CN112522815A - Oversized-tow carbon fiber, preparation method thereof, continuous fiber reinforced resin matrix composite material and wind power blade - Google Patents
Oversized-tow carbon fiber, preparation method thereof, continuous fiber reinforced resin matrix composite material and wind power blade Download PDFInfo
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- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention relates to an oversized-tow carbon fiber and a preparation method thereof, a continuous fiber reinforced resin matrix composite material and a wind power blade, wherein the composite material comprises a resin matrix and the oversized-tow continuous carbon fiber doped in the resin matrix, and the oversized-tow continuous carbon fiber is obtained by pre-oxidizing and carbonizing civil acrylic fibers; the main beam and/or the tail edge beam of the wind power blade are formed by stacking a plurality of the composite materials. Compared with the prior art, the continuous fiber reinforced resin matrix composite material is introduced into the wind power blade, so that the cost of the existing carbon fiber composite material product can be greatly reduced, a more excellent cost ratio material is provided for the structural design of the wind power blade, and the competitiveness of the blade and a fan product is improved.
Description
Technical Field
The invention relates to the technical field of wind driven generators, in particular to an oversized-tow carbon fiber and a preparation method thereof, a continuous fiber reinforced resin matrix composite material and a wind power blade.
Background
Wind energy is a clean energy with large storage and high safety. The wind power generation needs to utilize the blades at the top end of the fan to drive the rotation by wind energy to generate lift force, and the lift force is further converted into torque through a transmission chain in the engine room to drive the generator to generate power. In the same case, the larger the impeller, the more wind energy that can be captured, and therefore the longer the blades of the fan. The weight of the blade is usually in a cubic relationship with the length of the blade, so that the weight of the blade increases sharply with the increase of the length, thereby placing higher and higher requirements on the design of the blade. The optimal design of the blade is one of the core technologies of wind power generation. At present, most of the traditional structural forms of the blades are still two shells which are divided into a pressure surface and a suction surface, and the shells are formed by pouring and curing a sandwich plate consisting of glass fiber reinforced plastics and core materials and main bearing parts, namely a main beam and a tail edge beam together. The main beam contributes most of the flapping stiffness, while the trailing edge beam contributes most of the shimmy stiffness. The web plate support is arranged inside the two shells to ensure the sufficient stability of the structure, and finally the web plate and the shells, and the shells are combined together by structural adhesive. The longer the blade, the more efficient material is needed to quickly increase the blade stiffness.
Generally, a traditional main beam of a wind power blade is laid in a main beam mold by adopting a glass fiber unidirectional fabric, resin is introduced in a vacuum infusion mode and finally cured, the main beam component is prefabricated, and then the main beam component and a shell are subjected to infusion curing again. The ultra-large blades simply adopt glass fibers, so that the extreme requirement on rigidity cannot be met, and therefore fibers with higher modulus need to be introduced.
Carbon fiber is an attractive option in this case, and with its high specific modulus, specific strength, the equivalent stiffness and strength levels of fiberglass blades can be achieved with very little material. Carbon fibers can be classified into aviation grade and industrial grade according to mechanical properties, and can be classified into small tows 1k,3k, 6k,12k,24k, large tows 24k,48k,50k and ultra-large tows 100k or more according to the number of monofilaments in a fiber tow. Currently, only a few manufacturers try to use 6k,12k carbon fiber prepreg, or 24k and 48k,50k carbon fiber pultruded panels as the material for the blade spar. Although the modulus of the carbon fiber composite material is 2 to 4 times that of the glass fiber composite material, the price is usually 10 times or more than that of the glass fiber composite material, and thus the cost performance is still difficult to be competitive enough. The traditional carbon fiber is prepared by pre-oxidizing and carbonizing industrial polyacrylonitrile precursor, and the process route has no great change from the beginning of the invention of the carbon fiber, so the price is always high, wherein the cost of the precursor accounts for about 50 percent of the cost of the carbon fiber.
Therefore, the development of more cost-effective carbon fibers to replace glass fibers to enable larger blades becomes a key technical direction.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a continuous fiber reinforced resin matrix composite material with higher cost performance, and particularly, civil large-tow acrylon with approximate chemical components is used for replacing the original industrial polyacrylonitrile precursor, so that the cost of the precursor can be reduced, and the subsequent pre-oxidation and carbonization efficiency is improved due to the increased number of tows, and finally the cost of the carbon fiber is reduced.
