CN114086386B - Surface treatment method for dry-jet wet-spinning high-modulus carbon fiber - Google Patents
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 78
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 78
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000004381 surface treatment Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002166 wet spinning Methods 0.000 title claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 56
- 238000005406 washing Methods 0.000 claims abstract description 41
- 238000001035 drying Methods 0.000 claims abstract description 34
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- 238000005087 graphitization Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 238000004513 sizing Methods 0.000 description 10
- 238000004804 winding Methods 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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Abstract
The invention discloses a surface treatment method for dry-jet wet-spinning high-modulus carbon fibers. According to the method, the dry-jet wet-spinning high-modulus carbon fiber is electrolyzed by connecting multiple electrolytic tanks in parallel, then washed by a washing tank, and finally dried by a contact drying mode. The invention is based on the surface treatment principle of anodic oxidation, reduces the total resistance of the surface treatment section by connecting a plurality of electrolytic tanks in parallel, and increases the surface treatment electric quantity to a greater extent in a safe voltage range; in the equipment layout, a mode of up-down superposition is adopted, so that the occupied area is reduced, the distance between connecting wires is shortened, and the surface treatment electric quantity is increased; and the regulation and control of different surface treatment degrees of the high-modulus carbon fiber are realized through the matching of the electrolyte concentration, the temperature and the total electrolysis electric quantity, and the method is suitable for preparing the dry-jet wet-spinning high-modulus carbon fiber with higher surface treatment degree.
Description
Technical Field
The invention belongs to the technical field of carbon fiber surface modification, and relates to a surface treatment method for dry-jet wet-spinning high-modulus carbon fibers.
Background
In addition to the characteristics of light weight, high modulus, high environmental tolerance, etc., the high modulus carbon fiber is increasingly used as a reinforcement in the fields of structural and functional composite materials with high rigidity and high dimensional stability requirements, such as the fields of aerospace with large acceleration load and large temperature alternation and the fields of space optical mirrors with high precision and dimensional stability requirements. However, compared with high-strength carbon fibers, the high-modulus carbon fibers have higher graphitization degree and large surface crystallite size, so that problems such as large surface inertia, weaker bonding ability with matrix resin and the like can exist in the application process, and deeper surface treatment is required.
The surface treatment process in the industrial production process of the carbon fiber mainly selects an anodic electrolytic oxidation method, and the surface of the carbon fiber is subjected to electrochemical etching through active oxygen atoms generated by an anode, so that the surface of the carbon fiber is activated. The existing surface treatment method of the high-strength medium-model carbon fiber is mature, and the surface modification method for the high-modulus carbon fiber is few. Chinese patent application CN109161947a discloses a surface treatment method for high modulus carbon fiber, which comprises first performing a first stage of anodic oxidation treatment on the high modulus carbon fiber by weak alkaline electrolyte, generating activated carbon atoms on the surface of the high modulus carbon fiber, then performing a second stage of anodic oxidation treatment on the carbon fiber by acidic electrolyte, and forming active groups on the surface of the carbon fiber. However, the method is of laboratory grade, and the application effect of the method has certain limitation in industrial production application. Chinese patent application CN104178790a discloses a method and a device for treating the surface of carbon fiber, in which dry-spray wet-spun carbon fiber bundles are electrolyzed by an electrolytic tank, washed with water, and dried by a contact drying method. However, the method is suitable for the dry-jet wet-spun high-strength medium-modulus carbon fiber with the modulus of less than 290GPa, and the surface treatment of the dry-jet wet-spun carbon fiber with higher modulus has lower interlayer shear strength improvement amplitude and can not meet the performance index requirements of products.
Disclosure of Invention
The invention aims to provide a surface treatment method for dry-jet wet-spinning high-modulus carbon fibers. The method is particularly suitable for preparing the dry-jet wet-spun high-modulus carbon fiber with higher requirements on surface treatment degree, and can improve the interlaminar shear strength (ILSS) of the high-modulus carbon fiber by more than 2 times.
