JPS633073B2 - - Google Patents
Info
- Publication number
- JPS633073B2 JPS633073B2 JP6778285A JP6778285A JPS633073B2 JP S633073 B2 JPS633073 B2 JP S633073B2 JP 6778285 A JP6778285 A JP 6778285A JP 6778285 A JP6778285 A JP 6778285A JP S633073 B2 JPS633073 B2 JP S633073B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- current density
- carbon fibers
- electrolytic bath
- fibers
- 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.)
- Expired
Links
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 43
- 239000004917 carbon fiber Substances 0.000 claims description 43
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000004381 surface treatment Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 description 13
- 239000008151 electrolyte solution Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Treatment Of Fiber Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
Description
〔産業上の利用分野〕
本発明は炭素繊維の電解表面処理法に関する。
〔従来技術〕
炭素繊維を用いた複合材料は、軽量、高強力、
高弾性等の卓越した特性をもつため、航空宇宙用
構造材、自動車・産業機械部品、スポーツ用品等
に広く使用されている。
しかしながら、炭素繊維をこれらの複合材用途
に使用する場合、炭素繊維自身の強度の重要性も
さることながら、加えて、樹脂などのマトリクス
との接着性を向上させ、複合材料としての強度、
層間剪断強度の向上をはかることが実用上、極め
て重要である。
こうしたマトリクスとの接着性を向上させるた
め、炭素繊維には通常、表面処理が施されるが、
その方法として、炭素繊維の表面を気相酸化、液
相酸化、電解酸化等により表面処理する方法が知
られている。
その中でも、特に、炭素繊維を陽極として、電
解質水溶液中で電解酸化処理する方法が、作業
性、品質の点から工業的には有用視されている。
炭素繊維の表面電解処理においては、繊維の表
面積あたりの電流密度が高すぎると炭素繊維の強
度が低下する。他方、低すぎた場合には表面処理
効果が不充分となり、樹脂マトリクスとの接着性
は向上されない。従つて電解浴内の電流密度分布
を均一にすることが、製品特性の向上、均一化の
上で極めて重要である。
一方、炭素繊維を陽極として電解を行なう場
合、炭素繊維の抵抗が、電解液の抵抗に比して大
きいために、特に陽極電流入力端子近傍で電流が
流れやすく、陽極電流入力端子から離れるにつれ
て電流密度が低下し、結果的に電流密度分布は不
均一となりやすい。
さらに、本発明者らの検討によれば、炭素繊維
を連続的に走行させて電解処理を行う場合は、特
に、、炭素繊維が電解液に浸漬しはじめる電解浴
入口側付近での電流密度が高く、不均一性が助長
されやすいことが判つた。
例えば、第１図に示す従来公知の電解処理装置
で炭素繊維を電解処理すると、炭素繊維走行方向
の電流密度分布は第４図―ａのようになり、両端
部、特に電解浴入口側の電流密度が高い。
電流密度分布の均一化をはかる方法として、例
えば、特公昭58―5288号公報には、炭素繊維と陰
極の相対的間隔を陽極電流入力端子からの距離に
応じて変化させる方法が開示されている。この方
