JPH0648867A - Production of boron carbide-coated carbon material - Google Patents
Production of boron carbide-coated carbon materialInfo
- Publication number
- JPH0648867A JPH0648867A JP4220710A JP22071092A JPH0648867A JP H0648867 A JPH0648867 A JP H0648867A JP 4220710 A JP4220710 A JP 4220710A JP 22071092 A JP22071092 A JP 22071092A JP H0648867 A JPH0648867 A JP H0648867A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- boron
- coating
- boron carbide
- carbon material
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—Carbides
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は炭化ホウ素質被覆炭素材
料の製造方法に関する。さらに詳しくは、炭化ホウ素の
膜厚を自由に制御でき、かつ汎用的工業炉で工業的有利
に製造できる炭化ホウ素質被覆炭素材料の製造方法に関
する。FIELD OF THE INVENTION The present invention relates to a method for producing a carbonaceous material coated with boron carbide. More specifically, the present invention relates to a method for producing a boron-carbide-coated carbon material, which can freely control the thickness of boron carbide and can be industrially advantageously produced in a general-purpose industrial furnace.
【０００２】[0002]
【従来の技術】炭素材料は軽量で、２５００℃近くまで
強度が低下せず、電気伝導性があり、かつ非磁性である
という特性を有している。特に炭素繊維強化炭素複合材
料は、高強度、高弾性率であり、セラミックス系材料で
あるに拘わらず破壊靭性が高く、極めて熱衝撃に強いと
いう特性を有している。さらには銅以上の熱伝導率を有
する。このため、高温で使われる構造部材、あるいは核
融合炉内のプラズマに最も近く位置してこれと相互作用
する材料、いわゆる第一壁材としての応用が進められて
いる。2. Description of the Related Art A carbon material is light in weight, does not deteriorate in strength up to about 2500 ° C., has electrical conductivity, and is non-magnetic. In particular, the carbon fiber reinforced carbon composite material has high strength and high elastic modulus, has high fracture toughness and is extremely resistant to thermal shock, despite being a ceramic material. Further, it has a thermal conductivity higher than that of copper. Therefore, application as a structural member used at high temperature or a material which is located closest to and interacts with plasma in the fusion reactor, that is, a so-called first wall material is being promoted.
【０００３】しかし炭素材料は水素プラズマと化学反応
し、５００℃前後の温度で炭化水素系の気体を生成す
る、いわゆるケミカルエロージョンによる消耗が激し
い。また水素の吸蔵量が多い等の問題点をも有してい
る。このような問題点を補うには、セラミックスのコー
テイングが有効である。各融合炉第一壁材の構成元素が
スパッタリングによるプラズマ中に不純物として取り込
まれると、プラズマの温度が低下し、この低下度は原子
番号の３乗に比例する。このため軽い元素で構成された
炭化ホウ素は被覆材料として適している。炭素材料は５
００℃以上での酸化消耗が顕著である。このため酸化性
雰囲気中では、炭素材料を高温度で使用することは困難
である。炭化ホウ素は酸化性雰囲気中５００℃以上でも
安定であり、炭素材料の耐酸化被覆材としても有効であ
る。However, a carbon material chemically reacts with hydrogen plasma to generate a hydrocarbon-based gas at a temperature of about 500 ° C., which is so much consumed by so-called chemical erosion. In addition, there is a problem that the hydrogen storage amount is large. Ceramic coating is effective in compensating for such problems. When the constituent elements of the first wall material of each fusion reactor are taken into the plasma by sputtering as impurities, the temperature of the plasma decreases, and the degree of decrease is proportional to the cube of the atomic number. Therefore, boron carbide composed of a light element is suitable as a coating material. 5 carbon materials
Oxidative consumption at 00 ° C or higher is remarkable. Therefore, it is difficult to use the carbon material at a high temperature in the oxidizing atmosphere. Boron carbide is stable even in an oxidizing atmosphere at 500 ° C. or higher, and is also effective as an oxidation resistant coating material for carbon materials.
【０００４】炭素材料に炭化ホウ素を被覆する方法は幾
つか提案されている。スパッタリングによる方法はもっ
とも簡便である。気相から炭化ホウ素を基材上に析出さ
せる気相化学蒸着法（ＣＶＤ法）もよく用いられる。Ｃ
ＶＤ法には化学反応を励起するエネルギー源として、
熱、光、プラズマ、マイクロ波等を用いるいくつかの方
法が知られている。上記の方法はいずれも、緻密な炭化
ホウ素被膜が得られるものの基材への膜の接着力が不十
分であるため、被覆と基材との熱膨張差に起因する応力
により膜が剥離し易く、苛酷な熱環境下での使用に適さ
ない。Several methods of coating a carbon material with boron carbide have been proposed. The method by sputtering is the simplest. A vapor phase chemical vapor deposition method (CVD method) for depositing boron carbide on a substrate from a vapor phase is also often used. C
In the VD method, as an energy source for exciting a chemical reaction,
Several methods using heat, light, plasma, microwave, etc. are known. In any of the above methods, although a dense boron carbide coating can be obtained, the adhesion of the film to the substrate is insufficient, so the film easily peels off due to the stress caused by the difference in thermal expansion between the coating and the substrate. Not suitable for use in harsh thermal environments.
