KR101864512B1 - Manufacturing method of carbon fiber - Google Patents
Manufacturing method of carbon fiber Download PDFInfo
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- KR101864512B1 KR101864512B1 KR1020160174756A KR20160174756A KR101864512B1 KR 101864512 B1 KR101864512 B1 KR 101864512B1 KR 1020160174756 A KR1020160174756 A KR 1020160174756A KR 20160174756 A KR20160174756 A KR 20160174756A KR 101864512 B1 KR101864512 B1 KR 101864512B1
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- carbon fiber
- prepare
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- carbon fibers
- solution
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M11/32—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
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M11/77—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 silicon or compounds thereof
- D06M11/79—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 silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
Abstract
The present invention relates to a method for producing a carbon fiber, comprising the steps of: mixing a titanium alkoxide with a silicate to prepare a mixed solution; Mixing the mixed solution with an aqueous hydrogen peroxide solution to prepare a coating solution; Impregnating the coating liquid with carbon fibers to produce impregnated carbon fibers; Drying the impregnated carbon fiber to prepare a surface-treated carbon fiber; And bonding the surface-treated carbon fibers and the thermoplastic resin to produce a composite carbon fiber.
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing carbon fibers, and more particularly, to a method for producing carbon fibers having improved strength and durability through surface treatment.
Carbon fiber has excellent mechanical strength and is widely used for aerospace materials, sports, leisure materials, and functional clothing materials.
These carbon fibers are produced by firing and carbonizing the fibers of the precursor thermoplastic resin bundled carbon fiber precursor fibers. In addition, since the carbon fiber can be used in a composite material form in combination with a matrix resin, it can be used in a variety of applications, so that it is often used in the form of a composite in combination with a resin.
In this case, since the adhesion between the carbon fibers and the matrix resin is insufficient, the surface of the carbon fibers is modified to improve the adhesiveness with the matrix resin in order to solve this problem.
Such surface modification is widely used, such as a liquid phase oxidation process such as an electrolytic oxidation process, a reaction liquid oxidation process, a gas phase oxidation process, a plasma process, and grafting. However, in order to perform such surface modification, post-treatment such as cleaning is often required, and an expensive and complicated manufacturing apparatus is required, which makes it difficult to control the manufacturing cost and process conditions.
For example, in Korean Patent Publication Nos. 10-1497286 and 10-0513960, an ozone solution is brought into contact with a carbon fiber to perform a surface treatment, A method of manufacturing a carbon fiber for improving adhesion is disclosed. Korean Patent Registration No. 10-1428423 discloses a method of surface-treating a carbon fiber with a coating solution containing a silane coupling agent and an AlOOH sol. In Korean Patent Registration No. 10-1482452, a carbon fiber is coated with Al 2 O 3 To the surface of the substrate.
However, in the surface treatment method of the prior art as described above, there are problems in the treatment of the waste solution after the reaction or it is difficult to obtain a sufficient adhesive force and it is difficult to process the composite into a composite.
SUMMARY OF THE INVENTION The present invention has been made in view of the above-described conventional techniques, and provides a method of manufacturing carbon fiber having improved adhesion to a thermoplastic resin by surface modification of the surface of carbon fibers with a coating solution containing titanium peroxide and silicate For that purpose.
It is another object of the present invention to provide a method for producing carbon fibers in which the coating layer formed by the surface modification includes titanium oxide particles, thereby improving the mechanical strength.
According to another aspect of the present invention, there is provided a method of manufacturing a carbon fiber, comprising: preparing a mixed solution by mixing titanium alkoxide and a silicate; Mixing the mixed solution with an aqueous hydrogen peroxide solution to prepare a coating solution; Impregnating the coating liquid with carbon fibers to produce impregnated carbon fibers; Drying the impregnated carbon fiber to prepare a surface-treated carbon fiber; And bonding the surface-treated carbon fibers and the thermoplastic resin to produce a composite carbon fiber.
At this time, the coating liquid contains titanium peroxide.
