JPH04108680A - Method and device for vapor-phase impregnation - Google Patents
Method and device for vapor-phase impregnationInfo
- Publication number
- JPH04108680A JPH04108680A JP22900990A JP22900990A JPH04108680A JP H04108680 A JPH04108680 A JP H04108680A JP 22900990 A JP22900990 A JP 22900990A JP 22900990 A JP22900990 A JP 22900990A JP H04108680 A JPH04108680 A JP H04108680A
- Authority
- JP
- Japan
- Prior art keywords
- molded body
- matrix
- matrix component
- gas
- phase impregnation
- 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.)
- Granted
Links
- 238000005470 impregnation Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 24
- 239000012808 vapor phase Substances 0.000 title claims description 15
- 239000011159 matrix material Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 abstract description 9
- 239000007789 gas Substances 0.000 description 40
- 238000001816 cooling Methods 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011226 reinforced ceramic Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- -1 and sialon Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、多孔質成形体の空隙に気相法によりマトリッ
クス成分を析出させることにより機械的特性に優れた緻
密体を作成するための気相含浸法およびその製造装置に
関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention is a method for producing a dense body with excellent mechanical properties by depositing a matrix component in the voids of a porous molded body by a gas phase method. This invention relates to a phase impregnation method and its manufacturing apparatus.
（従来技術）
近年、高強度材料や高温材料として、これまでの金属材
料に代わり、窒化珪素、炭化珪素、サイアロン等の非酸
化物セラミックス、あるいは酸化アルミニウム、酸化ジ
ルコニウム等の酸化物セラミックス等のセラミックスが
注目され、各種の研究開発が行われており、例えば、窒
化珪素、炭化珪素等はその優れた機械的特性、高温特性
からガスタービン用部品やディーゼルエンジン等の高温
用機械部品等への応用が進められている。(Prior art) In recent years, ceramics such as non-oxide ceramics such as silicon nitride, silicon carbide, and sialon, and oxide ceramics such as aluminum oxide and zirconium oxide have been used as high-strength and high-temperature materials in place of conventional metal materials. are attracting attention, and various research and development efforts are being carried out. For example, silicon nitride, silicon carbide, etc. are being applied to high-temperature mechanical parts such as gas turbine parts and diesel engines due to their excellent mechanical properties and high-temperature properties. is in progress.
しかしながら、上述したようなセラミックスは、いずれ
も脆性を存する材料として知られており、わずかな欠陥
で破壊するために信顛性に欠けることから高強度を必要
とする構造材料への応用が阻害されているのが現状であ
る。However, all of the above-mentioned ceramics are known to be brittle materials, and they lack reliability because they break at the slightest defect, which hinders their application to structural materials that require high strength. The current situation is that
そこで、このような問題を解決するために、セラミック
スにウィスカー、カーボン繊維等の無機質繊維状物質を
混入することによりセラミックス自体に靭性を付与した
、いわゆる繊維強化セラミックスの研究開発が盛んに行
われている。Therefore, in order to solve these problems, research and development of so-called fiber-reinforced ceramics, in which toughness is imparted to ceramics by mixing whiskers, carbon fibers, and other inorganic fibrous substances, has been actively conducted. There is.
二の繊維強化セラミックスとしては、具体的には、セラ
ミック粉末に無機繊維状勧賞を添加し焼成したもの、強
化繊維の表面に特定のセラミ７・クスを化学気相成長法
（ＣＶＤ法）Ｓこより析出したもの、あるいは強化繊維
により構成された成形体の空隙部に気相法（ＣＶＤ法）
により特定のセラミックスをマトリックス成分として析
出させた、いわゆる気相含浸法（Ｃｈｅｍｉｃａｌ Ｖ
ａｐｏｒ Ｉｎｆｉｌｔ−ｒａｔｉｏｎ）によるもの
等が知られている。Specifically, the second type of fiber-reinforced ceramics is one made by adding inorganic fibers to ceramic powder and firing it, or by chemical vapor deposition (CVD) using a specific ceramic 7.x on the surface of the reinforcing fibers. Vapor-phase method (CVD method)
The so-called vapor phase impregnation method (Chemical V
There are known methods such as those based on apor infiltration.
これらのうち、気相含浸法によるものは他に比較して非
常に優れた靭性を有する材料を得ることができるとして
特に注目されており、例えば、Ａ＋＋＋。Among these, those using the vapor phase impregnation method are attracting particular attention because they can produce materials with extremely superior toughness compared to other methods, such as A+++.
