JPH01118622A - High-strength and high-modulus carbon fiber - Google Patents
High-strength and high-modulus carbon fiberInfo
- Publication number
- JPH01118622A JPH01118622A JP27034587A JP27034587A JPH01118622A JP H01118622 A JPH01118622 A JP H01118622A JP 27034587 A JP27034587 A JP 27034587A JP 27034587 A JP27034587 A JP 27034587A JP H01118622 A JPH01118622 A JP H01118622A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- fiber
- strength
- cross
- fiber axis
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 abstract description 9
- 239000011295 pitch Substances 0.000 description 8
- 239000011302 mesophase pitch Substances 0.000 description 4
- 241000234282 Allium Species 0.000 description 3
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011337 anisotropic pitch Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、繊維横断面はラジアル構造であり、繊維軸方
向には発達した層状の黒鉛構造を有する高強度高弾性炭
素繊維に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a high-strength, high-modulus carbon fiber having a radial structure in the fiber cross section and a developed layered graphite structure in the fiber axis direction.
（従来の技術及びその問題点）
高強度、高弾性炭素繊維は、ポリアクリロニトリルを前
駆体とするもの、及びメソフェーズピッチを前駆体とす
るものが知られている。ポリアクリロニトリルを前駆体
とする炭素繊維は黒鉛化し難いため、弾性率を高めるこ
とには限界がある。(Prior Art and its Problems) High-strength, high-elasticity carbon fibers are known to use polyacrylonitrile as a precursor and mesophase pitch as a precursor. Since carbon fibers using polyacrylonitrile as a precursor are difficult to graphitize, there is a limit to increasing the elastic modulus.
このため高い弾性率を有する炭素繊維の製造法として、
メソフェーズピッチを原料とする方法が注目されている
。Therefore, as a method for producing carbon fiber with high elastic modulus,
A method using mesophase pitch as a raw material is attracting attention.
メソフェーズピッチ系炭素繊維は、その断面構造から、
ラジアル型、ランダム型及びオニオン型の３型に分類さ
れる。これらのうち、ラジアル型は、半径方向に亀裂が
入りやすいため、低い引張強度の炭素繊維しか得られな
いとされている。従って、メソフェーズピッチ系炭素繊
維としてランダム型及びオニオン型の断面構造を持つも
のが種々検討されている。Due to its cross-sectional structure, mesophase pitch carbon fiber has
It is classified into three types: radial type, random type, and onion type. Among these, the radial type is said to be able to produce carbon fibers with only low tensile strength because they tend to crack in the radial direction. Therefore, various types of mesophase pitch carbon fibers having random and onion cross-sectional structures have been studied.
特開昭５９−７６９２５号公報には、異方性ピッチを光
学的に等方性を示す温度まで加熱し、その温度で紡糸す
ることにより、ランダム型又はオニオン型の炭素繊維を
製造する方法が開示されている。JP-A-59-76925 discloses a method for producing random or onion-type carbon fibers by heating anisotropic pitch to a temperature that exhibits optical isotropy and spinning at that temperature. Disclosed.
特開昭５９−１６３４２２号公報、同５９−１６３４２
４号公報及び同６０−１０４５２８号公報には、ノズル
出口部がノズル内の最狭部より広い異形断面ノズルを用
いて紡糸することにより、ランダム型又はオニオン型の
炭素繊維を製造する方法が開示されている。JP-A-59-163422, JP-A No. 59-16342
Publication No. 4 and Publication No. 60-104528 disclose a method for producing random or onion-type carbon fibers by spinning using a modified cross-section nozzle in which the nozzle exit part is wider than the narrowest part in the nozzle. has been done.
このように、従来、高強度、高弾性の炭素繊維であるた
めには、その断面構造がランダム型又はオニオン型であ
ることが必要であるとされており、断面構造がラジアル
型であって、かつ高強度、高弾性の炭素繊維はいまだ知
られていない。In this way, conventionally, in order to have high strength and high elasticity carbon fiber, it is necessary that the cross-sectional structure is random or onion type, and the cross-sectional structure is radial type, Moreover, carbon fibers with high strength and high elasticity are still unknown.
（問題点を解決するための技術的手段）本発明の目的は
、断面構造がラジアル型であり、高い強度及び弾性率を
有する炭素繊維を提供することにある。(Technical means for solving the problems) An object of the present invention is to provide a carbon fiber having a radial cross-sectional structure and high strength and elastic modulus.
本発明の他の目的および利点は以下の発明から明らかと
なろう。Other objects and advantages of the invention will become apparent from the following invention.
