiber, acts as a sliding layer when the fiber-bonded ceramics breaks, and acts to prevent the progression of linear cracks. Have.
【００１４】繊維結合型セラミックスにおける無機物質
を構成する各元素の割合は、通常、Ｓｉ：２０〜６５重
量％、Ｍ：０．３〜４０重量％、好ましくは１〜１５重
量％、Ｏ：３０〜５５重量％であり、場合によっては５
重量％以下の炭素を含むことがある。The ratio of each element constituting the inorganic substance in the fiber-bonded ceramics is usually Si: 20 to 65% by weight, M: 0.3 to 40% by weight, preferably 1 to 15% by weight, O: 30. ~ 55% by weight, in some cases 5
May contain up to wt% carbon.
【００１５】つきに本発明の繊維結合型セラミックスの
製法について説明する。本発明で原料として使用される
無機繊維は、例えば特開昭６２−２８９６４１号公報に
記載の方法に従って、上記の（ａ）、（ｂ）及び（ｃ）
から構成される無機繊維を、酸化性雰囲気下に５００〜
１６００℃の範囲の温度で加熱することによって調製す
ることができる。この無機繊維（Ｍ：Ｔｉ）は宇部興産
株式会社からチラノ繊維（登録商標）として市販されて
いる。無機繊維の形態については特別の制限はなく、連
続繊維、連続繊維を切断したチョップ状短繊維、あるい
は連続繊維を一方向に引き揃えたシート状物又は織物で
あることができる。The method for producing the fiber-bonded ceramics of the present invention will be described. The inorganic fibers used as a raw material in the present invention are the above-mentioned (a), (b) and (c) according to the method described in, for example, JP-A-62-289641.
Inorganic fiber composed of
It can be prepared by heating at a temperature in the range of 1600 ° C. This inorganic fiber (M: Ti) is commercially available from Ube Industries, Ltd. as Tyranno fiber (registered trademark). The form of the inorganic fiber is not particularly limited, and may be a continuous fiber, a chopped short fiber obtained by cutting the continuous fiber, or a sheet-like material or a woven fabric in which the continuous fibers are aligned in one direction.
【００１６】上記の酸化性雰囲気での加熱処理によって
無機繊維の表面に形成される前記の（ｄ）、（ｅ）又は
（ｆ）からなる無機質物質の表面層の厚さＴ（μｍ）
が、Ｔ＝ａＤ（ここで、ａは０．０２３〜０．０５３の
範囲内の数値であり、Ｄは無機繊維の直径（単位μｍ）
である。）を満足するように、加熱処理条件を選択する
ことが必要である。表面層の厚さを上記範囲に厳密に制
御することにより、無機繊維の含有率が８０体積％以上
の繊維結合型セラミックスを調製することが可能にな
る。The thickness T (μm) of the surface layer of the inorganic substance consisting of the above (d), (e) or (f) formed on the surface of the inorganic fiber by the heat treatment in the oxidizing atmosphere.
Where T = aD (where a is a numerical value within the range of 0.023 to 0.053, and D is the diameter of the inorganic fiber (unit: μm)).
It is. It is necessary to select the heat treatment conditions so as to satisfy the above condition. By strictly controlling the thickness of the surface layer within the above range, it becomes possible to prepare a fiber-bonded ceramic having an inorganic fiber content of 80% by volume or more.
【００１７】ａの値が下限より小さいと、無機繊維表面
に存在する表面層は、最密充填された無機質繊維の間隙
を完全に充填するには不十分であり、結果として、最終
製品である繊維結合型セラミックスにおける無機質繊維
の間隙には欠陥としての空隙が残存することになり、最
終製品の力学的特性に悪影響を及ぼす。ａの値が０．０
５３より大きいと、相対的に無機質繊維間隙に存在する
無機物質の体積％が多くなって無機質繊維の体積含有率
の低下をもたらし、結果として、無機質繊維の最密充填
から遠のくために、最終製品の繊維結合型セラミックス
の高温下でのずり変形が起こりやすくなり、最終製品が
高温下で好ましくない塑性変形的な挙動を示すようにな
る。When the value of a is smaller than the lower limit, the surface layer existing on the surface of the inorganic fibers is insufficient to completely fill the gaps of the closest packed inorganic fibers, and as a result, the final product. Voids as defects remain in the voids of the inorganic fibers in the fiber-bonded ceramics, which adversely affects the mechanical properties of the final product. The value of a is 0.0
When it is larger than 53, the volume percentage of the inorganic substance existing in the interstices of the inorganic fibers becomes relatively large, resulting in a decrease in the volume content of the inorganic fibers, and as a result, it becomes far from the close packing of the inorganic fibers, so that the final product Shear deformation of the fiber-bonded ceramic of (3) is likely to occur at high temperatures, and the final product exhibits unfavorable plastic deformation behavior at high temperatures.