Ｃｅｒａｍ、 Ｓｏｃ、 Ｂｕｌｌ、、 ６５ ［２］
３４５−５０．１９８６にてＤａｖｉｄ Ｐ、５ｔｅ
ｎｔｏｎ等によって提案されている。Ceram, Soc, Bull,, 65 [2]
345-50.1986 by David P, 5te
It has been proposed by Nton et al.
そこで、この従来の方法について第４図に示した。ここ
で用いられる装置は、基本的に多孔質成形体２１と、こ
の多孔質成形体２１を保持するためのホルダー２２と、
マトリックス形成用ガスを導入するためのガス導入口２
３、ヒータ２４ならびに前記支持手段の片側を冷却する
ための水冷ジャケット２５から構成されている。この装
置によれば、加熱手段２４により高温領域が形成され、
この高温領域内に多孔質成形体２１がホルダー２２とと
もに配置される。そこへ、ガス導入口２３よりマトリッ
クス形成ガスを多孔質成形体２１内に導入すると、成形
体内部の空隙にマトリックス成分が析出する。しかしな
がら成形体が完全な均熱領域に存在する場合、成形体の
内部より先に成形体２１表面に析出してしまい、成形体
２１内部にマトリックスを析出することができない、そ
こで、この方法では、成形体２工に対してガス導入口側
を水冷ジャケット２５により冷却して低温とすることに
より成形体２１内部に温度勾配を形成し、成形体２１の
下部から徐々にマトリックスを析出することにより成形
体２１全体にマトリックスを析出させたものである。FIG. 4 shows this conventional method. The device used here basically includes a porous molded body 21, a holder 22 for holding this porous molded body 21,
Gas inlet 2 for introducing matrix forming gas
3. It consists of a heater 24 and a water cooling jacket 25 for cooling one side of the support means. According to this device, a high temperature region is formed by the heating means 24,
A porous molded body 21 and a holder 22 are placed in this high temperature region. When a matrix-forming gas is introduced into the porous molded body 21 through the gas inlet 23, matrix components are precipitated in the voids inside the molded body. However, if the molded body is in a complete soaking area, the matrix will precipitate on the surface of the molded body 21 before the inside of the molded body, and the matrix cannot be deposited inside the molded body 21. Therefore, in this method, The gas inlet side of the molded body 2 is cooled to a low temperature by the water cooling jacket 25 to form a temperature gradient inside the molded body 21, and the matrix is gradually precipitated from the bottom of the molded body 21, thereby forming the molded body. A matrix is deposited over the entire body 21.
（発明が解決しようとする問題点）
しかしながら、成形体２１内部に温度勾配を形成するた
めに成形体２１の片側を冷却するための水冷ジャケット
２５等の冷却手段を用いる方法では、その装置の構成自
体に限界があり、しかも均一に片側を冷却することを考
慮しても成形体として小型で且つ円板や平板等の単純な
形状品にしか適応できず、複雑形状品や大型形状品の作
製は殆ど困難であった。また、炉内が均熱である場合に
大型の成形体に対してマトリックスを析出させた場合、
表面部への析出が優先して生じるために成形体内部への
析出が出来ない等の問題があった。(Problems to be Solved by the Invention) However, in the method of using a cooling means such as a water cooling jacket 25 for cooling one side of the molded body 21 in order to form a temperature gradient inside the molded body 21, the configuration of the device is It has its own limitations, and even if you consider uniform cooling on one side, it can only be applied to small molded products and simple shaped products such as disks and flat plates, and it cannot be used to create complex shaped products or large shaped products. was almost difficult. In addition, when the matrix is deposited on a large compact when the furnace is uniformly heated,
There was a problem that precipitation occurred preferentially on the surface, and therefore precipitation could not occur inside the molded body.
（問題点を解決するだめの手段）
本発明は、上記の問題点に対して検討を重ねた結果、加
熱手段の制御により温度勾配を炉内および成形体内に形
成することにより特定の領域にマトリックス成分が析出
できる領域を形成するとともに、多孔質成形体をこのマ
トリックス析出領域に対して任意の位置に可動できるよ
うに成形体支持手段を支持することにより成形体の任意
の部分にマトリックス成分を析出させることができ、こ
れにより冷却手段を何ら必要とせずに大型品の成形体や
複雑形状品の成形体に対しても内部および表面部に均一
にマトリックス成分を析出できることを知見した。(Means for Solving the Problems) As a result of repeated studies on the above problems, the present invention has been developed to create a matrix in a specific area by forming a temperature gradient in the furnace and inside the molded body by controlling the heating means. The matrix component is precipitated in any part of the molded body by forming a region where the components can be precipitated and supporting a molded body support means so that the porous molded body can be moved to any position relative to this matrix precipitation region. The inventors have discovered that this allows the matrix component to be uniformly precipitated inside and on the surface of a large molded product or a molded product with a complex shape, without requiring any cooling means.
