JPH0681219A - Silica-containing carbon fiber, its production and fiber-reinforced cement material containing the fiber - Google Patents
Silica-containing carbon fiber, its production and fiber-reinforced cement material containing the fiberInfo
- Publication number
- JPH0681219A JPH0681219A JP23378092A JP23378092A JPH0681219A JP H0681219 A JPH0681219 A JP H0681219A JP 23378092 A JP23378092 A JP 23378092A JP 23378092 A JP23378092 A JP 23378092A JP H0681219 A JPH0681219 A JP H0681219A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- fiber
- carbon fiber
- containing carbon
- fine particles
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1066—Oxides, Hydroxides
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高層ビルの外壁材、床
材等に使用される繊維補強モルタルや繊維補強コンクリ
ートなどの繊維補強セメント系材料（以下ＣＦＲＣと略
称する）の補強用繊維として有用な改質された炭素繊維
の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a fiber for reinforcing a fiber reinforced cementitious material (hereinafter abbreviated as CFRC) such as a fiber reinforced mortar or a fiber reinforced concrete used for outer wall materials and floor materials of high-rise buildings. The present invention relates to a method for producing a useful modified carbon fiber.
【０００２】[0002]
【従来の技術】近年、ＣＦＲＣの補強用繊維としてピッ
チ系の短炭素繊維が多用されるようになってきている。
ＣＦＲＣは、通常、セメントマトリックスのペースト中
に短炭素繊維を分散させ、硬化させることによって製造
される。2. Description of the Related Art In recent years, pitch-based short carbon fibers have been widely used as CFRC reinforcing fibers.
CFRC is usually manufactured by dispersing and curing short carbon fibers in a cement matrix paste.
【０００３】ところが、従来の短炭素繊維を用いてＣＦ
ＲＣを製造する場合、硬化後のセメントマトリックスと
炭素繊維表面との間の接着強度が低いため、セメントマ
トリックスから繊維が引き抜け易く、炭素繊維の強度の
割りには補強効率が低いという問題があった。However, CF using conventional short carbon fibers
When producing RC, since the adhesive strength between the cement matrix and the carbon fiber surface after curing is low, the fibers are easily pulled out from the cement matrix, and there is a problem that the reinforcing efficiency is low relative to the strength of the carbon fibers. It was
【０００４】このような問題を解決する目的で補強用炭
素繊維の表面物性を改善する方法が種々検討されてい
る。代表的な方法としては次のような方法がある。Various methods for improving the surface properties of the reinforcing carbon fiber have been studied for the purpose of solving such problems. The following methods are typical methods.
【０００５】先ず、繊維に科学的酸化処理を施し、繊維
表面上に酸性基を導入する方法がある（セメント技術年
報、第４０巻．ｐ４７９〜４８２，１９８５等）。この
方法は、炭素繊維の表面を硝酸等で科学的に酸化するこ
とにより、セメントマトリックスと繊維との親和性を高
め、接着強度を改善するものである。しかし、この方法
では、酸化処理により繊維の表面に傷が生じ、繊維自身
の強度が低下するため、繊維強度の高いポリアクリロニ
トリル系繊維以外では、ＣＦＲＣの強度を向上させる効
果は認められない。First, there is a method in which a fiber is chemically oxidized and an acidic group is introduced onto the surface of the fiber (Annual Report of Cement Technology, Vol. 40, p. 479-482, 1985). According to this method, the surface of the carbon fiber is chemically oxidized with nitric acid or the like to enhance the affinity between the cement matrix and the fiber and improve the adhesive strength. However, in this method, the surface of the fiber is damaged by the oxidation treatment, and the strength of the fiber itself is lowered. Therefore, the effect of improving the strength of CFRC is not recognized except for the polyacrylonitrile fiber having high fiber strength.
【０００６】次に、繊維表面をシリカやアルミナの微粒
子を含有するエポキシ樹脂等で被覆する方法がある（特
開昭６３−２０３９８７６号公報等）。この方法は、セ
メントマトリックス成分と化学反応を起こし易いシリカ
やアルミナを含むコーティング剤等で繊維表面を処理
し、セメントマトリックスへの定着性を改善しようとす
るものであるが、実質的には、コーティング膜と繊維と
の接着強度が弱く、大きな改善効果は望めない。Next, there is a method of coating the fiber surface with an epoxy resin or the like containing fine particles of silica or alumina (JP-A-63-2039876, etc.). This method is to improve the fixability to the cement matrix by treating the fiber surface with a coating agent or the like containing silica or alumina, which easily causes a chemical reaction with the cement matrix component. Since the adhesive strength between the membrane and the fiber is weak, a large improvement effect cannot be expected.