The technical scheme for realizing the purpose of the invention is as follows:
the surface treatment method for the dry-jet wet-spinning high-modulus carbon fiber comprises the following specific steps:
step (1), adopting multi-stage electrolytic tanks with multi-layer space layout, and adopting a parallel connection mode for each stage of electrolytic tanks, and sequentially electrolyzing the dry-jet wet-spun high-modulus carbon fiber through each stage of electrolytic tanks, wherein the temperature of each stage of electrolyte is 70-80 ℃, and the total electrolytic electric quantity is 50-100C/g; wherein the electrolyte in the first-stage electrolytic tank is acid electrolyte, the electrolyte in the second-stage electrolytic tank is alkaline electrolyte, and the electrolyte in the third-stage electrolytic tank is pyrolyzable electrolyte;
step (2), the electrolyzed carbon fiber tows pass through a washing tank, and deionized water flowing reversely to the carbon fibers is introduced into the washing tank for washing;
and (3) drying the carbon fiber tows after washing in a contact drying mode, wherein the drying temperature is 100-150 ℃.
The dry-jet wet-spun high-modulus carbon fiber disclosed by the invention is dry-jet wet-spun carbon fiber subjected to high-temperature carbonization or graphitization, and the modulus of the carbon fiber is 300-450 GPa.
Preferably, in step (1), the acidic electrolyte is sulfuric acid or nitric acid, the alkaline electrolyte is sodium hydroxide or ammonia water, and the pyrolyzable electrolyte is ammonium bicarbonate or ammonium carbonate. In a specific embodiment of the invention, the acidic electrolyte used is sulfuric acid, the alkaline electrolyte is sodium hydroxide, and the pyrolyzable electrolyte is ammonium bicarbonate.
Preferably, in step (1), the mass concentration of the electrolyte is 1% to 15%, preferably 2% to 5%. In a specific embodiment of the present invention, the concentration is 5% when the acid electrolyte is sulfuric acid; when the alkaline electrolyte is sodium hydroxide, the concentration is 2%; when the pyrolyzable electrolyte is ammonium bicarbonate, the concentration is 4%.
Preferably, in the step (1), the total treatment time of electrolysis is 60 to 150 seconds.
Preferably, in the step (2), the water washing temperature is 40 to 80 ℃.
Preferably, in the step (2), the washing tank is divided into 3-5 washing units, and the liquid level of each washing unit is sequentially increased by 2-10 mm along the running direction of the fiber.
Compared with the prior art, the invention has the following advantages:
(1) The multi-stage electrolytic cells with multi-layer space layout are adopted, the occupied area is reduced, the distance of connecting wires is shortened, the total surface treatment resistance is reduced in a parallel connection mode of all stages of electrolytic cells, the electrolytic electricity quantity is improved in a safe voltage range, the surface treatment capacity is obviously improved, and the method is suitable for industrial online matching;
(2) The inventor finds that when the temperature of the electrolyte is increased from the traditional temperature of 20-60 ℃ to 70-80 ℃, the conductivity of the electrolyte is increased by nearly 1 time, and the increase of the surface treatment temperature is also beneficial to OH - The reactivity with carbon atoms on the surface layer of the carbon fiber is more suitable for preparing the high-modulus carbon fiber with higher surface treatment degree requirement;
(3) The liquid level of each washing unit is sequentially increased by 2-10 mm along the fiber running direction, so that the conductivity concentration difference of each washing unit is increased, the washing effect is effectively improved, and the conductivity of a washing outlet is controlled below 10 mu s/cm;
(4) The method is particularly suitable for the surface treatment of the high-modulus carbon fiber prepared by dry-jet wet spinning precursor, and the surface of the dry-jet wet spinning precursor is smoother, so that the carbon fiber has fewer internal defects, the high-modulus carbon fiber treated by the method has better comprehensive performance, and the interlaminar shear strength of the treated carbon fiber is improved by more than 2 times.