即ち、本発明の気相含浸法は、反応炉内に多孔質成形体
を配置し、該成形体中にマトリックス形成用ガスを通過
させると同時に該成形体を加熱することにより前記成形
体内の空隙にマトリックス成分を析出させる気相含浸法
であり、前記炉内にマトリックス成分析出領域を形成し
、該析出領域に対して前記成形体を可動自在に保持し、
前記成形体の任意の部分にマトリックス成分を析出させ
ることを特徴とするもので、また、気相含浸装置によれ
ば、炉内に、多孔質成形体と、該成形体を保持する保持
手段と、前記成形体中にマトリックス形成用ガスを導入
するためのガス導入手段と、加熱手段を具備し、前記成
形体中にガスを導入すると同時に前記加熱手段により前
記成形体を所定の温度に加熱することにより前記成形体
内の空隙にマトリックス成分を析出させる気相含浸装置
において、前記炉内の特定の領域にマトリックス成分析
出領域が形成されるように前記加熱手段を制御するとと
もに、前記マトリックス成分析出領域に対して前記成形
体を任意の位置にて保持できるように前記保持手段を可
動自在にしたことを特徴とするものである。That is, in the gas phase impregnation method of the present invention, a porous molded body is placed in a reaction furnace, and the voids in the molded body are filled by passing a matrix-forming gas through the molded body and heating the molded body at the same time. This is a gas phase impregnation method in which a matrix component is precipitated in the furnace, and a matrix component detection region is formed in the furnace, the molded body is movably held with respect to the precipitation region,
The method is characterized in that a matrix component is precipitated in any part of the molded body, and according to the vapor phase impregnation apparatus, a porous molded body and a holding means for holding the molded body are placed in a furnace. , comprising a gas introducing means for introducing a matrix-forming gas into the molded body and a heating means, and at the same time as introducing the gas into the molded body, the heating means heats the molded body to a predetermined temperature. In the vapor phase impregnation apparatus for depositing a matrix component in the voids in the molded body, the heating means is controlled so that a matrix component deposition region is formed in a specific region in the furnace, and the matrix component is deposited in a specific region in the furnace. It is characterized in that the holding means is movable so that the molded body can be held at any position with respect to the exit area.
（実施例）
以下、本発明の製造方法および製造装置の一例を示す第
１図乃至第４図をもとに説明する。(Example) An example of the manufacturing method and manufacturing apparatus of the present invention will be described below with reference to FIGS. 1 to 4.
第１図は、本発明における気相含浸装置の概略図である
。第１１１１によれば、反応炉Ａ内には、多孔質成形体
１がホルダー２により支持される。FIG. 1 is a schematic diagram of a gas phase impregnation apparatus according to the present invention. According to No. 1111, inside the reactor A, a porous molded body 1 is supported by a holder 2.
ホルダー２は、それ自体グラファイト等の耐熱性物質か
らなる筒体から構成され、成形体１はその筒体の上部に
て支持されている。ホルダー２の内部には反応炉の外部
からマトリックス形成用ガスを導入するためのガス導入
管３が導設されており、ホルダー２内はシール４によっ
てその外部から実質的に密閉されている。さらにホルダ
ー２は、反応炉１の外部に設置されモータ（図示せず）
により上下駆動するテーブル５に連結されており、テー
ブル５の上下動によりホルダー２並びに成形体１も反応
炉内を上下動できるように構成されている。The holder 2 itself is composed of a cylindrical body made of a heat-resistant material such as graphite, and the molded body 1 is supported at the upper part of the cylindrical body. A gas introduction pipe 3 for introducing a matrix-forming gas from the outside of the reactor is installed inside the holder 2, and the inside of the holder 2 is substantially sealed from the outside by a seal 4. Furthermore, the holder 2 is installed outside the reactor 1 and is equipped with a motor (not shown).
