JPS63144153A - Carbon fiber reinforced cement composite material and manufacture - Google Patents
Carbon fiber reinforced cement composite material and manufactureInfo
- Publication number
- JPS63144153A JPS63144153A JP61289040A JP28904086A JPS63144153A JP S63144153 A JPS63144153 A JP S63144153A JP 61289040 A JP61289040 A JP 61289040A JP 28904086 A JP28904086 A JP 28904086A JP S63144153 A JPS63144153 A JP S63144153A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- composite material
- reinforced cement
- fiber reinforced
- cement composite
- 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.)
- Pending
Links
- 239000004568 cement Substances 0.000 title claims description 105
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 102
- 239000004917 carbon fiber Substances 0.000 title claims description 102
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 78
- 239000002131 composite material Substances 0.000 title claims description 67
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000000835 fiber Substances 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims 1
- 238000009832 plasma treatment Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000005452 bending Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011150 reinforced concrete Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 1
- 239000003677 Sheet moulding compound Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical group [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011271 tar pitch Substances 0.000 description 1
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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/386—Carbon
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は炭素繊維強化セメント／コンクリート複合材料
、特に曲げ強度および層間剪断強度の優れた上記腹合材
料並びにその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a carbon fiber reinforced cement/concrete composite material, particularly to the above composite material having excellent bending strength and interlaminar shear strength, and a method for producing the same.
（従来の技術）
これまでセメント系材料の欠点を補強するために、アス
ベスト、ガラス繊維、鋼繊維及び炭素繊維等が試験的に
用いられたり、あるいは実際に使用されたりしてきた。(Prior Art) Asbestos, glass fiber, steel fiber, carbon fiber, etc. have been used experimentally or actually in order to reinforce the defects of cement-based materials.
その中でも、アスベストは古くから使用されてきたが、
発ガン性物質を含む点から現在では使用が規制され、や
がては禁止されようとしている。また、ガラス繊維は、
耐アルカリ性のものでも、使用してから１〜２年の材令
で強度は半減するために広く使用されるに至っていない
。鋼繊維は、密度が高いことや、使用した際に、腐蝕が
生じこれによってセメント材料にひび割れが発生するた
めに、防錆処理が必要となり、コスト高になる等の問題
がある。Among them, asbestos has been used since ancient times,
Due to the fact that it contains carcinogenic substances, its use is currently regulated and may eventually be banned. In addition, glass fiber
Even alkali-resistant materials are not widely used because their strength is halved within one to two years of use. Steel fibers have problems such as their high density, and when they are used, they corrode and cause cracks in the cement material, requiring antirust treatment and increasing costs.
それに対し、炭素繊維は、軽量で高い引っ張り強度をも
ち、耐蝕性に優れていることから、フリーアクセスフロ
ア−の床材料や、ビルディングの外装材に最近使用され
るようになった。これら従来の炭素繊維強化セメント複
合材料の製造方法を第２図に示す。同図において、複合
材料は、長さ２ｍｍ〜ｌ Ｑｍｍ程度の炭素短繊維を、
オムニミキサーでモルタル中に分散、混合し、型枠中に
流しこんだのちオートクレーブ中で養生することによっ
て製造される。この方法で、汎用炭素繊維（弾性率４、
ｌ ｘ １０３ｋｇ／ｍｆｌ＋２）を使用して作られ
た炭素繊維強化セメント複合材料は、２ｖｏ １％〜５
ｖｏ １％の炭素繊維混入率で、７０ｋｇ／ｃｍ２〜
２１０ｋｇ／ｃｍ２程度の曲げ強度を示し、また、高性
能炭素繊維（弾性率３８ｘｌＱ３ｋｇ／ｍｍりを用いて
同様の方法で製造した炭素繊維強化セメント複合材料の
曲げ強度は、ｌｖｏβ％〜５ｖＯ１％の炭素繊維混入率
で、２００ｋｇ／Ｃｍ” 〜７００ｋｇ／ｃｍ”程度で
ある。しかしながら、これら炭素繊維強化セメント複合
材料中のセメント水和物と炭素繊維との接着性は良好で
なく、炭素繊維の特性を十分に発揮していないのが現状
である。Carbon fiber, on the other hand, is lightweight, has high tensile strength, and has excellent corrosion resistance, so it has recently come to be used as flooring materials for raised floors and as exterior materials for buildings. A method of manufacturing these conventional carbon fiber reinforced cement composite materials is shown in FIG. In the figure, the composite material consists of short carbon fibers with a length of about 2 mm to 1 Q mm.
It is manufactured by dispersing and mixing it in mortar using an omnimixer, pouring it into a mold, and curing it in an autoclave. With this method, general-purpose carbon fiber (modulus of elasticity 4,
Carbon fiber reinforced cement composite material made using 2vo 1%~5
vo 70kg/cm2~ at 1% carbon fiber mixing rate
It shows a bending strength of about 210 kg/cm2, and the bending strength of a carbon fiber-reinforced cement composite material manufactured in a similar manner using high-performance carbon fiber (modulus of elasticity 38xlQ3kg/mm) is as follows: The fiber mixing rate is about 200 kg/cm" to 700 kg/cm".However, the adhesion between cement hydrate and carbon fiber in these carbon fiber reinforced cement composite materials is not good, and the characteristics of carbon fiber are The current situation is that it is not fully utilized.
