JPH055942B2 - - Google Patents
Info
- Publication number
- JPH055942B2 JPH055942B2 JP23374884A JP23374884A JPH055942B2 JP H055942 B2 JPH055942 B2 JP H055942B2 JP 23374884 A JP23374884 A JP 23374884A JP 23374884 A JP23374884 A JP 23374884A JP H055942 B2 JPH055942 B2 JP H055942B2
- Authority
- JP
- Japan
- Prior art keywords
- ozone
- treatment
- fibers
- carbon fibers
- present
- 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 - Lifetime
Links
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 18
- 239000004917 carbon fiber Substances 0.000 claims description 18
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は炭素繊維表面の酸化処理方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for oxidizing the surface of carbon fibers.
炭素繊維はマトリツクス樹脂とのぬれ性を改善
し、接着強度を向上させる目的で表面酸化処理が
施されるのが一般的であり、工業的には多くの場
合電解酸化法がとられているが、工程の煩雑さ、
電解液の廃液処理の問題、処理糸中の残存電解質
によるトラブル等、湿式法であるがゆえの問題が
多くあり、これらの点で乾式方法即ち気相酸化に
よる表面酸化方法が工業的にみてより優れた方法
である。
Carbon fibers are generally subjected to surface oxidation treatment to improve wettability with matrix resin and increase adhesive strength, and in many industrial cases electrolytic oxidation is used. , complexity of the process,
There are many problems due to the wet method, such as the problem of electrolyte waste disposal and problems caused by residual electrolyte in the treated yarn.In these points, the dry method, that is, the surface oxidation method using gas phase oxidation, is superior from an industrial perspective. This is an excellent method.
気相酸化方法によれば、空気中で加熱処理する
ことを基本技術とし、多くの改良方法が提案され
ておりその一つとしてオゾンを利用した気相酸化
反応が知られている。 According to the gas phase oxidation method, the basic technology is heat treatment in air, and many improved methods have been proposed, one of which is known as a gas phase oxidation reaction using ozone.
オゾンを利用して気相酸化を行う場合、通常は
加熱器を有するチヤンバー内にオゾン化空気を導
入して炭素繊維を処理することが行われる。オゾ
ンは非常に分解し易く、特に高温程分解が激しい
ため低温で行なわれるのが一般的であるが、この
場合酸化反応はきわめて遅くなる。更に、炭素繊
維トウが包含する空気を置換してトウ内部へオゾ
ン拡散していく段階が律速となるためトウ内で、
不均一反応となりやすいという欠点を有してい
る。 When performing gas phase oxidation using ozone, carbon fibers are usually treated by introducing ozonized air into a chamber having a heater. Ozone is very easy to decompose, and the decomposition is particularly severe at higher temperatures, so it is common to carry out the oxidation reaction at lower temperatures, but in this case the oxidation reaction is extremely slow. Furthermore, the rate-determining step is that the air contained in the carbon fiber tow is replaced and ozone diffuses into the tow.
It has the disadvantage that it tends to cause a heterogeneous reaction.
そのためにオゾンによる酸化反応は工業的には
利用されていないのが現状であるがオゾンによる
気相酸化は簡便であり、酸化効果も大きいため、
工業的に利用されればその意義は大きい。 For this reason, oxidation reactions using ozone are not currently used industrially, but gas phase oxidation using ozone is simple and has a large oxidation effect, so
It will be of great significance if it is used industrially.
本発明はオゾンをできるだけ分解させることな
く効率よく炭素繊維の酸化反応を行なわせしめる
と同時に、短時間に均一に酸化せしめる処理方法
を見出すことにある。
The object of the present invention is to find a treatment method that allows the oxidation reaction of carbon fibers to be carried out efficiently without decomposing ozone as much as possible, and at the same time, oxidizes the fibers uniformly in a short time.
すなわち本発明はオゾンを含む酸化性雰囲気中
で走行する炭素繊維の表面を処理するに際して、
表面処理チヤンバー内での酸化性のガス流方向を
繊維の走行に対して並流となして20〜40℃で処理
した後、10〜50℃／秒の昇温速度で160℃以上に
加熱し、引き続き160〜250℃で処理することにあ
る。
That is, when the present invention treats the surface of carbon fiber running in an oxidizing atmosphere containing ozone,
After treatment at 20 to 40°C with the oxidizing gas flow direction parallel to the running of the fibers in the surface treatment chamber, the fibers are heated to 160°C or higher at a heating rate of 10 to 50°C/sec. , followed by processing at 160~250℃.