法の実施に用いる装置の一例を第２図に示す。こ
の方法により電解処理したときの電流密度分布は
第４図―ｂのようになり、陰極に面した部分の電
流密度はある程度均一化されるが、第４図―ｂに
示す如く、電解浴入口部での高電流密度はいぜん
解消されない。また、この方法においては、陰極
形状を特殊なものにしたり、或いは電解浴内に糸
道を設置したりする必要があり、操作性、保守性
の上で難点があり、場合によつては毛羽、糸切れ
の原因となつたりする。
〔発明が解決しようとする問題点〕
本発明者らは、炭素繊維の電解表面処理時の電
流密度の均一化、特に電解浴入口部における電流
密度の均一化をはかり、特性及び均一性のすぐれ
た炭素繊維を得る方法について鋭意検討し、本発
明を見い出すに到つた。
〔問題点を解決するための手段〕
本発明は、連続的に走行する炭素繊維を陽極と
して、電解質水溶液中で電解表面処理する方法に
おいて、電解浴を出た直後に設けた陽極電流入力
端子から炭素繊維に電流を供給するとともに、電
解浴に入る直前の炭素繊維の電位を陰極電位に等
しくすることを特徴とする炭素繊維の電解表面処
理法である。
本発明において、電流は電解浴を出た直後に設
けた陽極電流入力端子より炭素繊維に供給され
る。かかる陽極電流入力端子としては、例えばカ
ーボンロール等の導電性ロール、あるいは非接触
型陽極電流入力端子等公知のものが用いられる。
供給する電流、電圧は、炭素繊維の種類、本
数、処理速度、電解質の種類等に応じて適宜選定
される。通常、電流は炭素繊維束１本あたり約
10mAから5A、電圧は約500mVから10V程度で
ある。
使用する電解質は電解に際し、陽極に本質的に
酸素を生成するものであればよく、例えば、硫
酸、硝酸、リン酸等の酸、硫酸アンモニウム、硝
酸アンモニウム、炭酸アンモニウム等の塩等公知
のものが用いられる。また、電解質の濃度、電解
液の温度は電解質の種類及びその他の装置条件に
よるが、通常、濃度は0.1ないし10％程度、温度
は室温ないし80℃程度で行われる。
陰極としては電解質溶液に対し耐腐食性の導電
材料、例えば、グラフアイト、ニツケル、ステン
レススチール等公知のものが用いられ、形状、寸
法等は装置に大きさ、操作性、保守性等を考慮し
て適宜決められる。
本発明においては、電解浴に入る直前の炭素繊
維の電位を実質的に陰極電位に等しくすることが
重要であり、これによりはじめて電解浴入口部で
の高電流密度が解消される。このための手段とし
ては、例えば、電解浴に入る直前に陽極電流入力
端子と同様の導電性ロール、非接触型端子等を設
け、それらの端子と陰極を導線で接続することが
簡単でよい。
第３図は本発明の方法を実施するのに使用する
装置の一例である。同図において、炭素繊維１は
電解浴２に入る直前に設けた端子３を介して電解
液中の陰極４と電気的に接続されている。一方、
直流電源５より、電解浴を出た直後に設けた陽極
電流入力端子６を介して炭素繊維１に電流が供給
され、電解浴内において炭素繊維を陽極として電
解がおこなわれる。
なお、本発明において電流密度とは、陽極であ
る炭素繊維の単位表面積から電解液を通じて陰極
に向けて流れる電流量を言うが、この値は、電解
浴内の炭素繊維の近傍の任意の距離ｌcm離れた２
点における電解液の電位の差ΔE（Ｖ）を測定し、
電解液の比抵抗ρ（Ω・cm）とから次式を用いて
算出することができる。
ｉ＝ΔE／ρ×ｌ（Ａ／cm2）
ｉ：電流密度
〔発明の効果〕
本発明の方法によれば、何ら特殊で複雑な装置
を必要とせず電解浴内、特に電解浴入口部におけ
る電流密度分布を均一化することができ、斑のな
い、均一な表面処理が可能となる。また、入口部
の未処理繊維に急激に過大な電流が流れることが
なくなるので、得られる炭素繊維の強度、接着性
ともすぐれたものとなる。さらに従来法のように
何ら特殊な装置、糸道を必要とせず、簡単に実施
できるので、工業的にも極めて有利である。
〔実施例〕
以下に実施例を挙げて本発明を具体的に説明す
る。
実施例 １
単糸繊度1.3dデニール、12000フイラメントの
アクリル系長繊維を最終的に1300℃の窒素雰囲気
中で焼成して得た炭素繊維を第３図に示す電解装
置を用いて電解表面処理した。電解質として１％