Drawings
Fig. 1 is a schematic view of a surface treatment apparatus for dry-jet wet-spinning high modulus carbon fibers according to the present invention, wherein 1: carbon fiber, 2-1 to 2-4: anode graphite roller, 3, cathode graphite plate, 4: a surface treatment tank, 5, a washing roller, 6 and a washing tank.
Detailed Description
According to the surface treatment method for the dry-jet wet-spinning high-modulus carbon fiber, the total resistance of the surface treatment section is reduced in a parallel multistage electrolytic tank mode, and the surface treatment electric quantity is increased to a greater extent in a safe voltage range; in the equipment layout, a mode of up-down superposition is adopted, so that the occupied area is reduced, the distance between connecting wires is shortened, and the surface treatment electric quantity is increased; by combining the matching of the electrolyte concentration, the temperature and the total electrolysis electric quantity, the high-modulus carbon fiber is subjected to deep surface treatment by the obtained large electric quantity, so that the technical effect of improving the shearing strength between the high-modulus carbon fiber layers by more than 2 times is realized.
The technical scheme of the present invention will be clearly and completely described in the following in connection with the embodiments and the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, tensile strength and modulus were measured as specified in GB/T3362, and abrasion resistance was found to be the weight of carbon fiber filaments remaining after passing through a nonwoven fabric under a pressure of 0.3MPa under a tension of 15.+ -. 2N for carbon fibers having a length of 30 m; interlaminar shear strength was measured according to the ISO 14130 short beam method.
Comparative example 1
The high-modulus carbon fiber is subjected to dry-jet wet spinning after graphitization treatment at 2150 ℃, and is directly subjected to sizing, drying and winding without surface treatment and water washing. The obtained carbon fiber has a tensile strength of 5.56GPa, a modulus of 333GPa, an abrasion resistance of 1.5mg/30m and an interlaminar shear strength of 42MPa.
Comparative example 2
The graphitized dry-spray wet-spun high-modulus carbon fiber at 2150 ℃ is subjected to primary electrolytic anodic oxidation surface treatment, wherein electrolyte is ammonium bicarbonate, the surface treatment electric quantity is 1C/g, the electrolyte concentration is 2%, the electrolyte temperature is 70 ℃, and the surface treatment time is 60s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ by a contact drying mode. And finally, sizing, drying and winding. The obtained carbon fiber has a tensile strength of 5.55GPa, a modulus of 332GPa, an abrasion resistance of 1.6mg/30m and an interlaminar shear strength of 70MPa.
Comparative example 3
The dry-jet wet-spinning high-modulus carbon fiber subjected to graphitization treatment at 2150 ℃ is subjected to two-stage electrolytic anodic oxidation surface treatment, wherein the first-stage electrolyte is sodium hydroxide, the electrolyte concentration is 2%, and the surface treatment electric quantity is 30C/g; the second-stage electrolyte is sulfuric acid, the electrolyte concentration is 5%, and the surface treatment electric quantity is 30C/g; the two-stage electrolyte temperatures are 70 ℃ and the surface treatment time is 60s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ by a contact drying mode. And finally, sizing, drying and winding. The obtained carbon fiber has the tensile strength of 5.42GPa, the modulus of 333GPa, the wear resistance of 1.6mg/30m and the interlayer shear strength of 82MPa.
Comparative example 4
The dry-jet wet-spinning high-modulus carbon fiber subjected to graphitization treatment at 2150 ℃ is subjected to three-stage electrolytic anodic oxidation surface treatment, wherein electrolyte sequentially comprises sulfuric acid, sodium hydroxide and ammonium bicarbonate, the surface treatment electric quantity is 20C/g, the electrolyte concentration is 5%, 2% and 4% in sequence, the electrolyte temperature is 40 ℃, and the surface treatment time is 20s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ by a contact drying mode. And finally, sizing, drying and winding. The obtained carbon fiber has a tensile strength of 5.50GPa, a modulus of 333GPa, an abrasion resistance of 1.5mg/30m and an interlaminar shear strength of 94MPa.