【０００７】さらに、繊維にねじりや凹凸を持たせ、物
理的に繊維が引き抜け難くする方法も試みられている
（特開平１−２３９０４４号公報等）。この方法は、繊
維の形状を変えることにより、セメントマトリックス中
でアンカーとして働き、補強効果を高めるものである。
しかしながら、この方法においては、繊維の製造プロセ
ス中で、繊維に物理的応力を作用させたあとに、熱処理
を施しているので、繊維に熱的歪みが残り、繊維の強度
が低下するため期待したほどの補強効果の向上は得られ
ていない。Further, a method has also been attempted in which the fibers are twisted or uneven so that the fibers are not easily pulled out (Japanese Patent Laid-Open No. 1-239044). This method acts as an anchor in the cement matrix by changing the shape of the fiber and enhances the reinforcing effect.
However, in this method, since heat treatment is applied after physical stress is applied to the fiber in the fiber manufacturing process, thermal strain remains in the fiber and the strength of the fiber decreases, which is expected. The reinforcement effect is not so improved.
【０００８】[0008]
【発明が解決しようとする課題】前記のとおり、ＣＦＲ
Ｃの繊維補強効率を高めるため、繊維表面に化学的、物
理的な処理を施す方法が検討されてきたが、いずれの方
法によっても、繊維の特性、特に強度が損なわれたり、
コーティング剤を使用する場合にはコーティング剤と繊
維との接着性が悪いなどの問題があり、炭素繊維の強度
を十分に利用できる、補強効率の高いＣＦＲＣの製造方
法は見出されていなかった。As mentioned above, the CFR
In order to enhance the fiber reinforcing efficiency of C, a method of chemically or physically treating the fiber surface has been studied, but by any of the methods, the characteristics of the fiber, particularly the strength is impaired,
When a coating agent is used, there is a problem such as poor adhesion between the coating agent and the fiber, and a method for producing CFRC having a high reinforcing efficiency that can sufficiently utilize the strength of carbon fiber has not been found.
【０００９】本発明の目的は、前記従来技術における問
題点を解決し、炭素繊維の強度を損なうことなく、セメ
ントマトリックスへの接着強度を高め、ＣＦＲＣの補強
用に使用した際の補強効率を高めることのできる炭素繊
維、その製造方法及びそれを使用したＣＦＲＣを提供す
ることにある。The object of the present invention is to solve the above-mentioned problems in the prior art, increase the adhesive strength to the cement matrix without impairing the strength of the carbon fiber, and increase the reinforcing efficiency when used for reinforcing CFRC. It is to provide a carbon fiber that can be produced, a method for producing the same, and a CFRC using the same.
【００１０】[0010]
【課題を解決するための手段】本発明は、炭素繊維の表
面および内部にシリカ微粒子が均一に分散しているシリ
カ含有炭素繊維であり、又、該炭素繊維を製造する方法
であって、芳香族スルホン酸類又はそれらの塩がメチレ
ン型結合を介して結合した高分子化合物の水溶液に、該
水溶液中の高分子化合物の０．０４〜４．０重量％相当
量のシリカ微粒子が分散してなる紡糸原液を紡糸し、得
られる前駆体繊維を熱処理して炭化させることを特徴と
するシリカ含有炭素繊維の製造方法である。又本発明
は、炭素繊維の表面および内部にシリカ微粒子が均一に
分散しているシリカ含有炭素繊維を補強材として使用し
た繊維補強セメント系材料である。The present invention is a silica-containing carbon fiber in which silica fine particles are uniformly dispersed on the surface and inside of the carbon fiber, and a method for producing the carbon fiber. An aqueous solution of a polymer compound in which a group sulfonic acid or a salt thereof is bound via a methylene type bond is dispersed with silica fine particles in an amount of 0.04 to 4.0% by weight of the polymer compound in the aqueous solution. A method for producing a silica-containing carbon fiber, which comprises spinning a spinning dope, and heat-treating the resulting precursor fiber for carbonization. The present invention is also a fiber-reinforced cementitious material using silica-containing carbon fibers, in which silica fine particles are uniformly dispersed on the surface and inside of the carbon fibers, as a reinforcing material.