本発明の利点は酸化性ガス流の方向を繊維の走
行方向に並流となし、処理と共に温度勾配をつけ
ることによつて効率よく酸化反応を進めることに
ある。 An advantage of the present invention is that the direction of the oxidizing gas flow is parallel to the running direction of the fibers, and the oxidation reaction can be carried out efficiently by creating a temperature gradient along with the treatment.
本発明の第一の特徴は実質的にオゾン濃度の低
下がおこらない20〜40℃の温度範囲で処理するこ
とによつてトウの包含する空気を置換しオゾンの
トウ内部への拡散を十分に行なわしめることにあ
る。 The first feature of the present invention is that the air contained in the tow is replaced by treatment at a temperature range of 20 to 40°C, where ozone concentration does not substantially decrease, and ozone is sufficiently diffused into the tow. It's about getting things done.
第二の特徴はきわめて短時間内に160℃以上に
加熱することによりオゾンを強制的に短時間に熱
分解せしめ、その際発生する励起分子によつて炭
素繊維を酸化させることにある。 The second feature is that ozone is forcibly thermally decomposed in a short period of time by heating to 160°C or higher within an extremely short period of time, and the carbon fibers are oxidized by the excited molecules generated at this time.
本発明において予備的にトウ内の空気をオゾン
化空気と置換させるためにオゾンが実質的に分解
しない温度範囲が好ましく20〜40℃で処理され
る。又該温度での滞在時間は炭素繊維トウのフイ
ラメント数やトウ本数および処理速度によつて適
宜選ばれるものであるが通常数分以内である。 In the present invention, in order to preliminarily replace the air in the tow with ozonized air, the treatment is preferably carried out at a temperature range of 20 to 40°C in which ozone is not substantially decomposed. The residence time at this temperature is appropriately selected depending on the number of filaments and tows of the carbon fiber tow and the processing speed, but is usually within several minutes.
120℃までの昇温速度はできるだけ早いのが好
ましいが、処理速度等から10〜50℃／秒の範囲と
なる。最終処理温度と時間は処理速度と目標処理
レベルによつて選ばれるべきものであり160〜250
℃で10秒〜３分が好ましい。 It is preferable that the temperature increase rate to 120°C be as fast as possible, but it will be in the range of 10 to 50°C/sec depending on the processing speed, etc. The final processing temperature and time should be selected depending on the processing speed and target processing level.
C. 10 seconds to 3 minutes is preferred.
本発明でのオゾンの処理温度は少なくとも160
℃以上となし、実質的にオゾンの一部が分解し活
性な励起分子を発生させうる温度範囲をとる。 The ozone treatment temperature in the present invention is at least 160
℃ or higher, within a temperature range in which a portion of ozone is substantially decomposed and active excited molecules are generated.
本発明でいう炭素繊維とはPAN系、ピツチ系、
セルロース系いずれの炭素繊維でもよく、更に加
熱処理された黒鉛繊維であつてもよい。オゾン濃
度は工業的に効率よく酸化反応が進む範囲にあれ
ばよく、特に制限はない。 The carbon fibers used in the present invention are PAN-based, pitch-based,
Any cellulose-based carbon fiber may be used, and further heat-treated graphite fiber may be used. The ozone concentration is not particularly limited as long as it is within a range where the oxidation reaction can proceed industrially efficiently.
以下実施例により本発明をより具体的に説明す
る。
EXAMPLES The present invention will be explained in more detail with reference to Examples below.