Comparative example 5
The high-modulus carbon fiber is subjected to dry-jet wet spinning after graphitization treatment at 2500 ℃, and is directly subjected to sizing, drying and winding without surface treatment and water washing. The obtained carbon fiber has a tensile strength of 5.22GPa, a modulus of 381GPa, an abrasion resistance of 1.6mg/30m and an interlaminar shear strength of 30MPa.
Comparative example 6
The graphitized dry-spray wet-spun high-modulus carbon fiber is subjected to primary electrolytic anodic oxidation surface treatment, wherein electrolyte is sodium hydroxide, the surface treatment electric quantity is 40C/g, the electrolyte concentration is 3%, the electrolyte temperature is 50 ℃, and the surface treatment time is 30s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ by a contact drying mode. And finally, sizing, drying and winding. The obtained carbon fiber has a tensile strength of 5.08GPa, a modulus of 381GPa, an abrasion resistance of 1.9mg/30m and an interlaminar shear strength of 75MPa.
Example 1
The dry-jet wet-spinning high-modulus carbon fiber subjected to graphitization treatment at 2150 ℃ is subjected to three-stage electrolytic anodic oxidation surface treatment, wherein electrolyte sequentially comprises sulfuric acid, sodium hydroxide and ammonium bicarbonate, the surface treatment electric quantity is 20C/g, the electrolyte concentration is 5%, 2% and 4% in sequence, the electrolyte temperature is 70 ℃, and the surface treatment time is 30s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ by a contact drying mode. And finally, sizing, drying and winding. The obtained carbon fiber has a tensile strength of 5.45GPa, a modulus of 333GPa, an abrasion resistance of 1.4mg/30m and an interlaminar shear strength of 107MPa.
In the embodiment, the deep surface treatment of the dry-jet wet-spinning high-modulus carbon fiber is realized through three-stage electrolytic oxidation anode surface treatment, the interlaminar shear strength is improved by 254% compared with that before the treatment, and each performance is obviously better than that of comparative examples 1-4.
Example 2
The dry-jet wet-spinning high-modulus carbon fiber subjected to graphitization treatment at 2150 ℃ is subjected to three-stage electrolytic anodic oxidation surface treatment, wherein electrolyte sequentially comprises sulfuric acid, sodium hydroxide and ammonium bicarbonate, the surface treatment electric quantity is 40C/g, the electrolyte concentration is 5%, 2% and 4% in sequence, the electrolyte temperature is 70 ℃, and the surface treatment time is 30s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ by a contact drying mode. And finally, sizing, drying and winding. The tensile strength of the obtained carbon fiber is 4.87GPa, the modulus is 332GPa, the wear resistance is 1.4mg/30m, and the interlaminar shear strength is 112MPa.
According to the embodiment, under the condition of the same electrolyte concentration and current cabinet, the surface treatment electric quantity is improved by adopting three-stage electrolytic oxidation anode surface treatment and a series connection mode, so that the higher surface treatment degree is realized, and the interlayer shearing strength is further improved.
Example 3
The dry-jet wet-spinning high-modulus carbon fiber subjected to graphitization treatment at 2500 ℃ is subjected to three-stage electrolytic anodic oxidation surface treatment, wherein electrolyte sequentially comprises sulfuric acid, sodium hydroxide and ammonium bicarbonate, the surface treatment electric quantity is 20C/g, the electrolyte concentration is 5%, 2% and 4% in sequence, the electrolyte temperature is 70 ℃, and the surface treatment time is 30s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ in a contact drying mode, and finally sizing, drying and winding. The obtained carbon fiber has a tensile strength of 5.10GPa, a modulus of 381GPa, an abrasion resistance of 1.8mg/30m and an interlaminar shear strength of 97MPa.