【００１８】前記の酸化性雰囲気の具体例としては、空
気、純酸素、オゾン、水蒸気、炭酸ガスが挙げられる。
選択する酸化性雰囲気の種類により原料無機繊維の酸化
速度は異なるが、いずれの雰囲気においても、上記した
ように、表面層の厚さを制限を満足する酸化時間内で処
理を行うことが重要である。Specific examples of the oxidizing atmosphere include air, pure oxygen, ozone, water vapor, and carbon dioxide gas.
The rate of oxidation of the raw material inorganic fibers differs depending on the type of oxidizing atmosphere selected, but in any atmosphere, as described above, it is important to perform the treatment within the oxidizing time that satisfies the restriction on the thickness of the surface layer. is there.
【００１９】本発明においては、上記の無機繊維からな
る積層物を作成し、ついで所望の形状に成形した後に、
不活性ガス中でホットプレスすることにより、最終製品
である繊維結合型セラミックスが得られる。ホットプレ
スする際の圧力は５０〜１０００ｋｇ／ｃｍ２であり、
温度は１５５０〜１８５０℃の範囲である。In the present invention, a laminate comprising the above-mentioned inorganic fibers is prepared, and then formed into a desired shape,
By hot pressing in an inert gas, the final product, fiber-bonded ceramics, can be obtained. The pressure during hot pressing is 50 to 1000 kg / cm 2 ,
The temperature ranges from 1550 to 1850 ° C.
【００２０】Ｓｉ、Ｍ及びＯを含有する無機繊維の表面
層は１５５０〜１６００℃の範囲の温度で液相を形成す
るが、無機繊維の内部から出てくる炭素を液相中に存在
するＭと効果的に反応させてＭＣを生成させるために、
少なくとも１５５０℃以上のホットプレス温度が必要で
ある。ホットプレス温度が１８５０℃より高くなると、
上記の液相の粘性がきわめて低くなり、生成したＭＣの
移動度が大きくなってＭＣ同士の衝突頻度が増大して、
ＭＣの異常粒成長が起こると共に、ＭＣが無機質繊維と
無機物質との境界部に偏析し、粒子分散機能を果たせな
い状態になる。The surface layer of the inorganic fiber containing Si, M and O forms a liquid phase at a temperature in the range of 1550 to 1600 ° C., but the carbon emanating from the inside of the inorganic fiber is present in the liquid phase M. In order to effectively react with and generate MC,
A hot pressing temperature of at least 1550 ° C or higher is required. When hot press temperature is higher than 1850 ℃,
The viscosity of the liquid phase becomes extremely low, the mobility of the generated MC increases, the frequency of collision between MCs increases,
With abnormal grain growth of MC, MC segregates at the boundary between the inorganic fiber and the inorganic substance, and the particle cannot be dispersed.
【００２１】[0021]
【実施例】以下に実施例及び比較例を示す。以下におい
て、最終製品の力学的特性はつぎのようにして測定し
た。 層間剪断強度 幅６ｍｍ、高さ３ｍｍ、長さ２１ｍｍの一方向強化材を
用い、スパン間距離１０ｍｍで、ＪＩＳ Ｋ７０５７に
準じて測定した。 室温４点曲げ強度 島津製オートグラフ（ＤＳＳ−５００）を用いて測定し
た。試験片は、幅４ｍｍ、高さ３ｍｍ、長さ４０ｍｍの
一方向強化材を用い、上部支点間距離１０ｍｍ、下部支
点間距離３０ｍｍで行った。 準静的破壊エネルギー ＪＩＳ Ｒ１６０７に準じて、シェブロンノッチ試験片
を用いた３点曲げ試験により測定した。なお、支点間距
離は３０プラス・マイナス０．５ｍｍとした。EXAMPLES Examples and comparative examples are shown below. In the following, the mechanical properties of the final product were measured as follows. Interlaminar shear strength A unidirectional reinforcing material with a width of 6 mm, a height of 3 mm and a length of 21 mm was used, and the distance between spans was 10 mm, and the measurement was performed according to JIS K7057. Room temperature 4 point bending strength It measured using Shimadzu autograph (DSS-500). The test piece used was a unidirectional reinforcing material having a width of 4 mm, a height of 3 mm, and a length of 40 mm, and the distance between the upper fulcrums was 10 mm and the distance between the lower fulcrums was 30 mm. Quasi-static Fracture Energy According to JIS R1607, it was measured by a 3-point bending test using a chevron notch test piece. The distance between fulcrums was 30 plus / minus 0.5 mm.