この点を改善するための一つの試みとして、炭素繊維の
表面を硝酸で酸化し、カルボキシル基などの含酸素基を
導入することによって、炭素繊維の表面を改質し、炭素
繊維強化セメント１合材料の強度を増強しようとするこ
とが行われた。しかしながら硝酸による酸化は、繊維表
面だけにとどまらず繊維内部にまで及ぶために、炭素繊
維自体の強度が低下し、炭素繊維強化セメント複合材料
の強度増強には効果的ではなかった。As an attempt to improve this point, the surface of carbon fibers was oxidized with nitric acid to introduce oxygen-containing groups such as carboxyl groups, thereby modifying the surface of carbon fibers. Attempts were made to increase the strength of the material. However, oxidation by nitric acid does not only affect the fiber surface but also extends to the inside of the fiber, resulting in a decrease in the strength of the carbon fiber itself, and has not been effective in increasing the strength of carbon fiber reinforced cement composite materials.
一方低温プラズマによる各種材料の表面処理技術が最近
発達してきた。この低温プラズマによる表面処理は、エ
レクトロニクス産業を中心にして発達したもので、極め
て精密かつ微細な処理を、室温付近の低い温度で、クリ
ーンに行うことが可能であると共に、短時間で大量に処
理することのできる技術である。ところがこれまでにプ
ラズマによる表面処理が、炭素繊維強化セメント複合材
料の製造に利用されたことはない。On the other hand, surface treatment techniques for various materials using low-temperature plasma have recently been developed. This surface treatment using low-temperature plasma was developed mainly in the electronics industry, and it is possible to perform extremely precise and fine processing cleanly at a low temperature near room temperature, and can also process large quantities in a short time. It is a technology that can be used to However, surface treatment using plasma has never been used to manufacture carbon fiber-reinforced cement composite materials.
（発明が解決しようとする問題点）
本発明者は上記の低温プラズマ処理によって炭素繊維表
面を改質し、炭素繊維のセメント水和物に対する濡れ性
を高め、上述の問題点を解決することに成功したもので
ある。(Problems to be Solved by the Invention) The present inventor has solved the above-mentioned problems by modifying the carbon fiber surface by the above-mentioned low-temperature plasma treatment and increasing the wettability of the carbon fibers to cement hydrate. It was a success.
すなわち、本発明の目的は、著しく増大した曲げ強度、
たわみ性および層間剪断強度を有する炭素繊維強化セメ
ント複合材料を提供するにある。That is, the object of the present invention is to provide significantly increased bending strength;
An object of the present invention is to provide a carbon fiber reinforced cement composite material having flexibility and interlaminar shear strength.
本発明の別の目的は耐熱性並びに上記強度特性において
極めて浸れた炭素繊維強化セメン）１合材料を提供する
にある。Another object of the present invention is to provide a carbon fiber-reinforced cementitious material which has excellent heat resistance as well as the above-mentioned strength properties.
更に別の目的は、強固な堅牢度を恒久的に維持し且つ軽
量なセメントコンクリート構造物を比較的安価に提供す
ることにある。Still another object is to provide a lightweight cement concrete structure at a relatively low cost while permanently maintaining strong solidity.
（問題点を解決するための手段）
上述の目的は、酸素、アルゴン、二酸化炭素、アンモニ
アおよび窒素よりなる群から選ばれた少なくとも１種の
気体の低温プラズマで表面処理された炭素繊維を強化材
として含有してなることを構成する炭素繊維強化セメン
ト複合材料によって達成され、またか＼る複合材料の製
造法は、炭素繊維を酸素、アルゴン、二酸化炭素、アン
モニアおよび窒素よりなる群から選ばれた少なくとも１
（重の気体の低温プラズマで表面処理した後、水−セメ
ント比が２０〜１００重量％のセメントペーストと合体
して上記炭素繊維を上記セメントペースト中に実質的に
均一に配置した成形体となし、該成形体を硬化せしめる
ことを構成する。(Means for Solving the Problems) The above object is to create a reinforcing material using carbon fibers whose surface has been treated with low-temperature plasma of at least one gas selected from the group consisting of oxygen, argon, carbon dioxide, ammonia and nitrogen. This is achieved by a carbon fiber-reinforced cement composite material comprising carbon fibers containing carbon fibers selected from the group consisting of oxygen, argon, carbon dioxide, ammonia and nitrogen. at least 1
(After surface treatment with heavy gas low-temperature plasma, it is combined with cement paste having a water-cement ratio of 20 to 100% by weight to form a molded body in which the carbon fibers are substantially uniformly arranged in the cement paste.) , and curing the molded body.
以下、本発明の構成をその作用とともに、添付図面を参
照し二詳述する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of the present invention, together with its functions, will be described in detail below with reference to the accompanying drawings.
本発明による炭素繊維強化セメント複合材料の製造工程
フローシートを第１図に示す。A manufacturing process flow sheet for a carbon fiber-reinforced cement composite material according to the present invention is shown in FIG.
原料の炭素繊維は、ポリアクリルニトリル（ＰＡＮ）繊
維等から出発した所謂、高性能炭素繊維および、タール
・ピッチを出発原料とする所謂、汎用炭素繊維の何れで
もよいが、経済性のみを考慮すれば後者が好ましい。The carbon fiber used as a raw material may be either a so-called high-performance carbon fiber made from polyacrylonitrile (PAN) fiber or the like, or a so-called general-purpose carbon fiber made from tar pitch, but only economical efficiency should be considered. The latter is preferred.