本発明の上記目的および利点は、繊維軸に垂直な断面の
構造が基本的に褶曲したラジアル構造であり、繊維軸方
向には長く成長した黒鉛構造を有する炭素繊維によって
達成される。The above-mentioned objects and advantages of the present invention are achieved by a carbon fiber having a basically folded radial structure in a cross section perpendicular to the fiber axis and a graphite structure that grows long in the fiber axis direction.
本発明の炭素繊維を、以下添付図面を参照しつつ説明す
る。第１図および第２図は、本発明の炭素繊維の繊維軸
に垂直方向の断面の凹微鏡写真であり、第１図と第２図
とは倍率が相違する。第３図は本発明の炭素繊維の繊維
軸方向の断面の顕微鏡写真である。The carbon fiber of the present invention will be explained below with reference to the accompanying drawings. 1 and 2 are concave microscopic photographs of a cross section of the carbon fiber of the present invention in a direction perpendicular to the fiber axis, and the magnifications of FIG. 1 and FIG. 2 are different. FIG. 3 is a micrograph of a cross section of the carbon fiber of the present invention in the fiber axis direction.
本発明の炭素繊維は、その断面構造が第１図に示すよう
に基本的にラジアル構造となっている。The carbon fiber of the present invention basically has a radial cross-sectional structure as shown in FIG.
このラジアル構造は、第２図に示すように半径方向に激
しく褶曲している。This radial structure is severely folded in the radial direction, as shown in FIG.
公知のラジアル構造の炭素繊維においては、ラジアル構
造が半径方向にほぼ直線的に存在しているために、引張
強度の著しい低下を招いていた。In known carbon fibers with a radial structure, the radial structure exists substantially linearly in the radial direction, resulting in a significant decrease in tensile strength.
従って、弾性率は高くても、上記の低い引＋３！強度の
ため、実用に供しうる炭素繊維ではなかった。Therefore, even if the elastic modulus is high, the above-mentioned low pull +3! Due to its strength, it was not a carbon fiber that could be put to practical use.
これに比して、本発明の炭素繊維は、半径方向に褶曲し
たラジアル構造の断面を有しているため、亀裂に対する
抵抗性が高いという特徴を有する。In contrast, the carbon fiber of the present invention has a cross section with a radial structure folded in the radial direction, and therefore has a characteristic of high resistance to cracking.
従って、本発明の炭素繊維は、当業者の予期に反して、
断面構造がラジアル型であるにもかかわらず、高い弾性
率と共に、高い引張強度を示す。Therefore, the carbon fiber of the present invention, contrary to the expectations of those skilled in the art,
Despite having a radial cross-sectional structure, it exhibits high elastic modulus and high tensile strength.
本発明の炭素繊維は、第３図に示すように、黒鉛化層の
（００２）帯層間隔ｄ００２が３．４２Å以下であるこ
とが好ましい。ｄ ０１１２が３．４２Å以下であるこ
とにより、より高い弾性率を有する炭素繊維となる。As shown in FIG. 3, the carbon fiber of the present invention preferably has a (002) band spacing d002 of the graphitized layer of 3.42 Å or less. When d 0112 is 3.42 Å or less, the carbon fiber has a higher elastic modulus.
本発明の炭素繊維は、例えば以下の方法に従って製造す
ることができる。The carbon fiber of the present invention can be produced, for example, according to the following method.
石油類の流動接触分解法によって得られる重質油を水素
化触媒の存在下又は不存在下に、水素加圧化又は自生圧
下に、３５０〜５５０℃の範囲の温度で加熱処理し、得
られた反応混合物を、それに含有される固形分を分離除
去した後に、２５０〜４００℃に加熱して、留出する軽
沸留分を除去し、得られる残渣を不活性ガス雰囲気中で
減圧下に３５０〜５５０℃の範囲の温度で処理すること
によってピッチのメソフェーズ化を行い、紡糸用ピッチ
をまず製造する。得られる紡糸用ピッチは、２６０〜３
４０℃の軟化点、５０〜９０％のトルエン不溶解骨、１
０〜４０％のキノリンネ溶解分、及び７０〜９０％の光
学的異方性を有する。The heavy oil obtained by fluid catalytic cracking of petroleum is heat-treated at a temperature in the range of 350 to 550 ° C. in the presence or absence of a hydrogenation catalyst, under hydrogen pressure or autogenous pressure. After separating and removing the solid content contained in the reaction mixture, it is heated to 250 to 400°C to remove the light boiling fraction, and the resulting residue is heated under reduced pressure in an inert gas atmosphere. Pitch for spinning is first produced by mesophasing the pitch by treating it at a temperature in the range of 350-550°C. The resulting spinning pitch is 260-3
Softening point of 40℃, 50-90% toluene insoluble bone, 1
It has a quinoline solubility of 0 to 40% and an optical anisotropy of 70 to 90%.
