CN114032669A - Electrophoretic deposition-electropolymerization synchronous modification method for carbon fiber surface interface and carbon fiber composite material thereof - Google Patents

Electrophoretic deposition-electropolymerization synchronous modification method for carbon fiber surface interface and carbon fiber composite material thereof Download PDF

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CN114032669A
CN114032669A CN202111535642.8A CN202111535642A CN114032669A CN 114032669 A CN114032669 A CN 114032669A CN 202111535642 A CN202111535642 A CN 202111535642A CN 114032669 A CN114032669 A CN 114032669A
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carbon fiber
composite material
electropolymerization
resin
modified carbon
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邹华维
孙通
梁梅
陈洋
张雪琴
邱宝伟
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Sichuan University
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Sichuan University
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Abstract

The invention belongs to the technical field of carbon fiber composite materials, and particularly relates to a method for synchronously modifying a carbon fiber surface interface by electrophoretic deposition-electropolymerization and a carbon fiber composite material thereof. The modified carbon fiber provided by the invention is prepared by the following method: the carbon fiber is modified by combining electrophoretic deposition of the graphene material and polymer electropolymerization. The invention also provides a modified carbon fiber/resin composite material. The modified carbon fiber and the resin matrix in the composite material have better bonding performance, higher interlaminar shear strength, glass transition temperature and storage modulus, can be used for manufacturing aerospace aircrafts, transportation tools, high-performance equipment, sports equipment and the like, and have important application prospect.

Description

Electrophoretic deposition-electropolymerization synchronous modification method for carbon fiber surface interface and carbon fiber composite material thereof
Technical Field
The invention belongs to the technical field of carbon fiber composite materials, and particularly relates to a method for synchronously modifying a carbon fiber surface interface by electrophoretic deposition-electropolymerization and a carbon fiber composite material thereof.
Background
The carbon fiber composite material has excellent physicochemical, mechanical and thermal properties. It has wide application in the fields of traffic equipment, sports equipment, aerospace, national defense and the like. The resin matrix adopted by the carbon fiber reinforced resin matrix composite material is divided into two categories: thermosetting resins and thermoplastic resins are mainly thermosetting resins at present. Among thermosetting resins, since epoxy resin has the advantages of excellent adhesive property, good dimensional stability, good comprehensive properties and the like, carbon fiber reinforced epoxy resin based composite materials become the most widely used carbon fiber reinforced resin based composite materials in recent years, however, after the resin is cured, the bonding property with carbon fibers is deteriorated, and the interlaminar shear strength of the composite material is weak, which limits the application thereof.
Therefore, it is necessary to improve the bonding between the carbon fibers and the polymer matrix for the purpose of improving the mechanical properties of the composite material, such as the interlaminar shear strength.
The method is a way to improve the bonding between the carbon fiber and the polymer matrix by modifying the carbon fiber and improving the bonding between the carbon fiber and the polymer matrix by utilizing the performance of the modifier.
The graphene material has the characteristics of micro-nano size, large specific surface area, rich functional groups, excellent mechanical transfer behavior and the like. It has wide application prospect in polymer composite materials. The graphene material is introduced into the composite material of the polymer and the carbon fiber, so that the surface area of the carbon fiber can be enlarged, the wettability of the carbon fiber and a matrix is increased, and the interface bonding performance of the composite material is improved. In the traditional graphene material modified carbon fiber surface treatment method, the electrophoretic deposition method has the excellent characteristics of environmental friendliness, convenience in operation and uniformity in plating, and can be used for large-scale continuous production and preparation of carbon fiber multi-scale interface composite. For example, chinese patent "CN 108286187B a method for preparing graphene oxide modified carbon fiber by inducing electrophoretic deposition with silane coupling agent" provides a method for modifying graphene oxide on the surface of carbon fiber by electrophoretic deposition.
However, only the graphene material is used for modifying the carbon fiber, the improvement of the performance of the composite material is still not enough to meet the performance requirements of people on the material, and the chinese patent "CN 109608668A preparation of carbon fiber/graphene oxide/epoxy resin prepreg and carbon fiber composite material" discloses a carbon fiber composite material, which utilizes graphene oxide to improve the bonding performance of carbon fiber and epoxy resin, and further improves the bending strength and the interlaminar shear strength of the composite material. However, in this prior art, the improvement of the interlaminar shear strength can be achieved only by 16.74%, and the improvement range is limited. And the glass transition temperature and the storage modulus of the material are also lower.
On the other hand, the carbon fiber surface is previously modified with a polymer, and the bonding performance between the carbon fiber and the polymer matrix can be enhanced by the action between the functional group in the polymer previously modified and the polymer matrix.
Chinese patent CN 201610382926.0A preparation method of polyacrylonitrile-based conductive fiber material provides a method for polymerizing polymer monomers on carbon fibers by utilizing an electropolymerization method to form a compact coating layer. The electropolymerization method can be matched with a carbon fiber production line, and the electropolymerization produced can enhance the interface bonding force through the bonding action of functional groups.
In the existing carbon fiber modification technology, the method for electrophoretically depositing and modifying the graphene material and electropolymerizing and modifying the polymer is not simultaneously exemplified in a one-step process. Whether the carbon fiber material modified by the graphene material and the polymer material simultaneously can exert a better synergistic effect or not and whether the performance of the modified carbon fiber composite material can be further improved or not is unknown.