【０００５】気体の酸化ホウ素と固体の炭素材料とを反
応させることにより、炭素材料表面に炭化ホウ素の被覆
を形成する方法も知られている。この方法で得られた被
覆は、膜と基材との界面が不明瞭であり、膜の基材への
接着力が高く、熱衝撃を加えても膜が剥離することはな
いという利点を有している。A method is also known in which a coating of boron carbide is formed on the surface of a carbon material by reacting gaseous boron oxide with a solid carbon material. The coating obtained by this method has the advantages that the interface between the film and the substrate is unclear, the adhesion of the film to the substrate is high, and the film does not peel off even when a thermal shock is applied. is doing.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
方法は、反応の進行速度が遅く、炭素と炭化ホウ素の混
合物層が形成され易く、炭化ホウ素単体の膜を得るため
には長い反応時間が必要である。反応時間を長くする
と、被膜の厚さが大きくなる。即ち被膜の厚さと膜の組
成を独立に制御することは困難であった。However, the above-mentioned method has a slow reaction progress rate, is likely to form a mixture layer of carbon and boron carbide, and requires a long reaction time to obtain a film of boron carbide simple substance. Is. The longer the reaction time, the thicker the film. That is, it is difficult to independently control the thickness of the coating and the composition of the coating.
【０００７】本発明の目的は、炭素材料表面の炭化ホウ
素被膜が、適宜の厚さで、かつ炭素材料との接着性に優
れた状態で形成された炭化ホウ素質被覆炭素材料を、工
業的有利に製造できる方法を提供するにある。An object of the present invention is to industrially provide a boron carbide-based carbon material in which a boron carbide coating film on the surface of the carbon material is formed to have an appropriate thickness and excellent adhesion to the carbon material. To provide a method that can be manufactured.
【０００８】[0008]
【課題を解決するための手段】本発明は、炭素材料の表
面に炭化ホウ素を被覆する方法において、酸化ホウ素の
気体と炭素材料の炭素とを反応させて炭素と炭化ホウ素
の混合物からなる被覆を形成し、ついで混合物からなる
被覆とホウ素とを反応させて炭化ホウ素の被覆を形成す
ることを特徴とする炭化ホウ素質被覆炭素材料の製造方
法を提供する。The present invention provides a method for coating a surface of a carbon material with boron carbide, which comprises reacting a gas of boron oxide with carbon of a carbon material to form a coating composed of a mixture of carbon and boron carbide. Provided is a method for producing a boron-carbide-coated carbon material, which comprises forming and then reacting a coating of a mixture with boron to form a coating of boron carbide.
【０００９】本発明で用いられる炭素材料は特に限定さ
れるものではない。例えば粒子強化型炭素材料、炭素繊
維を補強繊維とし炭素をマトリックスとする炭素繊維強
化炭素複合材料が例示される。炭素材料は一般にその使
用目的に応じて黒鉛化処理が施されるが、この処理温度
も特に限定されるものではない。粒子強化型の炭素材料
には、強化粒子の粒径や黒鉛化度、あるいは使用された
バインダーの種類により種々の種類があるが、これらに
ついても特に限定されるものではない。炭素繊維強化炭
素複合材料は、炭素繊維をフェノール樹脂等の熱硬化性
樹脂やピッチを用いて成形し、ついで炭化あるいは黒鉛
化して製造する方法、炭素繊維を熱硬化性樹脂やピッチ
に含浸し、ついで炭化あるいは黒鉛化する方法を繰り返
して製造する方法、熱分解炭素の沈積による緻密化処理
を加えて製造する方法等の種々の方法によって製造され
る。The carbon material used in the present invention is not particularly limited. Examples thereof include a particle-reinforced carbon material and a carbon fiber-reinforced carbon composite material having carbon fibers as reinforcing fibers and carbon as a matrix. The carbon material is generally graphitized according to the purpose of use, but the treatment temperature is also not particularly limited. There are various types of particle-reinforced carbon materials depending on the particle size of the reinforcing particles, the degree of graphitization, and the type of binder used, but these are not particularly limited. Carbon fiber reinforced carbon composite material, a method of molding the carbon fiber using a thermosetting resin such as phenolic resin or pitch, then carbonized or graphitized to produce, carbon fiber impregnated into the thermosetting resin or pitch, Then, it is manufactured by various methods such as a method of repeating the method of carbonizing or graphitizing and a method of manufacturing by adding a densification treatment by deposition of pyrolytic carbon.