The application also aims to provide a wind power blade applying the composite material.
It is also an object of the present application to provide an oversized-tow continuous carbon fiber.
The application also aims to provide a preparation method of the oversized-tow continuous carbon fiber.
In order to achieve the object of the present invention, the present application provides the following technical solutions.
In a first aspect, the application provides a continuous fiber reinforced resin matrix composite, the composite comprises a resin matrix and super large tow continuous carbon fibers doped in the resin matrix, and the super large tow continuous carbon fibers are obtained by pre-oxidizing and carbonizing civil acrylic fibers. Carbon fibres can provide the required stiffness of the blade more efficiently with their high specific modulus than glass fibres.
In one embodiment of the first aspect, the doped volume percentage of the extra large tow continuous carbon fibers in the composite material is between 40% and 80%. If the doping ratio is too low, the rigidity of the composite material is too low to reach the design modulus; if the doping ratio is too large, the process is difficult to realize.
In one embodiment of the first aspect, the number of filaments in the super large tow continuous carbon fiber is 100k or more.
In one embodiment of the first aspect, the composite material is doped with hybrid fibers, and the doping percentage of the hybrid fibers is 0 to 20%. The addition of other fibers can not only enhance the functionality of the composite material, such as impact resistance, electrical conductivity and thermal conductivity, but also can obtain the composite material with specific modulus and strength by adding fibers with different ratios.
In one embodiment of the first aspect, the hybrid fiber includes one or more of carbon fiber, glass fiber, aramid fiber, boron fiber, basalt fiber, and ultra-high modulus polyethylene fiber, wherein the number of filaments in the carbon fiber is 12-50 k, and the modulus of the ultra-high modulus polyethylene fiber is 87-172 GPa.
In one embodiment of the first aspect, the resin matrix comprises a thermosetting resin or a thermoplastic resin, wherein the thermosetting resin comprises one of an epoxy resin, a vinyl resin, an unsaturated polyester resin, a polyurethane resin, or a phenolic resin, and the thermoplastic resin comprises one of a polypropylene, a polyethylene, a polyvinyl chloride, a polystyrene, a polyacrylonitrile-butadiene-styrene, a polyamide, a polyetheretherketone, or a polyphenylene sulfide resin.
In a second aspect, the present application provides a wind power blade, wind power blade includes two casings and webs, the casing includes sandwich panel and main load-bearing part, main load-bearing part includes girder and/or trailing edge roof beam, girder and/or trailing edge roof beam are formed by the polylith as above continuous fibers reinforcing resin base combined material piles up.
In one embodiment of the second aspect, the main and/or trailing edge beams are stacked from 1 to 300 pieces of composite material.
In a third aspect, the application further provides an oversized-tow continuous carbon fiber, wherein the oversized-tow continuous carbon fiber is obtained by pre-oxidizing and carbonizing civil acrylic fibers.
In one embodiment of the third aspect, the number of filaments in the super large tow continuous carbon fiber is 100k or more.
In one embodiment of the third aspect, the acrylic fibers for civil use are fibers containing a copolymer or homopolymer of acrylonitrile having 85% or more acrylonitrile.
In a fourth aspect, the present application also provides a preparation method of the extra large tow continuous carbon fiber, the preparation method comprising the following steps:
(1) dipping the civil acrylic fibers in an organic amine solution or an oxidation reduction solution, and then drying to obtain the pretreated civil acrylic fibers;
(2) and placing the pretreated civil acrylic fibers in an air atmosphere for preoxidation, and then placing the pretreated civil acrylic fibers in an inert gas atmosphere for carbonization to obtain the super-large-tow continuous carbon fibers.
In one embodiment of the fourth aspect, the organic amine solution comprises one of an aqueous solution of amine acetate, amine formate, guanidine hydrochloride, ethylene diamine tetraacetic acid, triethylamine, urea, trimethylamine, dicyanodiamine, n-hexylamine, dihexylamine, cyanamide, pentylamine, diethylamine, hexylamine, t-butylamine, n-butylamine, propylamine, isopropylamine, monoethanolamine, diethanolamine, triethanolamine, propylenediamine, benzylamine, piperidine, pyridine, piperazine, or imidazole.
