CN110983775B - Surface modified fiber for filling reinforcement, preparation method thereof and fiber reinforced composite material - Google Patents
Surface modified fiber for filling reinforcement, preparation method thereof and fiber reinforced composite material Download PDFInfo
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Abstract
The invention belongs to the field of composite materials, and particularly relates to a surface modified fiber for filling reinforcement, a preparation method thereof and a fiber reinforced composite material. The surface modified fiber for filling and reinforcing consists of a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating consists of a polyvinyl alcohol matrix and carbon-based nano materials dispersed in the polyvinyl alcohol matrix, and the mass ratio of the polyvinyl alcohol to the carbon-based nano materials in the hybrid coating is (0.5-5): (0.1-5). The surface modified fiber for filling and reinforcing can increase the surface roughness and the surface energy of the fiber surface, can improve the composite effect of the fiber and a matrix, increase the interface layer density and improve the composite strength when preparing a fiber reinforced composite material.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a surface modified fiber for filling reinforcement, a preparation method thereof and a fiber reinforced composite material.
Background
The fiber reinforced composite material is a composite material which takes fibers as reinforcing agents to reinforce various matrixes, can overcome the defect of a single material, and meets the actual use requirement. But the weak interface bonding force between the fiber and the matrix limits the exertion of the high performance of the fiber, so that the composite material shows extremely low shear strength. In order to improve the comprehensive mechanical properties of the composite material and expand the application field of the fiber composite material, the surface of the fiber is often modified to improve the interface bonding force between the fiber and the matrix.
The surface modification of the fiber is to change the specific surface area and the surface polarity of the fiber surface, improve the compatibility with a matrix, improve the interface performance and improve the interlaminar shear force of the composite material. The prior methods for modifying the surface of the fiber mainly comprise the following steps: (1) a coating method; (2) a plasma treatment method; (3) surface oxidation; (4) surface grafting method; (5) electrochemical deposition method, etc. The methods can improve the interface performance of the composite material, but all the methods need to carry out pre-treatment such as desizing, pre-oxidation and the like on fibers, for example, in the preparation method of the graphene-coated glass fiber composite material disclosed in the Chinese patent application with the application publication No. CN104591551A, the glass fibers need to be washed by acetone and hydrochloric acid in advance to remove a sizing agent on the surfaces of the fibers, the modification process has certain damage to the mechanical properties of fiber strands, the effect of modifying the surfaces of the fibers is not ideal, and the shearing resistance of the material compounded with a matrix is poor.
Disclosure of Invention
The invention aims to provide a surface modified fiber for filling reinforcement, which aims to solve the problem of poor composite effect of the modified fiber and a matrix.
The invention also aims to provide a preparation method of the surface modified fiber for filling reinforcement, which aims to solve the problem that the mechanical property of fiber protofilament is damaged by the existing fiber surface modification method.
The third purpose of the invention is to provide a fiber reinforced composite material to solve the problem of low shear strength of the existing fiber composite material.
In order to achieve the purpose, the technical scheme of the surface modified fiber for filling reinforcement provided by the invention specifically comprises the following steps:
the surface modified fiber for filling and reinforcing comprises a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating consists of a polyvinyl alcohol matrix and a carbon-based nano material dispersed in the polyvinyl alcohol matrix, the carbon-based nano material is at least one of graphene oxide and carbon oxide nano tubes, and the mass ratio of the polyvinyl alcohol to the carbon-based nano material in the hybrid coating is (0.5-5): (0.1-5).
The surface modified fiber for filling reinforcement is characterized in that a hybrid coating consisting of polyvinyl alcohol and a carbon-based nano material is loaded on the surface of a fiber body, the polyvinyl alcohol contains a large number of hydroxyl groups, the carbon-based nano material is oxidized to introduce a large number of polar oxygen-containing groups on the surface of the carbon-based nano material, can chemically react with oxygen-containing functional groups (hydroxyl groups, carboxyl groups and epoxy groups) in a sizing agent on the surface of the fiber body or form hydrogen bonding action, and participates in a curing reaction with a resin matrix in the forming process of the composite material to form a strong interaction force, a multiphase and multilevel interface structure, and the carbon-based nano material is oxidized to contain the oxygen-containing functional groups, so that the carbon-based nano material is more beneficial to being uniformly dispersed in the polyvinyl alcohol solution and enhancing the interface bonding force.
The surface modified fiber for filling and reinforcing can increase the surface roughness and the surface energy of the fiber body, is favorable for forming good wetting property and mechanical embedding or meshing force between the fiber and resin when preparing a fiber reinforced composite material, can improve the composite effect of the fiber and a matrix, increases the density of an interface layer and improves the composite strength. Compared with a hybrid fiber composite material prepared from unmodified fibers, the interlaminar shear strength of the fiber reinforced composite material prepared from the fibers and the matrix prepared from the surface modified fibers for filling and reinforcing can be improved by 49 percent to the maximum extent.
In order to improve the dispersion uniformity of the carbon-based nano material in the polyvinyl alcohol matrix, the particle size of the carbon-based nano material is 3-15 nm.
In order to make the surface of the fiber body fully contact with the mixed liquid, the fiber body is specifically selected from fiber untwisted yarns.
The preparation of graphene oxide and carbon oxide nanotubes is prior art.
The technical scheme of the preparation method of the surface modified fiber for filling reinforcement is as follows:
a preparation method of the surface modified fiber for filling reinforcement comprises the following steps: mixing polyvinyl alcohol, carbon-based nano material and water to prepare a mixed solution, putting the fiber body into the mixed solution for soaking, then pulling out the fiber, and drying to obtain the carbon-based nano fiber.
The preparation method of the surface modified fiber for filling reinforcement is a continuous preparation method, is simple to operate, has high efficiency and is easy for industrial production. Polyvinyl alcohol has good film forming property, and generally, water-soluble polyvinyl alcohol can be selected to meet the requirement. Any method can be adopted for forming the mixed solution, for example, the polyvinyl alcohol and the carbon-based nano material are added simultaneously or sequentially, and only the uniform dispersion of all substances in the finally obtained mixed solution is ensured. Because the polyvinyl alcohol is dissolved in water to ensure that the liquid has certain viscosity and the carbon-based nano material cannot be dissolved in water, the carbon-based nano material can be dispersed in the water and uniformly mixed, and then the polyvinyl alcohol is added, so that the mixed liquid can be simply and efficiently obtained.
In order to improve the fiber modification effect, the mass fraction of the polyvinyl alcohol in the mixed solution is 0.5-5%, and the mass fraction of the carbon-based nano material is 0.1-5%.
In order to make the fiber body fully contact with the mixed solution, various soaking treatment modes can be selected, for example, soaking is carried out under the assistance of ultrasound; the system can also be soaked for a long time under the condition of stirring, and the system can also be subjected to heating treatment on the basis of the soaking for improving the treatment efficiency.
In order to fully soak the fiber body in the mixed liquid, the ultrasonic power is 200-1600W, and the ultrasonic treatment time is 2-10 h.
The technical scheme of the fiber reinforced composite material provided by the invention specifically comprises the following steps:
the fiber reinforced composite material is compounded by the surface modified fiber for filling and reinforcing and the resin matrix in the technical scheme.
The fiber reinforced composite material is formed by compounding the surface modified fibers for filling and reinforcing and a resin matrix, has strong interaction force and a multi-phase and multi-level interface structure, and the shear strength of the composite material is obviously improved.
On the basis of a single fiber reinforced composite material, in order to further improve the comprehensive performance of the fiber reinforced composite material, more than two types of surface modified fibers for filling and reinforcing and a resin matrix are compounded to form a hybrid fiber reinforced composite material, the composite material has more excellent comprehensive performance and higher freedom of material selection in design, interface layers are more unevenly transited due to the difference of the surface structures and the compositions of various fibers and the influence of the hybrid structures of the surface structures and the compositions of various fibers, different characteristics are presented, and the requirements of various structural materials can be met.
According to the requirement on the performance of the composite material, the fiber body in the hybrid fiber reinforced composite material is selected from at least two of glass fiber, carbon fiber and Kevlar fiber.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of a glass fiber that has not been surface modified;
FIG. 2 is a scanning electron micrograph of the surface of a surface modified glass fiber of the present invention;
FIG. 3 is a scanning electron micrograph of the surface of carbon fiber without surface modification;
FIG. 4 is a scanning electron microscope image of the surface modified carbon fiber of the present invention;
FIG. 5 is a flow chart of a pultrusion process for preparing the fiber-reinforced composite of the present invention;
FIG. 6 is a schematic cross-sectional view of a concentric hybrid fiber in a fiber-reinforced composite of the present invention.
Detailed Description
The following examples are provided to further illustrate the practice of the invention. Examples 1 to 6 are examples of the surface-modified fiber for filling and reinforcing of the present invention, examples 7 to 12 are examples of the method for producing the surface-modified fiber for filling and reinforcing of the present invention, and examples 13 to 18 are examples of the fiber-reinforced composite material of the present invention.
1. Specific examples of the surface-modified fiber for filling reinforcement of the present invention
Example 1
The surface-modified fiber for filling reinforcement in the embodiment comprises a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating comprises a polyvinyl alcohol matrix and graphene oxide dispersed in the polyvinyl alcohol matrix, the mass ratio of the polyvinyl alcohol to the graphene oxide in the hybrid coating is 5. The fiber body is carbon fiber and glass fiber with the volume ratio of 1. In other implementations, a single fiber, such as carbon fiber or glass fiber, may be used.
Scanning electron micrographs of the surfaces of the glass fibers before and after surface modification are respectively shown in fig. 1 and fig. 2, and scanning electron micrographs of the surfaces of the carbon fibers before and after surface modification are respectively shown in fig. 3 and fig. 4, and it can be known by comparison that the surfaces of the glass fibers and the carbon fibers without surface modification are smooth, and the surfaces of the carbon fibers are provided with grooves arranged along the axial direction of the fibers, and the grooves are defects formed in the production process of the carbon fibers, and are beneficial to mechanical engagement between the carbon fibers and matrix resin although the strength of the carbon fibers is damaged; the surface-modified glass fiber and carbon fiber are uniformly covered with the modified substances, the surface roughness of the glass fiber and the carbon fiber is obviously increased, a lamellar structure and a large number of burr structures are presented, and some granular structures formed by agglomeration of partial graphene oxide/carbon oxide nanotubes appear. The structure is beneficial to enhancing the mechanical riveting and friction force between the fiber and the matrix resin and enhancing the interface bonding force between the fiber and the resin. Comparing fig. 3 and fig. 4, it can be known that the depth of the groove on the surface of the carbon fiber is obviously reduced, which makes up the defect of the carbon fiber to a certain extent and is beneficial to improving the strength of the carbon fiber.
Example 2
The surface-modified fiber for filling reinforcement in the embodiment comprises a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating comprises a polyvinyl alcohol matrix and graphene oxide dispersed in the polyvinyl alcohol matrix, the mass ratio of the polyvinyl alcohol to the graphene oxide in the hybrid coating is 0.5. The fiber body is carbon fiber and glass fiber with the volume ratio of 1.
Example 3
The surface-modified fiber for filling reinforcement in the embodiment comprises a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating comprises a polyvinyl alcohol matrix and graphene oxide dispersed in the polyvinyl alcohol matrix, the mass ratio of the polyvinyl alcohol to the graphene oxide in the hybrid coating is 2. The fiber body is carbon fiber and glass fiber with the volume ratio of 1.
Example 4
The surface-modified fiber for filling and reinforcing of the embodiment comprises a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating comprises a polyvinyl alcohol matrix and graphene oxide dispersed in the polyvinyl alcohol matrix, the mass ratio of the polyvinyl alcohol to the graphene oxide in the hybrid coating is 4. The fiber body is carbon fiber and glass fiber with the volume ratio of 1.
Example 5
The surface-modified fiber for filling reinforcement in the embodiment comprises a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating comprises a polyvinyl alcohol matrix and graphene oxide dispersed in the polyvinyl alcohol matrix, the mass ratio of the polyvinyl alcohol to the graphene oxide in the hybrid coating is 1. The fiber body is carbon fiber and glass fiber with the volume ratio of 1. In other implementations, a single fiber, such as carbon fiber or glass fiber, may be used.
Example 6
The surface modified fiber for filling and reinforcing of the embodiment comprises a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating comprises a polyvinyl alcohol matrix and carbon oxide nanotubes dispersed in the polyvinyl alcohol matrix, the mass ratio of the polyvinyl alcohol to the carbon oxide nanotubes in the hybrid coating is 0.5. The fiber body is carbon fiber and glass fiber with the volume ratio of 1.
2. Specific examples of the production method of the surface-modified fiber for filling reinforcement of the invention
Example 7
In this example, a method for producing a surface-modified fiber for filling reinforcement in example 1 will be described, which comprises the steps of:
(1) Processing graphene by using a Hummers method to obtain graphene oxide, wherein the thickness of a lamella of the graphene oxide is 3-8 nm;
(2) Dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to prepare a uniform mixed solution of graphene oxide and water with the mass fraction of 0.1%;
(3) Adding polyvinyl alcohol (PVA-L-8, the type is that of kohlrabi, japan) into a mixed solution of graphene oxide and water with the mass fraction of 0.1%, fully dissolving at 100 ℃, and uniformly dispersing by ultrasonic to prepare a polyvinyl alcohol/graphene oxide uniform mixed solution with the mass fraction of 5% of polyvinyl alcohol and the mass fraction of 0.1% of graphene oxide;
(4) Completely immersing carbon fibers and glass fibers with the volume ratio of 1.
Example 8
In this example, a method for producing the surface-modified fiber for filling reinforcement in example 2 is described, which includes the steps of:
(1) Processing graphene by using a Hummers method to obtain graphene oxide, wherein the thickness of a lamella of the graphene oxide is 3-8 nm;
(2) Dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to prepare a uniform mixed solution of graphene oxide and water, wherein the mass fraction of the mixed solution is 5%;
(3) Adding polyvinyl alcohol (type: japanese Coli, PVA-L-8) into a mixed solution of 5% by mass of graphene oxide and water, fully dissolving at 100 ℃, and uniformly dispersing by ultrasonic to obtain a polyvinyl alcohol/graphene oxide uniform mixed solution with the mass fraction of 0.5% by mass of the polyvinyl alcohol and the mass fraction of the graphene oxide of 5%;
(4) Completely immersing carbon fibers and glass fibers in a volume ratio of 1.
Example 9
In this example, a method for producing the surface-modified fiber for filling reinforcement in example 3 will be described, which includes the steps of:
(1) Processing graphene by a Hummers method to obtain graphene oxide, wherein the thickness of a lamella of the graphene oxide is 3-8 nm;
(2) Dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain a uniform mixed solution of graphene oxide and water with the mass fraction of 3%;
(3) Adding polyvinyl alcohol (type: japanese Coli, PVA-L-8) into a mixed solution of 3% by mass of graphene oxide and water, fully dissolving at 100 ℃, and uniformly dispersing by ultrasonic to obtain a polyvinyl alcohol/graphene oxide uniform mixed solution with the mass fraction of 2% by mass of the polyvinyl alcohol and the mass fraction of 3% by mass of the graphene oxide;
(4) Completely immersing carbon fibers and glass fibers with the volume ratio of 1.
Example 10
In this example, a method for producing a surface-modified fiber for filling reinforcement in example 4 will be described, which comprises the steps of:
(1) Processing graphene by using a Hummers method to obtain graphene oxide, wherein the thickness of a lamella of the graphene oxide is 3-8 nm;
(2) Dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain a uniform mixed solution of graphene oxide and water with the mass fraction of 1%;
(3) Adding polyvinyl alcohol (PVA-L-8, the model of which is kohli, japan) into a mixed solution of 1% by mass of graphene oxide and water, fully dissolving at 100 ℃, and uniformly dispersing by ultrasonic to prepare a polyvinyl alcohol/graphene oxide uniform mixed solution of 4% by mass of polyvinyl alcohol and 1% by mass of graphene oxide;
(4) Completely immersing carbon fibers and glass fibers with the volume ratio of 1.
Example 11
In this example, a method for producing the surface-modified fiber for filling reinforcement in example 5 is described, which comprises the steps of:
(1) Processing graphene by a Hummers method to obtain graphene oxide, wherein the thickness of a lamella of the graphene oxide is 3-8 nm;
(2) Dispersing graphene oxide in deionized water, and performing ultrasonic dispersion to obtain a uniform mixed solution of graphene oxide and water with the mass fraction of 1%;
(3) Adding polyvinyl alcohol (PVA-L-8, the type: nippon Coli) into a mixed solution of graphene oxide and water with the mass fraction of 1%, fully dissolving at 100 ℃, and uniformly dispersing by ultrasonic to prepare a polyvinyl alcohol/graphene oxide uniform mixed solution with the mass fraction of 1% of polyvinyl alcohol and the mass fraction of 1% of graphene oxide;
(4) Completely immersing carbon fibers and glass fibers with the volume ratio of 1.