The holder 2 and the molded body 1 are connected to a table 5 which is moved up and down by means of a vertical movement of the table 5, so that the holder 2 and the molded body 1 can also be moved up and down in the reactor.
一方、反応炉内Ａの外周部には、炉の各部の温度をそれ
ぞれ独立に制御できるヒータ６ａ、６ｂ、６Ｃが設置さ
れている。On the other hand, heaters 6a, 6b, and 6C are installed at the outer periphery of the inside of the reactor A, which can independently control the temperature of each part of the reactor.
この装置によれば、マトリックス形成用ガスはガス導入
管３からホルダー２内に導入された後に多孔質成形体１
内部を通過しつつヒータにより加熱により適宜反応して
マトリックス成分を析出させた後にホルダー２の外部に
排出され、最終的に炉の底部に設けられた排気ロアより
排気される。According to this device, the matrix-forming gas is introduced into the holder 2 from the gas introduction pipe 3 and then the porous molded body 1
As it passes through the interior, it is heated by a heater to react appropriately and precipitate matrix components, and then is discharged to the outside of the holder 2, and finally exhausted from an exhaust lower provided at the bottom of the furnace.
次に、上記の装置を用いて本発明における多孔質成形体
に所定のマトリックス成分を気相含浸させる方法につい
て説明する。Next, a method for impregnating a porous molded body with a predetermined matrix component in a vapor phase according to the present invention using the above-mentioned apparatus will be described.
まず、上記装置において各ヒータ６を次のように温度制
御する。本発明のよれば、ヒータ６ａ、６ｂ、６ｃのそ
れぞれの設定温度をｔａ、ｔｂ、ｔｃとした時、ｔ ａ
＞ｔ ｂ≧ｔｃの関係になるように制御することが重要
であり、これにより炉内の温度は第２図に示す温度分布
からなる。第２図において縦軸は炉の長さ方向の距離、
横軸は各位置での炉中心部の温度を示す。このとき温度
ｔａは、マトリックス形成用ガスから気相反応によりマ
トリックス成分が析出する最低温度Ｔに対してｔａ≧Ｔ
になるように設定される。これにより、第２図において
温度分布曲線と温度Ｔとの交点から高温側付近にマトリ
ックス成分析出領域Ｂが形成される。First, in the above device, the temperature of each heater 6 is controlled as follows. According to the present invention, when the set temperatures of the heaters 6a, 6b, and 6c are ta, tb, and tc, ta
It is important to control the temperature so that the relationship of >t b≧tc is satisfied, and thereby the temperature inside the furnace has the temperature distribution shown in FIG. 2. In Figure 2, the vertical axis is the distance in the longitudinal direction of the furnace,
The horizontal axis shows the temperature at the center of the furnace at each position. At this time, the temperature ta is ta≧T with respect to the lowest temperature T at which matrix components are precipitated from the matrix forming gas by a gas phase reaction.
is set to be. As a result, a matrix component detection region B is formed near the high temperature side from the intersection of the temperature distribution curve and the temperature T in FIG.
次に、第３ａ図、第３ｂ図、第３ｃ図に多孔質成形体中
の空隙にマトリックス成分を析出させるためのプロセス
を図示した。Next, FIGS. 3a, 3b, and 3c illustrate a process for precipitating matrix components in the voids in the porous molded body.
まず、初期の工程において、第３ａ図に示すようにマト
リックス成分析出領域Ｂに対して、テーブル５を上昇さ
せホルダー２に支持された多孔質成形体１の上部がマト
リックス成分析出領域Ｂに達するように位置させる。こ
のとき、炉内の温度勾配に基づき、多孔質成形体工の内
部にはガス導入側よりもガス排出側が高温となる温度勾
配が形成される。そこへマトリックス生成用ガスをガス
導入管より供給すると、マトリックス生成用ガスは温度
勾配を有する多孔質成形体内を通過する際、低温のガス
導入側では反応せず、マトリックス成分析出頭域Ｂに達
し、マトリックス析出条件を満たす成形体上部の成形体
内部の空隙部にマトリ。First, in the initial process, as shown in FIG. position to reach. At this time, based on the temperature gradient in the furnace, a temperature gradient is formed inside the porous compact in which the gas discharge side is higher in temperature than the gas introduction side. When the matrix-generating gas is supplied from the gas inlet pipe, the matrix-generating gas does not react on the low-temperature gas inlet side when passing through the porous molded body having a temperature gradient, and reaches the matrix-generating region B. , the matrix is deposited in the void inside the molded body above the molded body that satisfies the matrix precipitation conditions.