かＮる炭素繊維は、繊維径５〜２０μｍ程度の連続繊維
またはその織布、網状物、あるいは６０ｍｍ以下のチョ
ツプドストランド等の短繊維をそのまま、あるいはラン
ダムに配置した厚さＱ、 ｌ＋ｔ＋ｍ〜ｌｌＴ１ｍ１望
ましくは約０．３ｍｍのシート、または、厚さ１ ｍｌ
’ｎ〜ｌＱｍｍ、望ましくは約５ｍｍのフェルトないし
はチョツプドストランドマットとして使用する。The carbon fibers are continuous fibers with a fiber diameter of about 5 to 20 μm, woven fabrics thereof, net-like materials, or short fibers such as chopped strands of 60 mm or less, either as they are or randomly arranged, with a thickness Q, l + t + m ~. llT1m1 preferably about 0.3mm sheet or 1ml thick
It is used as a felt or chopped strand mat having a thickness of 'n to lQmm, preferably about 5mm.
炭素繊維の表面改質は、繊維表面に親水性を付与させる
ことから、酸素プラズマ、アルゴンプラズマ、二酸化炭
素プラズマ、アンモニアプラズマまたは窒素プラズマを
単独または併用した低温プラズマ処理を常法に従って施
す。適用するガスとしては酸素、アルゴン、二酸化炭素
が枠に好ましい。Since the surface modification of carbon fibers imparts hydrophilicity to the fiber surface, low-temperature plasma treatment using oxygen plasma, argon plasma, carbon dioxide plasma, ammonia plasma, or nitrogen plasma alone or in combination is performed according to a conventional method. As the gas to be applied, oxygen, argon, and carbon dioxide are preferable for the frame.
低温プラズマで処理した炭素繊維表面は、肉眼的にも、
走査型電子顕微鏡的にも変化はみられないが、極めて親
水性に改質される。特に、酸素プラズマの場合には、炭
素繊維表面に含酸素基が導入される。これらのプラズマ
処理した炭素繊維シートまたはフェルトは、セメントと
水とからなるセメントペースト中に含浸させる場合、プ
ラズマ処理なしの炭素繊維に比べてその含浸速度が著し
く早められる。Visually, the carbon fiber surface treated with low-temperature plasma shows
Although no change is observed under a scanning electron microscope, it is modified to be extremely hydrophilic. In particular, in the case of oxygen plasma, oxygen-containing groups are introduced onto the carbon fiber surface. When these plasma-treated carbon fiber sheets or felts are impregnated into a cement paste consisting of cement and water, the impregnation rate is significantly accelerated compared to carbon fibers without plasma treatment.
本発明腹合材料の他方の原料であるセメントとしては、
ケイ酸カルシウムを主成分とする通常のポルトランドセ
メント、またはアルミナセメント、スラグセメントを始
め、プラスター類まで何れも適用可能であるが、就中、
耐熱性良好なアルミナセメントは耐熱性複合材料を与え
るという点で特に好ましい。これらセメントの水性ペー
ストを織布、シート、フェルト等の炭素繊維構造物中に
充分に含浸させるには、セメント粒子は極力細かいこと
が良く、特にアルミナセメントは、比表面債にして３．
０００〜９．０００ｃｍ”／ｇ、望ましくは７，５００
〜８、５００ｃｍ２／ｇの微細粉状のものを使用するの
が効果的である。The cement, which is the other raw material for the material of the present invention, is as follows:
Any of the following can be applied, including ordinary Portland cement whose main component is calcium silicate, alumina cement, slag cement, and even plasters.
Alumina cement, which has good heat resistance, is particularly preferred in that it provides a heat-resistant composite material. In order to sufficiently impregnate these aqueous cement pastes into carbon fiber structures such as woven fabrics, sheets, and felt, cement particles should be as fine as possible, and alumina cement in particular has a specific surface of 3.
000 to 9.000 cm”/g, preferably 7,500
It is effective to use a fine powder of ~8,500 cm2/g.
炭素繊維強化セメン）１合材料の強度は、セメントペー
ストの水−セメント比すなわちセメント重量に対する水
の重量百分率によって影響される。The strength of carbon fiber reinforced cement composite materials is influenced by the water-cement ratio of the cement paste, ie the weight percentage of water to cement weight.
水−セメント比が大きすぎると、セメントペーストの流
動性は高くなり、炭素繊維シートまたはフェルトへの含
浸は容易になるが、製造された炭素繊維強化セメント複
合材料の強度は低い。それに対し、水−セメント比が低
すぎると、凝結速度は速いが流動性が小さいために、炭
素繊維シートや炭素繊維フェルトの空隙内に、セメント
ペーストは含浸されないので、強度の高い複合材料は製
造できない。従って、セメントペーストの望丈しい水−
セメント比は、製造時の作業性と炭素繊維強化セメント
複合材料の強度の点から２５〜４０％である。If the water-cement ratio is too large, the fluidity of the cement paste will be high and the impregnation into carbon fiber sheets or felts will be easy, but the strength of the produced carbon fiber reinforced cement composite will be low. On the other hand, if the water-cement ratio is too low, the setting speed is fast but the fluidity is low, and the cement paste is not impregnated into the voids of the carbon fiber sheet or carbon fiber felt, resulting in the production of a strong composite material. Can not. Therefore, the desirability of cement paste water-
The cement ratio is 25 to 40% from the viewpoint of workability during manufacturing and the strength of the carbon fiber reinforced cement composite material.
また、セメントペースト中に砂、ケイ砂等のｉ′■骨材
を使用すること、減水剤やその他の混和剤を添加するこ
ともできる。It is also possible to use i' aggregate such as sand or silica sand in the cement paste, and to add water reducers and other admixtures.