【００１０】使用される炭素繊維としては、ＰＡＮ系炭
素繊維あるいはピッチ系炭素繊維のいずれでもよく、ま
たその前駆体を用いてもよい。補強材としての炭素繊維
の形態も特に限定されるものではない。例えば一方向
材、短繊維をランダムに配置したシートを積層したフェ
ルト、クロス積層、三次元織物、短繊維状等である。炭
化ホウ素の被覆面は、繊維の強化方向とは無関係に自由
に選択することができる。The carbon fiber used may be either PAN-based carbon fiber or pitch-based carbon fiber, or a precursor thereof. The form of the carbon fiber as the reinforcing material is not particularly limited. For example, a unidirectional material, felt in which sheets in which short fibers are randomly arranged are laminated, cloth lamination, three-dimensional woven fabric, short fiber shape and the like. The boron carbide coated surface can be chosen freely regardless of the direction of fiber reinforcement.
【００１１】気体の酸化ホウ素と炭素繊維強化炭素複合
材料との反応は、炭化ホウ素を酸化ホウ素と炭素との混
合物から作る反応と基本的に同じであり、以下の反応式
（１）に示す通りである。 ２Ｂ2Ｏ3＋７Ｃ→Ｂ4Ｃ＋６ＣＯ （１）The reaction between gaseous boron oxide and the carbon fiber reinforced carbon composite material is basically the same as the reaction in which boron carbide is made from a mixture of boron oxide and carbon, and as shown in the following reaction formula (1): Is. 2B 2 O 3 + 7C → B 4 C + 6CO (1)
【００１２】反応温度は、１６００℃から２５００℃、
さらに好ましくは１８００℃から２２００℃である。反
応温度が低すぎると反応速度が著しく遅く実用的ではな
い。また反応温度が高すぎると生成した炭化ホウ素が分
解するので好ましくない。反応雰囲気は、不活性ガス、
好ましくはアルゴン等の不活性ガス雰囲気である。窒素
は反応を著しく阻害することはないが、窒化物を生成す
るので好ましくない。反応後の炉からは、適切な温度ま
で冷えてから取り出すのが好ましい。数百度で炉を大気
開放すると、炭化ホウ素の表面が酸化され、被膜中の酸
素濃度が増加するので好ましくない。The reaction temperature is 1600 ° C to 2500 ° C,
More preferably, it is 1800 ° C to 2200 ° C. If the reaction temperature is too low, the reaction rate will be too slow to be practical. Further, if the reaction temperature is too high, the generated boron carbide is decomposed, which is not preferable. The reaction atmosphere is an inert gas,
The atmosphere is preferably an inert gas such as argon. Nitrogen does not significantly inhibit the reaction, but it is not preferable because it forms a nitride. After the reaction, it is preferable to cool the furnace to an appropriate temperature before taking it out. When the furnace is opened to the atmosphere at several hundreds of degrees, the surface of boron carbide is oxidized and the oxygen concentration in the coating increases, which is not preferable.
【００１３】ホウ素と炭素との反応式を次の式（２）に
示す通りである。 ４Ｂ＋Ｃ→Ｂ4Ｃ （２） 反応温度は、１８００℃から２５００℃、好ましくは２
０００℃から２４００℃である。式（２）の反応は固体
炭素とホウ素との反応であるが、炭化ホウ素と炭素との
混合物固体中の炭素とホウ素との間でも進行する。ホウ
素の沸点２４５０℃を超えても反応は進行するが、原料
ホウ素の蒸発による消耗が多くなるので、２４５０℃を
超えた温度での反応は好ましくない。また２４００℃を
超えると、生成した炭化ホウ素の分解が生じ、ホウ素が
蒸発するので好ましくない。この反応は不活性ガス雰囲
気中で実施される。反応雰囲気中に炭化水素系の気体が
微量でも存在すると、この気体とホウ素が反応し、ホウ
素粉末あるいはホウ素膜表面がホウ素粉末あるいはホウ
素膜内部より早く炭化ホウ素となり、生成した被膜の炭
素材料への接着性が損なわれるので、炭化水素系気体が
反応系に存在することは好ましくない。。昇温速度は特
に限定されるものではない。反応時間は３０分程度で十
分である。The reaction formula of boron and carbon is as shown in the following formula (2). 4B + C → B 4 C (2) The reaction temperature is 1800 ° C. to 2500 ° C., preferably 2
The temperature is from 000 ° C to 2400 ° C. The reaction of formula (2) is a reaction between solid carbon and boron, but it also proceeds between carbon and boron in a mixture solid of boron carbide and carbon. The reaction proceeds even if the boiling point of boron exceeds 2450 ° C., but the consumption at a temperature higher than 2450 ° C. is not preferable because the consumption of boron as a raw material increases. On the other hand, if the temperature exceeds 2400 ° C, the generated boron carbide is decomposed and the boron is evaporated, which is not preferable. This reaction is carried out in an inert gas atmosphere. If a minute amount of hydrocarbon-based gas is present in the reaction atmosphere, this gas reacts with boron, and the surface of the boron powder or the boron film becomes boron carbide faster than the inside of the boron powder or the boron film. It is not preferable that a hydrocarbon-based gas be present in the reaction system because the adhesiveness will be impaired. . The heating rate is not particularly limited. A reaction time of about 30 minutes is sufficient.