硝酸を用い、電流500mA、電圧5.5V、処理時間
20秒で連続的に処理を行なつた。電解浴内の電流
密度分布は第４図―ｃに示すごとくであり、電解
浴入口部における不均一は見られなかつた。
電解処理した繊維を引き続き水洗、サイジング
付与、乾燥した後巻取つた。
未処理繊維および処理繊維について、JIS―
R7601に準じ、同解説例２の樹脂を用いてストラ
ンド強度を測定したところ、それぞれ406Kg／mm2
及び410Kg／mm2であつた。
さらに、樹脂との接着性を見るために、エポキ
シ樹脂（チバガイギー社、MY720、100部、ジア
ミノジフエニルスルホン30部、三弗化ホウ素モノ
エチルアミン1.5部）のメチルエチルケトン溶液
を含浸したプリプレグを130℃×60分、ついで180
℃×120分、加熱硬化し、平板試験片を作成し、
三点曲げシヨートビーム法（Ｌ／Ｄ＝４）で層間
剪断強度（以下、「ILSS」という）を測定した。
未処理糸及び処理糸のILSSの値はそれぞれ、8.3
Kg／mm2及び13.1Kg／mm2であつた。
実施例 ２
実施例１で用いた炭素繊維を、実施例１と同様
な装置を用い、同様な条件で、処理本数を８本に
して同時に電解表面処理をおこなつた。得られた
繊維は、引続いて、水洗、サイジング、乾燥して
巻取り、物性測定に供した。
８本の繊維について、引張強度及びILSSの平
均値及びバラツキは表１の通りであつた。
一方、８本のうちの１本について、長さ方向に
５分割して測定した引張強度及びILSSの平均値
及びバラツキを同じく表１に示す。
表１からも明らかなように、本発明の方法で得
られた繊維は特性及び均一性ともに極めて良好で
ある。
比較例 １
実施例１で用いた炭素繊維を第３図に示す装置
を用いて、端子３と陰極２の間を接続せずに実施
例１と同一条件で電解処理した。その時の電流密
度分布は第４図―ｄに示す如きであり、電解浴入
口部で高電流密度を示した。得られた炭素繊維の
引張強度は394Kg／mm2、ILSSは12.1Kg／mm2であつ
た。
比較例 ２
第１図に示す従来法装置で、電解浴の前後両側
より通電して、実施例２と同様の条件で電解処理
を行なつた。得られた８本の繊維の特性及びその
うちの１本について長さ方向に５分割して測定し
た特性の平均値及びバラツキを表１に示す。
この時の電流密度分布は第４図―ａに示す如く
であつた。
[Industrial Field of Application] The present invention relates to a method for electrolytic surface treatment of carbon fibers. [Prior art] Composite materials using carbon fiber are lightweight, highly strong,
Because it has outstanding properties such as high elasticity, it is widely used in aerospace structural materials, automobile and industrial machinery parts, sporting goods, etc. However, when carbon fibers are used for these composite materials, it is important not only to maintain the strength of the carbon fibers themselves, but also to improve their adhesion to matrices such as resins, thereby increasing the strength of the composite materials.
In practice, it is extremely important to improve interlaminar shear strength. Carbon fibers are usually surface treated to improve their adhesion to these matrices.
As a method for this purpose, methods are known in which the surface of carbon fibers is treated by gas phase oxidation, liquid phase oxidation, electrolytic oxidation, or the like. Among these, a method in which electrolytic oxidation treatment is performed in an electrolyte aqueous solution using carbon fiber as an anode is considered to be particularly useful industrially from the viewpoint of workability and quality. In surface electrolytic treatment of carbon fibers, if the current density per surface area of the fibers is too high, the strength of the carbon fibers will decrease. On the other hand, if it is too low, the surface treatment effect will be insufficient and the adhesion to the resin matrix will not be improved. Therefore, it is extremely important to make the current density distribution in the electrolytic bath uniform in order to improve and make the product characteristics uniform. On the other hand, when performing electrolysis using carbon fiber as an anode, the resistance of the carbon fiber is greater than the resistance of the electrolytic solution, so current tends to flow particularly near the anode current input terminal, and the further away from the anode current input terminal the current flows. The density decreases, and as a result, the current density distribution tends to become non-uniform. Furthermore, according to the studies of the present inventors, when carrying out electrolytic treatment by running carbon fibers continuously, the current density is particularly high near the inlet side of the electrolytic bath where the carbon fibers begin to be immersed in the electrolytic solution. It was found that this was high and that non-uniformity was likely to be promoted. For example, when carbon fibers are electrolytically treated using the conventionally known electrolytic treatment apparatus shown in Fig. 1, the current density distribution in the running direction of the carbon fibers becomes as shown in Fig. 4-a, and the current density at both ends, especially at the entrance of the electrolytic bath, is High density. As a method for making the current density distribution uniform, for example, Japanese Patent Publication No. 58-5288 discloses a method in which the relative spacing between the carbon fiber and the cathode is changed according to the distance from the anode current input terminal. . An example of the apparatus used to carry out this method is shown in FIG. The current density distribution when electrolyzed by this method is as shown in Figure 4-b, and the current density in the part facing the cathode is made uniform to some extent, but as shown in Figure 4-b, the current density distribution at the entrance of the electrolytic bath is The high current density in the area is not resolved at all. In addition, this method requires a special cathode shape or a thread path installed in the electrolytic bath, which poses difficulties in terms of operability and maintainability, and in some cases may cause fluff. , which may cause thread breakage. [Problems to be Solved by the Invention] The present inventors have attempted to make the current density uniform during the electrolytic surface treatment of carbon fibers, especially the current density at the entrance of the electrolytic bath, and have achieved excellent characteristics and uniformity. The inventors conducted extensive research on methods for obtaining carbon fibers and discovered the present invention. [Means for Solving the Problems] The present invention provides a method for electrolytically treating a surface in an electrolyte aqueous solution using a continuously running carbon fiber as an anode. This is an electrolytic surface treatment method for carbon fibers characterized by supplying a current to the carbon fibers and making the potential of the carbon fibers equal to the cathode potential immediately before entering the electrolytic bath. In the present invention, current is supplied to the carbon fiber from an anode current input terminal provided immediately after exiting the electrolytic bath. As such an anode current input terminal, a known one such as a conductive roll such as a carbon roll or a non-contact type anode current input terminal is used. The current and voltage to be supplied are appropriately selected depending on the type and number of carbon fibers, processing speed, type of electrolyte, etc. Normally, the current per carbon fiber bundle is approximately
10mA to 5A, voltage is approximately 500mV to 10V. The electrolyte to be used may be one that essentially generates oxygen at the anode during electrolysis, and for example, known ones such as acids such as sulfuric acid, nitric acid, and phosphoric acid, and salts such as ammonium sulfate, ammonium nitrate, and ammonium carbonate are used. . Although the concentration of the electrolyte and the temperature of the electrolytic solution depend on the type of electrolyte and other equipment conditions, the concentration is usually about 0.1 to 10%, and the temperature is about room temperature to 80°C. As the cathode, a conductive material that is resistant to corrosion by the electrolyte solution, such as graphite, nickel, stainless steel, etc., is used, and the shape and dimensions are determined based on the device's size, operability, maintainability, etc. It can be decided as appropriate. In the present invention, it is important to make the potential of the carbon fibers immediately before entering the electrolytic bath substantially equal to the cathode potential, and only then can the high current density at the entrance of the electrolytic bath be eliminated. A simple means for this purpose is, for example, to provide a conductive roll similar to the anode current input terminal, a non-contact type terminal, etc. immediately before entering the electrolytic bath, and connect these terminals and the cathode with a conductive wire. FIG. 3 is an example of an apparatus used to carry out the method of the invention. In the figure, a carbon fiber 1 is electrically connected to a cathode 4 in an electrolytic solution via a terminal 3 provided immediately before entering an electrolytic bath 2. on the other hand,
A current is supplied from a DC power supply 5 to the carbon fiber 1 via an anode current input terminal 6 provided immediately after exiting the electrolytic bath, and electrolysis is performed in the electrolytic bath using the carbon fiber as an anode. In the present invention, the current density refers to the amount of current flowing from the unit surface area of the carbon fiber serving as the anode to the cathode through the electrolytic solution. away 2
Measure the potential difference ΔE (V) of the electrolyte at the point,
It can be calculated from the specific resistance ρ (Ω·cm) of the electrolytic solution using the following formula. i=ΔE/ρ×l (A/cm 2 ) i: Current density [Effects of the invention] According to the method of the present invention, the current density in the electrolytic bath, especially at the inlet of the electrolytic bath, can be reduced without the need for any special or complicated equipment. The current density distribution can be made uniform, making it possible to perform uniform surface treatment without spots. Furthermore, since an excessive current does not suddenly flow through the untreated fibers at the entrance, the resulting carbon fibers have excellent strength and adhesive properties. Furthermore, unlike the conventional method, it does not require any special equipment or thread guide and can be easily carried out, so it is extremely advantageous from an industrial perspective. [Example] The present invention will be specifically explained with reference to Examples below. Example 1 Carbon fibers obtained by finally firing 12,000 filament acrylic long fibers with a single fiber fineness of 1.3 d denier in a nitrogen atmosphere at 1,300°C were subjected to electrolytic surface treatment using the electrolytic apparatus shown in Fig. 3. . 1% as electrolyte
Using nitric acid, current 500mA, voltage 5.5V, treatment time
Processing was performed continuously for 20 seconds. The current density distribution within the electrolytic bath was as shown in Figure 4-c, and no non-uniformity was observed at the entrance of the electrolytic bath. The electrolytically treated fibers were subsequently washed with water, sized, dried, and then wound. Regarding untreated fibers and treated fibers, JIS-
According to R7601, the strand strength was measured using the resin of Explanation Example 2, and it was 406Kg/mm 2 respectively.
and 410Kg/ mm2 . Furthermore, in order to check the adhesion with the resin, prepreg impregnated with a methyl ethyl ketone solution of epoxy resin (Ciba Geigy, MY720, 100 parts, diaminodiphenylsulfone 30 parts, boron trifluoride monoethylamine 1.5 parts) was heated at 130°C. 60 minutes, then 180 minutes
Cure by heating for 120 minutes to create a flat test piece.
The interlaminar shear strength (hereinafter referred to as "ILSS") was measured by the three-point bending shot beam method (L/D=4).
The ILSS value of untreated yarn and treated yarn is 8.3, respectively.
Kg/ mm2 and 13.1Kg/ mm2 . Example 2 The carbon fibers used in Example 1 were subjected to electrolytic surface treatment at the same time using the same apparatus as in Example 1 and under the same conditions, with the number of fibers treated being 8. The obtained fibers were subsequently washed with water, sized, dried, wound up, and subjected to physical property measurements. Table 1 shows the average values and variations in tensile strength and ILSS for the eight fibers. On the other hand, Table 1 also shows the average values and dispersion of the tensile strength and ILSS of one of the eight pieces, which were measured by dividing into five pieces in the length direction. As is clear from Table 1, the fibers obtained by the method of the present invention have extremely good properties and uniformity. Comparative Example 1 The carbon fiber used in Example 1 was electrolytically treated using the apparatus shown in FIG. 3 under the same conditions as in Example 1, without connecting terminal 3 and cathode 2. The current density distribution at that time was as shown in Figure 4-d, with a high current density at the entrance of the electrolytic bath. The obtained carbon fiber had a tensile strength of 394 Kg/mm 2 and an ILSS of 12.1 Kg/mm 2 . Comparative Example 2 Electrolytic treatment was carried out using the conventional apparatus shown in FIG. 1 under the same conditions as in Example 2, by applying electricity from both the front and back sides of the electrolytic bath. Table 1 shows the characteristics of the eight fibers obtained and the average value and variation of the characteristics measured by dividing one of the fibers into five in the length direction. The current density distribution at this time was as shown in FIG. 4-a.
