CN117626662A - Method for preparing sized carbon fiber by step-by-step sizing and application of sized carbon fiber and sized carbon fiber - Google Patents
Method for preparing sized carbon fiber by step-by-step sizing and application of sized carbon fiber and sized carbon fiber Download PDFInfo
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Abstract
The invention relates to the technical field of carbon fiber preparation, and discloses a method for preparing sizing carbon fibers by step sizing and application of the sizing carbon fibers. Pre-oxidizing polyacrylonitrile-based precursor, carbonizing at low temperature, carbonizing at high temperature, performing surface treatment, washing, sizing, drying, winding and collecting the precursor to obtain sized carbon fibers; sizing and drying comprises the following steps: firstly, presoaking and presoaking the carbon fiber tows after water washing by using a presoaking agent containing conductive polymer particles and polyvinyl alcohol to obtain initial carbon fibers; secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by using resorcinol formaldehyde latex to obtain the sized carbon fiber; the contact angle of the pre-sizing agent is less than or equal to 20 DEG and the surface tension is less than or equal to 70mN/m. The contact angle of the pre-sizing agent in the method is smaller than or equal to 20 degrees, the surface tension is smaller than or equal to 70mN/m, and the binding force of the sizing carbon fiber and the rubber matrix is obviously improved on the premise of meeting the conductivity requirement of the sizing carbon fiber by combining with a specific sizing method.
Description
Technical Field
The invention relates to the technical field of carbon fiber preparation, in particular to a method for preparing sizing carbon fibers by step sizing and sizing carbon fibers and application of the sizing carbon fibers.
Background
With the development of the electronic industry, the requirements for conductive functional materials are also gradually increasing. The high-performance conductive rubber composite material prepared by adding the high-conductivity carbon fiber material into the rubber matrix can improve the electric conductivity and the heat conductivity of the product on one hand and improve the physical and mechanical properties on the other hand. However, carbon fibers have poor interfacial bonding ability with rubber materials due to high surface inertness, and a polymer sizing agent is usually required to be coated on the surface. However, the traditional epoxy sizing agent has poor interface modification effect on the rubber matrix, and also affects effective propagation of electronic signals on the channel. Therefore, a sizing agent capable of improving both the interfacial properties and the electrical properties of carbon fiber reinforced rubber-based composites is urgently needed to be developed.
CN111057379a discloses a high thermal conductivity insulating silicon rubber composite material containing carbon fiber and a preparation method thereof, the method adds the carbon fiber into the graphene oxide solution, and the carbon fiber is stirred, filtered, deposited, washed and dried to obtain carboxylated carbon fiber, thus improving the volume resistivity, but being only applicable to electronic components needing insulation. And more applications require the conductivity of carbon fiber reinforced rubber composites.
CN111423632a discloses a preparation method of a conductive rubber composite material, conductive fillers and conductive plasticizers which are subjected to surface modification treatment are added to prepare conductive rubber with good conductive performance, but the fillers can only improve the conductive performance and have no effect on physical performance.
In the current industrial carbon fiber production process, a surface interface treatment method is generally adopted to solve the two-phase combination problem of the carbon fiber and the rubber matrix, including electrochemical treatment, acid-base treatment, surface sizing and the like, wherein the most common method is to adopt resorcinol formaldehyde latex (RFL emulsion for short) for sizing treatment. However, in practical applications, it was found that the use of only RFL emulsion did not effectively improve the adhesion between the carbon fiber and the rubber matrix after sizing, nor did it result in electrical conductivity.
Disclosure of Invention
The invention aims to solve the problems of poor adhesion between sizing carbon fiber and rubber matrix and poor conductivity in the prior art, and provides a method for preparing sizing carbon fiber by step sizing, sizing carbon fiber and application of sizing carbon fiber. By adopting the specific pre-sizing agent and the specific sizing method, the prepared sizing carbon fiber has good conductivity and the binding force between the sizing carbon fiber and the rubber matrix is obviously improved.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing sized carbon fibers by step sizing, the method comprising: the sizing carbon fiber is obtained after pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, sizing drying and winding wire collection of polyacrylonitrile-based precursor;
the sizing and drying method comprises the following steps:
firstly, pre-sizing and pre-drying a carbon fiber strand after washing by adopting a pre-sizing agent containing conductive polymer particles and polyvinyl alcohol to obtain initial carbon fibers;
secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by adopting resorcinol formaldehyde latex to obtain the sized carbon fiber;
wherein the contact angle of the pre-sizing agent is less than or equal to 20 degrees and the surface tension is less than or equal to 70mN/m.