クスが析出する。具体的には、成形体が繊維状物質から
構成される場合には、マトリックス成分はまずその繊維
体の表面に析出しその析出量が増すことにより成形体の
空隙全部に充填される。さらに、析出したマトリックス
はそれ自体が熱伝達媒体となり、マトリックス析出領域
は、ガス排出側からガス導入側へ移動する。この時、成
形体が小型形状である場合には、この連鎖的マトリック
スの析出により、成形体全体にまでマトリックスを析出
させることができるが、大型形状の成形体に対しては熱
の伝達に限界があるために到底成形体全体にまでマトリ
ックスを析出させることができない。The residue is deposited. Specifically, when the molded body is composed of a fibrous material, the matrix component first precipitates on the surface of the fibrous body, and as the amount of precipitation increases, all the voids in the molded body are filled. Furthermore, the deposited matrix itself becomes a heat transfer medium, and the matrix deposition region moves from the gas outlet side to the gas inlet side. At this time, if the molded object is small in shape, it is possible to deposit the matrix over the entire molded object through this chain of matrix precipitation, but for large shaped molded objects, there is a limit to heat transfer. Because of this, it is impossible to deposit the matrix over the entire molded body.
そこで、本発明によれば、第２ｂ図に示すように、テー
ブル５を上昇させることによりマトリックス析出領域Ｂ
が成形体１のガス導入側に移動しこれによりさらにマト
リックスの析出が可能となる。Therefore, according to the present invention, as shown in FIG. 2b, by raising the table 5, the matrix precipitation area B is removed.
moves to the gas introduction side of the molded body 1, thereby making further precipitation of the matrix possible.
このテーブル５の上昇を適宜行った後、最終的シこ第２
ｃ図に示すように、マトリックス析出領域を成形体１の
最下部に位置させることにより成形体内部全体にマトリ
ックスを析出することができる。After ascending this table 5 appropriately, the final stage 2
As shown in Figure c, by locating the matrix precipitation region at the lowest part of the molded body 1, the matrix can be deposited throughout the interior of the molded body.
このテーブル５の移動によるマトリックス生成領域の移
動は、マトリックス成分の析出速度、および成形体の大
きさに応じ、断続的あるいは連続的に行うことができる
。This movement of the matrix generation region by movement of the table 5 can be performed intermittently or continuously depending on the precipitation rate of the matrix component and the size of the molded body.
上述した装置並びに方法によれば、多孔質成形体として
は、カーボン、ＳｉＣ等の炭素質繊維からなる二次元織
物、織物の積層品、三次元織物あるいはＳｉＣウィスカ
ー、５ｉｚＮ４ウィスカーＡｈＯ：ｔウィスカー等のセ
ラミンクウィスカーからなる成形体等が採用でき、また
この多孔質成形体の空隙に充填されるマトリックス成分
としては、炭化珪素や熱分解炭素、窒化珪素、サイアロ
ン、アルミナ等が適用される。According to the above-described apparatus and method, the porous molded body may be a two-dimensional fabric made of carbon fibers such as carbon or SiC, a laminate of fabrics, a three-dimensional fabric, or a porous molded body such as SiC whiskers, 5izN4 whiskers, AhO:t whiskers, etc. A molded body made of ceramic whiskers or the like can be used, and silicon carbide, pyrolytic carbon, silicon nitride, sialon, alumina, etc. can be used as the matrix component to fill the voids of this porous molded body.
これらの中でも特に、炭化珪素繊維からなる多孔質成形
体に対して炭化珪素を気相含浸することにより高温強度
を有し、高靭性の構造体を作製することができる。Among these, a structure having high temperature strength and high toughness can be produced by impregnating a porous molded body made of silicon carbide fibers with silicon carbide in a vapor phase.
また、多孔質成形体を構成する繊維としてはその平均径
（短径）が１〜３０μｍのものが適当であり、これを平
織あるいは三次元織したものが適当である。またマトリ
ックスを析出させるための反応ガスとしてはトリクロル
メチルシランや四塩化珪素、メタン、三塩化アルミニウ
ムが用いられ、これらのガスは水素等のキャリアガスに
混合されて供給される。Further, the fibers constituting the porous molded body are suitably those having an average diameter (minor diameter) of 1 to 30 μm, and plain weave or three-dimensional weave of these is suitable. In addition, trichloromethylsilane, silicon tetrachloride, methane, and aluminum trichloride are used as reaction gases for precipitating the matrix, and these gases are supplied mixed with a carrier gas such as hydrogen.