【００２２】実施例１ 繊維径１０μｍのチラノ繊維（登録商標：宇部興産株式
会社製）を１１００℃の空気中で１７時間加熱処理して
原料の無機繊維を得た。繊維表面にはａ＝０．０２７に
相当する平均約２７０ｎｍの均一な表面層が形成されて
いた。この無機繊維を一方向に引き揃えた厚さ１５０μ
ｍのシート状物１５０枚を積層した後、９０×９０ｍｍ
角に切断し、ホットプレスのカーボンダイス中にセット
し、アルゴン気流下に５００ｋｇ／ｃｍ２の圧力下に、
１７５０℃まで昇温し、同温度に１時間保持して繊維結
合型セラミックスを得た。Example 1 Tyranno fiber (registered trademark: manufactured by Ube Industries, Ltd.) having a fiber diameter of 10 μm was heat-treated in air at 1100 ° C. for 17 hours to obtain a raw material inorganic fiber. A uniform surface layer with an average of about 270 nm corresponding to a = 0.027 was formed on the fiber surface. This inorganic fiber has a thickness of 150μ
90 x 90 mm after stacking 150 sheets of m
Cut into square pieces, set in a hot press carbon die, and under an argon stream under a pressure of 500 kg / cm 2 ,
The temperature was raised to 1750 ° C. and the temperature was maintained for 1 hour to obtain a fiber-bonded ceramic.
【００２３】得られた繊維結合型セラミックスの無機質
繊維の含有率は８９体積％であった。無機質繊維の間隙
に存在する無機物質を透過型電子顕微鏡、制限視野電子
線回折装置及びエネルギー分散型Ｘ線分析装置で観察し
た結果、無機物質中には粒径１００ｎｍ以下のＴｉＣ粒
子の分散が認められた。また、無機質繊維と無機物質と
の界面には薄い境界炭素層の生成が認められた。図１は
上記の透過型電子顕微鏡像であり、上述のＴｉＣの分散
状態並びに境界炭素層の生成状態が分かる。The content of inorganic fibers in the obtained fiber-bonded ceramics was 89% by volume. As a result of observing the inorganic substance existing in the interstices of the inorganic fibers with a transmission electron microscope, a selected area electron diffraction device and an energy dispersive X-ray analysis device, dispersion of TiC particles having a particle size of 100 nm or less is recognized in the inorganic substance. Was given. In addition, formation of a thin boundary carbon layer was observed at the interface between the inorganic fiber and the inorganic substance. FIG. 1 is the transmission electron microscope image, which shows the dispersion state of TiC and the generation state of the boundary carbon layer.
【００２４】この繊維結合型セラミックスの層間剪断強
度は約１００ＭＰａ、室温４点曲げ強度は７８０ＭＰ
ａ、準静的破壊エネルギーは約８８００Ｊ／ｍ２であっ
た。準静的破壊エネルギーの値は炭素繊維で強化された
炭素複合材料（Ｃ／Ｃコンポジット）の値に匹敵し、ま
た、層間剪断強度及び室温４点曲げ強度は、いずれも、
Ｃ／Ｃコンポジットのそれらを大幅に上回っている。こ
の繊維結合型セラミックスの１４００℃の空気中におけ
る４点曲げ試験の測定結果を図２に示す。図２から、こ
の繊維結合型セラミックスは１４００℃の空気中におい
ても塑性変形的な挙動を示しておらず、室温強度を保持
していることが分かる。The fiber-bonded ceramics has an interlaminar shear strength of about 100 MPa and a room temperature four-point bending strength of 780 MP.
a, the quasi-static fracture energy was about 8800 J / m 2 . The value of quasi-static fracture energy is comparable to the value of carbon composite material reinforced with carbon fiber (C / C composite), and the interlaminar shear strength and room temperature 4-point bending strength are
It greatly exceeds those of C / C composites. FIG. 2 shows the measurement result of the 4-point bending test of this fiber-bonded ceramic in air at 1400 ° C. It can be seen from FIG. 2 that this fiber-bonded ceramic does not exhibit plastically deformable behavior even in the air at 1400 ° C. and retains room temperature strength.