上記炭素繊維またはそのシート状繊維構造物は、セメン
トペーストと合体されセメントペースト中に実質的に均
一に配置される。既述の通り、炭素繊維はプラズマ処理
によってその表面のセメント水性ペーストに対する濡れ
性すなわち親和性が増大しているため、合体は頗る迅速
容易に行なわれる。か５る合体は、セメントペースト中
に、その型込め、注入等の成形に先立って炭素短繊維を
均一に混入分数せしめたプレミックスとなすこと、セメ
ントペーストを吹き付ける際、噴出嘴近傍で短繊維を混
入すること、炭素繊維織布、シート、マット等の繊維構
造物に予めセメントペーストを含浸させプリプレグによ
りシートモールディングコンパウンドとなすこと、ハン
ドレイアップ法によること、ストランド状プリプレグに
よりフィラメントワインディングと すこと等、通常繊
維強化樹脂の製造に慣用されている方法に準じて行なう
ことができる。The carbon fibers or sheet-like fibrous structures thereof are combined with the cement paste and are substantially uniformly disposed within the cement paste. As mentioned above, the plasma treatment of the carbon fibers increases the wettability or affinity of the surfaces of the carbon fibers to the aqueous cement paste, so coalescence is extremely quick and easy. In order to achieve this, it is necessary to uniformly mix short carbon fibers into the cement paste prior to molding, injection, etc., to form a premix, and when spraying the cement paste, the short fibers should be mixed near the spouting beak. By pre-impregnating fiber structures such as carbon fiber fabrics, sheets, mats, etc. with cement paste and using prepreg to create a sheet molding compound, by hand lay-up method, and by using strand-like prepreg to create a filament winding compound. etc., can be carried out according to methods commonly used in the production of fiber-reinforced resins.
この際、プラズマ処理したチョツプドストランド状の炭
素繊維のセメントペースト中への均一分散は、従来法の
ようにオムニミキサーを使用する必要はなく、通常のモ
ルタルミキサーで十分可能である。At this time, uniform dispersion of plasma-treated chopped strand-like carbon fibers into the cement paste does not require the use of an omni-mixer as in the conventional method, and can be sufficiently achieved with an ordinary mortar mixer.
炭素繊維強化セメント複合材料中の炭素繊維混入率は、
炭素繊維シートまたはフェルトの積層枚数によって、あ
るいはセメントペースト中に分散させる炭素繊維量によ
って調節できる。これによって、製造される複合材料の
強度やたわみ等の諸特性も制御される。The carbon fiber content in carbon fiber reinforced cement composite material is
It can be adjusted by the number of laminated carbon fiber sheets or felts or by the amount of carbon fibers dispersed in the cement paste. This also controls various properties such as strength and deflection of the manufactured composite material.
本発明の炭素繊維強化セメント複合材料は、従来法と同
様、オートクレーブ中で養生し得ることは勿論、単なる
水中養生だけで高強度となすことができる。The carbon fiber reinforced cement composite material of the present invention can of course be cured in an autoclave as in the conventional method, and can be made to have high strength simply by curing in water.
具体的には、例えばアルゴンプラズマで処理した炭素繊
維シートを用い、極微粉のアルミナセメント（比表面積
８０００ｃｍ２／ｇ）から作られた、炭素繊維強化セメ
ント複合材料（炭素繊維混入率３．３ｖｏＲ９６） は
、５３０ｇ／ｃｒｎ”の曲げ強度を示すことが確認され
た。この強度は、プラズマ処理なしの炭素繊維シートか
ら同じ条件で作られた複合材料よりも約１，３倍高い。Specifically, for example, a carbon fiber-reinforced cement composite material (carbon fiber content ratio 3.3voR96) made from ultrafine alumina cement (specific surface area 8000cm2/g) using a carbon fiber sheet treated with argon plasma is , 530 g/crn'', which is about 1.3 times higher than a composite made under the same conditions from carbon fiber sheets without plasma treatment.
また、プラズマ処理した炭素繊維強化セメント複合材料
のたわみは、無処理のものよりも約２．８倍大きい。Also, the deflection of the plasma-treated carbon fiber reinforced cement composite material is about 2.8 times greater than that of the untreated one.
さらに、酸素プラズマで処理した炭素繊維シートを用い
、炭素繊維混入率を４，５ｖｏＡ％と高くした複合材料
は、１０００ｋｇ／ｃｍ２の曲げ強度を示すことも確認
された。この強度は、炭素繊維がランダムに配置された
炭素繊維強化セメント複合材料であるにもかかわらず、
これまでの炭素繊維強化セメント複合材料よりもはかる
かに高いもので、プラズマ処理なしの炭素繊維シートか
ら作られた複合材料（曲げ強度７２Ｑｋｇ／ｃｍ２）よ
りも１．３倍高い。Furthermore, it was confirmed that a composite material using a carbon fiber sheet treated with oxygen plasma and having a carbon fiber content as high as 4.5 voA% exhibited a bending strength of 1000 kg/cm2. This strength is achieved despite the fact that it is a carbon fiber reinforced cement composite material with randomly arranged carbon fibers.
This is much higher than conventional carbon fiber-reinforced cement composite materials, and 1.3 times higher than composite materials made from carbon fiber sheets without plasma treatment (flexural strength of 72Q kg/cm2).
また、従来法では実施できなかった厚さ１ｍｍ程度の炭
素繊維強化セメント複合材料薄板の製造も可能である。Furthermore, it is also possible to manufacture carbon fiber-reinforced cement composite material thin plates with a thickness of about 1 mm, which has not been possible using conventional methods.
そして、型枠を使用することによりパイプ、丸棒、角棒
またはＵ字型等各種形状の炭素繊維強化セメント複合ｔ
オ科も、簡単な方法で製造できる。By using formwork, carbon fiber-reinforced cement composite t-shirts can be made into various shapes such as pipes, round bars, square bars, or U-shapes.
Okinawa can also be produced using a simple method.