The silicate is any one of TEOS (tetraethylorthosilicate), TMOS (tetramethylorthosilicate), and silicon tetrachloride (SiCl 4 ), and the thermoplastic resin is any one of polyethylene, polypropylene, polystyrene, and nylon.
The method may further include the step of forming the composite carbon fiber in the form of a fabric through the step of producing the composite carbon fiber.
The method for producing a carbon fiber according to the present invention can provide a method for producing carbon fiber having improved adhesion to a thermoplastic resin by surface modification of the surface of the carbon fiber with a coating liquid containing titanium peroxide and silicate.
In addition, the coating layer formed through the surface modification includes titanium oxide particles, so that carbon fibers having improved mechanical strength can be produced.
1 is a process diagram showing a method for producing carbon fiber according to the present invention.
Hereinafter, the present invention will be described in more detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.
The method for producing carbon fiber according to the present invention comprises the steps of: mixing a titanium alkoxide with a silicate to prepare a mixed solution; Mixing the mixed solution with an aqueous hydrogen peroxide solution to prepare a coating solution; Impregnating the coating liquid with carbon fibers to produce impregnated carbon fibers; Drying the impregnated carbon fiber to prepare a surface-treated carbon fiber; And bonding the surface-treated carbon fibers and the thermoplastic resin to produce a composite carbon fiber.
The advantage of surface modification of the carbon fibers with an aqueous solution of peroxide is that the surface free energy of the carbon fibers can be increased to increase the adhesion at the interface with the thermoplastic resin.
When titanium alkoxide and silicate are mixed, Ti-O-Si bond is formed. This bond is formed by hydrolysis and polycondensation reaction of titanium alkoxide and silicate.
The titanium alkoxide may be selected from the group consisting of titanium ethoxide, titanium isopropoxide and titanium tetrabutoxide. Examples of the silicate include tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS) ), And silicon tetrachloride (SiCl 4 ).
Hydrolysis and polycondensation reaction can be carried out by adding water and an acid catalyst. When an acid catalyst such as hydrochloric acid or sulfuric acid is added, hydrolysis and polycondensation reaction are accelerated. However, in the subsequent reaction with hydrogen peroxide, It is possible to cause hydrolysis and polycondensation reaction by merely adding water corresponding to the stoichiometry.
Titanium peroxide can be prepared by reacting a titanium alkoxide with an aqueous hydrogen peroxide solution. In this case, when a titanium peroxide is reacted with a silicate, hydrolysis and polycondensation reaction by water are complicated, and Ti- O-Ti bond and Si-O-Si bond, and thus it can not be used as a coating solution.
The peroxide solution is prepared by mixing a titanium alkoxide with an aqueous hydrogen peroxide solution. It is known that the following reaction occurs in this process.
[Hydrolysis and polycondensation reaction]
TiOR '+ SiOR 4 → [(RO) 3 SiO] 3 -Ti-O-Si [OSi (RO) 3 ] 3
[Peroxide Formation Reaction]
[(RO) 3 SiO] 3 -Ti-OSi [OSi (RO) 3] 3 + H 2 O 2
→ [(RO) 3 SiO] 3 -Ti-O-OH + [(RO) 3 SiO] 3 -Si-OH
[Radical formation reaction]
[(RO) 3 SiO] 3 -Ti-O-OH → [(RO) 3 SiO] 3 -Ti-OO + H 2 O
The coating solution consisting of these peroxides forms radical ions suitable for causing surface modification of highly reactive carbon fibers. Therefore, when the carbon fiber is impregnated in the coating solution and then dried, the surface-treated carbon fiber is obtained.
That is, as shown in FIG. 1, the titanium hydrolyzate is bound to the surface of the carbon fiber to be surface-treated, and the desired carbon fiber is obtained through the process in which the silane group and the thermoplastic resin react with each other and are laminated on the outer surface .
At this time, when the carbon fiber is acid-treated with nitric acid or oxalic acid to increase the surface roughness, it is possible to obtain a surface-treated carbon fiber having higher adhesive strength.
In addition, the drying step is preferably performed for 10 to 20 minutes at a temperature of 100 to 110 ° C in order to form a coating film on the carbon fiber surface by causing a dehydration reaction. If the temperature is too high or the drying time is more than 20 minutes, the Ti-OO-bond may be broken or the Si-O-Ti bond may be broken to damage the coating layer. It is essential to keep the time not exceeding 20 minutes and the drying time of 10 minutes or more in which the dehydration reaction can sufficiently take place.
Therefore, the drying conditions should be very mild and rapid, and it is particularly preferable to dry them using a vacuum dryer. When drying in a conventional oven, the degree of drying varies depending on the position in the oven or the amount of the sample, so that it is very difficult to find a process optimum condition. Vacuum drying may be performed continuously while passing carbon fibers through a vacuum chamber equipped with a vacuum pump.
The surface-treated carbon fibers obtained as described above can be easily laminated by laminating a thermoplastic resin.
The thermoplastic resin is preferably any one of polyethylene, polypropylene, polystyrene, and nylon.
Further, in order to laminate the thermoplastic resin, the carbon fibers may be immersed in an aqueous hydrochloric acid solution having a pH of 3 to 5 and then reacted with the thermoplastic resin liquid, or may be laminated by impregnating the thermoplastic resin liquid and drying it.
The carbon fiber thus formed may be formed into a fabric form as necessary. The fabric can be processed in the form of nonwoven fabric, mesh, film or the like.
Further, the surface-treated carbon fibers may be processed into a fabric, and then the thermoplastic resin may be laminated to form a composite material.
Further, such a laminate may further perform heating and pressing to improve adhesion between the surface-treated carbon fiber and the thermoplastic resin. In this case, the heating process is preferably performed at a temperature of 150 to 200 ° C, and the pressing process is preferably performed at a pressure of 5 to 10 MPa.
In order to verify the effect of surface treatment using the coating solution of the present invention, carbon fiber (Comparative Example 1) surface-treated with a silane coupling agent and an AlOOH sol as disclosed in Korean Patent Publication No. 10-1428423, and hydrogen peroxide The carbon fiber prepared by laminating the polypropylene resin to the carbon fiber surface treated with the water (Comparative Example 2) was compared with the carbon fiber of the present invention, and the mechanical strength and adhesion were tested.
The carbon fibers prepared in this example were prepared by mixing titanium isopropoxide and tetraethyl orthosilicate in a molar ratio of 1: 1, adding a chemical equivalent of water, and subjecting the solution obtained through hydrolysis and polycondensation to a coating solution The PAN-based carbon fiber was impregnated into the coating solution, and the carbon fiber was dried in a vacuum dryer at 110 ° C for 15 minutes to prepare surface-treated carbon fibers, and a polypropylene resin was laminated thereon. For comparison, carbon fiber was prepared by laminating a polypropylene resin on a surface treated by drying in a vacuum dryer at 110 캜 for 30 minutes (Comparative Example 3).
In order to evaluate the adhesion of each carbon fiber, a nonwoven fabric was prepared from the carbon fiber, and the bending strength in a direction perpendicular to the fiber direction was measured by a three-point bending short beam method according to ASTM D790.
In addition, strength and modulus of elasticity were measured according to ASTM D4018.
The measurement results are shown in Table 1.
The results of Table 1 show that the bending strength of the embodiment using the titanium based coating solution is significantly higher than that of Comparative Example 1 using the aluminum based coating solution and Comparative Example 2 using the hydrogen peroxide solution. This suggests that the bonding strength between the carbon fiber and the resin is greatly improved by optimizing the kind of the coating liquid and the mechanical stability of the laminated portion is greatly improved.
Particularly, when the drying time of the coating liquid is prolonged, the Ti-O-Si bond or the Si-O-Si bond coated on the surface of the carbon fiber is destroyed, so that the bonding strength is rapidly deteriorated. Therefore, optimization of the drying process is essential for obtaining high-quality carbon fibers.
It is to be understood that the invention is not limited to the disclosed embodiment, but is capable of many modifications and variations within the scope of the appended claims. It is self-evident.
Claims (5)
Mixing the mixed solution with an aqueous hydrogen peroxide solution to prepare a coating solution;
Impregnating the coating liquid with carbon fibers to produce impregnated carbon fibers;
Drying the impregnated carbon fiber to prepare a surface-treated carbon fiber;
Bonding the surface-treated carbon fiber and the thermoplastic resin to produce a composite carbon fiber;
/ RTI >
Wherein the carbon fiber is carbon fiber treated with an acid with nitric acid or oxalic acid to increase the surface roughness.
Wherein the coating liquid comprises titanium peroxide.
Wherein the silicate is at least one selected from the group consisting of tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS), and silicon tetrachloride (SiCl 4 ).
Wherein the thermoplastic resin is one of polyethylene, polypropylene, polystyrene, and nylon.
Further comprising the step of forming the composite carbon fiber obtained through the step of producing the composite carbon fiber in the form of a fabric.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160174756A KR101864512B1 (en) | 2016-12-20 | 2016-12-20 | Manufacturing method of carbon fiber |
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| KR1020160174756A KR101864512B1 (en) | 2016-12-20 | 2016-12-20 | Manufacturing method of carbon fiber |
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| KR101864512B1 true KR101864512B1 (en) | 2018-06-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074869A (en) * | 2022-06-24 | 2022-09-20 | 河北师范大学 | Hollow carbon fiber material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920004191B1 (en) * | 1986-10-03 | 1992-05-30 | 피이피이지이 인더스트리이즈 인코포레이팃드 | A multi-componernt organoal koxysilane/ metal oxide sol-gel compositions and method for its production and coating |
| KR100513960B1 (en) | 2003-02-03 | 2005-09-13 | 한국화학연구원 | A method for preparing a carbon fiber reinforced composite having an improved mechanical property |
| KR101428423B1 (en) | 2013-11-15 | 2014-08-08 | 주식회사 포스코 | Manufacturing method of carbon fiber reinforced thermoplastic composite and the composite manufactured by the same |
| KR101482452B1 (en) | 2013-11-15 | 2015-01-14 | 주식회사 포스코 | Manufacturing method of carbon fiber reinforced thermoplastic composite and the composite manufactured by the same |
| KR101497286B1 (en) | 2011-08-02 | 2015-02-27 | 미쯔비시 레이온 가부시끼가이샤 | Carbon fiber manufacturing method and carbon fiber |
-
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- 2016-12-20 KR KR1020160174756A patent/KR101864512B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920004191B1 (en) * | 1986-10-03 | 1992-05-30 | 피이피이지이 인더스트리이즈 인코포레이팃드 | A multi-componernt organoal koxysilane/ metal oxide sol-gel compositions and method for its production and coating |
| KR100513960B1 (en) | 2003-02-03 | 2005-09-13 | 한국화학연구원 | A method for preparing a carbon fiber reinforced composite having an improved mechanical property |
| KR101497286B1 (en) | 2011-08-02 | 2015-02-27 | 미쯔비시 레이온 가부시끼가이샤 | Carbon fiber manufacturing method and carbon fiber |
| KR101428423B1 (en) | 2013-11-15 | 2014-08-08 | 주식회사 포스코 | Manufacturing method of carbon fiber reinforced thermoplastic composite and the composite manufactured by the same |
| KR101482452B1 (en) | 2013-11-15 | 2015-01-14 | 주식회사 포스코 | Manufacturing method of carbon fiber reinforced thermoplastic composite and the composite manufactured by the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115074869A (en) * | 2022-06-24 | 2022-09-20 | 河北师范大学 | Hollow carbon fiber material and preparation method and application thereof |
| CN115074869B (en) * | 2022-06-24 | 2023-07-18 | 河北师范大学 | Hollow carbon fiber material and preparation method and application thereof |
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