なお、マトリックス生成時における析出温度は析出する
マトリックスの種類により代わるが、炭化珪素を析出さ
せる場合には９００℃〜９５０°Ｃであることが望まし
く、この範囲ではβ−３ｉＣが析出するとともに析出速
度が遅く制御が容易であるためで、これに対して温度が
１０００℃〜１１５０°Ｃではβ−３ｉＣとＳｉの２相
が析出するために高純度のＳｉＣが生成されず、１２０
０°Ｃ〜１３００°Ｃではβ−３ｉＣが析出するが析出
速度が速すぎるために成形体内部にマトリックスを十分
に形成できないからである。The precipitation temperature during matrix formation varies depending on the type of matrix to be precipitated, but in the case of precipitating silicon carbide, it is preferably 900°C to 950°C, and in this range β-3iC is precipitated and the precipitation rate is low. On the other hand, at a temperature of 1000°C to 1150°C, two phases of β-3iC and Si are precipitated, so high purity SiC is not produced, and 120°C is slow and easy to control.
This is because β-3iC precipitates at 0°C to 1300°C, but the precipitation rate is too fast to form a sufficient matrix inside the molded body.
また、反応炉内の圧力はマトリックスの析出速度に大き
く関係し、その濃度が高い程析出速度は早い。この気相
含浸法によれば、多孔質成形体にマトリックスを析出さ
せる場合には、その速度が速すぎると十分なマトリック
スの形成ができないためにむしろ遅い方がよい。好まし
くは１００Ｔｏｒｒ以下がよい。また、ガス濃度も析出
速度を決定する大きな要因であり、特にガス中に０．４
〜１０体積％の割合で前述した所定のガスを混合するこ
とが望ましい。Further, the pressure within the reactor is greatly related to the precipitation rate of the matrix, and the higher the concentration, the faster the precipitation rate. According to this gas phase impregnation method, when depositing a matrix in a porous molded body, if the rate is too fast, sufficient matrix cannot be formed, so it is better to slow down. Preferably it is 100 Torr or less. In addition, gas concentration is also a major factor that determines the deposition rate, especially 0.4
It is desirable to mix the above-mentioned predetermined gases at a ratio of ~10% by volume.
以下、本発明を具体的な実施例に基づき説明する。The present invention will be explained below based on specific examples.
実施例
多孔質成形体としてその大きさが１００×１０１００Ｘ
５で、炭素質長繊維の平織からなるものを準備した。こ
の成形体を第１図の気相含浸装置内のホルダー２にセッ
トした。Example porous molded body whose size is 100×10100×
In step 5, a plain weave of carbonaceous long fibers was prepared. This molded body was set in the holder 2 in the gas phase impregnation apparatus shown in FIG.
そして、ヒータ６ａ、６ｂ、６Ｃの温度をそれぞれ１２
００°Ｃ１９５０°Ｃ１７５０″Ｃに設定した。Then, the temperature of heaters 6a, 6b, and 6C is set to 12
The temperature was set at 00°C, 1950°C, and 1750″C.
炉内の温度が均熱状態になったことをｔｉ認し、炉内の
温度分布を測定したところ、最高温度と最低温度との温
度差が４５０°Ｃであった。これによる成形体内におけ
る温度勾配は最大２２０°Ｃ乙こなることを確認した。After confirming that the temperature inside the furnace had become uniform, the temperature distribution inside the furnace was measured, and the temperature difference between the highest and lowest temperatures was 450°C. It was confirmed that the temperature gradient within the molded body due to this was a maximum of 220°C.
次に、炉内のマトリックス成分析出形成領域Ｂに対して
成形体ｌを第３ａ図の位置に調整し、マトリックス形成
用ガスとしてＣＨ３Ｓ ｉｃＩ ｚガスを１体積％の割
合で含有するＨ２ガスを炉内に導入した。Next, the molded body l is adjusted to the position shown in Fig. 3a with respect to the matrix component deposition formation area B in the furnace, and H2 gas containing CH3SicIz gas at a ratio of 1% by volume is used as the matrix forming gas. was introduced into the furnace.