【００２５】比較例１ 繊維径１０μｍのチラノ繊維（登録商標：宇部興産株式
会社製）を１１５０℃の空気中で２３時間加熱処理して
原料の無機繊維を得た。繊維表面にはａ＝０．０７２に
相当する平均約７２０ｎｍの均一な表面層が形成されて
いた。この無機繊維を使用した以外は実施例１における
と同様にして、繊維結合型セラミックスを得た。Comparative Example 1 Tyranno fiber (registered trademark: manufactured by Ube Industries, Ltd.) having a fiber diameter of 10 μm was heat-treated in air at 1150 ° C. for 23 hours to obtain a raw material inorganic fiber. A uniform surface layer with an average of about 720 nm corresponding to a = 0.072 was formed on the fiber surface. A fiber-bonded ceramic was obtained in the same manner as in Example 1 except that this inorganic fiber was used.
【００２６】この繊維結合型セラミックスの無機質繊維
の含有率は７２体積％と低かった。但し、実施例１で得
られたものと同様に、無機質繊維の間隙に存在する無機
物質中には粒径１００ｎｍ以下のＴｉＣ粒子の分散が認
められ、無機質繊維と無機物質との界面には薄い均一な
境界炭素層の生成が認められた。The content of inorganic fibers in this fiber-bonded ceramic was as low as 72% by volume. However, similar to the one obtained in Example 1, dispersion of TiC particles having a particle size of 100 nm or less was observed in the inorganic substance existing in the gaps of the inorganic fiber, and the interface between the inorganic fiber and the inorganic substance was thin. Formation of a uniform boundary carbon layer was observed.
【００２７】この繊維結合型セラミックスの室温４点曲
げ強度は７２０ＭＰａであり、準静的破壊エネルギーも
約８３０Ｊ／ｍ２と高かったが、１４００℃における４
点曲げ試験の測定結果は、図３に示すように、塑性変形
的な挙動を示し、強度も低下していた。The fiber-bonded ceramics had a room temperature 4-point bending strength of 720 MPa and a quasi-static fracture energy of about 830 J / m 2 , which was high at 4400 at 1400 ° C.
As shown in FIG. 3, the measurement result of the point bending test showed a behavior of plastic deformation and the strength was lowered.
【００２８】比較例２ ホットプレス温度を１９００℃に変更した以外は実施例
１を繰り返して、繊維結合型セラミックスを得た。得ら
れた繊維結合型セラミックスの室温４点曲げ強度を準静
的破壊エネルギーは、それぞれ、７６５ＭＰａ及び８７
２０Ｊ／ｍ２と良好であった。しかし、透過型電子顕微
鏡像観察の結果、無機質繊維間の無機物質中に存在する
ＴｉＣ結晶は、食い合いによる異常粒成長を起こしてお
り、また、無機質繊維近傍に存在していることから、粒
子分散の効果を示さず、層間剪断強度は４０ＭＰａ程度
であった。Comparative Example 2 Example 1 was repeated except that the hot pressing temperature was changed to 1900 ° C. to obtain a fiber-bonded ceramic. The room temperature 4-point bending strength and the quasi-static fracture energy of the obtained fiber-bonded ceramics were 765 MPa and 87, respectively.
It was as good as 20 J / m 2 . However, as a result of observation with a transmission electron microscope image, TiC crystals existing in the inorganic substance between the inorganic fibers cause abnormal grain growth due to the interlocking, and since they are present in the vicinity of the inorganic fibers, The effect of dispersion was not shown, and the interlaminar shear strength was about 40 MPa.
【図１】図１は、実施例１で得られた繊維結合型セラミ
ックスの粒子構造を示す図面に代わる透過電子顕微鏡写
真である。FIG. 1 is a transmission electron microscope photograph as a substitute for a drawing, which shows the particle structure of the fiber-bonded ceramics obtained in Example 1.