本発明によって製造された炭素繊維強化セメント複合材
料は、プラズマを使用しない従来の方法で作られたもの
よりも、はるかに大きな曲げ強度、たわみおよび可撓性
等を有している。その他に、炭素繊維強化セメント複合
材料は、電気的には伝導性を、表面状況は堅牢性と光沢
を示している。Carbon fiber reinforced cement composite materials produced by the present invention have much greater bending strength, deflection, flexibility, etc. than those made by conventional methods that do not use plasma. In addition, carbon fiber-reinforced cement composite materials exhibit electrical conductivity and surface conditions that are robust and glossy.
従って、本発明は、炭素繊維強化セメント複合材料の特
性をより高める製造方法を開発したものである。Therefore, the present invention has developed a manufacturing method that further enhances the properties of carbon fiber reinforced cement composite materials.
更に本発明複合材料は従来の耐アルカリガラス繊維強化
セメントと相違し、その強度、堅牢性は恒久的であり、
また、鋼、鉄補強コンクリートに比し著しく軽量である
という利点もある。Furthermore, the composite material of the present invention differs from conventional alkali-resistant glass fiber reinforced cement in that its strength and robustness are permanent;
It also has the advantage of being significantly lighter than steel or iron-reinforced concrete.
（実施例） 本発明の具体例を、下記の実施例により説明する。(Example) Specific examples of the present invention will be explained by the following examples.
実施例Ｉ
ＰＡＮ系の高性能炭素繊維（直径７．５μｍ、強度３０
０ｋｇ／＋ｎ＋ｎ２、弾性率２３ ｘ １０’ｋｇ／ｍ
ｍ２）を長さ２ Ｑｍｒｎ程度に切断し、それをランダ
ムに配列した、厚さＱ、 ３ｍｍのシート（目イ寸３３
ｇ／ｍ２．５ｃｍＸ］Ｑｃｍ）をプラズマ処理装置内に
設置し、アルゴンを１００ｍβ／ｍ１ｎ流しながら、真
空ポンプで装置内をＱ、 ５ｔｏｒｒの減圧にした。三
役の平行平板型の電極間に周波数１３、５６！、ｌＨｚ
の高周波を出力２５Ｗで印加し、アルゴンプラズマを発
生させ、この状態に１０分間保持した。Example I PAN-based high-performance carbon fiber (diameter 7.5 μm, strength 30
0kg/+n+n2, elastic modulus 23 x 10'kg/m
m2) into lengths of about 2 Qmrn and randomly arranged them into sheets with a thickness of Q and 3 mm (measuring size of 33 mm).
g/m2.5 cm Frequency 13,56 between triple parallel plate type electrodes! , lHz
A high frequency wave with an output of 25 W was applied to generate argon plasma, and this state was maintained for 10 minutes.
プラズマ処理後の炭素繊維シートは親水性を示した。The carbon fiber sheet after plasma treatment showed hydrophilicity.
また、同じ処理条件で、酸素プラズマまたは二酸化炭素
プラズマで炭素繊維シートを処理した場合も、親水性を
示した。Furthermore, when the carbon fiber sheet was treated with oxygen plasma or carbon dioxide plasma under the same treatment conditions, it also showed hydrophilicity.
実施例２
上記実施例１によりアルゴンプラズマで処理した炭素繊
維シート１２枚を、アルミナセメント （比表面積８０
００ｃｍ２／ｇ） ３００ ｇに水１００ｇを加えて調
製したセメントペースト中に漬けて十分に含浸させ、型
枠（長さ１００ｍｍ 、幅５０ｍｍ、厚さ５ ｍｍ）の
中に積層した。炭素繊維とセメント水和物との複合物は
、−日後に脱型し、水中でオ令７日まで養生した。Example 2 Twelve carbon fiber sheets treated with argon plasma according to Example 1 above were coated with alumina cement (specific surface area: 80
00 cm2/g) and 100 g of water to make it sufficiently impregnated, and then stacked in a mold (length 100 mm, width 50 mm, thickness 5 mm). The composite of carbon fiber and cement hydrate was demolded after - days and cured in water until 7 days old.
作られた炭素繊維強化セメント複合材料の嵩密度は、１
．９ｇ／ｃｍ３、炭Ｓ繊維含有率は３，３ｖｏｊ％であ
った。この複合材料の曲げ強度測定時の荷重（強度）−
たわみ曲線を第３図の１に示す。この複合材料の曲げ強
度は５３０ｋｇ／ｃｍ２を示し、プラズマ処理なしく第
３図の３）に比べ１．３倍、アルミナセメント水和物（
第３図の４）より８倍も高くなった。そして、プラズマ
処理した炭素繊維強化セメント複合材料の最大荷重点の
たわみは１．７ｍｍ、層間剪断強度は４７ｋｇ／ｃｍ２
でプラズマ処理なしの場合に比べ前者では２．８倍、後
者では１．４倍も大きくなった。The bulk density of the carbon fiber reinforced cement composite material made is 1
．． 9 g/cm3, and the charcoal S fiber content was 3.3 voj%. Load (strength) when measuring the bending strength of this composite material -
The deflection curve is shown at 1 in Figure 3. The bending strength of this composite material was 530 kg/cm2, which is 1.3 times that of alumina cement hydrate (3) in Figure 3 without plasma treatment.
This is eight times higher than 4) in Figure 3. The deflection at the maximum load point of the plasma-treated carbon fiber reinforced cement composite material was 1.7 mm, and the interlaminar shear strength was 47 kg/cm2.
Compared to the case without plasma treatment, the former was 2.8 times larger, and the latter 1.4 times larger.