ついで、上記紡糸用ピッチを紡糸し、得られるピッチ繊
維を酸素ガス含有雰囲気中で加熱して不敵化して炭化し
た後、２０００〜３０００℃で黒鉛化することによって
、本発明の高強度高弾性炭素繊維を得ることができる。Next, the pitch for spinning is spun, and the resulting pitch fibers are heated in an oxygen gas-containing atmosphere to make them invincible and carbonized, and then graphitized at 2000 to 3000°C to obtain the high-strength, high-elasticity fibers of the present invention. Carbon fiber can be obtained.
（実施例） 以下に実施例を示す。(Example) Examples are shown below.
実施例 １
石油の流動接触分解で得られる重質油３０ｋｇをオート
クレーブに仕込み、オートクレーブ内部を窒素置換した
後、４３０℃に加熱し、同温度で１時間改質処理した。Example 1 30 kg of heavy oil obtained by fluidized catalytic cracking of petroleum was charged into an autoclave, the inside of the autoclave was purged with nitrogen, and then heated to 430° C. and reformed at the same temperature for 1 hour.
得られた改質油から固形分を除去し、ついで５ｘｘＨｇ
の圧力下で３５０℃で留出する留分を除去した。得られ
た残渣を２１１１８８以下の圧力下で４５０℃まで４０
分間で昇温し、分解物を留出除去しながらピッチのメソ
フェーズ化を行い、４．！５ｋｇの紡糸用ビッチヲ得た
。The solid content was removed from the obtained reformed oil, and then 5xxHg
The fraction distilled out at 350° C. under a pressure of 350° C. was removed. The resulting residue was heated to 450°C under a pressure below 211188
4. Raise the temperature for 1 minute and convert the pitch into mesophase while distilling off the decomposed products. ! I got 5kg of spinning bitch.
上記紡糸用ピッチを口径０．２ｕのストレートノズルを
用い、３３０℃、紡糸速度２００＋／分で紡糸し、紡糸
して得られた繊維を３００℃で空気中で不融化した。不
融化繊維を１４００℃で炭化し、ついで２８００℃で黒
鉛化した。The above-mentioned spinning pitch was spun at 330° C. and a spinning speed of 200+/min using a straight nozzle with a diameter of 0.2 u, and the resulting fiber was infusible in air at 300° C. The infusible fibers were carbonized at 1400°C and then graphitized at 2800°C.
得られた黒鉛化糸は、繊維径１１．０μｌ、引張強度３
３０ｋｇ／ｚｚ”、弾性率６５ｔ／ｉ＋ｚ”であった、
この黒鉛化糸の断面構造を第１図及び第２図に、繊維軸
方向の断面構造を第３＠に示す。また、Ｘ線回折及びＴ
ＥＭ暗視野像から求めた、上記黒鉛化糸の黒鉛構造の（
００２）帯層間隔ｄ １１１６２は３．３７人であった
。The obtained graphitized yarn has a fiber diameter of 11.0 μl and a tensile strength of 3.
30kg/zz", elastic modulus 65t/i+z",
The cross-sectional structure of this graphitized yarn is shown in FIGS. 1 and 2, and the cross-sectional structure in the fiber axis direction is shown in FIG. In addition, X-ray diffraction and T
The graphite structure (
002) The zonal spacing d 11162 was 3.37 people.
実施例 ２
ピッチのメソフェーズ化温度を４６０℃に変えた以外は
実施例１を同様の方法を繰り返して、黒鉛化糸を得た。Example 2 A graphitized yarn was obtained by repeating the same method as in Example 1 except that the pitch mesophase temperature was changed to 460°C.
得られた黒鉛化糸は、繊維径１０１．５μｌ、引張強度
３６５１ｇ／ａｘ２、弾性率７５ｔ／ａｘ２であった。The obtained graphitized yarn had a fiber diameter of 101.5 μl, a tensile strength of 3651 g/ax2, and an elastic modulus of 75 t/ax2.
この黒鉛化糸の断面構造は褶曲したラジアル構造であり
、Ｘ線回折及びＴ Ｅ Ｍ暗視野像から求めた、上記黒
鉛化糸の黒鉛構造の（００２＞帯層間隔ｄ００２は３．
３２人であった。The cross-sectional structure of this graphitized yarn is a folded radial structure, and the graphite structure of the graphitized yarn determined from X-ray diffraction and TEM dark field images has a (002>band layer spacing d002 of 3.
There were 32 people.
第１図および第２図は本発明の炭素繊維の例の繊維軸に
垂直方向の断面の顕微鏡写真である。
第３図は本発明の炭素繊維の例の繊維軸方向の断面の顕
微鏡写真である。FIGS. 1 and 2 are micrographs of a cross section of an example of the carbon fiber of the present invention in a direction perpendicular to the fiber axis. FIG. 3 is a micrograph of a cross section in the fiber axis direction of an example of the carbon fiber of the present invention.