In one embodiment of the fourth aspect, the redox solution comprises one of phenol, benzoic acid, potassium permanganate, potassium dichromate, hydrogen peroxide, hydrazine hydrate, hydroxylamine solutions. The dipping temperature is 10-150 ℃, and the dipping time is 1-600 min.
In one embodiment of the fourth aspect, the dipping temperature is 10 to 150 ℃, and the dipping time is 1 to 600 min.
In one embodiment of the fourth aspect, the temperature of the drying is 30 to 100 ℃.
In one embodiment of the fourth aspect, the pre-oxidation temperature is 200 to 300 ℃, and the pre-oxidation time is 10 to 120 min.
In one embodiment of the fourth aspect, the inert gas comprises one of nitrogen, helium, neon, or argon.
In one embodiment of the fourth aspect, the temperature of the carbonization is 300 to 1700 ℃, and the time of the carbonization is 1 to 20 min.
Compared with the prior art, the invention has the beneficial effects that:
based on a key force bearing part designed by the wind power blade, the high-cost-performance-ratio extra-large tow carbon fiber pre-oxidized and carbonized by introducing civil acrylic protofilament is taken as a composite material made of hybrid fiber, so that the unit cost modulus of the composite material unidirectional plate can be increased from 1-1.5GPa/RMB/kg to 1.8-3GPa/RMB/kg, and the cost of the wind power blade made of the fiber reinforced composite material is further reduced by 10% -20% compared with that of the wind power blade made of 24k or 48k common tow carbon fiber in the market, thereby providing support for the large scale of the wind power blade and the high efficiency of material utilization.
Drawings
FIG. 1 is a typical cross-sectional view of a wind blade according to the present invention;
FIG. 2 is a cross-sectional view of a wind blade main beam of the present invention;
fig. 3 is a cross-sectional view of the composite material for wind power in example 1.
In the attached drawings, 1 is a wind power blade, 2 is a front edge, 31 is a main beam, 32 is a tail edge beam, 4 is a web plate, 5 is a pressure surface, 6 is a suction surface, 7 is a tail edge, 8 is a composite material plate, 9 is glass fiber, 10 is boron fiber, 11 is a resin matrix, and 12 is ultra-large tow continuous carbon fiber.
Detailed Description
It should be noted that the components in the figures may be exaggerated and not necessarily to scale for illustrative purposes. In the figures, identical or functionally identical components are provided with the same reference symbols.
In the present invention, "disposed on …", "disposed over …" and "disposed over …" do not exclude the presence of an intermediate therebetween, unless otherwise specified. Further, "disposed on or above …" merely indicates the relative positional relationship between two components, and may also be converted to "disposed below or below …" and vice versa in certain cases, such as after reversing the product direction.
In the present invention, the embodiments are only intended to illustrate the aspects of the present invention, and should not be construed as limiting.
In the present invention, the terms "a" and "an" do not exclude the presence of a plurality of elements, unless otherwise specified.
It is further noted herein that in embodiments of the present invention, only a portion of the components or assemblies may be shown for clarity and simplicity, but those of ordinary skill in the art will appreciate that, given the teachings of the present invention, required components or assemblies may be added as needed in a particular scenario.
It is also noted herein that, within the scope of the present invention, the terms "same", "equal", and the like do not mean that the two values are absolutely equal, but allow some reasonable error, that is, the terms also encompass "substantially the same", "substantially equal". By analogy, in the present invention, the terms "perpendicular", "parallel" and the like in the directions of the tables also cover the meanings of "substantially perpendicular", "substantially parallel".
The numbering of the steps of the methods of the present invention does not limit the order of execution of the steps of the methods. Unless specifically stated, the method steps may be performed in a different order.
Glass fiber is added into a main beam or a tail edge beam of a traditional wind power blade, but the rigidity of the traditional wind power blade cannot be met along with the increase of the wind power blade. Therefore, in the prior art, the carbon fibers with the monofilament number below 100k are added, so that the rigidity of the wind power blade is increased, but the rigidity of the material is not greatly improved due to the high price of the carbon fibers and the unit price of unit weight, so that the practical application prospect is poor. The purpose of this application is through the introduction of the super low-cost carbon fiber that super large silk bundle civilian acrylic fiber precursor made through preoxidation and carbonization, promotes the specific stiffness of blade owner load-carrying structure girder, promotes the holistic comprehensive price/performance ratio of blade. The forming process may include fiber pultrusion, vacuum infusion, or prepreg forming. In order to achieve the purpose, the continuous fiber reinforced resin matrix composite material for the wind power blade is super-large tow carbon fiber formed by pre-oxidizing and carbonizing textile grade super-large tow civil acrylic fiber precursor.
In the composite material of the present invention, in addition to the ultra-large tow continuous carbon fibers, one or more of hybrid fibers such as carbon fibers, glass fibers, aramid fibers, boron fibers, basalt fibers, and ultra-high modulus polyethylene fibers may or may not be included.
In the composite material of the present invention, the resin matrix contains a thermosetting resin such as an epoxy resin, a vinyl resin, an unsaturated polyester resin, a polyurethane resin, a phenol resin, or a thermoplastic resin such as polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyacrylonitrile-butadiene-styrene, polyamide, polyetheretherketone, polyphenylene sulfide resin.
Examples
The following will describe in detail the embodiments of the present invention, which are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
Example 1
Preparing super large tow continuous carbon fiber:
(1) will be purchased commercially
(delinted) L900 civil acrylic fibers are dipped in an ethylenediamine solution at normal temperature, taken out after 5 hours and dried, and the drying temperature is 60 ℃. Drying for 2h to obtain pretreated civil acrylic fibers;
(2) pre-oxidizing the pretreated civil acrylic fiber in an air atmosphere at the pre-oxidation temperature of 200 ℃. And pre-oxidizing for 2h, and then carbonizing in a nitrogen gas atmosphere at 1000 ℃ for 15min to obtain the ultra-large tow continuous carbon fiber.
Preparing a continuous fiber reinforced resin matrix composite material:
100kg of ultra-large tow continuous carbon fiber 12 is hung on a creel, simultaneously, the glass fiber 9 and the boron fiber 10 are also respectively hung on different rollers of the creel, proper drawing force is applied to straighten the fibers and have certain tension, the ultra-large tow continuous carbon fiber 12, the glass fiber 9, the boron fiber 10 and epoxy resin are uniformly mixed, a plate made of a continuous fiber reinforced resin matrix composite material is obtained through pultrusion through a mold with a specific cross section shape, the plate is structurally shown in figure 3, the epoxy resin is used as a resin matrix 11, the ultra-large tow continuous carbon fiber 12, the glass fiber 9 and the boron fiber 10 are uniformly doped in the plate, and in the embodiment, the volume ratio of the tow ultra-large continuous carbon fiber 12 to the glass fiber 9 to the boron fiber 10 to the resin matrix 11 is 60:1:1: 38.
A plurality of composite material sheets 8 (7 are shown as an example) are stacked to form a main beam 31 as shown in fig. 2.
Preparing a wind power blade:
the prepared main beams 31, the sandwich plate and the tail edge beam 32 are jointly poured to form two shells, wherein the sandwich plate is composed of glass fiber reinforced plastics and core materials, the tail edge beam 32 is made of the existing glass fiber pouring materials, the two shells are butted end to form the wind power blade 1, the wind power blade 1 comprises a front edge 2, a pressure surface 5, a suction surface 6 and a tail edge 7, meanwhile, a web plate 4 is fixed between the two main beams 31, and the concrete structure is shown in figure 1.
Example 2
Preparing super large tow continuous carbon fiber:
(1) will be purchased from Delhi company
(Derong) L900 was immersed in a 10 ℃ solution of ammonium acetate, taken out after 10 hours and dried at a drying temperature of 30 ℃. Drying for 4h to obtain pretreated civil acrylic fibers;
(2) pre-oxidizing the pretreated civil acrylic fiber in an air atmosphere at the pre-oxidation temperature of 250 ℃. And (3) oxidizing for 1.5h, and then carbonizing in a nitrogen gas atmosphere at the carbonization temperature of 800 ℃ for 10min to obtain the oversized-tow continuous carbon fiber.
Preparing a continuous fiber reinforced resin matrix composite material:
the ultra-large tow continuous carbon fiber and the glass fiber are mixed and woven into a single-layer hybrid fabric, then the multiple layers of hybrid fabrics are uniformly and sequentially laid in a main beam mold, a resin matrix is introduced in a vacuum environment, and the mixture is cured and formed, so that the hybrid fiber tail edge beam is prefabricated. In this example, the volume ratio between the ultra large tow continuous carbon fibers, the glass fibers, and the resin matrix was 65:10: 25.