【００１４】反応に供するホウ素の形態は特に限定され
るものではなく、粉末状、膜状のいずれてあってもよ
い。ただし、炭素と炭化ホウ素の混合物からなる被覆上
に均一に配分することが、均一な被覆が得られ易く好ま
しい。例えば粉末状ホウ素を使用する場合には、ホウ素
と室温で反応しない液体、例えばアルコールに分散させ
でスラリーを作り、このスラリーをスプレーや刷毛塗り
等の方法により、被膜上に均一に塗布し、その後液体を
蒸発等の方法により除去すればよい。ホウ素の膜を使用
する場合には、スパッタ法、気相化学蒸着法、溶射等の
一般的に使用されている製膜法を採用できる。反応に供
したホウ素の９９重量％以上が炭化ホウ素として被覆を
形成するので、ホウ素との反応により追加される炭化ホ
ウ素被覆の厚さは、反応させるホウ素の量で制御するこ
とができる。反応に供したホウ素の殆ど全てが反応する
ので、膜厚の制御が容易である。また炉を汚染する心配
も少なく、特別な設備を用意する必要がなく、汎用的な
工業炉で製造することができる。さらには、酸化ホウ素
の気体のみを用いた方法よりも短時間で炭化ホウ素質被
覆炭素材料を製造できるという利点がある。The form of boron used in the reaction is not particularly limited, and it may be in the form of powder or film. However, it is preferable that the coating is uniformly distributed on the coating made of a mixture of carbon and boron carbide because a uniform coating can be easily obtained. For example, when powdered boron is used, a liquid that does not react with boron at room temperature, for example, is dispersed in alcohol to form a slurry, and this slurry is evenly applied on the coating by a method such as spraying or brushing, and then The liquid may be removed by a method such as evaporation. When a boron film is used, a commonly used film forming method such as a sputtering method, a vapor phase chemical vapor deposition method, or a thermal spraying method can be adopted. Since 99% by weight or more of the boron subjected to the reaction forms a coating as boron carbide, the thickness of the boron carbide coating added by the reaction with boron can be controlled by the amount of boron reacted. Almost all of the boron used in the reaction reacts, so that it is easy to control the film thickness. Further, there is little concern that the furnace will be contaminated, there is no need to prepare special equipment, and the furnace can be manufactured in a general-purpose industrial furnace. Furthermore, there is an advantage that the carbon material coated with boron carbide can be produced in a shorter time than the method using only the gas of boron oxide.
【００１５】[0015]
試料：炭素繊維強化炭素複合材料として、炭素繊維を一
方向に引き揃えた一方向材と、数センチの炭素短繊維を
ランダムに配したシートを積層したフェルト材の２種類
を用いた。用いた炭素繊維は、石炭ピッチ系の高弾性炭
素繊維である。これらの炭素繊維強化複合材料を２５ｍ
ｍ×２５ｍｍ、厚さ２０ｍｍに切断し、試料として用い
た。一方向材では繊維と垂直な面に、フェルト材では積
層したシートと垂直な面にそれぞれ被覆を施した。Sample: As the carbon fiber reinforced carbon composite material, two kinds of unidirectional material in which carbon fibers were aligned in one direction and felt material in which sheets in which carbon short fibers of several cm were randomly arranged were laminated were used. The carbon fiber used is a coal-pitch-based highly elastic carbon fiber. 25m of these carbon fiber reinforced composite materials
It was cut into m × 25 mm and 20 mm in thickness and used as a sample. The unidirectional material was coated on the surface perpendicular to the fiber, and the felt material was coated on the surface perpendicular to the laminated sheet.
【００１６】酸化ホウ素気体と炭素材料の炭素との反応
条件：直径４５ｍｍ、深さ５０ｍｍの円筒状黒鉛製坩堝
に酸化ホウ素粉末を３８ｇ入れた。該坩堝の開口部直上
に、黒鉛の治具を用いて試料を支持し、坩堝の底で発生
した酸化ホウ素気体と試料とを反応させた。坩堝と酸化
ホウ素との反応を抑制するため、坩堝の内側に窒化ホウ
素粉末を塗布した。試料を入れた坩堝をさらに大きな黒
鉛製坩堝に入れ、アルゴン雰囲気中で１９００℃で３時
間反応させた。外側の黒鉛製坩堝には穴を明けた蓋をか
ぶせておいた。昇温は酸化ホウ素の融点付近では１℃／
分と遅くし、それ以外の温度域では１０℃／分とした。
以上の反応により炭化ホウ素と炭素の混合物で被覆され
たＣ／Ｃ複合材を得た。Reaction conditions of boron oxide gas and carbon of carbon material: 38 g of boron oxide powder was put into a cylindrical graphite crucible having a diameter of 45 mm and a depth of 50 mm. The sample was supported right above the opening of the crucible using a graphite jig, and the boron oxide gas generated at the bottom of the crucible was reacted with the sample. Boron nitride powder was applied to the inside of the crucible in order to suppress the reaction between the crucible and boron oxide. The crucible containing the sample was placed in a larger graphite crucible and reacted in an argon atmosphere at 1900 ° C. for 3 hours. The outer graphite crucible was covered with a perforated lid. The temperature rise is 1 ° C near the melting point of boron oxide
The temperature was set to 10 minutes / minute in the other temperature range.
Through the above reaction, a C / C composite material coated with a mixture of boron carbide and carbon was obtained.
【００１７】ホウ素と混合物中の炭素との反応条件：上
記反応で得られた被覆の上に、ホウ素粉末を単位面積当
たり５、１０および２０ｍｇ／ｃｍ2塗布し、アルゴン
気流中（３リットル／分）、２２５０℃で３０分間加熱
した。昇温速度は８.３℃／分とした。ホウ素粉末の塗
布は、ホウ素粉末をイソプロピルアルコールに分散させ
たサスペンジョンを、被覆上に塗布後、９０℃でアルコ
ールを蒸発除去して実施した。Reaction conditions of boron and carbon in the mixture: Boron powder was applied on the coating obtained in the above reaction at 5, 10 and 20 mg / cm 2 per unit area, and the mixture was fed in an argon stream (3 liters / minute). ) Heated at 2250 ° C. for 30 minutes. The heating rate was 8.3 ° C./min. The application of the boron powder was carried out by applying a suspension prepared by dispersing the boron powder in isopropyl alcohol onto the coating and then removing the alcohol by evaporation at 90 ° C.
【００１８】被覆の分析方法：被覆表面にＸ線を照射し
ながら、θ−２θ法によりＸ線回折パターン（Ｃｕ−Ｋ
α、４０ＫＶ、３０ｍＡ）を測定して、被覆物質の同定
および被膜の組成を調べた。被膜の形態および厚さは、
被覆に垂直に試料を切断し、光学顕微鏡および走査型電
子顕微鏡により試料断面を観察して調べた。Coating analysis method: X-ray diffraction pattern (Cu-K
(α, 40 KV, 30 mA) was measured to examine the identification of the coating material and the composition of the coating. The morphology and thickness of the coating are
The sample was cut perpendicular to the coating and examined by observing the cross section of the sample with an optical microscope and a scanning electron microscope.
【００１９】図１は基材に一方向炭素繊維強化炭素複合
材料を用いた試料の測定結果である。図２は基材にフェ
ルトタイプ炭素繊維強化炭素複合材料を用いた試料の測
定結果である。上記図１および図２に示す２つの試料の
反応させたホウ素の単位面積当たりの重量は、５ｍｇ／
ｃｍ2である。反応させたホウ素の量が、１０と２０ｍ
ｇ／ｃｍ2の試料においても、図１および図２と同様な
結果が得られた。FIG. 1 shows the measurement results of a sample using a unidirectional carbon fiber reinforced carbon composite material as a base material. FIG. 2 shows the measurement results of a sample using a felt type carbon fiber reinforced carbon composite material as a base material. The weight per unit area of reacted boron of the two samples shown in FIGS. 1 and 2 is 5 mg /
cm 2 . The amount of reacted boron is 10 and 20 m
The same results as in FIGS. 1 and 2 were obtained also for the sample of g / cm 2 .
【００２０】いずれの回折パターンも被覆が炭化ホウ素
と炭素とからなることを示した。炭化ホウ素の最強回折
ピーク強度に対する炭素の最強回折ピーク強度の比は、
一方向炭素繊維強化炭素複合材料では２２.４％、フェ
ルトタイプの炭素繊維強化炭素複合材料では５０.０％
であった。これらの値は、比較例で示す酸化ホウ素との
反応のみによる被覆の値より小さく、ホウ素との反応に
より炭化ホウ素の濃度が高くなったことを示す。Both diffraction patterns showed that the coating consisted of boron carbide and carbon. The ratio of the strongest diffraction peak intensity of carbon to the strongest diffraction peak intensity of boron carbide is
Unidirectional carbon fiber reinforced carbon composite material 22.4%, felt type carbon fiber reinforced carbon composite material 50.0%
Met. These values are smaller than the values of the coating only by the reaction with boron oxide shown in the comparative example, indicating that the concentration of boron carbide was increased by the reaction with boron.