【００１１】シリカ微粒子が表面および内部に分散して
いる本発明の炭素繊維では、表面のシリカ微粒子がセメ
ントマトリックスへの分散性、定着性へ関与し、内部の
シリカ微粒子が繊維自体の強度へ関与すると考えられ、
ＣＦＲＣの補強効果を高めることができる。このような
炭素繊維は次に説明する方法により製造することができ
る。In the carbon fiber of the present invention in which silica particles are dispersed on the surface and inside, the silica particles on the surface contribute to the dispersibility and fixability to the cement matrix, and the silica particles inside contribute to the strength of the fiber itself. Thought,
The reinforcing effect of CFRC can be enhanced. Such a carbon fiber can be manufactured by the method described below.
【００１２】先ず、本発明で使用する紡糸原液の主成分
である芳香族スルホン酸類又はそれらの塩がメチレン型
結合を介して結合した高分子化合物（以下、高分子化合
物と略称する）は、フェノール類スルホン酸、ナフタレ
ンスルホン酸、アントラセンスルホン酸、フェナントレ
ンスルホン酸等の各種芳香族スルホン酸化合物又はそれ
らの塩もしくはこれらの混合物をメチレン型結合を介し
て結合させた数平均分子量２０００〜５０００程度のも
のであって、これらの芳香族スルホン酸類をホルマリン
等のアルデヒド化合物と縮合反応させるなど、それ自体
公知の方法により製造することができる。この高分子化
合物の好ましい例としては、セメント用減水剤などに用
いられているナフタレンスルホン酸のホルマリン縮合物
があげられる。First, a polymer compound (hereinafter, abbreviated as polymer compound) in which aromatic sulfonic acids or salts thereof, which are the main components of the spinning dope used in the present invention, are bound via a methylene type bond is phenol. Aromatic sulfonic acid, naphthalene sulfonic acid, anthracene sulfonic acid, various aromatic sulfonic acid compounds such as phenanthrene sulfonic acid, or salts thereof or a mixture thereof through a methylene type bond having a number average molecular weight of about 2000 to 5000 The aromatic sulfonic acids can be produced by a method known per se, such as a condensation reaction with an aldehyde compound such as formalin. A preferable example of this polymer compound is a formalin condensate of naphthalene sulfonic acid used in a water reducing agent for cement and the like.
【００１３】これらの高分子化合物は、そのまま、ある
いは中和した形で水溶液として使用するが、アンモニウ
ム塩の形で使用すると、安定で、しかも水やメタノール
等のアルコール系溶媒に容易に溶解し、又、シリカ微粒
子としてコロイダルシリカを添加した場合は、コロイダ
ルシリカの電位バランスを損ない凝集させる強酸イオン
をほとんど含まないので特に好ましい。These high molecular compounds are used as an aqueous solution as they are or in a neutralized form, but when they are used in the form of ammonium salts, they are stable and easily dissolved in water or an alcohol solvent such as methanol, Further, when colloidal silica is added as the silica fine particles, it is particularly preferable because it does not contain strong acid ions for aggregating which impairs the potential balance of the colloidal silica.
【００１４】以下、プロセスに従い、本発明の方法を詳
細に説明する。The method of the present invention will be described in detail below according to the process.
【００１５】前記高分子化合物の水溶液にシルカ微粒子
を分散させるためには、コロイダルシリカ等のシリカ微
粒子の水溶液あるいはスラリーを添加するとよい。次
に、得られた混合液には、必要により紡糸助剤として適
量のポリビニルアルコール、ポリエチレングリコール等
の水溶性高分子化合物を添加したのち、５０℃における
粘度が５０〜２０００ポイズとなるように水分量を調整
して紡糸原液とする。In order to disperse the silica fine particles in the aqueous solution of the polymer compound, it is advisable to add an aqueous solution or slurry of silica fine particles such as colloidal silica. Next, an appropriate amount of a water-soluble polymer compound such as polyvinyl alcohol or polyethylene glycol is added to the obtained mixed solution as a spinning aid, if necessary, and water is added so that the viscosity at 50 ° C. is 50 to 2000 poise. Adjust the amount to make the spinning dope.
【００１６】紡糸原液中の高分子化合物の濃度は、高分
子化合物の種類、必要により添加する紡糸助剤やシリカ
微粒子の種類及び添加量等によって異なるが、通常２０
〜８０重量％、好ましくは４０〜７０重量％である。The concentration of the polymer compound in the spinning dope varies depending on the type of polymer compound, the type and amount of spinning aid or silica fine particles to be added, if necessary, and is usually 20
-80% by weight, preferably 40-70% by weight.