In a second aspect, the present invention provides a sized carbon fiber prepared by the preparation method of the first aspect.
The third aspect of the invention provides an application of the sized carbon fiber in rubber materials.
Through the technical scheme, the method for preparing the sized carbon fiber by step sizing provided by the invention has the following beneficial effects that:
(1) The adhesive force between the sized carbon fiber and the rubber matrix is remarkably improved by utilizing the methods of step sizing and step drying, and by matching a presoaking agent with a contact angle less than or equal to 20 degrees and a surface tension less than or equal to 70mN/m for presoaking and matching resorcinol formaldehyde latex for secondary sizing.
(2) The pre-sizing agent contains conductive polymer particles and polyvinyl alcohol components, so that the interpenetration of the pre-sizing agent, the secondary sizing agent and the multiphase interface on the surface of the carbon fiber can be promoted, the binding force between the carbon fiber and the rubber matrix is improved, and meanwhile, the carbon fiber-rubber composite material also has certain conductivity.
(3) The pre-sizing agent and the secondary sizing agent have low cost and wide industrial application prospect, and the method for sizing in steps is simple, convenient and feasible and is suitable for the existing carbon fiber industrial production.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for preparing sized carbon fibers by step sizing, which is characterized by comprising the following steps of: the sizing carbon fiber is obtained after pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, water washing, sizing drying and winding wire collection of polyacrylonitrile-based precursor;
the sizing and drying method comprises the following steps:
firstly, pre-sizing and pre-drying a carbon fiber strand after washing by adopting a pre-sizing agent containing conductive polymer particles and polyvinyl alcohol to obtain initial carbon fibers;
secondly, carrying out secondary sizing and secondary drying on the initial carbon fiber by adopting resorcinol formaldehyde latex to obtain the sized carbon fiber;
wherein the contact angle of the pre-sizing agent is less than or equal to 20 degrees and the surface tension is less than or equal to 70mN/m.
In the invention, the production process of pre-oxidation is respectively carried out in an oxidation furnace with 4 heating temperature areas, and the temperatures of the 4 heating temperature areas are respectively 0-250 ℃, 0-300 ℃ and 0-350 ℃. The pre-oxidation time of each temperature zone is the same, and the total pre-oxidation time is 30-80min. The draft ratio in the oxidation furnace of each temperature zone is controlled to be 0-1.8, 0.8-1 and 0.8-1 respectively.
In the invention, the low-temperature carbonization production process is respectively carried out in a low-temperature carbonization furnace with 5 heating temperature areas, and the temperatures of the 5 heating temperature areas are respectively 0-700 ℃, 0-800 ℃, 0-950 ℃ and 0-950 ℃. When the pre-oxidized filament bundles run in a low-temperature carbonization furnace, the draft ratio is controlled to be 1-1.2, and the total residence time in the low-temperature carbonization furnace is 1-10min, so that the low-temperature carbonized filament is obtained.
In the invention, the high-temperature carbonization production process is respectively carried out in high-temperature carbonization furnaces with 5 heating temperature areas, and the temperatures of the 5 heating temperature areas are respectively 0-1300 ℃, 0-1400 ℃, 0-1700 ℃, 0-1900 ℃ and 0-2200 ℃. When the tows run in the high-temperature carbonization furnace, the draft ratio is controlled to be 0.6-0.95, and the total residence time in the high-temperature carbonization furnace is 1-10min, so that the high-temperature carbonized yarns are obtained.