In addition, if the processes of electrophoretically depositing a modified graphene material and electropolymerizing a modified polymer are to be performed simultaneously, there are also problems as follows: (1) the deposition solution used for electrophoretic deposition is a suspension of a graphene material, and the stability of the deposition solution is poor, and if a polymerization monomer required for electropolymerization is directly added into the suspension of the graphene material, the graphene material in the suspension is aggregated and precipitated; (2) the existing electropolymerization and electrophoretic deposition technologies are not matched in time scale, have high electropolymerization efficiency and can be completed in only tens of seconds; whereas electrophoretic deposition takes tens of minutes to complete. If the time is too short, the amount of the graphene material modified on the surface of the carbon fiber by electrophoretic deposition is too small; if the time is long, the polymerized monomers on the surface of the carbon fiber generate multi-layer polymerization, the inner layer is firmly combined with the surface of the carbon fiber, but the cohesion of the polymer is not strong, the microcosmic interface of the obtained composite material is a weak interface, and the combination performance between the carbon fiber and the resin matrix cannot be improved.
In summary, the prior art lacks a process for modifying a carbon fiber material by combining an electrophoretic deposition modified graphene material method with an electropolymerization modified polymer method.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a modified carbon fiber and a resin matrix composite thereof by an electrophoretic deposition-electropolymerization one-step method. The purpose is as follows: the electrophoretic deposition of the graphene material and the electropolymerization of the polymer are realized on the surface of the carbon fiber, so that the prepared modified carbon fiber has better binding capacity with a resin matrix.
An electrolyte for producing a modified carbon fiber, which is prepared by dispersing the following components in an aqueous solution containing 0.01 to 0.7mol/L of an acid:
25-2000mg/L of graphene material and 5-500mmol/L of electropolymerization monomer.
Preferably, the electropolymerized monomer is selected from at least one of styrene, ethyl carbazole, caprolactam, methyl acrylate, pyrrole and derivatives thereof, thiophene and derivatives thereof, aniline and derivatives thereof, itaconic acid, aminobenzoic acid, itaconic acid acrylic acid, phenol, o-aminophenol derivatives or m-phenylenediamine;
and/or the graphene material is selected from at least one of graphene, carboxylated graphene oxide or aminated graphene oxide, and the size of the graphene material is 200 nanometers-50 micrometers;
and/or the concentration of the aqueous solution of the acid is 0.1mol/L, and/or the acid is selected from at least one of hydrochloric acid, sulfuric acid or nitric acid, preferably sulfuric acid, and/or the concentration of the graphene material is 250mg/L, and/or the electropolymerized monomer is a combination of itaconic acid and aminobenzoic acid, the concentration of the itaconic acid is 0.1mol/L, and the concentration of the aminobenzoic acid is 0.1 mol/L.
The present invention also provides a modified carbon fiber obtained by simultaneously carrying out electrophoretic deposition and electropolymerization using a carbon fiber as an anode in the electrolyte according to claim 1 or 2.
Preferably, the method for simultaneously performing electrophoretic deposition and electropolymerization comprises: applying direct current to the carbon fiber as an anode for electrochemical treatment;
preferably, the time of the electrochemical treatment is 10 to 600s, preferably 60 to 240s, preferably 90 to 150s, and more preferably 120 s; and/or the direct current density is 0.1-2mA/cm2Preferably 0.5mA/cm2(ii) a And/or, the electrochemical treatment process is assisted by using ultrasound; and/or in the electrochemical treatment process, two graphite electrodes are used as cathodes, the anode is positioned between the two cathodes, and the distance between the anode and the cathode is 1-2cm, preferably 1 cm; and/or drying the carbon fiber at 60-90 ℃ for 24 hours, preferably at 80 ℃ for 24 hours after electrochemical treatment to obtain the modified carbon fiber.
The invention also provides a preparation method of the modified carbon fiber, which comprises the following steps:
(1) taking the electrolyte;
(2) and (2) taking the carbon fiber as an anode, and simultaneously carrying out electrophoretic deposition and electropolymerization in the electrolyte in the step (1) to obtain the modified carbon fiber.
The invention also provides a modified carbon fiber/resin composite material, which is characterized in that: the modified carbon fiber is prepared by compounding the modified carbon fiber of claim 3 or 4 with a resin matrix, wherein the resin matrix is thermosetting resin or thermoplastic resin.
The invention also provides the composite material prepared by the method, the thermosetting resin is epoxy resin, phenolic resin, bismaleimide resin or polyimide resin, and the thermoplastic resin is polyphenylene sulfide, polyether ether ketone, nylon or polypropylene; the epoxy resin is preferably bisphenol A epoxy resin; and/or the volume fraction of the modified carbon fibers in the composite material is 30-60%.
The invention also provides a preparation method of the composite material, which comprises the following steps: and mixing the resin matrix and the curing agent, fully infiltrating the modified carbon fibers, and curing the resin matrix to obtain the carbon fiber reinforced plastic composite material.
Preferably, the using proportion of the resin matrix to the curing agent is 100: 20-30, preferably 100: 26; and/or the resin matrix and the curing agent are mixed at 50-100 ℃, preferably at 80 ℃; and/or the curing process is firstly curing for 1.5-2.5h under the conditions of 120-140 ℃ and 5MPa, preferably curing for 2h under the conditions of 135 ℃ and 5MPa, then curing for 1-3h under the conditions of 160-185 ℃ and 10MPa, preferably then curing for 2h under the conditions of 175 ℃ and 10MPa, and/or the curing agent is DDM.
The modified carbon fiber and/or the composite material are also used for manufacturing traffic equipment, sports equipment, space flight and aviation equipment or national defense and military products.
Through the technical scheme of the invention, the following beneficial effects are achieved:
(1) the invention successfully prepares the electrolyte with uniform dispersion and stability, and can be used for simultaneously carrying out electrophoretic deposition and electropolymerization modification on the carbon fiber. The process can simultaneously carry out two modifications in one step, and is simpler and more efficient.