【図２】図２は、実施例１で得られた繊維結合型セラミ
ックスの１４００℃における４点曲げ試験結果を示す図
である。FIG. 2 is a diagram showing the results of a 4-point bending test at 1400 ° C. of the fiber-bonded ceramics obtained in Example 1.
【図３】図３は、比較例１で得られた繊維結合型セラミ
ックスの１４００℃における４点曲げ試験結果を示す図
である。FIG. 3 is a diagram showing the results of a 4-point bending test at 1400 ° C. of the fiber-bonded ceramics obtained in Comparative Example 1.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 布上 俊彦 山口県宇部市大字小串1978番地の５ 宇部 興産株式会社宇部研究所内 (72)発明者 神徳 泰彦 山口県宇部市大字小串1978番地の５ 宇部 興産株式会社宇部研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshihiko Nunoue 5 1978, Ogushi, Ube, Yamaguchi Prefecture 5 1978, Ube Research Co., Ltd. (72) Inventor Yasuhiko Shintoku 5 Ube, 1978, Ube, Yamaguchi Prefecture 5 Ube Usan Laboratory, Kosan Co., Ltd.
Claims (2)
物質、（ｂ）β−ＳｉＣ、ＭＣ及びＣの結晶質超微粒子
と、ＳｉＯ２及びＭＯ２の非晶質物質との集合体（Ｍは
Ｔｉ又はＺｒを示す。）、又は（ｃ）上記（ａ）の非晶
質物質と上記（ｂ）の集合体との混合物を含有する無機
質繊維と、この無機質繊維の間隙を充填するように存在
する、（ｄ）Ｓｉ及びＯ、場合によりＭからなる非晶質
物質、（ｅ）結晶質のＳｉＯ２及び／又はＭＯ２からな
る結晶質物質、又は（ｆ）上記（ｄ）の非晶質物質と上
記（ｅ）の結晶質物質との混合物を含有し、かつ１００
ｎｍ以下の粒径のＭＣからなる結晶質微粒子が分散した
無機物質とからなり、上記無機質繊維の含有量が８０体
積％以上であり、さらに、上記の無機質繊維と上記の無
機物質との境界層として１〜２００ｎｍの非晶質及び／
又は結晶質の炭素からなる層が存在することを特徴とす
る繊維結合型セラミックス。1. An amorphous substance consisting of (a) Si, M, C and O, (b) crystalline ultrafine particles of β-SiC, MC and C, and an amorphous substance of SiO 2 and MO 2. (M represents Ti or Zr), or (c) an inorganic fiber containing a mixture of the amorphous substance of (a) and the aggregate of (b), and a gap between the inorganic fibers. (D) an amorphous substance consisting of Si and O, optionally M, (e) a crystalline substance consisting of crystalline SiO 2 and / or MO 2 , or (f) above (). containing a mixture of the amorphous substance of d) and the crystalline substance of (e) above, and
and a boundary layer between the inorganic fiber and the inorganic substance, wherein the inorganic fiber has a content of 80% by volume or more. 1 to 200 nm of amorphous and /
Alternatively, a fiber-bonded ceramics having a layer made of crystalline carbon.
て、内面層が（ａ）Ｓｉ、Ｍ、Ｃ及びＯからなる非晶質
物質、（ｂ）β−ＳｉＣ、ＭＣ及びＣの結晶質超微粒子
と、ＳｉＯ２及びＭＯ２の非晶質物質との集合体（Ｍは
Ｔｉ又はＺｒを示す。）、又は（ｃ）上記（ａ）の非晶
質物質と上記（ｂ）の集合体との混合物を含有する無機
質物質で構成され、表面層が、（ｄ）Ｓｉ及びＯ、場合
によりＭからなる非晶質物質、（ｅ）結晶質のＳｉＯ２
及び／又はＭＯ２からなる結晶質物質、又は（ｆ）上記
（ｄ）の非晶質物質と上記（ｅ）の結晶質物質との混合
物を含有する無機質物質で構成され、かつ、表面層の厚
さＴ（単位μｍ）がＴ＝ａＤ（ここで、ａは０．０２３
〜０．０５３の範囲内の数値であり、Ｄは無機繊維の直
径（単位μｍ）である。）を満足する無機繊維の積層物
を、不活性ガス中、５０〜１０００ｋｇ／ｃｍ２の圧力
下に１５５０〜１８５０℃の範囲の温度でホットプレス
することを特徴とする繊維結合型セラミックスの製造方
法。2. An inorganic fiber comprising an inner surface layer and a surface layer, wherein the inner surface layer comprises (a) an amorphous substance composed of Si, M, C and O, and (b) β-SiC, MC and C. An aggregate of crystalline ultrafine particles and an amorphous substance of SiO 2 and MO 2 (M represents Ti or Zr), or (c) the amorphous substance of (a) and the amorphous substance of (b). The surface layer is composed of an inorganic substance containing a mixture with the aggregate, and the surface layer is (d) an amorphous substance consisting of Si and O, and optionally M, (e) crystalline SiO 2
And / or a crystalline substance consisting of MO 2 or (f) an inorganic substance containing a mixture of the amorphous substance of (d) above and the crystalline substance of (e) above, and The thickness T (unit: μm) is T = aD (where a is 0.023).