Claims (1)
アル構造であり、繊維軸方向には長く成長した黒鉛構造
を有することを特徴とする高強度高弾性炭素繊維。 ２、黒鉛構造の（００２）帯層間隔ｄ＿０＿０＿２が３
．４２Å以下であることを特徴とする特許請求の範囲第
１項に記載の高強度高弾性炭素繊維。[Claims] 1. A high-strength, high-elastic carbon fiber characterized in that the structure in a cross section perpendicular to the fiber axis is basically a folded radial structure, and has a graphite structure that grows long in the fiber axis direction. . 2. The (002) band spacing d_0_0_2 of the graphite structure is 3
．． The high-strength, high-modulus carbon fiber according to claim 1, characterized in that the carbon fiber has a thickness of 42 Å or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27034587A JPH01118622A (en) | 1987-10-28 | 1987-10-28 | High-strength and high-modulus carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27034587A JPH01118622A (en) | 1987-10-28 | 1987-10-28 | High-strength and high-modulus carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01118622A true JPH01118622A (en) | 1989-05-11 |
Family
ID=17484967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27034587A Pending JPH01118622A (en) | 1987-10-28 | 1987-10-28 | High-strength and high-modulus carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01118622A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020524202A (en) * | 2017-06-19 | 2020-08-13 | サウジ アラビアン オイル カンパニー | Integrated heat treatment for interlayer pitch generation, asphaltene removal, crude and residue upgrades |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5936726A (en) * | 1982-08-24 | 1984-02-29 | Agency Of Ind Science & Technol | Precursor pitch fiber for carbon fiber |
| JPS6183319A (en) * | 1984-09-14 | 1986-04-26 | Kureha Chem Ind Co Ltd | Carbon fiber and its production |
| JPS6197423A (en) * | 1984-10-17 | 1986-05-15 | Agency Of Ind Science & Technol | Production of pitch carbon fiber |
| JPS61167022A (en) * | 1985-01-19 | 1986-07-28 | Agency Of Ind Science & Technol | Production of carbon yarn and device therefor |
-
1987
- 1987-10-28 JP JP27034587A patent/JPH01118622A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5936726A (en) * | 1982-08-24 | 1984-02-29 | Agency Of Ind Science & Technol | Precursor pitch fiber for carbon fiber |
| JPS6183319A (en) * | 1984-09-14 | 1986-04-26 | Kureha Chem Ind Co Ltd | Carbon fiber and its production |
| JPS6197423A (en) * | 1984-10-17 | 1986-05-15 | Agency Of Ind Science & Technol | Production of pitch carbon fiber |
| JPS61167022A (en) * | 1985-01-19 | 1986-07-28 | Agency Of Ind Science & Technol | Production of carbon yarn and device therefor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020524202A (en) * | 2017-06-19 | 2020-08-13 | サウジ アラビアン オイル カンパニー | Integrated heat treatment for interlayer pitch generation, asphaltene removal, crude and residue upgrades |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4822587A (en) | High modulus pitch-based carbon fiber and method for preparing same | |
| US6156287A (en) | Method for preparing pan-based activated carbon fabrics | |
| JPH0314624A (en) | Production of carbon yarn | |
| JPH01118622A (en) | High-strength and high-modulus carbon fiber | |
| US4356158A (en) | Process for producing carbon fibers | |
| JPS6065090A (en) | Preparation of pitch for carbon fiber spinning | |
| GB2125391A (en) | Process for producing carbon fibers | |
| JPS6241320A (en) | Carbon yarn having section with wavy structure | |
| JPH0718057B2 (en) | Pitch-based fiber manufacturing method | |
| JPH0545685B2 (en) | ||
| JPH0150269B2 (en) | ||
| JPH05272017A (en) | Carbon fiber and its production | |
| JPH06146120A (en) | Pitch-based carbon fiber having high strength and high elastic modulus and its production | |
| JPS616316A (en) | Graphite fiber | |
| JPH0150271B2 (en) | ||
| JPH02221418A (en) | Pitch-base carbon fiber | |
| JPH01201524A (en) | Production of mesophase pitch based carbon fiber | |
| JPH0144751B2 (en) | ||
| JPH03279422A (en) | Production of hollow carbon fiber | |
| JPH0841730A (en) | Production of high-thermal conductivity carbon fiber | |
| JPH0144750B2 (en) | ||
| JPH0148315B2 (en) | ||
| JPH03294520A (en) | High-strength carbon fiber and precursor fiber | |
| JPH054433B2 (en) | ||
| JPS62177220A (en) | Production of pitch based carbon fiber |