実施例 １
有効処理長が３ｍであるチヤンバーの内温を第
１図に示した温度分布になる様に設定し、弾性率
24tom／mm2の炭素繊維を処理速度３ｍ／分で走行
通過せしめ、１m3／hrの割合でオゾン濃度2vol％
の空気をチヤンバーの入口側から炭素繊維の走行
方向に対して並流に供給し、出口側から排気せし
め、表面処理を行なつた。得られた炭素繊維につ
いてESCAを用いて表面導入酸素量を定量したと
ころO1s／C1sの組成比は0.20となり、有効に表面
処理の行なわれていることが明らかとなつた。Example 1 The internal temperature of a chamber with an effective processing length of 3 m was set to have the temperature distribution shown in Figure 1, and the elastic modulus was
24 tom/mm 2 carbon fiber was passed through at a processing speed of 3 m/min, and the ozone concentration was 2 vol% at a rate of 1 m 3 /hr.
Air was supplied from the inlet side of the chamber in a parallel flow with respect to the running direction of the carbon fibers, and was exhausted from the outlet side to perform surface treatment. When the amount of oxygen introduced into the surface of the obtained carbon fiber was determined using ESCA, the composition ratio of O 1 s/C 1 s was 0.20, which revealed that the surface treatment had been effectively carried out.
実施例 ２
処理速度を１ｍ／分とした他は実施例１と同様
にして表面処理を施し得られた炭素繊維のESCA
を測定したところO1S／C1Sの組成比は0.25とな
つた。Example 2 ESCA of carbon fiber obtained by surface treatment in the same manner as in Example 1 except that the processing speed was 1 m/min.
When measured, the composition ratio of O 1 S/C 1 S was 0.25.
実施例 ３
弾性率30ton／mm2の炭素繊維について第２図に
示した温度分布に設定した他は実施例１と同様に
して表面処理を行なつた。ESCAによるO1s／C1s
組成比は0.25であつた。Example 3 A carbon fiber having an elastic modulus of 30 ton/mm 2 was subjected to surface treatment in the same manner as in Example 1, except that the temperature distribution was set as shown in FIG. O 1 s/C 1 s by ESCA
The composition ratio was 0.25.
比較例 １
第１図において繊維の走行方向を逆にした他は
実施例１と同様にして表面処理を行なつたところ
ESCAによるO1s／C1sの比は0.13であつた。Comparative Example 1 Surface treatment was carried out in the same manner as in Example 1 except that the running direction of the fibers was reversed in Figure 1.
The ratio of O 1 s/C 1 s by ESCA was 0.13.
本発明によつて表面酸化された炭素繊維は、マ
トリツクスの接着性に優れ、剥離強度が大きい複
合材料を得ることができる。
The surface-oxidized carbon fiber according to the present invention has excellent matrix adhesion and can provide a composite material with high peel strength.
第１〜２図は本発明を説明するチヤンバー内の
繊維の走行方向における温度分布を示すものであ
る。
Figures 1 and 2 illustrate the temperature distribution in the running direction of the fibers within the chamber to explain the present invention.
Claims (1)
繊維の表面を処理するに際して、表面処理チヤン
バー内での酸化性のガス流方向を繊維の走行に対
して並流となして20〜40℃で処理した後、10〜50
℃／秒の昇温速度で160℃以上に加熱し、引き続
き160〜250℃で処理することを特徴とする炭素繊
維の酸化処理方法。1. When treating the surface of carbon fibers running in an oxidizing atmosphere containing ozone, the oxidizing gas flow direction within the surface treatment chamber is parallel to the running of the fibers, and the treatment is carried out at 20 to 40°C. After that, 10-50
A method for oxidizing carbon fibers, which comprises heating to 160°C or higher at a temperature increase rate of °C/sec, and then continuing treatment at 160 to 250°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23374884A JPS61113878A (en) | 1984-11-06 | 1984-11-06 | Oxidation treatment of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23374884A JPS61113878A (en) | 1984-11-06 | 1984-11-06 | Oxidation treatment of carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61113878A JPS61113878A (en) | 1986-05-31 |
| JPH055942B2 true JPH055942B2 (en) | 1993-01-25 |
Family
ID=16959955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23374884A Granted JPS61113878A (en) | 1984-11-06 | 1984-11-06 | Oxidation treatment of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61113878A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4608402A (en) * | 1985-08-09 | 1986-08-26 | E. I. Du Pont De Nemours And Company | Surface treatment of pitch-based carbon fibers |
-
1984
- 1984-11-06 JP JP23374884A patent/JPS61113878A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61113878A (en) | 1986-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |