CN117626657A - Preparation method of sizing carbon fiber for reinforcing rubber materials and sizing carbon fiber - Google Patents
Preparation method of sizing carbon fiber for reinforcing rubber materials and sizing carbon fiber Download PDFInfo
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Abstract
The invention relates to the technical field of carbon fiber preparation, and discloses a preparation method of sizing carbon fiber for reinforced rubber materials and the sizing carbon fiber. 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, pre-sizing and pre-drying are carried out by adopting a pre-sizing agent containing polyacrylate and polyvinyl alcohol, so as 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; the contact angle of the pre-sizing agent is less than or equal to 30 DEG and the surface tension is less than or equal to 75mN/m. The contact angle of the pre-sizing agent in the method is smaller than 30 degrees, the surface tension is smaller than 75mN/m, and the binding force of the prepared sizing carbon fiber and a rubber matrix can be obviously improved on the premise of meeting the bundling 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 preparation method of sizing carbon fiber for reinforced rubber materials and the sizing carbon fiber.
Background
Carbon fiber is one of the most promising high-performance fibers for industrial application, and can make up for the advantages of two or more materials after being compounded with matrix resin. The carbon fiber reinforced rubber-based composite material can integrate the rigidity of carbon fibers and the flexibility of rubber materials, has excellent comprehensive characteristics of tensile property, elastic modulus, heat resistance, fatigue resistance and the like, and is widely applied in the industrial field. But the carbon fiber has strong surface inertia and weak two-phase bonding capability with rubber materials. At present, a layer of sizing agent is coated on the surface in the carbon fiber preparation engineering, an epoxy emulsion material is used as a main material, the improvement of two-phase interface combination is not effective, and the performance advantages of the carbon fiber are difficult to fully develop. Meanwhile, the carbon fiber for reinforcing the rubber material has better bundling property so as to meet the severe requirements of winding, braiding and other procedures in the subsequent processing, and the processing efficiency of the carbon fiber is improved.
CN110758982a discloses a carbon fiber core rubber conveyer belt and a manufacturing method thereof, which adopts thermoplastic elastomer polymer materials to coat carbon fiber bundles, can effectively solve the defects of high brittleness and the like of the carbon fiber bundles, so that the carbon fiber bundles are not easy to break, and then surface treatment is carried out to improve the compounding capability. The method is difficult to be practically applied because of the problems of high melting temperature, difficult dissolution of the solvent, poor stability and the like of the thermoplastic elastomer.
CN104710716a discloses a rubber sizing agent, which is composed of polyvinyl alcohol, sodium acetate, acetic acid, diketene, sodium salt of butenoate and butenoic acid copolymer, etc., and has a certain film forming effect, but has no good effect on improving two-phase interface.
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 application, it is found that the bonding capability between the RFL emulsion and the surface of the carbon fiber is not strong, and the bonding property between the carbon fiber and the rubber matrix after sizing cannot be effectively improved by only adopting the RFL emulsion.
Disclosure of Invention
The invention aims to solve the problems that only RFL emulsion is adopted to slurry carbon fibers in the prior art, and the bonding force between the sized carbon fibers and a rubber matrix is not strong, and provides a preparation method of the sized carbon fibers for reinforced rubber materials and the sized carbon fibers. The invention combines a specific pre-sizing agent with a specific sizing method, and can obviously improve the binding force between the prepared sizing carbon fiber and the rubber matrix on the premise of meeting the basic bundling requirement of the sizing carbon fiber.
In order to achieve the above object, a first aspect of the present invention provides a method for producing sized carbon fibers for reinforcing rubber materials, characterized by 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 agent containing polyacrylate and polyvinyl alcohol is adopted to pre-size and pre-dry carbon fiber tows after washing, so as 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 30 degrees and the surface tension is less than or equal to 75mN/m.
In a second aspect, the present invention provides a sized carbon fiber prepared by the preparation method of the first aspect.