実施例３
実施例１と同じ炭素繊維シートをプラズマ処理装置内に
入れ、酸素を１００ｍ ｆｆ／ｍｉｎ流しながらプラズ
マ処理を行った。その他の処理条件は、実施例１と同じ
である。プラズマ処理後の炭素繊維シートは親水性を、
浸漬した水溶液は酸性をそれぞれ示した。Example 3 The same carbon fiber sheet as in Example 1 was placed in a plasma treatment apparatus, and plasma treatment was performed while oxygen was flowing at 100 mff/min. Other processing conditions are the same as in Example 1. After plasma treatment, the carbon fiber sheet becomes hydrophilic,
The aqueous solutions immersed in each exhibited acidity.
酸素プラズマで処理した炭素繊維シート１２枚を、水セ
メント比３０％のアルミナセメントペースト中に漬け、
実施例２の場合と同じようにして厚さ６ｍｍの炭素繊維
強化セメント複合材料を製造した。Twelve carbon fiber sheets treated with oxygen plasma were soaked in alumina cement paste with a water-cement ratio of 30%.
A carbon fiber reinforced cement composite material having a thickness of 6 mm was produced in the same manner as in Example 2.
製造された複合材料の嵩密度は２． Ｑｇ／ｃｍ３で、
炭素繊維含有率は３．５ｖｏβ％であった。この祠科の
曲げ強度測定時の荷重（強度）−たわみ曲線を第３図の
２に示す。この複合材料の曲げ強度は４８０ｋｇ／Ｃｍ
２を示し、プラズマ処理なしの場合に比べて１．２倍も
高くなった。また、プラズマ処理した炭素繊維強化セメ
ント複合材料の最大荷重点のたわみは１、５ｍｍで、プ
ラズマ処理なしの複合材料の場合＜０．５ｍｍ）よりも
２．５倍哩大きくなった。また、酸素プラズマで処理し
た炭ｆｆ１ｕＪ維強化セメント腹合材料の層間剪断強度
は、５２ｋｇ／ｃｍ２で、処理なしのものに比べ１．２
倍も高くなった。The bulk density of the manufactured composite material is 2. Qg/cm3,
The carbon fiber content was 3.5 voβ%. The load (strength)-deflection curve when measuring the bending strength of this shrine is shown in 2 in Fig. 3. The bending strength of this composite material is 480kg/Cm
2, which was 1.2 times higher than that without plasma treatment. Additionally, the maximum load point deflection of the plasma-treated carbon fiber reinforced cement composite was 1.5 mm, which was 2.5 times greater than that of the non-plasma treated composite (<0.5 mm). In addition, the interlaminar shear strength of the carbon ff1uJ fiber-reinforced cement material treated with oxygen plasma was 52 kg/cm2, which was 1.2 kg/cm2 compared to that without treatment.
It has become twice as expensive.
実施例４
実施例１と同じ炭素繊維シートをプラズマ処理装置内に
入れ、酸素を１００ｍ ｌ ／ｍｉｎ流しながらプラズ
マ処理を行った。酸素プラズマで処理した炭素繊維シー
ト２５改を使用し、水セメント比３０％のアルミナセメ
ントペースト中に；ｎげ、実、肩側２の場合と同じよう
にして型枠（長さ１００ｍｍ 、幅５Ｑｍｍ、厚さ１０
ｍｍ）の中に積層させ、炭素繊維強化セメント複合材料
を製造した。作られた複合材料の嵩密度は２．１ｇ／Ｃ
ｍ３、炭素繊維含有率は４，６ｖｏβ％であった。この
複合材料の曲げ強度は１０００ｋｇ／ｃｍ２を示し、プ
ラズマ処理なしに比べ１．３倍も強度は大きくなった。Example 4 The same carbon fiber sheet as in Example 1 was placed in a plasma treatment apparatus, and plasma treatment was performed while oxygen was flowing at 100 ml/min. Using carbon fiber sheet 25 modified treated with oxygen plasma, formwork (length 100mm, width 5Qmm , thickness 10
mm) to produce a carbon fiber reinforced cement composite material. The bulk density of the composite material made is 2.1g/C
m3, and the carbon fiber content was 4.6 voβ%. The bending strength of this composite material was 1000 kg/cm2, which was 1.3 times higher than that without plasma treatment.
（発明の効果）
本発明による炭素繊維強化セメント複合材料は、炭素繊
維を酸素、アルゴン、または二酸化炭素などの低温プラ
ズマによって、炭素繊維の表面のみを改質し、炭素繊維
とセメント水和物との接着強度を高めたから、従来の炭
素繊維強化セメン）１合材料よりも、高強度、高たわみ
性および、すぐれた可撓性等の機截的特性に優れ、軽量
であると共に、その表面は、緻密で光沢のある堅牢性と
耐水性等をもつので、化粧タイル、キッチン用品の天板
、水［曹、屋根材、床材、ビルディング外装材、高温用
の濾過は、各種セメント二次製品およびモルタルを４書
の補強材料等へ使用できる。また、酎熱性の炭素繊維強
化セメン）１合材料はその電導性を利用し、寒冷地の融
雪用や、家畜舎の暖房用あるいは家庭用の面状発熱体、
ビルディング外壁の電波遮蔽材料等へも利用できる。更
に比較的安価な汎用炭素繊維を短繊維状で適用したもの
は経済的にも可成り有利であり、広汎な利用と普及とが
期待される。(Effect of the invention) The carbon fiber-reinforced cement composite material according to the present invention modifies only the surface of carbon fibers with low-temperature plasma such as oxygen, argon, or carbon dioxide, and combines carbon fibers with cement hydrate. Because of its increased adhesive strength, it has superior mechanical properties such as high strength, high flexibility, and excellent flexibility compared to conventional carbon fiber-reinforced cement composite materials.It is lightweight, and its surface is Because of its dense, glossy, solidity, and water resistance, it can be used in various secondary cement products such as decorative tiles, kitchen utensil top plates, water [soak], roofing materials, flooring materials, building exterior materials, and high-temperature filtration. and mortar can be used as reinforcing material etc. In addition, carbon fiber-reinforced cement (Cement) 1 composite material, which is heat-resistant, can be used as a sheet heating element for snow melting in cold regions, for heating livestock barns, or for home use, by utilizing its conductivity.