【表】
比較例 ３
第２図に示す装置を用い、実施例１と同様の条
件で電解処理を行つた。電流密度分布は第４図―
ｂの如くであり、電解浴入口部で高電流密度を示
した。[Table] Comparative Example 3 Electrolytic treatment was carried out under the same conditions as in Example 1 using the apparatus shown in FIG. The current density distribution is shown in Figure 4.
b, and showed a high current density at the inlet of the electrolytic bath.
第１図および第２図は従来法の炭素繊維電解酸
化表面処理に用いる装置の断面図であり、第３図
は本発明の炭素繊維電解酸化表面処理に用いる装
置の一例を示す断面図である。第４図は、第１図
〜第３図に示す装置を用いて炭素繊維電解酸化表
面処理を行つた時の電解浴内電流密度分布を示す
曲線である。
１：炭素繊維、２：電解浴、３：通電端子、
４：陰極、５：直流電源、６：陽極電流入力端
子。
第２図において、縦軸および横軸はそれぞれ、
電解浴内の電流密度および位置の相対値である。
FIGS. 1 and 2 are cross-sectional views of an apparatus used for conventional carbon fiber electrolytic oxidation surface treatment, and FIG. 3 is a cross-sectional view showing an example of the apparatus used for carbon fiber electrolytic oxidation surface treatment of the present invention. . FIG. 4 is a curve showing the current density distribution in the electrolytic bath when carbon fiber electrolytic oxidation surface treatment is performed using the apparatus shown in FIGS. 1 to 3. 1: Carbon fiber, 2: Electrolytic bath, 3: Current-carrying terminal,
4: Cathode, 5: DC power supply, 6: Anode current input terminal. In Figure 2, the vertical and horizontal axes are, respectively,
Relative values of current density and position within the electrolytic bath.
Claims (1)
解質水溶液中で電解表面処理する方法において、
電解浴を出た直後に設けた陽極電流入力端子から
炭素繊維に電流を供給するとともに、電解浴に入
る直前の炭素繊維の電位を陰極電位に等しくする
ことを特徴とする炭素繊維の電解表面処理方法。1. In a method of electrolytic surface treatment in an electrolyte aqueous solution using a continuously running carbon fiber as an anode,
An electrolytic surface treatment for carbon fibers characterized by supplying current to the carbon fibers from an anode current input terminal provided immediately after exiting the electrolytic bath, and making the potential of the carbon fibers just before entering the electrolytic bath equal to the cathode potential. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6778285A JPS61231266A (en) | 1985-03-30 | 1985-03-30 | Electrolytic surface treatment of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6778285A JPS61231266A (en) | 1985-03-30 | 1985-03-30 | Electrolytic surface treatment of carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61231266A JPS61231266A (en) | 1986-10-15 |
| JPS633073B2 true JPS633073B2 (en) | 1988-01-21 |
Family
ID=13354870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6778285A Granted JPS61231266A (en) | 1985-03-30 | 1985-03-30 | Electrolytic surface treatment of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61231266A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01143080U (en) * | 1988-03-15 | 1989-09-29 | ||
| JPH0498275U (en) * | 1990-07-24 | 1992-08-25 |
-
1985
- 1985-03-30 JP JP6778285A patent/JPS61231266A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01143080U (en) * | 1988-03-15 | 1989-09-29 | ||
| JPH0498275U (en) * | 1990-07-24 | 1992-08-25 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61231266A (en) | 1986-10-15 |
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