【００１７】ここで使用するシリカ源としては、特にコ
ロイダルシリカに限るものではないが、コロイダルシリ
カのように予め水溶液中にシリカ微粒子を分散させたも
のは前記高分子化合物水溶液と容易に混合できるので好
ましい。The silica source used here is not particularly limited to colloidal silica, but colloidal silica such as silica particles in which silica fine particles are previously dispersed can be easily mixed with the aqueous polymer compound solution. preferable.
【００１８】使用するシリカ微粒子の粒径が大きくなり
すぎると、紡糸原液中での分散性が悪くなるとともに炭
素繊維の強度が低下し、ＣＦＲＣの補強効果が減少する
ので、使用するシリカ微粒子の粒径はできるだけ細かい
ことが望ましい。シリカ微粒子の好ましい大きさは平均
粒径で１０〜１５０ｎｍ、さらに好ましくは１０〜３０
ｎｍの範囲である。When the particle size of the silica fine particles to be used is too large, the dispersibility in the spinning dope is deteriorated and the strength of the carbon fibers is lowered, so that the CFRC reinforcing effect is reduced. It is desirable that the diameter is as small as possible. The average size of silica fine particles is preferably 10 to 150 nm, more preferably 10 to 30 nm.
It is in the range of nm.
【００１９】シリカ微粒子の添加量は、シリカ分に換算
して高分子化合物の水溶液中の高分子化合物の０．０４
〜４．０重量％相当量とする。この量は、ここで使用す
る高分子化合物の炭化収率が約３５〜６０％であること
から、シリカ含有炭素繊維の段階でシリカ含有率が約
０．１〜１０重量％となる量に相当する。シリカ微粒子
の添加量が０．０４重量％未満では効果が少なく、また
４．０重量％を超えるとシリカ微粒子の分散液がゲル化
しやすくなり、紡糸工程に支障をきたすので好ましくな
い。The amount of the silica fine particles added is 0.04 of the polymer compound in the aqueous solution of the polymer compound in terms of silica content.
Up to 4.0% by weight. This amount corresponds to an amount that the silica content becomes about 0.1 to 10% by weight at the stage of the silica-containing carbon fiber since the carbonization yield of the polymer compound used here is about 35 to 60%. To do. If the addition amount of the silica fine particles is less than 0.04% by weight, the effect is small, and if it exceeds 4.0% by weight, the dispersion liquid of the silica fine particles is apt to gel, which is not preferable because the spinning process is hindered.
【００２０】このようにして調製した紡糸原液を乾式紡
糸し、前駆体繊維（径１０〜１４０μｍ程度）を得る。
この前駆体繊維は、熱溶融しないという特性を有してお
り、通常のＰＡＮ系やピッチ系の炭素繊維では必須の工
程である不融化処理工程が必要なく、そのまま、不活性
雰囲気中で、８００〜１２００℃の温度で熱処理を施す
ことにより、シリカ含有炭素繊維とすることができる。
尚、前駆体繊維は、乾式紡糸後に延伸乾燥を経て得られ
るのが普通である。又、熱処理前に前駆体繊維を所望の
長さに裁断しておくとよい（１〜３０ｍｍ程度）。The spinning dope thus prepared is dry-spun to obtain a precursor fiber (diameter: 10 to 140 μm).
This precursor fiber has the property of not being melted by heat, and does not require the infusibilizing treatment step, which is an essential step for ordinary PAN-based or pitch-based carbon fibers, and can be used as it is in an inert atmosphere at 800 A silica-containing carbon fiber can be obtained by performing a heat treatment at a temperature of up to 1200 ° C.
The precursor fiber is usually obtained by dry spinning and then stretching and drying. In addition, it is preferable to cut the precursor fiber into a desired length before the heat treatment (about 1 to 30 mm).
【００２１】このようにして得られた本発明のシリカ含
有炭素繊維は、表面及び内部にシリカ微粒子が分散した
炭素繊維である。この状態はＳＥＭ等で観察することが
できる。この繊維においては添加したシリカ粒子の大き
さが小さいため、繊維の強度に悪影響を与えることはな
く、逆に添加率０．０４〜４．０重量％の範囲内におい
ては、シリカの添加量が増加するに従いシリカ含有炭素
繊維の強度が向上する。これはシリカと炭素とが反応
し、一部ＳｉＣ結合が生成し、その結果、シリカ含有炭
素繊維の強度が増加するものと考えられるが、その詳細
は明らかではない。本発明のシリカ含有炭素繊維をＣＦ
ＲＣの補強用に使用すると、炭素繊維表面上のシリカ成
分がセメントと化学反応（ポゾラン反応）を起こし、セ
メントマトリックス中に水和物として結晶化することに
より炭素繊維とセメントマトリックスとの間の定着性が
著しく改良され、炭素繊維による補強効率の高いＣＦＲ
Ｃを得ることができる。シリカ含有炭素繊維は通常、セ
メントマトリックスあたり０．５〜５容量％の使用量で
優れた補強効果を得ることができる。The silica-containing carbon fiber of the present invention thus obtained is a carbon fiber in which fine silica particles are dispersed on the surface and inside. This state can be observed by SEM or the like. Since the size of the silica particles added in this fiber is small, it does not adversely affect the strength of the fiber. Conversely, when the addition rate is within the range of 0.04 to 4.0% by weight, the amount of silica added is The strength of the silica-containing carbon fiber improves as the number increases. It is considered that silica and carbon react with each other to form a part of SiC bond, and as a result, the strength of the silica-containing carbon fiber increases, but the details are not clear. The silica-containing carbon fiber of the present invention is CF
When used for RC reinforcement, the silica component on the carbon fiber surface undergoes a chemical reaction (pozzolanic reaction) with the cement and is crystallized as a hydrate in the cement matrix, thereby fixing between the carbon fiber and the cement matrix. CFR with significantly improved properties and high carbon fiber reinforcement efficiency
C can be obtained. Silica-containing carbon fibers can usually obtain an excellent reinforcing effect when used in an amount of 0.5 to 5% by volume per cement matrix.
【００２２】[0022]
【実施例】以下、実施例により本発明の方法をさらに具
体的に説明する。EXAMPLES The method of the present invention will be described in more detail below with reference to examples.
【００２３】（実施例１〜３、比較例１〜２）ナフタレ
ンスルホン酸ホルマリン縮合物アンモニウム塩（数平均
分子量約３２００）の４０％水溶液中に、該水溶液のナ
フタレンスルホン酸ホルマリン縮合物アンモニウム塩に
対し０．０４，１．０，４．０及び４．５重量％相当量
のシリカを含む平均粒径１６ｎｍのコロイダルシリカ
（日産化学製、スノーテックＯ）の水溶液を添加し、さ
らに全水溶液の０．８重量％相当量のポリビニルアルコ
ールを添加し、十分に混合した。次いで１μｍのフィル
ターでろ過し、ろ液を濃縮して、Ｂ型粘度計で測定した
５０℃における粘度が４００〜５００ポイズの紡糸原液
を得た。(Examples 1 to 3, Comparative Examples 1 and 2) A 40% aqueous solution of a naphthalenesulfonic acid formalin condensate ammonium salt (number average molecular weight of about 3200) was added to the naphthalenesulfonic acid formalin condensate ammonium salt of the aqueous solution. On the other hand, an aqueous solution of colloidal silica (Snowtec O manufactured by Nissan Chemical Co., Ltd.) having an average particle size of 16 nm containing 0.04, 1.0, 4.0 and 4.5% by weight of silica was added, and 0.8 wt% equivalent of polyvinyl alcohol was added and mixed well. Then, the mixture was filtered through a 1 μm filter, and the filtrate was concentrated to obtain a spinning dope having a viscosity of 400 to 500 poise at 50 ° C. measured by a B-type viscometer.
【００２４】この紡糸原液を口径０．２ｍｍのノズルを
用いて乾式紡糸し、得られた前駆体繊維を切断したの
ち、不活性雰囲気下に１０００℃で熱処理して炭化し、
長さ約３ｍｍのシリカ含有炭素繊維を得た。なお、４．
５重量％相当量のコロイダルシリカを添加したものは、
紡糸原液の一部にゲル化した部分が認められ、円滑な紡
糸を行うことができず、シリカ含有炭素繊維を得ること
はできなかった。炭化収率はいずれも約４０％で、ほぼ
一定であった。得られたシリカ含有炭素繊維の性状及び
物性値を表１に示す。This spinning dope was dry-spun using a nozzle having a diameter of 0.2 mm, the obtained precursor fiber was cut, and then heat treated at 1000 ° C. in an inert atmosphere to carbonize,
A silica-containing carbon fiber having a length of about 3 mm was obtained. In addition, 4.