In the present invention, the surface treatment conditions include: the ammonium bicarbonate aqueous solution is used as electrolyte, the voltage is 15-25V, the concentration of the electrolyte is 10-30wt%, and the treatment time is 50-80 seconds.
In the present invention, the conditions for washing with water include: washing with water at 40-60deg.C and water flow of 2500-6500L/h.
In the present invention, the winding and filament receiving may be performed under a tension of 2000 to 4000 cN.
According to the invention, the polyvinyl alcohol is an aqueous solution of polyvinyl alcohol.
In the invention, the polyvinyl alcohol can be selected from polyvinyl alcohols with different alcoholysis degrees, and preferably partially-alcoholyzed polyvinyl alcohol.
According to the invention, the alcoholysis of the polyvinyl alcohol is 78 to 99mol%, preferably 88 to 92mol%.
According to the invention, the polyvinyl alcohol has a number average molecular weight of 20000 to 200000, preferably 50000 to 150000.
According to the present invention, the conductive polymer particles are selected from at least one of polyacetylene, polyaniline, polypyrrole, polythiophene, polyisothiaindene, and polyethylene dioxythiophene.
In the invention, the conductive polymer particles are selected from the above types, and can enhance the conductivity of the sizing carbon fiber while ensuring the adhesion between the sizing carbon fiber and the rubber matrix.
In the present invention, the conductive polymer particles are polyacetylenes.
According to the invention, the mass ratio of the polyvinyl alcohol to the conductive polymer particles is 1:0.1-1:0.4.
In the invention, the mass ratio of the polyvinyl alcohol to the conductive polymer particles satisfies the above range, so that the permeability and the binding force of the two-phase interface of the sizing carbon fiber and the rubber matrix can be obviously improved, and the conductivity of the sizing fiber can be improved.
According to the invention, the mass ratio of the polyvinyl alcohol to the conductive polymer particles is 1:0.2-1:0.3.
According to the present invention, the presize agent has a contact angle of 10 ° or less and a surface tension of 65mN/m or less.
According to the invention, in the first step, the pre-drying mode is electric heating hot roller drying.
According to the invention, the temperature of the pre-drying is 60-100 ℃, preferably 70-90 ℃.
According to the invention, in the second step, the secondary drying mode is horizontal hot air drying.
In the invention, the horizontal hot air drying temperature is 90-240 ℃, preferably 110-190 ℃.
In the present invention, the horizontal hot air drying may be performed in a plurality of temperature zones, preferably in 4 temperature zones.
Further, the first temperature range is 90-210 ℃, the second temperature range is 120-240 ℃, the third temperature range is 120-240 ℃, and the fourth temperature range is 110-230 ℃.
In the invention, the resorcinol formaldehyde latex contains a rubber emulsion.
In the present invention, the resorcinol formaldehyde latex (RFL emulsion) may be an acrylic rubber emulsion, an acrylonitrile-butadiene rubber emulsion, an isoprene rubber emulsion, a polyurethane rubber emulsion, an ethylene-propylene rubber emulsion, a chloroprene rubber emulsion, a silicone rubber emulsion, a hydrogenated nitrile rubber emulsion, a styrene-butadiene rubber emulsion, a polysulfide rubber emulsion, a natural rubber emulsion, a butadiene rubber emulsion, a butyl rubber emulsion, etc., and the present invention is preferably a butyl rubber emulsion.
According to the invention, the resorcinol to formaldehyde molar ratio in the resorcinol formaldehyde latex is in the range of 1:3 to 1:25, preferably 1:8 to 1:18.
In the present invention, the resorcinol formaldehyde latex may be prepared by conventional emulsion polymerization methods.
In the present invention, the pre-sizing amount of the pre-sizing agent is 0.1 to 30wt%, preferably 0.5 to 20wt%, based on the mass of the carbon fiber tow after washing.
In the invention, the secondary sizing amount of the secondary sizing agent is 5-35wt%, preferably 10-20wt%, based on the mass of the carbon fiber tows after water washing.
In a second aspect, the present invention provides a sized carbon fiber prepared by the preparation method of the first aspect.
The third aspect of the invention provides an application of the sized carbon fiber in rubber materials.