Example 3
Preparing super large tow continuous carbon fiber:
(1) will be purchased from Delhi company
(Derong) L900 was immersed in a triethylamine solution at 100 ℃ for 1 hour, and then taken out and dried to obtain a dry temperature of 100 ℃. Drying for 1h to obtain pretreated civil acrylic fibers;
(2) pre-oxidizing the pretreated civil acrylic fiber in an air atmosphere at the pre-oxidation temperature of 300 ℃. And pre-oxidizing for 10min, and then carbonizing in a nitrogen gas atmosphere at 1700 ℃ for 1min to obtain the ultra-large tow continuous carbon fiber.
Preparing a continuous fiber reinforced resin matrix composite material:
and (3) uniformly laying the ultra-large tow continuous carbon fibers on the resin matrix film to prepare the carbon fiber prepreg. And then sequentially laying a plurality of layers of carbon fiber prepregs in a main beam mold, and heating to cure and mold the carbon fiber prepregs so as to prepare the prefabricated main beam. In this example, the volume ratio between the oversized-tow continuous carbon fibers and the resin matrix was 80: 20.
A plurality of composite material sheets are stacked to form a main beam and a trailing edge beam.
Example 4
Preparing super large tow continuous carbon fiber:
(1) will be purchased from Delhi company
(delinted) L900 civil acrylic fibers are dipped in an ethylenediamine solution at normal temperature, taken out and dried after 5 hours, the drying temperature is 60 ℃, and the drying time is 2 hours, so that the pretreated civil acrylic fibers are obtained;
(2) pre-oxidizing the pretreated civil acrylic fiber in an air atmosphere at the pre-oxidation temperature of 250 ℃. And pre-oxidizing for 80min, and then carbonizing in a nitrogen gas atmosphere at 1200 ℃ for 10min to obtain the ultra-large tow continuous carbon fiber.
Preparing a continuous fiber reinforced resin matrix composite material:
taking the super-large tow continuous carbon fiber, applying a proper drawing force to straighten the fiber and have a certain tension, uniformly mixing the super-large tow continuous carbon fiber with the aramid fiber, the basalt fiber and the polystyrene resin, and performing pultrusion through a die with a specific section shape to obtain a plate made of the continuous fiber reinforced resin matrix composite material, wherein in the embodiment, the mass ratio of the super-large tow continuous carbon fiber to the aramid fiber to the basalt fiber to the resin matrix is 40: 10:10:40.
A plurality of composite material sheets are stacked to form a main beam and a trailing edge beam.
Example 5
Preparing super large tow continuous carbon fiber:
(1) will be purchased from Delhi company
(delinted) L900 civil acrylic fibers are dipped in a potassium permanganate solution at normal temperature, and are taken out and dried after 4 hours, the drying temperature is 50 ℃, and the drying time is 2 hours, so that the pretreated civil acrylic fibers are obtained;
(2) pre-oxidizing the pretreated civil acrylic fiber in an air atmosphere at the pre-oxidation temperature of 200 ℃. And pre-oxidizing for 2h, and then carbonizing in a nitrogen gas atmosphere at the carbonization temperature of 300 ℃ for 20min to obtain the ultra-large tow continuous carbon fiber.
The method comprises the steps of taking 100kg of ultra-large tow continuous carbon fiber, hanging the ultra-large tow continuous carbon fiber on a creel, simultaneously hanging basalt fiber and 100GPa ethylene fiber on different rolling shafts of the creel respectively, applying proper drawing force to straighten the fiber and provide certain tension, uniformly mixing the ultra-large tow continuous carbon fiber, the basalt fiber, the ethylene fiber and epoxy resin, and performing pultrusion through a die with a specific cross section shape to obtain a plate made of a continuous fiber reinforced resin matrix composite material, wherein the volume ratio of the ultra-large tow continuous carbon fiber, the basalt fiber, the ethylene fiber and a resin matrix is 50:10:10:30 in the embodiment.
A plurality of composite material sheets are stacked to form a main beam and a trailing edge beam.
Example 6
Preparing super large tow continuous carbon fiber:
(1) will be purchased from Delhi company
(delinted) L900 civil acrylic fibers are dipped in a hydrazine hydrate solution at normal temperature, taken out and dried after 3 hours, the drying temperature is 80 ℃, and the drying time is 2 hours, so that the pretreated civil acrylic fibers are obtained;
(2) pre-oxidizing the pretreated civil acrylic fiber in an air atmosphere at the pre-oxidation temperature of 270 ℃. And pre-oxidizing for 1h, and then carbonizing in a nitrogen gas atmosphere at 800 ℃ for 15min to obtain the ultra-large tow continuous carbon fiber.