Through the technical scheme, the preparation method of the sizing carbon fiber for the reinforced rubber material, provided by the invention, has the following beneficial effects:
(1) The sizing and drying method of pre-sizing, pre-drying, secondary sizing and secondary drying is carried out on the carbon fiber tows subjected to pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment and water washing, and the sizing and drying method is combined with a pre-sizing agent with a contact angle less than or equal to 30 degrees and a surface tension less than or equal to 75mN/m, so that the surface structure and composition of the sized carbon fiber can be accurately regulated, and finally, the interface effect between the sized carbon fiber and a rubber matrix is enhanced, and the binding force is improved.
(2) The pre-sizing agent contains polyacrylate and polyvinyl alcohol, so that the interpenetration of multiphase interfaces can be promoted, and the bundling performance of sizing fibers can be effectively improved while the sizing carbon fibers and a rubber matrix are ensured to have excellent binding force.
(3) The preparation method is suitable for the existing carbon fiber industrial production line, excessive transformation and upgrading are not needed, and the process adaptability is high; and the pre-sizing agent and the secondary sizing agent have low cost and wide industrial application prospect.
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 first aspect of the invention provides a method for preparing sizing carbon fibers for reinforced rubber materials, which is characterized by comprising the following steps: 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 agent containing polyacrylate and polyvinyl alcohol is adopted to perform pre-sizing and pre-drying on the carbon fiber tows after water washing, so as 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 30 degrees and the surface tension is less than or equal to 75mN/m.
In the invention, the inventor researches and discovers that after pre-oxidizing, carbonizing at low temperature, carbonizing at high temperature, surface treating and washing, the polyacrylonitrile-based precursor is subjected to stepped sizing by combining a method of pre-sizing, pre-drying, secondary sizing and secondary drying, and the contact angle of the pre-sizing agent is less than or equal to 30 degrees, and the surface tension is less than or equal to 75mN/m, so that the situation that the RFL emulsion is only used for sizing in the prior art, the poor wetting and spreading on the surface of the inert carbon fiber is caused, and the discontinuous and unstable bonding point is caused can be overcome.
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 present invention, the high temperature carbonization process is carried out in a high temperature carbonization furnace divided into 5 heating temperature zones, the temperatures of the 5 heating temperature zones 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%.
In the present invention, the number average molecular weight of the polyvinyl alcohol is 20000 to 200000, preferably 50000 to 150000.
In the invention, the polyacrylate is at least one selected from polymethyl acrylate, polyethyl acrylate, polypropylene acrylate and polybutyl acrylate.
In the invention, the polyacrylate is selected from the above types, and is cooperated with the polyvinyl alcohol, 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 when the pre-sizing agent is applied, and the bundling property of the sizing fiber can be improved to a certain extent.
According to the invention, the polyacrylate is polybutyl acrylate.
According to the invention, the polyacrylate has a number average molecular weight of 2000 to 6000, preferably 3000 to 5000.
According to the invention, the mass ratio of the polyvinyl alcohol to the polyacrylate is 1:0.4-1:0.8.
In the invention, when the mass ratio of the polyvinyl alcohol to the polyacrylate meets the above range, the binding force between the sizing carbon fiber and the rubber matrix can be further improved when the pre-sizing agent is applied.
According to the invention, the mass ratio of the polyvinyl alcohol to the polyacrylate is 1:0.5-1:0.7.
According to the present invention, the presize agent has a contact angle of 10 ° or less and a surface tension of 70mN/m or less.
In the invention, when the contact angle and the surface tension of the pre-sizing agent meet the above ranges, the binding force between the sizing carbon fiber and the rubber matrix can be improved while ensuring good bundling property of the sizing carbon fiber.
According to the present invention, in the first step, the pre-drying mode is a first infrared radiation drying mode.
According to the invention, the temperature of the pre-drying is 60-100 ℃, preferably 70-90 ℃.
According to the present invention, in the second step, the secondary drying mode is as follows: sequentially performing second infrared radiation drying and heat conduction oil roller drying;
according to the invention, the second infrared radiation drying temperature is 60-210 ℃, preferably 80-160 ℃.
According to the invention, the drying temperature of the heat conducting oil hot roller is 90-240 ℃, preferably 110-190 ℃.