According to the invention, when the sizing carbon fiber is applied to rubber materials, the binding force between the sizing carbon fiber and the rubber materials can be improved.
In the present invention, the rubber material may be a rubber material commonly used in the art, for example, acrylic rubber, acrylonitrile-butadiene rubber, isoprene rubber, urethane rubber, ethylene-propylene rubber, chloroprene rubber, silicone rubber, hydrogenated nitrile rubber, styrene-butadiene rubber, polysulfide rubber, natural rubber, butadiene rubber, butyl rubber, etc., and is preferably the same kind as the rubber emulsion in the RFL emulsion.
The present invention will be described in detail by examples.
In the following preparation examples and examples, each parameter was obtained by the following method.
Contact angle: the pre-sizing agent is uniformly coated on a glass slide, and after being placed for 12 hours at room temperature, the film sample is obtained by drying at 50 ℃. At room temperature, deionized water is dripped onto the surface of the glass sheet by using an OCA20 high-speed contact angle measuring instrument, and the static contact angle formed by the water drop on the surface of the pre-sizing agent is tested.
Surface tension: the pre-sizing agent was diluted with water to a concentration of 2wt%, and the surface tension was measured using a dynamic surface tensiometer at 25 ℃.
Sizing amount: and weighing the mass of the fiber before and after sizing, and calculating the sizing amount according to the formula. Sizing amount= (mass of carbon fiber after sizing-mass of carbon fiber before sizing)/mass of carbon fiber before sizing x 100%.
Volume resistivity: and (3) measuring the resistance in the lamination direction by using a PC digital high resistance meter, and calculating the volume resistivity by using a four-terminal method.
Adhesive force: the sized carbon fiber was embedded in an unvulcanized natural rubber block (wherein the mass of the sized carbon fiber was 20wt% of the mass of the natural rubber block), and vulcanized at 140℃for 40 minutes under a pressing pressure of 3 MPa. The vulcanization formula system comprises 100 parts of natural rubber, 4 parts of zinc oxide, 1.5 parts of stearic acid, 330 parts of carbon black N, 1.2 parts of accelerator DM, 0.2 part of accelerator TMTD and 3 parts of sulfur. On a universal strength tester, the sizing carbon fiber is pulled out at the speed of 200 mm/min, and the tension required for pulling out the sizing carbon fiber to 1 cm length is the binding force between the sizing carbon fiber and rubber.
KTM-3 epoxy emulsion, polyvinyl alcohol PVA1788 and conductive polyacetylene particles are all purchased from national medicine reagent;
wherein, the number average molecular weight of the PVA1788 is 80000, and the alcoholysis degree is 88mol%.
The following preparation examples are presented to illustrate the preparation of the pre-sizing agent
Preparation examples 1 to 6
Adding a proper amount of deionized water into a reaction kettle, heating to 90 ℃, adding polyvinyl alcohol and conductive polymer particles, and stirring at a high speed to obtain a stable dispersion liquid with uniform distribution, wherein the stable dispersion liquid is the pre-sizing agents A1-A6. Wherein the conductive polymer particles are conductive polyacetylene particles PANa1 (average particle diameter 220 nm), PANa2 (average particle diameter 450 nm) and PANa3 (average particle diameter 750 nm).
The components and the amounts of the components in the pre-sizing agent are shown in Table 1, and the mass ratio of the polyvinyl alcohol to the conductive polymer particles in the pre-sizing agent is shown in Table 2.