The one with 5% by weight equivalent of colloidal silica added,
A gelled portion was observed in a part of the spinning dope, smooth spinning could not be performed, and silica-containing carbon fiber could not be obtained. The carbonization yields were all about 40%, which was almost constant. Table 1 shows the properties and physical properties of the obtained silica-containing carbon fiber.
【００２５】さらに比較例１としてシリカ分を添加しな
い以外は同様にして製造したシリカ無添加の炭素繊維の
例を、また、比較例２として平均粒径２００ｎｍのシリ
カ微粒子を１．０重量％を添加し、実施例と同様にして
製造したシリカ含有炭素繊維の例も併せて表１に示す。Further, as Comparative Example 1, an example of a carbon fiber containing no silica added was prepared in the same manner as above except that no silica was added, and as Comparative Example 2, 1.0% by weight of silica fine particles having an average particle size of 200 nm was added. An example of the silica-containing carbon fiber added and manufactured in the same manner as in the example is also shown in Table 1.
【００２６】[0026]
【表１】 （実施例４）実施例１で使用したコロイダルシリカの代
わりに２．０重量％相当量の平均粒径１５０ｎｍの微粒
子状シリカを使用した他は実施例１と同様に操作し、シ
リカ含有炭素繊維を製造した。紡糸性は若干低下した
が、炭化収率約４０％で、表２に示すシリカ含有炭素繊
維を得ることができた。[Table 1] (Example 4) The silica-containing carbon fiber was operated in the same manner as in Example 1 except that 2.0% by weight of an equivalent amount of particulate silica having an average particle diameter of 150 nm was used in place of the colloidal silica used in Example 1. Was manufactured. Although the spinnability was slightly lowered, the carbon fiber containing silica shown in Table 2 could be obtained with a carbonization yield of about 40%.
【００２７】[0027]
【表２】 表１及び表２の結果から、本発明のシリカ含有炭素繊維
は、シリカ分を含有しているにもかかわらず、シリカ無
添加の炭素繊維に比較して高い引っ張り強度と弾性率を
有する繊維であることが分かる。また、添加するシリカ
微粒子の粒径が大きくなると、得られるシリカ含有炭素
繊維の引っ張り強度及び弾性率が低下する傾向にあるこ
とが分かる。なお、これらの繊維は表面及び内部にシリ
カ微粒子が均一に分散した炭素繊維であることがＳＥＭ
観察により確認された。[Table 2] From the results of Table 1 and Table 2, the silica-containing carbon fiber of the present invention is a fiber having high tensile strength and elastic modulus as compared with the carbon fiber containing no silica although the silica fiber is contained. I know there is. Further, it is understood that when the particle size of the silica fine particles to be added becomes large, the tensile strength and elastic modulus of the obtained silica-containing carbon fiber tend to decrease. It should be noted that these fibers are carbon fibers in which silica fine particles are uniformly dispersed on the surface and inside the SEM.
Confirmed by observation.
【００２８】（実施例５）上記実施例及び比較例で得ら
れた炭素繊維を用い、早強セメント（Ｃ）及び細骨材と
しての微粒硅砂（Ｓ）を使用してＣＦＲＣの製造試験を
行った。製造条件は、Ｗ／Ｃ＝０．８１、Ｓ／Ｃ＝０．
８４、炭素繊維の添加量は２．０重量％とし、ほかに適
量の増粘剤、消泡剤を添加して混練後、４×４×１６ｃ
ｍの型枠に流し込み、５時間蒸気養生したのち、オート
クレーブ中で１８０℃で４時間処理して硬化させた。(Example 5) Using the carbon fibers obtained in the above Examples and Comparative Examples, a CFRC production test was conducted using early-strength cement (C) and fine silica sand (S) as fine aggregate. It was Manufacturing conditions are W / C = 0.81, S / C = 0.
84, the amount of carbon fiber added is 2.0% by weight, and an appropriate amount of thickener and defoaming agent are added and kneaded, and then 4 × 4 × 16c
It was poured into a m-shaped mold and steam-cured for 5 hours, and then cured at 180 ° C. for 4 hours in an autoclave.