(2) In the prior art, electropolymerization only needs tens of seconds, and electrophoretic deposition needs at least 20 minutes, so that the time mismatch of the electropolymerization and the electrophoretic deposition is difficult to perform in the same process; on the other hand, if the two processes of electrophoretic deposition and electropolymerization are respectively carried out, the process time needs to be dozens of minutes, and the process takes a long time. In the improved electrolyte and the carbon fiber modification method, electropolymerization has a promoting effect on electrophoretic deposition, so that the time required by electrophoretic deposition is greatly reduced, the time required by two processes is matched, and graphene materials and electropolymers can be formed on the surface of carbon fibers only within 10-600s when the two processes are carried out simultaneously.
(3) Test results show that the electrophoretic deposition of the graphene material and the modification of the electropolymerization one-step method improve the roughness of the surface of the carbon fiber, and increase the surface energy of the carbon fiber and the wettability of the resin matrix, so that the mechanical interlocking and the interface area of the fiber and the matrix can be increased. Meanwhile, the polymer on the surface of the carbon fiber can form a covalent bond with a resin matrix, so that the interlocking between the carbon fiber and the resin matrix can be improved, and the interfacial adhesion of the composite material is improved.
(4) According to the invention, by optimizing the time of electrochemical treatment, a uniform multi-scale three-dimensional reinforced structure is formed on the surface of the carbon fiber.
(5) Compared with unmodified carbon fibers, the interlaminar shear strength (ILSS) of the carbon fiber composite material modified by the method disclosed by the invention is increased by 33.8%, and is obviously higher than that of similar materials disclosed in the preparation of carbon fiber/graphene oxide/epoxy resin prepreg and carbon fiber composite material CN 109608668A.
(6) Compared with unmodified carbon fibers, the glass transition temperature and the storage modulus of the carbon fiber composite material modified by the method are both obviously improved. In the preferred embodiment, the glass transition temperature and the storage modulus reach 180.94 ℃ and 56.15GPa, which are respectively improved by 3.28 ℃ and 27.58GPa compared with the composite material of the unmodified carbon fiber.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a photograph of a graphene oxide suspension mixed with an electropolymerized monomer solution at different ratios and left stand;
FIG. 2 shows Zeta potentials after mixing and standing graphene oxide suspensions with different proportions and an electropolymerization monomer solution;
FIG. 3 is an infrared spectrum of modified and unmodified (Untreated-CF) carbon fibers;
FIG. 4 is a Raman spectrum of modified and unmodified (Untreated-CF) carbon fibers;
FIG. 5 is a graph of the thermogravimetric curves of modified and unmodified (Untreated-CF) carbon fibers;
FIG. 6 is an XPS broad spectrum and C1s spectra of modified and unmodified (Untreated-CF) carbon fibers;
FIG. 7 is an SEM image of modified and unmodified (Untreated-CF) carbon fibers; wherein, (a) Untated-CF, (b) CF-GO @ EPI60s，(c)CF-GO@EPI90s，(d)CF-GO@EPI120s，(e)CF-GO@EPI150s，(f)CF-GO@EPI240s；
FIG. 8 is an atomic force microscope image of modified and unmodified (Untreated-CF) carbon fibers;
FIG. 9 is a graph showing the wettability of modified and unmodified (Untreated-CF) carbon fibers with water;
FIG. 10 is a graph of the wettability of modified and unmodified (Untreated-CF) carbon fibers with uncured epoxy resin;
FIG. 11 is a graph showing interlaminar shear strength (a) and stress-strain curve (b) of a composite of carbon fiber and epoxy resin before and after modification in comparative example 1(Untreated-CF) and example 1;
FIG. 12 is an SEM image (parallel to the fiber direction) of a damaged surface of a composite material of carbon fiber and epoxy resin before and after modification of comparative example 1(Untreated-CF) and example 1;
FIG. 13 is an SEM image (perpendicular to the fiber direction) of a damaged surface of a composite material of carbon fiber and epoxy resin before and after modification of comparative example 1(Untreated-CF) and example 1;
FIG. 14 is a scanning electron microscope image after a micro-debonding experiment of a carbon fiber and epoxy resin composite before and after modification of comparative example 1(Untreated-CF) and example 1;
FIG. 15 shows the dynamic mechanical properties of the carbon fiber-epoxy composite before and after modification in comparative example 1(Untreated-CF) and example 1.
Detailed Description
The reagents and starting materials used in the following examples are shown in table 1:
TABLE 1 Experimental reagents and raw materials
Figure BDA0003413063350000061
Example 1
1. Preparing graphene oxide:
preparing graphene oxide powder by adopting an improved Hummers method: adding weighed 3g of natural crystalline flake graphite with the particle size of 325 meshes into a beaker fixed in an oil bath pan, and then pouring weighed 40mL of concentrated phosphoric acid H into the beaker3PO4Then, 360mL of concentrated sulfuric acid is slowly added into the beaker, the natural crystalline flake graphite, the concentrated phosphoric acid and the concentrated sulfuric acid are uniformly stirred at a constant speed, and 18g of KMnO is slowly added4Stirring is carried out, and the temperature of the mixed solution does not exceed 50 ℃ in the process. KMnO4After the addition, the temperature of the mixed solution is raised to 50 ℃ by using an oil bath kettle, and the mixed solution is reacted for 12 hours under the conditions of constant temperature and constant stirring. After the reaction is finished, taking out the beaker, standing and cooling to room temperature, adding 1000mL of deionized water ice blocks, and adding H after the ice blocks are completely melted2O2Solution (30% by weight) for reducing excess and unreacted KMnO4. Then standing for settling, pouring out supernatant, repeatedly washing the rest part with 5% hydrochloric acid, and washing with deionized water until the pH value of the supernatant is 6-7. And pouring out supernatant liquor to obtain brown black slurry, and performing low-speed centrifugation and freeze drying to obtain graphene oxide powder.