TABLE 1
TABLE 2
| Pre-sizing agent | Polyvinyl alcohol/conductive polymer particles | Contact angle (°) | Surface tension (mN/m) |
| A1 | 1:0.4 | 13 | 70 |
| A2 | 1:0.1 | 7 | 55 |
| A3 | 1:0.3 | 10 | 65 |
| A4 | 1:0.15 | 18 | 68 |
| A5 | 1:0.25 | 20 | 59 |
| A6 | 1:0.2 | 4 | 53 |
The following preparation examples are presented to illustrate the preparation of the secondary sizing agent
Preparation example 7
10g of sodium hydroxide and resorcinol were put into a reaction vessel, then a proper amount of water was added, stirred and warmed to 35 ℃, and a quantitative amount of formaldehyde was slowly added, wherein the total amount of resorcinol and formaldehyde was 30g. After 3 hours of reaction, slowly cooling to obtain a resin prepolymer; adding 97g of natural rubber emulsion into another reaction kettle, stirring and heating to 35 ℃, slowly dripping the synthesized resin prepolymer, continuously reacting for 20 hours, and slowly cooling to obtain RFL emulsion, wherein the mol ratio of resorcinol to formaldehyde in the RFL emulsion is 1:8.
Preparation examples 8 to 12
The total amount of resorcinol and formaldehyde was controlled to 30g in accordance with preparation 7, except that the molar ratio of resorcinol to formaldehyde in the RFL emulsion was controlled to be 1:25, 1:3, 1:14, 1:12 and 1:18, respectively.
The following examples are presented to illustrate the preparation of sized carbon fibers
Examples 1 to 6
Examples 1-6 are all a method for manufacturing 60K carbon fiber, comprising:
pre-oxidation: the polyacrylonitrile-based precursor sequentially passes through a No. 1 oxidation furnace, a No. 2 oxidation furnace, a No. 3 oxidation furnace and a No. 4 oxidation furnace for pre-oxidation treatment. The temperatures of the four heating temperature zones are 236 ℃, 246 ℃, 257 ℃ and 269 ℃ respectively. The pre-oxidation time is the same in each temperature zone, and the total pre-oxidation time is 56 minutes. The draft ratios between the oxidation furnaces of the four heating temperature zones are respectively 1.25, 0.99 and 0.96;
low temperature carbonization: taking nitrogen as a medium, sequentially passing the pre-oxidized filament bundles through 5 low-temperature carbonization furnaces with the temperature of 500 ℃, 595 ℃, 665 ℃, 780 ℃ and 830 ℃ respectively, controlling the draft ratio of each region to be 1.07, and controlling the total residence time in the low-temperature carbonization furnaces to be 1.2 minutes to prepare the low-temperature carbonized filament;
high temperature carbonization: taking nitrogen as a medium, sequentially passing the filament bundles through 5 high-temperature carbonization furnaces with the temperature of 935 ℃, 1200 ℃, 1260 ℃, 1320 ℃ and 1430 ℃ respectively, controlling the draft ratio of each region to be 0.77, and controlling the total residence time in the high-temperature carbonization furnaces to be 1.2 minutes to prepare high-temperature carbonized filaments;
surface treatment: the high-temperature carbonized wire enters a surface treatment tank through a traction device, an ammonium bicarbonate aqueous solution is used as electrolyte, the voltage is 20V, the concentration of the electrolyte is 13wt%, and the treatment time is 60 seconds, so that the carbon fiber after surface treatment is obtained;
washing: washing the surface-treated carbon fiber at the washing flow of 3100L/h and the washing temperature of 52 ℃ to obtain a washed carbon fiber tow;
sizing and drying: directly introducing the carbon fiber tows after washing into a first sizing tank for pre-sizing, and then performing pre-drying under the condition of setting technological parameters through an electric heating hot roller; then the carbon fiber enters a second sizing tank for secondary sizing, and then is subjected to secondary drying under the condition of set technological parameters by a horizontal hot air dryer to obtain sized carbon fiber;
winding and reeling: and winding and filament collecting the sized carbon fiber by using a carbon fiber winding machine under 2420-2550cN tension to obtain the sized carbon fiber for reinforcing the rubber material.
Wherein the kinds of the sizing agent, the pre-sizing amount, the secondary sizing amount and the kinds of the secondary sizing agent (molar ratio of resorcinol to formaldehyde) are shown in table 3, and the pre-drying and secondary drying process parameters are shown in table 4.
Comparative example 1
Comparative example 1 is a method for manufacturing 60K carbon fiber, which is identical to the method of example 1, except that the sizing and drying process is: and (3) dipping and sizing the unglued carbon fiber by adopting a commercial KTM-3 epoxy emulsion sizing agent, and drying by horizontal hot air at a drying temperature of 150 ℃.