Preparing a continuous fiber reinforced resin matrix composite material:
the method comprises the steps of weaving ultra-large tow continuous carbon fibers and glass fibers into a single-layer hybrid fabric in a mixed mode, then uniformly and sequentially laying a plurality of layers of hybrid fabrics in a main beam mold, introducing polystyrene in a vacuum environment, and curing and forming, so that the hybrid fiber tail edge beam is prefabricated. In this example, the volume ratio between the ultra large tow continuous carbon fiber, glass fiber, and polystyrene is 40:15: 45.
Comparative example 1
Preparation of continuous carbon fiber:
under certain polymerization conditions, under the action of an initiator, acrylonitrile is connected into linear polyacrylonitrile macromolecular chains, and the generated polyacrylonitrile spinning solution is subjected to spinning processes such as wet spinning or dry-jet wet spinning to obtain polyacrylonitrile protofilaments (namely common industrial acrylon).
Warping polyacrylonitrile precursor, feeding the warped polyacrylonitrile precursor into a pre-oxidation furnace to obtain pre-oxidized fibers, carbonizing the pre-oxidized fibers at low temperature and high temperature to obtain carbon fibers, and performing surface treatment and sizing on the carbon fibers to obtain carbon fiber products. The pre-oxidation temperature is controlled between 200 ℃ and 300 ℃. The polyacrylonitrile protofilament is converted into carbon fiber with a disordered graphite structure through preoxidation treatment, low-temperature carbonization and high-temperature carbonization, and finally the carbon fiber with the carbon content of more than 90% is formed. The number of the prepared carbon fiber tows is less than 50 k.
Preparing a continuous fiber reinforced resin matrix composite material:
taking continuous carbon fibers, applying a proper drawing force to straighten the fibers and have certain tension, and uniformly mixing the continuous carbon fibers, the glass fibers, the boron fibers and the epoxy resin to obtain a plate made of the composite material, wherein the volume ratio of the continuous carbon fibers, the glass fibers, the boron fibers and the resin matrix is 60:1:1: 38.
Performance testing
The composite materials prepared in examples 1-6 and comparative example 1 were subjected to modulus testing according to GB/T3354-.
The results are shown in the following table:
from the test results we can see that: the modulus of unit weight and unit price of the composite material made of the carbon fiber in the invention is between 1.8 and 3GPa/RMB/kg, which is far larger than that of 1.4GPa/RMB/kg of a comparative example, so that the cost of parts made of the material is lower when the material is used in the part design of the wind power blade and the same structural rigidity is achieved.
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (19)
1. The continuous fiber reinforced resin matrix composite material is characterized by comprising a resin matrix and super large tow continuous carbon fibers doped in the resin matrix, wherein the super large tow continuous carbon fibers are obtained by pre-oxidizing and carbonizing civil acrylic fibers.
2. The continuous fiber reinforced resin-based composite material according to claim 1, wherein the volume percentage of the extra large tow continuous carbon fibers doped in the composite material is 40% to 80%.
3. The continuous fiber reinforced resin-based composite material according to claim 1, wherein the number of filaments in the ultra-large tow continuous carbon fiber is 100k or more.
4. The continuous fiber reinforced resin-based composite material according to claim 1, wherein the composite material is doped with the hybrid fiber, and the doped volume percentage of the hybrid fiber is 0-20%.
5. The continuous fiber reinforced resin-based composite material of claim 4, wherein the hybrid fiber comprises one or more of carbon fiber, glass fiber, aramid fiber, boron fiber, basalt fiber or ultra-high modulus polyethylene fiber, wherein the number of monofilaments in the carbon fiber is 12k to 50k, and the modulus of the ultra-high modulus polyethylene fiber is 87 GPa to 172 GPa.
6. The continuous fiber reinforced resin based composite of claim 1, wherein the resin matrix comprises a thermosetting resin or a thermoplastic resin, wherein the thermosetting resin comprises one of an epoxy resin, a vinyl resin, an unsaturated polyester resin, a polyurethane resin, or a phenolic resin, and the thermoplastic resin comprises one of a polypropylene, a polyethylene, a polyvinyl chloride, a polystyrene, a polyacrylonitrile-butadiene-styrene, a polyamide, a polyetheretherketone, or a polyphenylene sulfide resin.