【００２１】炭化ホウ素の最強回折ピークは（０２１）
である。フェルトタイプの炭素繊維強化炭素複合材料を
基材とした被覆では、この（０２１）ピークが最強ピー
クであった（図２）。一方向炭素繊維強化炭素複合材料
を基材とした被覆では、（１０４）ピークが最強ピーク
であった。また一方向炭素繊維強化炭素複合材料では、
炭素の最強回折ピークも（００２）ではなく、（１０
１）であった（図１）。これらのデータから見て、一方
向炭素繊維強化炭素複合材料では炭素結晶が配向してお
り、この影響が炭化ホウ素結晶に受け継がれたことを示
すものと推定される。The strongest diffraction peak of boron carbide is (021)
Is. In the coating using the felt type carbon fiber reinforced carbon composite material as a base material, this (021) peak was the strongest peak (FIG. 2). In the coating based on the unidirectional carbon fiber reinforced carbon composite material, the (104) peak was the strongest peak. In the unidirectional carbon fiber reinforced carbon composite material,
The strongest diffraction peak of carbon is not (002) but (10
1) (Fig. 1). From these data, it is presumed that the carbon crystals are oriented in the unidirectional carbon fiber reinforced carbon composite material, and this effect is inherited by the boron carbide crystals.
【００２２】第一の酸化ホウ素との反応による被覆と第
二のホウ素との反応による被覆との境界は観察されず、
両者の接着性は良好なものと推定される。被覆層と基材
との界面の形態は、比較例の界面形態と変わらず、被覆
全体の基材に対する接着性は比較例と同等であると推定
される。上記２つの被覆の界面が明瞭でないので、比較
例との膜厚との差から、ホウ素との反応により追加され
た被覆の厚さを推算した。その結果、ホウ素との反応に
よる被覆の厚さは、塗布したホウ素が５ｍｇ／ｃｍ2で
は約５０μｍ、１０ｍｇ／ｃｍ2では約１００μｍ、２
０ｍｇ／ｃｍ2では約２００μｍであり、被覆の厚さ
は、塗布するホウ素の量によって制御できた。反応に供
したホウ素の９９重量％以上が炭化ホウ素として被覆を
形成した。No boundary between the coating by reaction with the first boron oxide and the coating by reaction with the second boron is observed,
The adhesiveness between the two is presumed to be good. The morphology of the interface between the coating layer and the substrate is the same as the interface morphology of the comparative example, and the adhesiveness of the entire coating to the substrate is presumed to be equivalent to that of the comparative example. Since the interface between the two coatings was not clear, the thickness of the coating added by the reaction with boron was estimated from the difference from the film thickness of the comparative example. As a result, the thickness of the coating due to the reaction with boron was about 50 μm when the applied boron was 5 mg / cm 2 , and about 100 μm when 10 mg / cm 2 was applied.
At 0 mg / cm 2 , it was about 200 μm and the coating thickness could be controlled by the amount of boron applied. 99% by weight or more of the boron used in the reaction formed a coating as boron carbide.
【００２３】[0023]
【比較例】基材となる炭素繊維強化炭素複合材料として
は、実施例で使用したのと同じ一方向材とフェルト材を
使用した。酸化ホウ素と炭素材料中の炭素との反応条件
は実施例と同じであり、ホウ素と被覆との反応を実施し
なかった点のみが実施例と異なる。Comparative Example As the carbon fiber reinforced carbon composite material serving as the base material, the same unidirectional material and felt material as used in the examples were used. The reaction conditions of boron oxide and carbon in the carbon material are the same as those in the example, and are different from the example only in that the reaction between the boron and the coating was not performed.
【００２４】図３は基材に一方向炭素繊維強化炭素複合
材料を用いた試料の測定結果である。図４は基材にフェ
ルトタイプ炭素繊維強化炭素複合材料を用いた試料の測
定結果である。被覆の回折パターンは、炭化ホウ素と炭
化とからなることを示した。炭化ホウ素の最強回折ピー
ク強度に対する炭素の最強回折ピーク強度の比は、一方
向炭素繊維強化炭素複合材料では４２.４％（図３）、
フェルトタイプの炭素繊維強化炭素複合材料では１５４
％（図４）であった。これらの値は実施例で得られた値
よりも大きい。また実施例と同様に、一方向炭素繊維強
化炭素複合材料を基材とした被覆では、炭素と炭化ホウ
素に結晶の配向が観察された。FIG. 3 shows the measurement results of a sample using a unidirectional carbon fiber reinforced carbon composite material as a base material. FIG. 4 shows the measurement results of a sample using a felt type carbon fiber reinforced carbon composite material as a base material. The diffraction pattern of the coating showed that it consisted of boron carbide and carbonization. The ratio of the strongest diffraction peak intensity of carbon to that of boron carbide is 42.4% in the unidirectional carbon fiber reinforced carbon composite material (Fig. 3),
154 for felt type carbon fiber reinforced carbon composite material
% (FIG. 4). These values are larger than those obtained in the examples. Further, as in the case of the example, in the coating using the unidirectional carbon fiber reinforced carbon composite material as a base material, crystal orientation was observed in carbon and boron carbide.