According to the invention, the pre-drying adopts an infrared radiation drying mode, the secondary drying adopts an infrared radiation and heat conduction oil hot roller drying mode in sequence, and the pre-drying is synergistic with the step sizing process, so that the surface structure and composition of the carbon fiber can be accurately regulated and controlled, and the effects of enhancing the interface between the carbon fiber and the rubber matrix and improving the bundling performance of the fiber are realized.
In the invention, the first infrared radiation and the second infrared radiation are each independently performed using an infrared radiation heating dryer containing a carbon medium wave infrared radiator.
In the invention, when the first infrared radiation is carried out, the distance between the carbon medium wave infrared radiator and the carbon fiber of the infrared radiation heating dryer is 45-75mm, and the power density is 27-45KW/m 2 。
In the invention, when the second infrared radiation is carried out, the distance between the carbon medium wave infrared radiator and the carbon fiber of the infrared radiation heating dryer is 45-158mm, and the power density is 27-95KW/m 2 。
According to the invention, the resorcinol formaldehyde latex contains a rubber emulsion.
According to the present invention, the rubber emulsion is at least one selected from the group consisting of acrylic rubber emulsion, acrylonitrile-butadiene rubber emulsion, isoprene rubber emulsion, polyurethane rubber emulsion, ethylene-propylene rubber emulsion, chloroprene rubber emulsion, silicone rubber emulsion, hydrogenated nitrile rubber emulsion, styrene-butadiene rubber emulsion, polysulfide rubber emulsion, natural rubber emulsion, butadiene rubber emulsion, and butyl rubber emulsion, preferably butyl rubber emulsion.
In the present invention, the resorcinol formaldehyde latex in the second step may be prepared by a method commonly used in the art.
In the resorcinol formaldehyde latex of the present invention, the molar ratio of resorcinol to formaldehyde is 1:3 to 1:25, preferably 1:8 to 1:18.
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.
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%.
Bundling properties: the bundling properties were evaluated by testing the tow width of the sized fibers. The smaller the tow width, the better the bundling.
Adhesive force: the sized carbon fiber was embedded in an unvulcanized natural rubber block (wherein the mass of the sized carbon fiber was 20% 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-2 epoxy emulsion and polyvinyl alcohol PVA1788 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 polybutyl acrylate, 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.
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 polyacrylate in the pre-sizing agent and the properties of the pre-sizing agent are shown in Table 2.
TABLE 1
TABLE 2
| Pre-sizing agent | Polyvinyl alcohol/polyacrylate | Contact angle (°) | Surface tension (mN/m) |
| A1 | 1:0.4 | 15 | 75 |
| A2 | 1:0.7 | 10 | 65 |
| A3 | 1:0.5 | 8 | 70 |
| A4 | 1:0.7 | 30 | 58 |
| A5 | 1:0.7 | 5 | 62 |
| A6 | 1:0.8 | 22 | 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 1:3.
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 1:13, 1:10, 1:8, 1:25 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 methods for producing a homogeneous 48K 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 four heating temperature zones are respectively 235 ℃, 243 ℃, 255 ℃ and 267 ℃. The pre-oxidation time is the same in each temperature zone, and the total pre-oxidation time is 60 minutes. The draft ratios between the oxidation furnaces of the four heating temperature zones are respectively 1.26, 0.99, 0.98 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 490 ℃ and 580 ℃ and 650 ℃ and 760 ℃ and 820 ℃ respectively, controlling the draft ratio of each region to be 1.06, 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 bundle through 5 high-temperature carbonization furnaces with the temperature of 920 ℃, 1180 ℃, 1230 ℃, 1300 ℃ and 1410 ℃ respectively, controlling the draft ratio of each region to be 0.76, 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 18V, the concentration of the electrolyte is 10wt%, and the treatment time is 60 seconds, so that the carbon fiber after surface treatment is obtained;
washing: washing the carbon fiber subjected to surface treatment at the washing flow of 2800L/h and the washing temperature of 50 ℃ to obtain a washed carbon fiber tow;
sizing and drying: directly introducing the washed carbon fiber tows into a first sizing tank for pre-sizing, and then, through an infrared radiation dryer, pre-drying under the condition of set technological parameters; then the carbon fiber enters a second sizing tank for secondary sizing, and then sequentially passes through an infrared radiation dryer and a heat conduction oil hot roller for secondary drying under the condition of setting technological parameters to obtain the sized carbon fiber;
winding and reeling: and winding and filament collecting the sized carbon fiber by using a carbon fiber winding machine under the tension of 2360-2480cN to obtain the sized carbon fiber for reinforcing the rubber material.