It can also be used as radio wave shielding material for building exterior walls. Furthermore, the use of comparatively inexpensive general-purpose carbon fiber in the form of short fibers is economically advantageous and is expected to be widely used and popularized.
第１図は、本発明による炭素繊維強化セメント複合材料
の製造工程フローシート、
第２図は、従来公知の炭素繊維強化セメント複合材料の
製造工程フローシートであり、また第３図は、本発明お
よび従来公知の炭素繊維強化セメント複合材料並びに非
強化セメントコンクリートのそれぞれ荷重−たわみ曲線
を示す線図である。
第１図FIG. 1 is a manufacturing process flow sheet for a carbon fiber reinforced cement composite material according to the present invention, FIG. 2 is a manufacturing process flow sheet for a conventionally known carbon fiber reinforced cement composite material, and FIG. 3 is a manufacturing process flow sheet for a carbon fiber reinforced cement composite material according to the present invention. FIG. 2 is a diagram showing load-deflection curves of a conventionally known carbon fiber reinforced cement composite material and a non-reinforced cement concrete, respectively. Figure 1
Claims (1)
素よりなる群から選ばれた少なくとも１種の気体の低温
プラズマで表面処理された炭素繊維を強化材として含有
してなることを特徴とする炭素繊維強化セメント複合材
料。 ２、セメントがアルミナセメントである特許請求の範囲
第１項記載の炭素繊維強化セメント複合材料。 ３、炭素繊維が繊維径約５〜２０μｍの短繊維である特
許請求の範囲第１項記載の炭素繊維強化セメント複合材
料 ４、短繊維が厚さ０．１〜１ｍｍのランダムシートを構
成する特許請求の範囲第３項記載の炭素繊維強化セメン
ト複合材料。 ５、短繊維が厚さ１〜１０ｍｍのチョップドストランド
マットを構成する特許請求の範囲第３項記載の炭素繊維
強化セメント複合材料。 ６、炭素繊維を酸素、アルゴン、二酸化炭素、アンモニ
アおよび窒素よりなる群から選ばれた少なくとも１種の
気体の低温プラズマで表面処理した後、水−セメント比
が２０〜１００重量％のセメントペーストと合体して上
記炭素繊維を上記セメントペースト中に実質的に均一に
配置した成形体となし、該成形体を硬化せしめることを
特徴とする炭素繊維強化セメント複合材料の製造法。 ７、水−セメント比が２５〜４０重量％である特許請求
の範囲第６項記載の炭素繊維強化セメント複合材料の製
造法。 ８、セメントペーストがアルミナセメントのペーストで
ある特許請求の範囲第６項記載の炭素繊維強化セメント
複合材料の製造法。 ９、アルミナセメントが３，０００〜９，０００ｃｍ＾
２／ｇの比表面積を有する細粒よりなる特許請求の範囲
第８項記載の炭素繊維強化セメント複合材料の製造法。 １０、前記比表面積が７，５００〜８，５００ｃｍ＾２
／ｇである特許請求の範囲第９項記載の炭素繊維強化セ
メント複合材料の製造法。 １１、炭素繊維が繊維径約５〜２０μｍの短繊維である
特許請求の範囲第６項記載の炭素繊維強化セメント複合
材料の製造法。 １２、短繊維が厚さ０．１〜１ｍｍのランダムシートを
構成する特許請求の範囲第１１項記載の炭素繊維強化セ
メント複合材料の製造法。 １３、短繊維が厚さ１〜１０ｍｍのチョップドストラン
ドマットを構成する特許請求の範囲第１１項記載の炭素
繊維強化セメント複合材料の製造法。[Claims] 1. Contains as a reinforcing material carbon fiber whose surface has been treated with low-temperature plasma of at least one gas selected from the group consisting of oxygen, argon, carbon dioxide, ammonia and nitrogen. Characteristic carbon fiber reinforced cement composite material. 2. The carbon fiber reinforced cement composite material according to claim 1, wherein the cement is alumina cement. 3. The carbon fiber reinforced cement composite material according to claim 1, in which the carbon fibers are short fibers with a fiber diameter of about 5 to 20 μm. 4. The patent in which the short fibers constitute a random sheet with a thickness of 0.1 to 1 mm. The carbon fiber reinforced cement composite material according to claim 3. 5. The carbon fiber reinforced cement composite material according to claim 3, wherein the short fibers constitute a chopped strand mat having a thickness of 1 to 10 mm. 6. After surface-treating the carbon fibers with a low-temperature plasma of at least one gas selected from the group consisting of oxygen, argon, carbon dioxide, ammonia and nitrogen, the carbon fibers are treated with a cement paste having a water-cement ratio of 20 to 100% by weight. A method for producing a carbon fiber-reinforced cement composite material, which comprises combining the carbon fibers to form a molded body in which the carbon fibers are substantially uniformly arranged in the cement paste, and curing the molded body. 7. The method for producing a carbon fiber reinforced cement composite material according to claim 6, wherein the water-cement ratio is 25 to 40% by weight. 8. The method for producing a carbon fiber reinforced cement composite material according to claim 6, wherein the cement paste is an alumina cement paste. 9. Alumina cement is 3,000 to 9,000 cm^
9. The method for producing a carbon fiber reinforced cement composite material according to claim 8, which comprises fine particles having a specific surface area of 2/g. 10. The specific surface area is 7,500 to 8,500 cm^2