この時、反応ガスの導入に際してはその圧力を高めて成
形体１を境に円筒状ホルダ−２内部を７６０ｔｏｒｒ、
ホルダー２の外部の雰囲気を２５ｔｏｒｒに設定し、圧
力勾配を形成した。At this time, when introducing the reaction gas, the pressure is increased to 760 torr inside the cylindrical holder 2 with the molded body 1 as a boundary.
The atmosphere outside the holder 2 was set at 25 torr to form a pressure gradient.
この状態で、反応を開始し多孔質成形体の空隙部にβ−
３ｉＣからなるマトリックスを析出した。In this state, the reaction starts and β-
A matrix consisting of 3iC was deposited.
これに引き続きテーブル５を段階的にゆっくり上昇させ
第３ｂ図に示す位置に、また最終的に成形体１が第３ｃ
図の位置になるように制御した。Subsequently, the table 5 is slowly raised step by step until it reaches the position shown in FIG.
It was controlled to be in the position shown in the figure.
これにより成形体全体に対してマトリックス成分を析出
することができた。This enabled the matrix component to be precipitated over the entire molded body.
得られた成形体は対理論密度比８５％であり、５ＥＮＢ
法により破壊靭性を測定した結果、２１ＭＰａ−ｍ””
であった。The obtained molded body had a theoretical density ratio of 85%, and 5ENB
As a result of measuring the fracture toughness by the method, it was 21MPa-m""
Met.
なお、従来のＳｉＣモノリシック材料の破壊靭性がおよ
そ５ＭＰａ−ｍ””である。Note that the fracture toughness of conventional SiC monolithic materials is approximately 5 MPa-m''.
（発明の効果）
以上詳述した通り、本発明によれば、炉内の特定の領域
にマトリックス生成領域を設定し、この領域に対して多
孔質成形体を上下動可能に支持したことにより、成形体
の形状の大きさに応じて多孔質成形体とマトリックス生
成領域とに位置を調整することにより、冷却手段を何ら
必要とせずに大型品の成形体や複雑形状品に成形体に対
しても内部および表面部に均一にマトリックス成分を析
出できる。これにより気相含浸による各種の構造材料等
の製造を実用化でき、その利用分野を大きく拡大するこ
とができる。(Effects of the Invention) As detailed above, according to the present invention, by setting a matrix generation region in a specific region in the furnace and supporting the porous molded body so as to be able to move up and down with respect to this region, By adjusting the positions of the porous molded body and the matrix generation region according to the size of the molded body, it is possible to easily handle large-sized molded bodies or complex-shaped molded bodies without the need for any cooling means. The matrix components can also be uniformly deposited inside and on the surface. This makes it possible to put into practical use the production of various structural materials by vapor phase impregnation, and to greatly expand the field of application.
第１図は、本発明の気相含浸装置の概略説明図、第２図
は炉内の温度分布を示す図、第３ａ乃至３ｃ図は、本発
明の気相含浸法を説明するだめの工程図、第４図は、従
来の気相含浸装置を説明するための概略図である。
Ａ・・・気相含浸装置
Ｂ・・・マトリックス成分析出頭域
１・・・多孔質成形体
２・・・ホルダー
３・・・ガス導入口
５・・・可動テーブル
６ａ〜６ｃ・・・ヒータ
特許出願人（６６３）京セラ株式会社Fig. 1 is a schematic explanatory diagram of the vapor phase impregnation apparatus of the present invention, Fig. 2 is a diagram showing the temperature distribution in the furnace, and Figs. 3a to 3c are the final steps for explaining the vapor phase impregnation method of the present invention. FIG. 4 is a schematic diagram for explaining a conventional gas phase impregnation apparatus. A... Gas phase impregnation device B... Matrix component analysis appearance area 1... Porous molded body 2... Holder 3... Gas inlet 5... Movable table 6a to 6c... Heater Patent applicant (663) Kyocera Corporation
Claims (6)
にマトリックス形成用ガスを通過させると同時に該成形
体を加熱することにより前記成形体内の空隙にマトリッ
クス成分を析出させる気相含浸法において、前記炉内に
マトリックス成分析出領域を形成し、該析出領域に対し
て前記成形体を可動自在に保持し、前記成形体の任意の
部分にマトリックス成分を析出させることを特徴とする
気相含浸法。(1) A porous molded body is placed in a reaction furnace, and a matrix-forming gas is passed through the molded body and the molded body is heated at the same time, so that matrix components are precipitated in the voids within the molded body. The phase impregnation method is characterized in that a matrix component deposition region is formed in the furnace, the molded body is movably held with respect to the precipitation region, and the matrix component is deposited on any part of the molded body. Gas phase impregnation method.