Wherein the types of the sizing agent, the pre-sizing amount, the secondary sizing amount and the types of the secondary sizing agent (the molar ratio of resorcinol to formaldehyde) are shown in table 3, and the pre-sizing drying and the secondary sizing drying process parameters are shown in table 4.
Comparative example 1
Comparative example 1 is a method for manufacturing 48K carbon fiber, which is identical to the method of example 1, except that the sizing and drying process is as follows: and (3) dipping and sizing the unglued carbon fiber by adopting a commercially available KTM-2 epoxy emulsion sizing agent, and drying by horizontal hot air at the drying temperature of 100 ℃.
Comparative example 2
Comparative example 2 is a method for manufacturing 48K carbon fiber, which is identical to the method of example 1, except that the sizing and drying process is as follows: 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 48K 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 is horizontal hot air dried, and the pre-drying temperature is 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 sizing carbon fibers prepared in examples and comparative examples were subjected to bundling and adhesion tests, and the results are shown in table 5.
TABLE 5
| Numbering device | Tow width (mm) | Cohesive force (N/cm) |
| Comparative example 1 | 35.6 | 103 |
| Comparative example 2 | 40.9 | 112 |
| Comparative example 3 | 30.3 | 126 |
| Example 1 | 26.5 | 169 |
| Example 2 | 25.5 | 182 |
| Example 3 | 25.8 | 162 |
| Example 4 | 25 | 179 |
| Example 5 | 26 | 173 |
| Example 6 | 24.5 | 166 |
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 polyacrylate and polyvinyl alcohol, the contact angle is less than or equal to 30 degrees, the surface tension is less than or equal to 75mN/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, the bundling property is improved, and the overall improvement effect is obvious.
Specifically, the binding force between the sizing carbon fiber and the rubber matrix is not lower than 162N/cm, and the tow width of the sizing carbon fiber is not higher than 27mm. The comparative example 1 only adopts the traditional epoxy emulsion KTM-1, the comparative example 2 only adopts the RFL emulsion, and the prepared carbon fiber has lower binding force with the rubber matrix and poorer bundling property. 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.
Compared with comparative examples 1-3, the sizing carbon fiber has improved bundling property and greatly improved adhesion with a rubber matrix.
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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Citations (5)
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|---|---|---|---|---|
| JP2005023481A (en) * | 2003-07-03 | 2005-01-27 | Toho Tenax Co Ltd | Carbon fiber cord for rubber reinforcement and fiber reinforced rubber material |
| CN101790608A (en) * | 2007-05-25 | 2010-07-28 | 日本板硝子株式会社 | Rubber reinforcing member and rubber product utilizing the same |
| JP2011241502A (en) * | 2010-05-18 | 2011-12-01 | Toho Tenax Co Ltd | Manufacturing method of carbon fiber for rubber reinforcement |
| KR20120048895A (en) * | 2010-11-08 | 2012-05-16 | 웅진케미칼 주식회사 | Manufacturing method of carbon fiber |
| 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 (5)
| 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 |
| CN101790608A (en) * | 2007-05-25 | 2010-07-28 | 日本板硝子株式会社 | Rubber reinforcing member and rubber product utilizing the same |
| JP2011241502A (en) * | 2010-05-18 | 2011-12-01 | Toho Tenax Co Ltd | Manufacturing method of carbon fiber for rubber reinforcement |
| KR20120048895A (en) * | 2010-11-08 | 2012-05-16 | 웅진케미칼 주식회사 | Manufacturing method of carbon fiber |
| 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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