【００２９】このようにして得られた試験片の曲げ強度
を、ＪＩＳ Ｒ５２０１のコンクリートの曲げ強度試験
方法に準じて、３点曲げ試験により測定した。結果を表
１に示す。尚、炭素繊維無添加を参考例として示した。The bending strength of the thus-obtained test piece was measured by a three-point bending test according to JIS R5201 Concrete bending strength test method. The results are shown in Table 1. Incidentally, no carbon fiber was added as a reference example.
【００３０】表１に示したＣＦＲＣの曲げ強度試験の結
果から、本発明の方法によって製造したシリカ含有炭素
繊維は、従来のシリカ無添加の炭素繊維に比較してセメ
ントマトリックスの強化効率が高く、ＣＦＲＣの強化用
繊維として、極めて優れた特性を有していることが分か
る。From the results of the CFRC flexural strength test shown in Table 1, the silica-containing carbon fiber produced by the method of the present invention has a higher cement matrix strengthening efficiency than the conventional silica-free carbon fiber, It can be seen that it has extremely excellent properties as a CFRC reinforcing fiber.
【００３１】なお、試験片の破断面の顕微鏡観察によ
り、繊維とセメントマトリックスとの間に層状の水和物
が観察された。By the microscopic observation of the fracture surface of the test piece, a layered hydrate was observed between the fiber and the cement matrix.
【００３２】[0032]
【発明の効果】本発明のシリカ含有炭素繊維は、セメン
トマトリックスへの分散性に優れ、しかもセメントマト
リックスへの定着性が極めて良好であり、更に炭素繊維
自体の強度も向上している特徴を有する。このシリカ含
有炭素繊維を使用することにより、容易に、繊維による
補強効率の高いＣＦＲＣを製造することができる。EFFECTS OF THE INVENTION The silica-containing carbon fiber of the present invention is characterized in that it has excellent dispersibility in a cement matrix, has extremely good fixability in the cement matrix, and has improved strength of the carbon fiber itself. . By using this silica-containing carbon fiber, it is possible to easily manufacture CFRC having a high fiber-reinforced efficiency.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 金丸 茂 福岡県北九州市若松区響町１丁目３番地 三井鉱山株式会社九州研究所内 (72)発明者 花下 和彦 福岡県北九州市若松区響町１丁目３番地 三井鉱山株式会社九州研究所内 (72)発明者 末永 龍夫 東京都調布市飛田給２丁目19番１号 鹿島 建設株式会社技術研究所内 (72)発明者 谷口 可一 東京都調布市飛田給２丁目19番１号 鹿島 建設株式会社技術研究所内 (72)発明者 遠山 幸三 東京都調布市飛田給２丁目19番１号 鹿島 建設株式会社技術研究所内 (72)発明者 武井 吉一 東京都調布市飛田給２丁目19番１号 鹿島 建設株式会社技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Shigeru Kanamaru 1-3 Kyocho-cho, Wakamatsu-ku, Kitakyushu, Fukuoka Prefecture Mitsui Mining Co., Ltd. Kyushu Research Center (72) Inventor, Kazuhiko Hanashita 1 Hibiki-cho, Wakamatsu-ku, Kitakyushu, Fukuoka 3-chome Mitsui Mining Co., Ltd. Kyushu Research Institute (72) Inventor Tatsuo Suenaga 2-191-1 Tobita-cho, Chofu-shi, Tokyo Kashima Construction Co., Ltd. Technical Research Institute (72) Inventor Keiichi Taniguchi 2-chome, Tobita-cho, Chofu-shi, Tokyo 19-1 Kashima Construction Co., Ltd. Technical Research Institute (72) Inventor Kozo Toyama 2-1-1, Tobita-cho, Chofu-shi, Tokyo Kashima Construction Co. Ltd. Technical Research Laboratory (72) Inventor Yoshikazu Takei 2 Tobita-cho, Chofu-shi, Tokyo No. 19-1 Kashima Construction Co., Ltd. Technical Research Center
Claims (4)
子が均一に分散していることを特徴とするシリカ含有炭
素繊維。1. A silica-containing carbon fiber, characterized in that fine silica particles are uniformly dispersed on the surface and inside of the carbon fiber.