Comparative example 2
Comparative example 2 is a method for manufacturing 60K carbon fiber, which is identical to the method of example 1, except that the sizing and drying process is: the unglued carbon fiber is dipped and sized by adopting the RFL emulsion prepared in the preparation example 7, and is dried by horizontal hot air at the drying temperature of 150 ℃.
Comparative example 3
Comparative example 3 is a method for manufacturing 60K carbon fiber, consistent with the method of example 1, except that the ungumped carbon fiber is pre-sized with a polyvinyl alcohol PVA1788 aqueous sizing agent, pre-dried to horizontal hot air drying, pre-drying temperature 80 ℃; and (3) carrying out secondary sizing on the carbon fiber by adopting the RFL emulsion prepared in the preparation example 7, wherein the secondary drying is horizontal hot air drying, and the secondary drying temperature is 165 ℃.
TABLE 3 Table 3
TABLE 4 Table 4
Test case
The sized carbon fibers prepared in examples and comparative examples were subjected to conductivity and adhesion tests, and the results are shown in table 5.
TABLE 5
| Numbering device | Volume resistivity (Ω cm) | Cohesive force (N/cm) |
| Comparative example 1 | 5.9×10 7 | 104 |
| Comparative example 2 | 4.4×10 7 | 110 |
| Comparative example 3 | 6.8×10 6 | 123 |
| Example 1 | 3.5×10 3 | 157 |
| Example 2 | 3.2×10 3 | 170 |
| Example 3 | 2.8×10 3 | 167 |
| Example 4 | 3×10 3 | 154 |
| Example 5 | 3.8×10 3 | 152 |
| Example 6 | 3.4×10 3 | 162 |
As can be seen from the data in tables 1 to 4 and the results in Table 5, examples 1 to 6 adopting the technical scheme of the present invention have good effects, the pre-sizing agent contains conductive polymer particles and polyvinyl alcohol, the contact angle is less than or equal to 20 degrees, the surface tension is less than or equal to 70mN/m, the specific sizing and drying process of the present invention is used for sizing the sizing carbon fiber and the rubber matrix in a synergistic step-by-step manner, the binding force of the finally prepared sizing carbon fiber and the rubber matrix is obviously improved, and the conductivity is improved. Specifically, the binding force of the sizing carbon fiber and the rubber matrix is not lower than 152N/cm, and the volume resistivity is not higher than 3.8X10 3 Omega cm, the overall improvement effect is obvious.
And in the comparative example 1, only the conventional epoxy emulsion KTM-3 is adopted, and in the comparative example 2, only the RFL emulsion prepared in the preparation example 7 is adopted to size the carbon fiber, so that the prepared carbon fiber has lower binding force with a rubber matrix and poor conductivity. The comparative example 3 adopts the pre-sizing polyvinyl alcohol solution with overlarge contact angle and surface tension, and the improvement effect is not obvious.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210985094.7A CN117626662A (en) | 2022-08-17 | 2022-08-17 | Method for preparing sized carbon fiber by step-by-step sizing and application of sized carbon fiber and sized carbon fiber |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005023481A (en) * | 2003-07-03 | 2005-01-27 | Toho Tenax Co Ltd | Carbon fiber cord for rubber reinforcement and fiber reinforced rubber material |
| US20190078247A1 (en) * | 2016-02-12 | 2019-03-14 | Istanbul Teknik Universitesi Rektorlugu | Device and method for continuous coating of carbon fibres with an electrochemical method |
| CN112760984A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing carbon fiber for composite material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005023481A (en) * | 2003-07-03 | 2005-01-27 | Toho Tenax Co Ltd | Carbon fiber cord for rubber reinforcement and fiber reinforced rubber material |
| US20190078247A1 (en) * | 2016-02-12 | 2019-03-14 | Istanbul Teknik Universitesi Rektorlugu | Device and method for continuous coating of carbon fibres with an electrochemical method |
| CN112760984A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing carbon fiber for composite material |
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