Example 12
In this example, a method for producing the surface-modified fiber for filling reinforcement in example 6 is described, which comprises the steps of:
(1) Adding a carbon nano tube into a mixed solution of concentrated sulfuric acid and concentrated nitric acid with a volume ratio of 3;
(2) Dispersing the carbon oxide nanotubes in deionized water, and performing ultrasonic dispersion to obtain a uniform mixed solution of the carbon oxide nanotubes and water, wherein the mass fraction of the mixed solution is 1%;
(3) Adding polyvinyl alcohol (type: nippon Coli, PVA-L-8) into a mixed solution of 1% by mass of carbon oxide nanotubes and water, fully dissolving at 100 ℃, and uniformly dispersing by ultrasonic to obtain a polyvinyl alcohol/carbon oxide nanotube uniform mixed solution of 1% by mass of polyvinyl alcohol and 1% by mass of carbon oxide nanotubes;
(4) Completely immersing carbon fibers and glass fibers with the volume ratio of 1.
3. Specific examples of the fiber-reinforced composite Material of the present invention
The fiber-reinforced composite materials of examples 13 to 18 were prepared by the pultrusion process of fig. 5 from the surface-modified fibers for filling reinforcement and polyurethane of examples 1 to 6, and were reinforced by the concentric hybrid of unidirectional continuous carbon fibers/glass fibers having a diameter of 9.0mm, and the schematic cross-sectional view of the hybrid structure thereof is shown in fig. 6, in which the core portion shown in white was glass fibers and the shell portion shown in black was carbon fibers.
4. Comparative example
The same process flow as in example 13 was used to prepare a 9.0mm diameter unidirectional continuous carbon/glass fiber concentric hybrid reinforced polyurethane composite using carbon and glass fibers and polyurethane in a volume ratio of 1.
5. Examples of the experiments
The unidirectional continuous carbon fiber/glass fiber concentric hybrid reinforced polyurethane composite materials of examples 13 to 18 were subjected to an interlaminar shear property test, and the test results obtained are shown in table 1. The shear performance test method specifically comprises the following steps: testing the interlaminar shear strength of the composite material sample by adopting a microcomputer-controlled electro-hydraulic servo universal testing machine (the maximum test force is 3000kN; the product model is SHT 4306-W) according to GB/T14208.4-2009; wherein the length of the sample is 8 times of the diameter, and the speed of the loading pressure head is 1mm/min.
TABLE 1 interlaminar shear strength of unidirectional continuous carbon fiber/glass fiber concentric hybrid reinforced polyurethane composites
The polyvinyl alcohol/carbon oxide based nano material hybrid coating modified carbon fiber/glass fiber concentric hybrid reinforced polyurethane composite material prepared by the preparation method of the surface modified fiber for filling reinforcement has higher interlaminar shear strength which is up to 70.5MPa, while the interlaminar shear strength of the carbon fiber/glass fiber concentric hybrid reinforced polyurethane composite material which is not subjected to surface modification is 47.2MPa, which is improved by 49 percent compared with the interlaminar shear strength.
Claims (5)
1. The surface modified fiber for filling and reinforcing is characterized by comprising a fiber body and a hybrid coating loaded on the surface of the fiber body, wherein the hybrid coating consists of a polyvinyl alcohol matrix and carbon-based nano materials dispersed in the polyvinyl alcohol matrix, the carbon-based nano materials are graphene oxide or carbon oxide nanotubes, and the fiber body is carbon fiber and glass fiber with the volume ratio of 1; the thickness of the graphene oxide sheet layer is 3-8 nm, and the diameter of the oxidized carbon nanotube is 3-15 nm;
when the carbon-based nano material is graphene oxide, the mass ratio of polyvinyl alcohol to the carbon-based nano material in the hybrid coating is 1;
when the carbon-based nano material is a carbon oxide nano tube, the mass ratio of the polyvinyl alcohol to the carbon-based nano material in the hybrid coating is 0.5.
2. A method for preparing the surface-modified fiber for filling reinforcement according to claim 1, which comprises the steps of: mixing polyvinyl alcohol, carbon-based nano material and water to prepare a mixed solution, putting the fiber body into the mixed solution for soaking, then pulling out the fiber, and drying to obtain the carbon-based nano fiber.
3. The method of preparing the surface-modified fiber for filling reinforcement according to claim 2, wherein the infiltrating is performed with the aid of ultrasound.
4. The method for preparing the surface-modified fiber for filling reinforcement according to claim 3, wherein the power of the ultrasonic wave is 200 to 1600W, and the time of the ultrasonic treatment is 2 to 10 hours.
5. A fiber-reinforced composite material comprising the surface-modified filler-reinforcing fiber according to claim 1 and a resin matrix.
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