2. Preparation of modified carbon fibers
Carbon fiber bundles are wound on polytetrafluoroethylene plates with fixed sizes in parallel to serve as anodes, two graphite plates serve as cathodes, the anodes are arranged between the two cathodes, and the distance between the anodes and the cathodes is 1 cm.
In order to prepare a uniform and stable electropolymerization solution, different parts of graphene oxide suspension are mixed with an electropolymerization monomer solution, and the dispersion and stable state are observed. At 0.1mol/L of H2SO4The electrolyte is prepared by adding the mixed solution into the electrolyte. In the final electrolyte, the concentration of the graphene oxide is 208mg/L, and the concentrations of the electropolymerized monomers itaconic acid and p-aminobenzoic acid are respectively 17 mmol/L.
Adopting direct current to carry out electrochemical treatment, wherein the current density is 0.5mA/cm2The electrochemical treatment time was 60s, 90s, 120s, 150s, and 240s, respectively. After electrochemical treatment, cleaning the surface of the fiber to remove residual electrolyte and unpolymerized monomers, and then drying at 80 ℃ for 24h to obtain modified carbon fiber samples respectively marked as CF-GO @ EPI60s、CF-GO@EPI90s、CF-GO@EPI120s、CF-GO@EPI150s、CF-GO@EPI240s。
3. Preparation of modified carbon fiber/epoxy resin composite material
And preparing the carbon fiber/epoxy resin composite material by adopting a manual die pressing method. Mixing and stirring bisphenol A type epoxy resin E-51 and curing agent DDM (mass ratio is 100:26) at 80 ℃ for 10min, adopting a manual coating method to fully infiltrate the uniformly mixed epoxy resin system into the modified carbon fiber bundle wound on the I-shaped frame, and putting the modified carbon fiber obtained in the last step into a mold sprayed with a release agent in advance. And curing the composite laminated plate under the conditions of 135 ℃/2h/5MPa +175 ℃/2h/10MPa to obtain the composite laminated plate. The proportion of the dosage of the bisphenol A epoxy resin E-51 and the modified carbon fiber is adjusted, so that the volume fraction of the modified carbon fiber in the cured composite material is 60 percent.
Comparative example 1
And preparing the carbon fiber/epoxy resin composite material by adopting a manual die pressing method. Mixing and stirring bisphenol A type epoxy resin E-51 and curing agent DDM (mass ratio is 100:26) at 80 ℃ for 10min, adopting a manual coating method to fully infiltrate the uniformly mixed epoxy resin system into the modified carbon fiber bundles wound on the I-shaped frame, and putting the unmodified carbon fiber bundles into a mold sprayed with a release agent in advance. And curing the composite laminated plate under the conditions of 135 ℃/2h/5MPa +175 ℃/2h/10MPa to obtain the composite laminated plate. The proportion of the amount of the bisphenol A epoxy resin E-51 to the amount of the carbon fiber is adjusted so that the volume fraction of the carbon fiber in the cured composite material is 60%.
Experimental example 1 stability of electrolyte
In this experimental example, in order to prepare a uniform and stable electropolymerization solution, different parts of graphene oxide suspensions were mixed with an electropolymerization monomer solution, and the dispersion and stable state of the mixed solution were observed. Wherein the concentration of the graphene oxide suspension is 250mg/L, and the concentrations of itaconic acid and p-aminobenzoic acid in the monomer solution are respectively 0.1 mol/L.
Fig. 1 is a photograph of a mixture of graphene oxide suspensions and electropolymerized monomer solutions at different ratios, and after standing, it can be seen that the mixed solution is unstable when the ratio of the graphene oxide suspension is low, and the stability of the mixed solution is improved when the ratio of the graphene oxide suspension is increased.
Fig. 2 shows Zeta potentials of mixed solutions of graphene oxide suspensions and electropolymerized monomer solutions in different proportions, wherein the larger the absolute value of the Zeta potential is, the higher the stability of the suspensions is, and it is generally considered that the absolute value of the Zeta potential is greater than 30, which means that the suspensions can be stably dispersed. As can be seen from the figure, when the ratio of the graphene oxide suspension to the electropolymerized monomer solution is greater than 5:1, the mixed solution of the graphene oxide suspension and the electropolymerized monomer solution can exist stably.
In the embodiment of the invention, the concentrations of the graphene oxide and the electropolymerization monomer in the electrolyte are determined by referring to the optimal ratio in the experimental example (the ratio of the 250mg/L graphene oxide suspension to the 0.1mol/L electropolymerization monomer solution is more than 5: 1).
Experimental example 2 characterization of modified carbon fiber
1. Infrared spectroscopy test (FTIR):
the method comprises preparing test sample by Nicolet 570 type Fourier transform infrared spectrometer manufactured by Nicolet corporation of America and potassium bromide sample, and scanning infrared spectrum of 4000cm-1-400cm-1。
The infrared spectrum of the carbon fiber is shown in fig. 3. For unmodified carbon fibers (Untreated-CF), except at 3420cm-1In addition to the characteristic peaks of adsorbed water (O-H stretching vibration), some organic group characteristic peaks can be found. At 2800cm-1-2980cm-1Stretching vibration absorption band in the range of methyl and methylene C-H, 1580cm-1-1699cm-1And 1050cm-1-1100cm-1Absorption peaks of stretching vibration of C ═ C and C — C, respectively. Compared with unmodified carbon fiber, the infrared spectrum of the carbon fiber is obviously changed after electrophoretic deposition and electropolymerization one-step modification. It can be clearly seen at 1735cm-1The absorption peak of C ═ O in the carboxyl group appears. At 1402cm-1A new absorption band is also appeared due to the graphene oxide deposited on the surface of the carbon fiber and the stretching vibration of COO-in the electro-polymer. And the hydroxyl absorption band is widened due to the introduction of electropolymerization N-H stretching vibration. At 1020cm-1-1250cm-1The peaks appeared to be attributed to the C — N stretching vibration, and the intensity of the absorption peaks gradually increased with the increase of the electric treatment time. 879cm-1The newly appearing peak is the in-plane bending vibration of the para-aromatic ring. These data indicate that electrophoretic deposition of graphene oxide in combination with a single electropolymerization step is successful in modifying the surface of carbon fibers.