【００２５】被覆に垂直に切断した試料断面は、被覆層
の厚さが場所により不規則に、かつ大きく変化し、巨視
的には界面付近で炭素と炭化ホウ素の量が内部から表面
に向かって連続的に変化する傾斜機能を有する。この傾
斜機能は、実施例でも述べたように、ホウ素との反応に
よる被覆を追加しても失われない。In the sample cross section cut perpendicular to the coating, the thickness of the coating layer changes irregularly and greatly depending on the location, and macroscopically, the amount of carbon and boron carbide near the interface goes from the inside to the surface. It has a continuously changing tilt function. This gradient function is not lost with the addition of the coating by reaction with boron, as described in the examples.
【００２６】被覆の厚さは、一方向炭素繊維強化炭素複
合材料を基材とした場合では約２００〜３００μｍであ
り、フェルトタイプの炭素繊維強化炭素複合材料を基材
とした場合では約１００〜２００μｍであった。基材に
より被覆層の厚さが異なる理由は、必ずしも明らかでな
いが、次ぎのように推定される。本反応は気体と固体と
の反応であり、被覆を基材内部に生成するためには、反
応気体が基材内部へ進入することが必要である。一方向
炭素繊維強化炭素複合材料は、繊維配向が進んでいるた
め、基材内部へ向かって表面に垂直な気孔が多い。一
方、フェルトタイプの炭素繊維強化炭素複合材料では、
繊維が積層面内でランダムであるため、表面にある角度
をもって気孔が存在し、また繊維の交差により気孔が閉
塞する。このため、フェルトタイプの炭素繊維強化炭素
複合材料では酸化ホウ素の気体が基材内部へ進入しにく
く、被覆厚さが薄くなったものと考えられる。The thickness of the coating is about 200 to 300 μm when the unidirectional carbon fiber reinforced carbon composite material is used as the base material, and about 100 to 100 μm when the felt type carbon fiber reinforced carbon composite material is used as the base material. It was 200 μm. The reason why the thickness of the coating layer differs depending on the base material is not necessarily clear, but is presumed as follows. This reaction is a reaction between a gas and a solid, and it is necessary for the reaction gas to enter the inside of the substrate in order to form the coating inside the substrate. Since the fiber orientation of the unidirectional carbon fiber reinforced carbon composite material is advanced, many pores are perpendicular to the surface toward the inside of the base material. On the other hand, in the felt type carbon fiber reinforced carbon composite material,
Since the fibers are random in the laminating plane, pores are present on the surface at an angle, and the crossing of the fibers closes the pores. Therefore, it is considered that in the felt-type carbon fiber reinforced carbon composite material, the gas of boron oxide does not easily enter the inside of the base material, and the coating thickness becomes thin.
【００２７】[0027]
【発明の効果】本発明によれば、被覆中の炭化ホウ素の
濃度を高くすることができると共に、膜厚を自由に制御
でき、これらを特別な製造設備を用いることなく、短時
間で製造できる炭化ホウ素質被覆炭素材料の製造方法が
提供される。According to the present invention, the concentration of boron carbide in the coating can be increased and the film thickness can be freely controlled, and these can be produced in a short time without using special production equipment. A method of making a boron carbide based carbon material is provided.
【図１】本発明で得られた一方向炭素繊維強化炭素複合
材料の被覆のＸ線回折パターンのグラフである。FIG. 1 is a graph of an X-ray diffraction pattern of a coating of a unidirectional carbon fiber reinforced carbon composite material obtained according to the present invention.
【図２】本発明で得られたフェルトタイプ炭素繊維強化
炭素複合材料の被覆のＸ線回折パターンのグラフであ
る。FIG. 2 is a graph of an X-ray diffraction pattern of a coating of felt-type carbon fiber reinforced carbon composite material obtained according to the present invention.
【図３】従来の方法で得られた一方向炭素繊維強化炭素
複合材料の被覆のＸ線回折パターンのグラフである。FIG. 3 is a graph of an X-ray diffraction pattern of a coating of a unidirectional carbon fiber reinforced carbon composite material obtained by a conventional method.
【図４】従来の方法で得られたフェルトタイプ炭素繊維
強化炭素複合材料の被覆のＸ線回折パターンのグラフで
ある。FIG. 4 is a graph of an X-ray diffraction pattern of a coating of felt-type carbon fiber reinforced carbon composite material obtained by a conventional method.