Is a numerical value within the range of 0.053, and D is the diameter (unit: μm) of the inorganic fiber. The method for producing fiber-bonded ceramics is characterized by hot pressing a laminate of inorganic fibers satisfying the condition (1) in an inert gas under a pressure of 50 to 1000 kg / cm 2 at a temperature in the range of 1550 to 1850 ° C. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07242262A JP3134729B2 (en) | 1995-08-17 | 1995-08-17 | Fiber-bonded ceramics and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07242262A JP3134729B2 (en) | 1995-08-17 | 1995-08-17 | Fiber-bonded ceramics and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0952776A true JPH0952776A (en) | 1997-02-25 |
| JP3134729B2 JP3134729B2 (en) | 2001-02-13 |
Family
ID=17086655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07242262A Expired - Lifetime JP3134729B2 (en) | 1995-08-17 | 1995-08-17 | Fiber-bonded ceramics and manufacturing method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP3134729B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0893420A2 (en) | 1997-07-22 | 1999-01-27 | Ube Industries, Ltd. | Sintered silicon carbide fibers bonded material |
| JP2001072475A (en) * | 1999-08-31 | 2001-03-21 | Ube Ind Ltd | Fastening structure element for high-temperature structure body |
| US7112547B2 (en) | 2002-08-09 | 2006-09-26 | Ube Industries, Ltd. | Highly heat-resistant inorganic fiber-bonded ceramic component and process for the production thereof |
| JP2010248065A (en) * | 2009-03-27 | 2010-11-04 | Ube Ind Ltd | Inorganic fibrous ceramic porous body, composite thereof and method for manufacturing them |
| WO2013146514A1 (en) | 2012-03-29 | 2013-10-03 | 宇部興産株式会社 | Process for producing inorganic-fiber-bonded ceramic material |
-
1995
- 1995-08-17 JP JP07242262A patent/JP3134729B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0893420A2 (en) | 1997-07-22 | 1999-01-27 | Ube Industries, Ltd. | Sintered silicon carbide fibers bonded material |
| EP0893420A3 (en) * | 1997-07-22 | 1999-07-21 | Ube Industries, Ltd. | Sintered silicon carbide fibers bonded material |
| JP2001072475A (en) * | 1999-08-31 | 2001-03-21 | Ube Ind Ltd | Fastening structure element for high-temperature structure body |
| US7112547B2 (en) | 2002-08-09 | 2006-09-26 | Ube Industries, Ltd. | Highly heat-resistant inorganic fiber-bonded ceramic component and process for the production thereof |
| EP1388527A3 (en) * | 2002-08-09 | 2007-10-10 | Ube Industries, Ltd. | Highly heat-resistant inorganic fiber bonded ceramic component and process for the production thereof |
| JP2010248065A (en) * | 2009-03-27 | 2010-11-04 | Ube Ind Ltd | Inorganic fibrous ceramic porous body, composite thereof and method for manufacturing them |
| WO2013146514A1 (en) | 2012-03-29 | 2013-10-03 | 宇部興産株式会社 | Process for producing inorganic-fiber-bonded ceramic material |
| US9701587B2 (en) | 2012-03-29 | 2017-07-11 | Ube Industries, Ltd. | Method for producing inorganic fiber-bonded ceramic material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3134729B2 (en) | 2001-02-13 |
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