2. Raman spectroscopy
In order to understand the change of the microstructure of the surface of the carbon fiber after the carbon fiber is deposited by the modified graphene oxide, Raman spectrum tests are carried out on different modified carbon fibers.
The results are shown in fig. 4, where the raman parameters of the modified carbon fibers were varied to a different extent than the unmodified carbon fibers. CF-GO @ EPI60sIncreases the R value of the unmodified carbon fiber to 0.94, and gradually increases the R value of the modified carbon fiber with increasing electrochemical treatment time, CF-GO @ EPI150sThe R value of (A) reaches 0.99. This indicates that the deposition of the modifying substance increases the disordered carbonaceous component of the surface of the carbon fiber, thereby increasing the structural defects of the surface of the fiber. The results show that after electrophoretic deposition and electropolymerization are combined, the deposition layer of the graphene oxide and the polymer can better cover the ordered graphite microcrystal structure on the surface of the carbon fiber, so that the disordered carbon structure on the surface of the fiber is increased, and the activity of the graphite microcrystal boundary on the surface is increased.
3. Analysis of thermal stability
The deposited layer of modified carbon fibers was further investigated by thermal gravimetric analysis and the results are shown in fig. 5. For unmodified carbon fibers, there was no significant mass loss under nitrogen. For the modified carbon fiber prepared in example 1, due to the removal of the oxygen-containing functional group of graphene oxide on the surface of the fiber and the degradation of the polymer, the thermal residual weight is gradually reduced at 700 ℃ along with the increase of the modification time, and the thermal residual weight is increased from 98.9% of the unmodified carbon fiber to CF-GO @ EPI240s96.1% of (A), indicates that the modifying substance coated on the surface of the fiber gradually becomes thicker as the electrochemical treatment time increases.
The thermal gravimetric analysis further proves that the coating of the graphene oxide and the polymer is successfully realized when the electrophoretic deposition and the electropolymerization one-step method are combined on the surface of the fiber. Consistent with the results of infrared and raman spectral data analysis.
4. XPS analysis
The elemental composition of the carbon fiber surface before and after modification was measured by XPS and quantitatively analyzed. FIG. 6 is the corresponding XPS survey and the C1s element spectrum, with peaks at 284.6eV, 532.2eV and 399.5eV due to the binding energy of carbon, oxygen and nitrogen elements. The peak fitting analysis is carried out on the C1s element spectrum of different carbon fibers, and the calculation result of the carbon fiber surface element composition is given in Table 2. Compared with the unmodified carbon fiber, the surface element composition of the modified carbon fiber is obviously changed. Wherein, the O/C ratio of the fiber surface is obviously improved from 15.51 percent to 52.80 percent at most. This is attributed to the fact that graphene oxide coated on the surface of the fiber contains a large amount of oxygen-containing functional groups and itaconic acid and p-aminobenzoic acid contain rich carboxyl groups.
The composition of the functional groups is also greatly changed, and compared with the unmodified fiber, the number of C-C bonds on the surface of all the modified carbon fibers is reduced, and the oxygen-containing functional groups are increased. After graphene oxide deposition and electropolymerization, the carboxyl content on the surface of the modified carbon fiber is increased from 1.44% to 5.64%, which shows that the polymer performs polyreaction on the surfaces of the graphene oxide and the carbon fiber, and more active oxygen-containing groups are introduced.
TABLE 2 surface element and functional group composition of modified and unmodified carbon fibers
Figure BDA0003413063350000091
Figure BDA0003413063350000101
The results show that the number of polar groups on the surface of the carbon fiber is increased through electrophoretic deposition of graphene oxide and electropolymerization. These reactive oxygen-containing functional groups facilitate interfacial bonding of the fibers to the epoxy matrix by improving the wettability of the fibers with the epoxy matrix and forming more reactive sites with the epoxy matrix during curing.
5. Surface microstructure characterization
The surface morphology of the fibers before and after modification was characterized by Scanning Electron Microscopy (SEM), and the results are shown in fig. 7. It can be seen that there is a significant difference in the surface morphology between the unmodified carbon fibers (a) and the modified carbon fibers (b-f). The surface of the unmodified carbon fiber is relatively flat and smooth, and the characteristic of the ravine stripe shape parallel to the fiber axis is obvious, which is the surface structure of the carbon fiber prepared by typical wet spinning, and for the carbon fiber, the surface defects limit the exertion of high performance of the fiber. Is modified by electrochemical treatmentAfter 60s (b, CF-GO @ EPI)60s) It can be seen that the graphene oxide sheets and the polymer are uniformly coated on the surface of the fiber, the ravine defects on the surface of the fiber are partially filled, and the modifying substance is wrinkled and protruded on the surface of the fiber. For CF-GO @ EPI90s(c) And CF-GO @ EPI120s(d) The three-dimensional stereo multi-scale structure is more obvious. The three-dimensional multi-scale structure not only realizes the efficient coating between the graphene oxide and the carbon fiber and fully plays the role of enhancing the graphene oxide, but also plays the role of enhancing a multi-scale interface by the functionalized modification generated by electropolymerization, greatly enhances the interaction between the fiber and a substrate and is beneficial to the improvement of the interface bonding strength.
CF-GO @ EPI when the modification time is increased to 240s240s(f) The surface is covered by excessive graphene oxide and polymer, and due to the agglomeration of the graphene oxide and the polymer, the three-dimensional structure of the fiber surface is converted into a large two-dimensional film structure, the covering may result in the reduction of the bonding sites on the fiber surface, which is not favorable for the interface bonding between the fiber and the matrix, and the thicker interface layer is also not favorable for stress transfer, which may result in the reduction of the interface bonding strength of the composite material.