The method for producing a carbon fiber reinforced cement composite material according to claim 9, wherein 11. The method for producing a carbon fiber-reinforced cement composite material according to claim 6, wherein the carbon fibers are short fibers with a fiber diameter of about 5 to 20 μm. 12. The method for producing a carbon fiber reinforced cement composite material according to claim 11, wherein the short fibers constitute a random sheet with a thickness of 0.1 to 1 mm. 13. The method for producing a carbon fiber reinforced cement composite material according to claim 11, wherein the short fibers constitute a chopped strand mat having a thickness of 1 to 10 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61289040A JPS63144153A (en) | 1986-12-05 | 1986-12-05 | Carbon fiber reinforced cement composite material and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61289040A JPS63144153A (en) | 1986-12-05 | 1986-12-05 | Carbon fiber reinforced cement composite material and manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63144153A true JPS63144153A (en) | 1988-06-16 |
Family
ID=17738047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61289040A Pending JPS63144153A (en) | 1986-12-05 | 1986-12-05 | Carbon fiber reinforced cement composite material and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63144153A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038866A (en) * | 1989-05-31 | 1991-01-16 | Res Dev Corp Of Japan | Carbon fiber and composite material therefrom |
| JPH0341000A (en) * | 1989-07-07 | 1991-02-21 | Nikkiso Co Ltd | Method for modifying whisker |
| JPH04219354A (en) * | 1990-11-13 | 1992-08-10 | Kazuji Fukunaga | Hardening of mortar and concrete |
| JP2006229069A (en) * | 2005-02-18 | 2006-08-31 | National Univ Corp Shizuoka Univ | Activated carbon, its manufacturing method and polarizable electrode for electric double layer capacitor |
| WO2009001964A1 (en) | 2007-06-28 | 2008-12-31 | Toyota Jidosha Kabushiki Kaisha | Electrode catalyst substrate, method for producing the same, and solid polymer fuel cell |
| WO2017149817A1 (en) * | 2016-03-04 | 2017-09-08 | 日産自動車株式会社 | High-pressure gas storage container and method for producing high-pressure gas storage container |
| WO2017149818A1 (en) * | 2016-03-04 | 2017-09-08 | 日産自動車株式会社 | Structure body, and method for manufacturing structure body |
| CN111074525A (en) * | 2020-01-02 | 2020-04-28 | 广州黑希复合材料科技有限公司 | Carbon fiber cloth surface treatment process |
-
1986
- 1986-12-05 JP JP61289040A patent/JPS63144153A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH038866A (en) * | 1989-05-31 | 1991-01-16 | Res Dev Corp Of Japan | Carbon fiber and composite material therefrom |
| JPH0341000A (en) * | 1989-07-07 | 1991-02-21 | Nikkiso Co Ltd | Method for modifying whisker |
| JPH04219354A (en) * | 1990-11-13 | 1992-08-10 | Kazuji Fukunaga | Hardening of mortar and concrete |
| JP2006229069A (en) * | 2005-02-18 | 2006-08-31 | National Univ Corp Shizuoka Univ | Activated carbon, its manufacturing method and polarizable electrode for electric double layer capacitor |
| JP4625950B2 (en) * | 2005-02-18 | 2011-02-02 | 国立大学法人静岡大学 | Activated carbon, manufacturing method thereof, and polarizable electrode for electric double layer capacitor |
| WO2009001964A1 (en) | 2007-06-28 | 2008-12-31 | Toyota Jidosha Kabushiki Kaisha | Electrode catalyst substrate, method for producing the same, and solid polymer fuel cell |
| US8940452B2 (en) | 2007-06-28 | 2015-01-27 | Toyota Jidosha Kabushiki Kaisha | Electrode catalyst substrate and method for producing the same, and polymer electrolyte fuel cell |
| WO2017149818A1 (en) * | 2016-03-04 | 2017-09-08 | 日産自動車株式会社 | Structure body, and method for manufacturing structure body |
| WO2017149817A1 (en) * | 2016-03-04 | 2017-09-08 | 日産自動車株式会社 | High-pressure gas storage container and method for producing high-pressure gas storage container |
| JPWO2017149817A1 (en) * | 2016-03-04 | 2018-12-20 | 日産自動車株式会社 | High pressure gas storage container and method for manufacturing high pressure gas storage container |
| JPWO2017149818A1 (en) * | 2016-03-04 | 2019-01-31 | 日産自動車株式会社 | Structure and manufacturing method of structure |
| US10940663B2 (en) | 2016-03-04 | 2021-03-09 | Nissan Motor Co., Ltd. | High-pressure gas storage container and method for producing high-pressure gas storage container |
| US11040479B2 (en) | 2016-03-04 | 2021-06-22 | Nissan Motor Co., Ltd. | Structure and method for manufacturing structure |
| US11590725B2 (en) | 2016-03-04 | 2023-02-28 | Nissan Motor Co., Ltd. | Method for producing high-pressure gas storage container |
| CN111074525A (en) * | 2020-01-02 | 2020-04-28 | 广州黑希复合材料科技有限公司 | Carbon fiber cloth surface treatment process |
| CN111074525B (en) * | 2020-01-02 | 2021-10-01 | 广州黑希复合材料科技有限公司 | Carbon fiber cloth surface treatment process |
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