チレン型結合を介して結合した高分子化合物の水溶液
に、該水溶液中の高分子化合物の０．０４〜４．０重量
％相当量のシリカ微粒子が分散してなる紡糸原液を紡糸
し、得られる前駆体繊維を熱処理して炭化させることを
特徴とするシリカ含有炭素繊維の製造方法。2. An aqueous solution of a polymer compound in which aromatic sulfonic acids or salts thereof are bound via a methylene type bond, and silica in an amount of 0.04 to 4.0% by weight of the polymer compound in the aqueous solution. A method for producing a silica-containing carbon fiber, which comprises spinning a spinning dope containing fine particles dispersed therein, and heat-treating the resulting precursor fiber for carbonization.
１５０ｎｍのコロイダルシリカである請求項２に記載の
シリカ含有炭素繊維の製造方法。3. The silica fine particles used have a particle size of 10 to 10.
The method for producing a silica-containing carbon fiber according to claim 2, which is 150 nm colloidal silica.
子が均一に分散しているシリカ含有炭素繊維を補強材と
して使用した繊維補強セメント系材料。4. A fiber-reinforced cementitious material using silica-containing carbon fibers, wherein silica fine particles are uniformly dispersed on the surface and inside of carbon fibers, as a reinforcing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4233780A JP2837586B2 (en) | 1992-09-01 | 1992-09-01 | Silica-containing carbon fiber, method for producing the same, and fiber-reinforced cementitious material using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4233780A JP2837586B2 (en) | 1992-09-01 | 1992-09-01 | Silica-containing carbon fiber, method for producing the same, and fiber-reinforced cementitious material using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0681219A true JPH0681219A (en) | 1994-03-22 |
| JP2837586B2 JP2837586B2 (en) | 1998-12-16 |
Family
ID=16960455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4233780A Expired - Lifetime JP2837586B2 (en) | 1992-09-01 | 1992-09-01 | Silica-containing carbon fiber, method for producing the same, and fiber-reinforced cementitious material using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2837586B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679149A (en) * | 1993-10-13 | 1997-10-21 | Mitsubishi Chemical Corporation | Short carbon fiber chopped strands and short carbon fiber reinforced hydraulic composite materials |
| JP2004036073A (en) * | 2002-07-10 | 2004-02-05 | Advanced Composite Materials Corp | Silicon carbide fiber practically containing no whisker and method for producing the same |
| JP2009514700A (en) * | 2005-11-04 | 2009-04-09 | ビービーエイ ブラックブル アクティーゼルスカブ | Reinforcement material for concrete element and method and system for producing reinforced concrete element |
| CN102965767A (en) * | 2012-11-23 | 2013-03-13 | 中国科学院化学研究所 | Hybrid carbon nanofiber and preparation method thereof |
| US9688583B2 (en) | 2006-03-30 | 2017-06-27 | Advanced Composite Materials, Llc | Composite materials and devices comprising single crystal silicon carbide heated by electromagnetic radiation |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712183B (en) * | 2009-10-20 | 2011-08-03 | 武汉理工大学 | Method for manufacturing chopped carbon fiber reinforced concrete |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0248445A (en) * | 1988-08-10 | 1990-02-19 | Asahi Chem Ind Co Ltd | Carbon fiber for reinforcing cement |
-
1992
- 1992-09-01 JP JP4233780A patent/JP2837586B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0248445A (en) * | 1988-08-10 | 1990-02-19 | Asahi Chem Ind Co Ltd | Carbon fiber for reinforcing cement |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679149A (en) * | 1993-10-13 | 1997-10-21 | Mitsubishi Chemical Corporation | Short carbon fiber chopped strands and short carbon fiber reinforced hydraulic composite materials |
| JP2004036073A (en) * | 2002-07-10 | 2004-02-05 | Advanced Composite Materials Corp | Silicon carbide fiber practically containing no whisker and method for producing the same |
| JP4612287B2 (en) * | 2002-07-10 | 2011-01-12 | アドヴァンスド・コンポジット・マテリアルズ・コーポレーション | Silicon carbide fiber substantially free of whiskers and method for producing the same |
| JP2009514700A (en) * | 2005-11-04 | 2009-04-09 | ビービーエイ ブラックブル アクティーゼルスカブ | Reinforcement material for concrete element and method and system for producing reinforced concrete element |
| US9688583B2 (en) | 2006-03-30 | 2017-06-27 | Advanced Composite Materials, Llc | Composite materials and devices comprising single crystal silicon carbide heated by electromagnetic radiation |
| CN102965767A (en) * | 2012-11-23 | 2013-03-13 | 中国科学院化学研究所 | Hybrid carbon nanofiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2837586B2 (en) | 1998-12-16 |
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