In order to further study the differences in surface morphology and roughness of the fibers before and after modification, AFM tests were performed on different fibers. As shown in fig. 8, the surface of the unmodified carbon fiber is quite smooth (Ra ═ 21.3nm), and after modification, the morphology of the modified fiber becomes rough due to deposition and polymerization of graphene oxide nano-flakes and polymer on the surface of the carbon fiber, and the roughness Ra increases to various degrees. For samples with electrochemical treatment times of 90-150s, the carbon fiber surface became very uneven with fiber surface roughness up to 33.3 nm. The increased surface roughness of the fibers can increase the mechanical interlocking and interface area between the fibers and the matrix, which is beneficial to improving the interface adhesion of the composite material.
When the modification time was increased to 240s, for CF-GO @ EPI240sThe fiber surface roughness is relatively reduced due to the excessively long polymerization time, the fiber surface is covered with excessive graphene oxide and polymer, and due to the oxidized stoneThe agglomeration of the graphene and the polymer results in a transformation of the three-dimensional structure of the fiber surface into a large two-dimensional film structure, consistent with the results observed by SEM.
6. Wetting Property
To further analyze the effect of the modification treatment on the wettability of the carbon fiber surface, the water contact angle of the single fibers and the contact angle of the fiber bundle with the uncured epoxy resin were measured, as shown in fig. 9 and 10.
FIG. 9 is a water contact angle for modified and unmodified carbon fibers, the water contact angle for unmodified fibers being 113.5 due to the inert and smooth surface of the graphite, whereas after modification, the water contact angle for modified carbon fibers gradually decreases with electrochemical treatment events for CF-GO @ EPI240sThe contact angle dropped to 97.9 °, indicating an increase in the wettability of the carbon fiber surface due to an increase in the polarity and roughness of the fiber surface.
The decrease in contact angle between the uncured epoxy resin and the different fiber bundles is more significant, as shown in fig. 10, from 138.5 ° to 77.4 ° of the unmodified carbon fiber, and the decrease is due to the aggregation of the nanostructure containing a large number of hydrophilic groups on the fiber surface, and the interconnected network structure not only increases the roughness of the fiber surface, but also increases the surface energy of the fiber, so that the epoxy liquid drops can be rapidly diffused on the fiber surface.
Therefore, the modified carbon fiber combining electrophoretic deposition and electropolymerization can improve the roughness and wettability of the fiber surface, which is beneficial to increasing the combination of the fiber and the epoxy resin matrix and can effectively improve the interface performance of the composite material.
EXAMPLE 3 interlaminar shear Strength (ILSS) of modified carbon fiber/epoxy resin composite Material
In this experimental example, the interlaminar shear strength of the carbon fiber/aminated graphene oxide/epoxy resin composite material was tested.
The interlaminar shear strength (ILSS) of the composites of comparative example 1 and example 1 was evaluated using the short beam bending test. The results are shown in FIG. 11. For CF-GO @ EPI60sThe interface strength of the composite material is improved to 48.6MPa, which is improved compared with that of unmodified carbon fiber (40.8MPa)19.1 percent. This is because the fiber surface modification increases interfacial adhesion. CF-GO @ EPI with increasing electrochemical treatment time120sThe interlaminar shear performance of the composite material is increased to 54.6MPa, and is increased by 33.8 percent compared with that of untreated carbon fiber.
The method is characterized in that a multi-scale interface structure is constructed on the surface of the fiber, so that the efficient coating of the graphene oxide is realized, and a functionalized substance is formed on the surfaces of the carbon fiber and the graphene oxide through electropolymerization, so that the defect of weak bonding between the graphene oxide and the surfaces of the carbon fiber and the matrix resin interface is overcome. The polymerization of the polymer on the carbon fiber and the graphene oxide successfully introduces active functional groups on the surface of the carbon fiber, increases reactable sites and wettability to an epoxy resin matrix, increases the binding force of the graphene oxide and the fiber, and fully exerts the advantages of excellent mechanical properties and multi-scale interface structure of the graphene oxide. And the modified carbon fiber surface is rich in a three-dimensional structure of carboxyl, so that the mechanical interlocking and chemical bonding with a matrix are greatly increased, the transmission of interface stress is facilitated, a good interface layer is formed, and the comprehensive performance of the composite material is improved.
CF-GO @ EPI as electrochemical treatment time increases150sAnd CF-GO @ EPI240sThe interlaminar shear strength of the composite material is increased by 22.1% and 13.2%, the interlaminar shear strength of the composite material is slightly reduced, because the modified substances coated on the surface of the fibers are thick, organic matters on the surface of the carbon fibers generate multi-layer polymerization, the inner layer is firmly combined with the surface of the carbon fibers, but the cohesion of the polymer is not strong, the thick interface layers are damaged during stress transmission, the load cannot be effectively transmitted under the action of external force, and the interlaminar performance of the composite material is reduced.
It is also apparent from the load-displacement curve shown in fig. 12 that the load-bearing capacity of the unmodified carbon fiber rapidly decreases and the interfacial failure rapidly propagates in the composite material upon failure. This demonstrates the poor interphase for the unmodified carbon fiber composite. The modulus of the composite material of the modified carbon fiber is obviously increased, the interface of the fiber and the matrix is not completely damaged during fracture damage, and the bearing capacity of the composite material is still kept.
The experimental example results show that the graphene oxide-polymer multi-scale structure generated on the surface of the fiber by the method can effectively enhance the interface bonding strength of the carbon fiber and the epoxy resin, so that the interlaminar shear strength of the composite material is improved. And the electrochemical treatment time is optimally 120 s.