Example 4
The dry-jet wet-spinning high-modulus carbon fiber subjected to graphitization treatment at 2500 ℃ is subjected to three-stage electrolytic anodic oxidation surface treatment, wherein electrolyte sequentially comprises sulfuric acid, sodium hydroxide and ammonium bicarbonate, the surface treatment electric quantity is 40C/g, the electrolyte concentration is 5%, 4% and 4% in sequence, the electrolyte temperature is 80 ℃, and the surface treatment time is 30s. And then sequentially passing through four sections of water washing units with the liquid level increased by 8mm along the fiber running direction, wherein the water washing temperature is 60 ℃. And then drying at 120 ℃ in a contact drying mode, and finally sizing, drying and winding. The obtained carbon fiber has tensile strength of 4.93GPa, modulus 381GPa, wear resistance of 1.8mg/30m and interlaminar shear strength of 103MPa.
In the embodiment, three-stage surface treatment is connected in parallel, and the surface treatment electric quantity is improved by matching with the electrolyte concentration and the electrolyte temperature.
Claims (3)
1. The surface treatment method for the dry-jet wet-spinning high-modulus carbon fiber is characterized by comprising the following specific steps of:
step (1), adopting multi-stage electrolytic tanks with multi-layer space layout, and adopting a parallel connection mode for each stage of electrolytic tanks, and sequentially electrolyzing the dry-jet wet-spun high-modulus carbon fiber through each stage of electrolytic tanks, wherein the temperature of each stage of electrolyte is 70-80 ℃, and the total electrolytic electric quantity is 50-100C/g; the electrolyte in the first-stage electrolytic tank is sulfuric acid with the concentration of 5%, the electrolyte in the second-stage electrolytic tank is sodium hydroxide with the concentration of 2%, the electrolyte in the third-stage electrolytic tank is ammonium bicarbonate with the concentration of 4%, the dry-jet wet-spun high-modulus carbon fiber is the dry-jet wet-spun carbon fiber after high-temperature carbonization or graphitization, and the carbon fiber modulus is 300-450 GPa;
step (2), the electrolyzed carbon fiber tows pass through a washing tank, deionized water flowing reversely to the carbon fibers is introduced into the washing tank for washing, the washing tank is divided into 3-5 washing units, and the liquid level of each washing unit is sequentially increased by 2-10 mm along the fiber running direction;
and (3) drying the carbon fiber tows after washing in a contact drying mode, wherein the drying temperature is 100-150 ℃.
2. The surface treatment method according to claim 1, wherein in the step (1), the total treatment time of electrolysis is 60 to 150 seconds.
3. The surface treatment method according to claim 1, wherein in the step (2), the water washing temperature is 40 to 80 ℃.
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| US4839006A (en) * | 1987-06-01 | 1989-06-13 | Mitsubishi Rayon Co., Ltd. | Surface treatment process for carbon fibers |
| JP4023226B2 (en) * | 2001-06-12 | 2007-12-19 | 東レ株式会社 | Carbon fiber bundle processing method |
| JP2008248424A (en) * | 2007-03-30 | 2008-10-16 | Toho Tenax Co Ltd | Method of multistage electrolytic treatment of carbon fiber |
| CN109161947A (en) * | 2018-08-30 | 2019-01-08 | 北京化工大学 | High modulus carbon fiber surface treatment method and device and its application |
| CN110409018A (en) * | 2019-08-08 | 2019-11-05 | 中复神鹰碳纤维有限责任公司 | The preparation method of dry-jet wet-spinning high-strength and high-modulus wear-resisting polypropene itrile group carbon fiber |
| CN111074381A (en) * | 2019-12-12 | 2020-04-28 | 中复神鹰碳纤维有限责任公司 | Preparation method of high-strength medium-modulus aviation carbon fiber based on dry jet wet spinning |
| CN111793857A (en) * | 2020-06-30 | 2020-10-20 | 镇江市高等专科学校 | Carbon fiber surface treatment method |
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