7. A wind power blade, wind power blade includes two casings and webs, the casing includes sandwich panel and main load-carrying parts, main load-carrying parts include girder and trailing edge roof beam, its characterized in that, girder and/or trailing edge roof beam are piled up by the polylith according to any one of claims 1 ~ 6 continuous fibers reinforcing resin base combined material.
8. The wind blade of claim 7 wherein the main and/or trailing edge beams are stacked from 1 to 300 pieces of composite material.
9. The oversized-tow continuous carbon fiber applied to the continuous fiber reinforced resin-based composite material as claimed in claim 1, wherein the oversized-tow continuous carbon fiber is obtained by pre-oxidizing and carbonizing civil acrylic fibers.
10. The extra large tow continuous carbon fiber of claim 9, wherein the number of filaments in the extra large tow continuous carbon fiber is 100k or more.
11. The extra large tow continuous carbon fiber of claim 9, wherein the civilian acrylic fibers are fibers of acrylonitrile copolymer or homopolymer having 85% or more acrylonitrile.
12. The method for preparing the extra-large tow continuous carbon fiber according to any one of claims 9 to 11, wherein the method comprises the following steps:
(1) dipping the civil acrylic fibers in an organic amine solution or an oxidation reduction solution, and then drying to obtain the pretreated civil acrylic fibers;
(2) and placing the pretreated civil acrylic fibers in an air atmosphere for preoxidation, and then placing the pretreated civil acrylic fibers in an inert gas atmosphere for carbonization to obtain the super-large-tow continuous carbon fibers.
13. The method of making extra large tow continuous carbon fiber according to claim 12, wherein the organic amine solution comprises one of an aqueous solution of amine acetate, amine formate, guanidine hydrochloride, ethylene diamine tetraacetic acid, triethylamine, urea, trimethylamine, dicyandiamide, n-hexylamine, dihexylamine, cyanamide, pentylamine, diethylamine, hexyldiamine, t-butylamine, n-butylamine, propylamine, isopropylamine, monoethanolamine, diethanolamine, triethanolamine, propylenediamine, benzylamine, piperidine, pyridine, piperazine, or imidazole.
14. The method of making oversized-tow continuous carbon fibers, according to claim 12, wherein the redox solution includes one of phenol, benzoic acid, potassium permanganate, potassium dichromate, hydrogen peroxide, hydrazine hydrate, hydroxylamine solutions.
15. The method for preparing extra large tow continuous carbon fiber according to claim 12, wherein in the step (1), the dipping temperature is 10 to 150 ℃ and the dipping time is 1 to 600 min.
16. The method of making oversized-tow continuous carbon fibers, according to claim 12, wherein the temperature of drying is 30 to 100 ℃.
17. The method for preparing oversized-tow continuous carbon fibers according to claim 12, wherein the pre-oxidation temperature is 200-300 ℃ and the pre-oxidation time is 10-120 min.
18. The method of making extra large tow continuous carbon fibers of claim 12, wherein the inert gas comprises one of nitrogen, helium, neon, or argon.
19. The method for preparing oversized-tow continuous carbon fibers according to claim 12, wherein the carbonization temperature is 300-1700 ℃, and the carbonization time is 1-20 min.
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| PCT/CN2021/071168 WO2022121081A1 (en) | 2020-12-08 | 2021-01-12 | Ultra-large tow of carbon fibers and preparation method therefor, continuous fiber reinforced resin-based composite material and wind power blade |
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| CN113583323A (en) * | 2021-07-07 | 2021-11-02 | 江阴爱科森博顿聚合体有限公司 | Carbon fiber material for wind power blade and preparation method thereof |
| CN113584875A (en) * | 2021-07-30 | 2021-11-02 | 北京化工大学常州先进材料研究院 | Modification method of large-tow polyacrylonitrile fibers |
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| CN114941188B (en) * | 2022-06-28 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Method for continuously preparing carbon fiber from acrylic fiber |
| CN117162561B (en) * | 2023-11-02 | 2024-03-22 | 中材科技风电叶片股份有限公司 | Thermoplastic composite girder forming method and wind power blade girder |
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