Experimental example 4 micro-morphology of damaged surface of modified carbon fiber/epoxy resin composite material
In order to further understand the mechanism of the modified fiber composite material for improving the interfacial adhesion, the fracture morphology of the composite material after ILSS testing is characterized by adopting SEM, as shown in fig. 12. For the composite material made of the unmodified carbon fiber in the comparative example 1, the surface of the carbon fiber on the damaged surface is smooth, no epoxy resin fragments are attached to the surface of the fiber, and the fiber with large holes among the fibers is easy to pull out from the epoxy resin matrix, so that the interface bonding between the fiber and the epoxy resin is weak. For the modified carbon fiber/epoxy composite sample of example 1, it can be seen that CF-GO @ EPI60sAnd CF-GO @ EPI90sMatrix residues exist on the surface of the carbon fiber of the sample destruction surface, which proves that the reaction site bridging of the three-dimensional structure formed by the graphene oxide and the polymer increases the interface bonding force between the fiber and the epoxy resin. In addition, the epoxy matrix wrapped around the fibers can be seen, a large amount of matrix remains between the fibers, and the matrix breaks into many pieces, indicating that the chemical bonding force of the fibers to the epoxy matrix is greatly increased. For CF-GO @ EPI120sThe epoxy matrix is tightly wrapped on the carbon fibers, grooves on the surfaces of the carbon fibers become fuzzy, more epoxy fragments exist on the damage surface of the composite material, more energy is consumed when the modified carbon fibers and the epoxy interface are damaged, and the interface effect of the carbon fibers and the epoxy matrix is greatly enhanced due to the formation of the multi-scale structure of the graphene oxide and the polymer.
FIG. 12 is a cross section of the composite material perpendicular to the fiber direction. For the composite material made of the unmodified carbon fiber in the comparative example 1, the carbon fiber is pulled out of the epoxy matrix, the cross section of the composite material is provided with a plurality of cavities, the connection between the fiber and the matrix is weak, and the interface bonding of the composite material is proved to be betterWeak. While the fibers extracted from the epoxy resin by the modified carbon fibers are relatively short, such as CF-GO @ EPI60sAlthough slight cracks exist between the fibers and the matrix, the interface bonding is obviously improved and the interface adhesion of the composite material is increased compared with the composite material of the unmodified carbon fibers. In CF-GO @ EPI120sThe composite material has almost no extracted carbon fiber, the fracture of the carbon fiber of the composite material is very level, cracks can not be basically seen between the carbon fiber of the damaged surface and the matrix, the matrix can well transmit external force to the carbon fiber, the composite material has perfect interface layer transmission stress, the carbon fiber has good bearing effect, the composite material has good interface adhesion, and the composite material presents a flat fracture surface. However, for CF-GO @ EPI150sAnd CF-GO @ EPI240sSome fine cracks may be observed on the fracture surface of the composite material due to the excessive coverage of the modified structure, and a part of the cross section is covered with resin and fiber fragments, and such excessive coverage may adversely affect the dissipation of external stress, resulting in a decrease in the interfacial strength of the composite material. These observations are consistent with ILSS results.
In order to further understand the micro interface enhancement trend of the carbon fiber epoxy composite material, the micro stripping surface morphology of the carbon fiber and epoxy resin composite material is researched by using SEM. As can be seen in fig. 14, the debonded surface of the unmodified carbon fiber was almost clean and clean, while only a small amount of epoxy chips remained at the epoxy debonded sites, indicating a weak fiber/matrix interface. With the modified carbon fiber of example 1, it is apparent that more epoxy fragments are attached to the carbon fiber, and it can be seen from the figure that the amount of residual epoxy on the surface of the carbon fiber is consistent with the change in the results of the interlaminar shear properties. In addition, part of the graphene oxide nano-sheets are still adhered to the surface of the fiber, which proves that the carbon fiber modification method enhances the connection between the carbon fiber and the graphene oxide, so that the interface of the composite material is obviously improved.
The experimental example results show that the graphene oxide-polymer multi-scale structure generated on the surface of the fiber by the method can effectively enhance the interface bonding strength of the carbon fiber and the epoxy resin, so that more energy is consumed when the interface of the modified carbon fiber and the epoxy resin is damaged. And the electrochemical treatment time is optimally 120 s.
Experimental example 5 dynamic mechanical properties of modified carbon fiber/epoxy resin composite Material
Fig. 15 shows changes with temperature of storage modulus (E') and loss factor Tan δ of the composite material of carbon fiber and epoxy resin before and after modification in comparative example 1 and example 1. Table 3 shows the glass transition temperature and storage modulus at 35 ℃ for different carbon fiber composites.
TABLE 3 glass transition temperature and storage modulus of the composites
Figure BDA0003413063350000141
As can be seen from fig. 15 and table 3, the glass transition temperature and storage modulus of the modified carbon fiber composite material are significantly improved compared to the sample of comparative example 1, wherein the glass transition temperature and storage modulus of the sample with the electrochemical treatment time of 120s are higher, which is consistent with the variation trend of the interlaminar shear strength.
In conclusion, the invention realizes the modification of the carbon fiber by a method combining electrophoretic deposition and electropolymerization, and prepares the modified carbon fiber/resin composite material. The modified carbon fiber obtained by the method has the advantages of increased surface disordered carbon structure, increased activity of the graphite microcrystal boundary on the surface, increased number of polar groups, formation of a multi-scale three-dimensional network structure, and improvement of roughness and wettability of the fiber surface, so that the bonding capacity of the modified carbon fiber and a resin matrix is enhanced. The composite material prepared from the modified carbon fiber and resin has higher interlaminar shear strength, glass transition temperature and storage modulus. Has good application prospect.