Claims (7)
方法において、酸化ホウ素の気体と炭素材料の炭素とを
反応させて炭素と炭化ホウ素の混合物からなる被覆を形
成し、ついで該被覆とホウ素とを反応させて炭化ホウ素
の被覆を形成することを特徴とする炭化ホウ素質被覆炭
素材料の製造方法。1. A method of coating a surface of a carbon material with boron carbide, wherein a gas of boron oxide and carbon of the carbon material are reacted to form a coating composed of a mixture of carbon and boron carbide, and then the coating and the boron. A method for producing a boron-carbide-coated carbon material, which comprises reacting with and forming a coating of boron carbide.
合物からなる被覆を形成し、ついで該被覆とホウ素とを
反応させて炭化ホウ素の被覆を形成するに当たり、混合
物からなる被覆の表面にホウ素粉末を塗布し、不活性雰
囲気中で加熱することを特徴とする請求項１記載の炭化
ホウ素質被覆炭素材料の製造方法。2. When a coating of a mixture of carbon and boron carbide is formed on the surface of a carbon material and then the coating and boron are reacted to form a coating of boron carbide, boron is formed on the surface of the coating of the mixture. The method for producing a boron carbide-based carbon material according to claim 1, wherein the powder is applied and heated in an inert atmosphere.
素をマトリックスとする炭素繊維強化炭素複合材料であ
る請求項１記載の炭化ホウ素質被覆炭素材料の製造方
法。3. The method for producing a boron carbide-based carbon material according to claim 1, wherein the carbon material is a carbon fiber-reinforced carbon composite material having carbon fibers as reinforcing fibers and carbon as a matrix.
えた繊維である請求項３記載の炭化ホウ素質被覆炭素材
料の製造方法。4. The method for producing a carbon material coated with boron carbide according to claim 3, wherein the reinforcing fiber is a fiber in which carbon fibers are aligned in one direction.
る請求項４記載の炭化ホウ素質被覆炭素材料の製造方
法。5. The method for producing a boron carbide-based carbon material according to claim 4, wherein the coating is formed on a surface perpendicular to the fiber axis.
したシートの積層物である請求項３記載の炭化ホウ素質
被覆炭素材料の製造方法。6. The method for producing a carbonaceous material coated with boron carbide according to claim 3, wherein the reinforcing fiber is a laminate of sheets in which short carbon fibers are randomly arranged.
請求項６記載の炭化ホウ素質被覆炭素材料の製造方法。7. The method for producing a boron carbide-based carbon material according to claim 6, wherein the coating is formed on a surface perpendicular to the sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22071092A JP3219314B2 (en) | 1992-07-28 | 1992-07-28 | Method for producing boron carbide-based carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22071092A JP3219314B2 (en) | 1992-07-28 | 1992-07-28 | Method for producing boron carbide-based carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0648867A true JPH0648867A (en) | 1994-02-22 |
| JP3219314B2 JP3219314B2 (en) | 2001-10-15 |
Family
ID=16755294
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22071092A Expired - Lifetime JP3219314B2 (en) | 1992-07-28 | 1992-07-28 | Method for producing boron carbide-based carbon material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005314173A (en) * | 2004-04-30 | 2005-11-10 | National Institute For Materials Science | Boron carbide nanobelt and manufacturing method thereof |
| US8961640B2 (en) | 2011-05-19 | 2015-02-24 | Koganei Corporation | Filter |
| US8992648B2 (en) | 2011-05-19 | 2015-03-31 | Koganei Corporation | Swirl flow generator |
| US9174225B2 (en) | 2011-05-19 | 2015-11-03 | Koganei Corporation | Filter |
| US9233327B2 (en) | 2011-12-01 | 2016-01-12 | Koganei Corporation | Filter |
-
1992
- 1992-07-28 JP JP22071092A patent/JP3219314B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005314173A (en) * | 2004-04-30 | 2005-11-10 | National Institute For Materials Science | Boron carbide nanobelt and manufacturing method thereof |
| JP4590599B2 (en) * | 2004-04-30 | 2010-12-01 | 独立行政法人物質・材料研究機構 | Boron carbide nanobelt and manufacturing method thereof |
| US8961640B2 (en) | 2011-05-19 | 2015-02-24 | Koganei Corporation | Filter |
| US8992648B2 (en) | 2011-05-19 | 2015-03-31 | Koganei Corporation | Swirl flow generator |
| US9174225B2 (en) | 2011-05-19 | 2015-11-03 | Koganei Corporation | Filter |
| US9233327B2 (en) | 2011-12-01 | 2016-01-12 | Koganei Corporation | Filter |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3219314B2 (en) | 2001-10-15 |
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