求項１記載の気相含浸法。(2) The vapor phase impregnation method according to claim 1, wherein the porous molded body is made of carbonaceous fiber.
１記載の気相含浸法。(3) The vapor phase impregnation method according to claim 1, wherein the matrix component comprises silicon carbide.
持手段と、前記成形体中にマトリックス形成用ガスを導
入するためのガス導入手段と、加熱手段を具備し、前記
成形体中にガスを導入すると同時に前記加熱手段により
前記成形体を所定の温度に加熱することにより前記成形
体内の空隙にマトリックス成分を析出させる気相含浸装
置において、前記炉内の特定の領域にマトリックス成分
析出領域が形成されるように前記加熱手段を制御すると
ともに、前記マトリックス成分析出領域に対して前記成
形体を任意の位置にて保持できるように前記保持手段を
可動自在にしたことを特徴とする気相含浸装置。(4) A porous molded body, a holding means for holding the molded body, a gas introduction means for introducing a matrix-forming gas into the molded body, and a heating means are provided in the furnace, and the molded body In a gas phase impregnation apparatus, a matrix component is precipitated in the voids within the molded body by introducing gas into the body and simultaneously heating the molded body to a predetermined temperature by the heating means, the matrix component is precipitated in the voids within the molded body. The heating means is controlled so that a component deposition region is formed, and the holding means is made movable so that the molded body can be held at an arbitrary position with respect to the matrix component deposition region. Characteristic gas phase impregnation equipment.
記載の気相含浸装置。(5) Claim 4, wherein the molded body is made of carbonaceous fiber.
The vapor phase impregnation device described.
４記載の気相含浸装置。(6) The vapor phase impregnation device according to claim 4, wherein the matrix component is made of silicon carbide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2229009A JP2849606B2 (en) | 1990-08-29 | 1990-08-29 | Gas phase impregnation method and its apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2229009A JP2849606B2 (en) | 1990-08-29 | 1990-08-29 | Gas phase impregnation method and its apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04108680A true JPH04108680A (en) | 1992-04-09 |
| JP2849606B2 JP2849606B2 (en) | 1999-01-20 |
Family
ID=16885329
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2229009A Expired - Fee Related JP2849606B2 (en) | 1990-08-29 | 1990-08-29 | Gas phase impregnation method and its apparatus |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5480678A (en) * | 1994-11-16 | 1996-01-02 | The B. F. Goodrich Company | Apparatus for use with CVI/CVD processes |
| US5853485A (en) * | 1994-11-16 | 1998-12-29 | The B. F. Goodrich Company | Pressure gradient CVI/CVD apparatus process and product |
| US6669988B2 (en) | 2001-08-20 | 2003-12-30 | Goodrich Corporation | Hardware assembly for CVI/CVD processes |
| US7476419B2 (en) | 1998-10-23 | 2009-01-13 | Goodrich Corporation | Method for measurement of weight during a CVI/CVD process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6021885A (en) * | 1983-07-18 | 1985-02-04 | 三井造船株式会社 | Manufacture of composite material |
-
1990
- 1990-08-29 JP JP2229009A patent/JP2849606B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6021885A (en) * | 1983-07-18 | 1985-02-04 | 三井造船株式会社 | Manufacture of composite material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5480678A (en) * | 1994-11-16 | 1996-01-02 | The B. F. Goodrich Company | Apparatus for use with CVI/CVD processes |
| US5853485A (en) * | 1994-11-16 | 1998-12-29 | The B. F. Goodrich Company | Pressure gradient CVI/CVD apparatus process and product |
| US5900297A (en) * | 1994-11-16 | 1999-05-04 | The B. F. Goodrich Company | Pressure gradient CVI/CVD apparatus, process and product |
| US6109209A (en) * | 1994-11-16 | 2000-08-29 | Rudolph; James W. | Apparatus for use with CVI/CVD processes |
| US6780462B2 (en) | 1994-11-16 | 2004-08-24 | Goodrich Corporation | Pressure gradient CVI/CVD process |
| US7476419B2 (en) | 1998-10-23 | 2009-01-13 | Goodrich Corporation | Method for measurement of weight during a CVI/CVD process |
| US6669988B2 (en) | 2001-08-20 | 2003-12-30 | Goodrich Corporation | Hardware assembly for CVI/CVD processes |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2849606B2 (en) | 1999-01-20 |
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