Claims (10)

1. An electrolyte for preparing modified carbon fiber is characterized in that: it is prepared by dispersing the following components in water solution containing 0.01-0.7mol/L acid:
25-2000mg/L of graphene material and 5-500mmol/L of electropolymerization monomer.
2. The electrolyte of claim 1, wherein: the electropolymerization monomer is selected from at least one of styrene, ethyl carbazole, caprolactam, methyl acrylate, pyrrole and derivatives thereof, thiophene and derivatives thereof, aniline and derivatives thereof, itaconic acid, aminobenzoic acid, itaconic acid acrylic acid, phenol, o-aminophenol derivatives or m-phenylenediamine;
and/or the graphene material is selected from at least one of graphene, carboxylated graphene oxide or aminated graphene oxide, and the size of the graphene material is 200 nanometers-50 micrometers;
and/or the concentration of the aqueous solution of the acid is 0.1mol/L, and/or the acid is selected from at least one of hydrochloric acid, sulfuric acid or nitric acid, and/or the concentration of the graphene material is 250mg/L, and/or the electropolymerization monomer is a combination of itaconic acid and aminobenzoic acid, the concentration of the itaconic acid is 0.1mol/L, and the concentration of the aminobenzoic acid is 0.1 mol/L.
3. A modified carbon fiber, characterized in that it is obtained by simultaneously carrying out electrophoretic deposition and electropolymerization using a carbon fiber as an anode in the electrolyte according to claim 1 or 2.
4. The modified carbon fiber according to claim 3, wherein: the method for simultaneously carrying out electrophoretic deposition and electropolymerization comprises the following steps: applying direct current to the carbon fiber as an anode for electrochemical treatment;
the time of the electrochemical treatment is 10-600s, preferably 60-240 s; and/or the direct current density is 0.1-2mA/cm2(ii) a And/or, the electrochemical treatment process is assisted by using ultrasound; and/or in the electrochemical treatment process, two graphite electrodes are used as cathodes, the anode is positioned between the two cathodes, and the distance between the anode and the cathode is 1-2 cm; and/or the carbon fibers are electrochemically treatedAnd drying the carbon fiber at 60-90 ℃ for 24 hours to obtain the modified carbon fiber.
5. The process for producing a modified carbon fiber according to claim 3 or 4, characterized by comprising the steps of:
(1) taking the electrolyte of claim 1 or 2;
(2) and (2) taking the carbon fiber as an anode, and simultaneously carrying out electrophoretic deposition and electropolymerization in the electrolyte in the step (1) to obtain the modified carbon fiber.
6. A modified carbon fiber/resin composite material is characterized in that: the modified carbon fiber is prepared by compounding the modified carbon fiber of claim 3 or 4 with a resin matrix, wherein the resin matrix is thermosetting resin or thermoplastic resin.
7. The composite material of claim 6, wherein: the thermosetting resin is epoxy resin, phenolic resin, bismaleimide resin or polyimide resin, and the thermoplastic resin is polyphenylene sulfide, polyether ether ketone, nylon or polypropylene; and/or the volume fraction of the modified carbon fibers in the composite material is 30-60%.
8. A method for preparing a composite material according to claim 6 or 7, characterized in that it comprises the following steps: mixing a resin matrix and a curing agent, fully infiltrating the modified carbon fiber of claim 5, and curing the resin matrix to obtain the carbon fiber composite material.
9. The method of claim 8, wherein: the mass ratio of the resin matrix to the curing agent is 100: 10-30 parts of; and/or, the resin matrix and the curing agent are mixed at 50-100 ℃; and/or the curing process comprises the steps of firstly curing for 1.5-2.5h under the conditions of 120-140 ℃ and 5MPa, and then curing for 1-3h under the conditions of 160-185 ℃ and 10 MPa.
10. Use of the modified carbon fiber of claim 5 and/or the composite material of claim 6 or 7 for the manufacture of transportation equipment, sports equipment, aerospace equipment or defense and military products.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115477816A (en) * 2022-09-06 2022-12-16 湖北合聚新材料有限公司 Dielectric composite material and preparation method thereof
CN115491784A (en) * 2022-08-24 2022-12-20 凯盛石墨碳材料有限公司 Preparation method of graphene/carbon fiber/polypropylene fiber with excellent conductivity
CN115584066A (en) * 2022-09-30 2023-01-10 上海熹贾精密技术有限公司 Wear-resistant butyronitrile material with high vulcanization speed and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104465121A (en) * 2014-11-28 2015-03-25 天津大学 Graphene oxide-polyaniline composite electrode material with three-dimensional structure and manufacturing method thereof
US20150204009A1 (en) * 2014-01-21 2015-07-23 Kyungpook National University Industry-Academic Cooperation Foundation Functionalized carbon nanoparticles and functional polymer fibers prepared using the same
CN105552399A (en) * 2015-12-15 2016-05-04 湖北大学 Graphene-doping conductive polymer modified metal bipolar plate of proton exchange membrane fuel cell and preparation method of metal bipolar plate
US20160348283A1 (en) * 2015-05-26 2016-12-01 Korea Institute Of Science And Technology Nanocarbon composite carbon fiber with low cost and high performance and their preparation method
CN108755126A (en) * 2018-05-08 2018-11-06 中国科学院宁波材料技术与工程研究所 The method and carbon fibre composite of electrochemical polymerization modified surface Treatment of Carbon
CN112323482A (en) * 2020-11-02 2021-02-05 四川大学 Carbon fiber obtained by electrophoretic deposition-electropolymerization combined modification and resin matrix composite material thereof
CN113564913A (en) * 2021-07-02 2021-10-29 北京化工大学 Modification treatment method for surface of high-performance carbon fiber

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150204009A1 (en) * 2014-01-21 2015-07-23 Kyungpook National University Industry-Academic Cooperation Foundation Functionalized carbon nanoparticles and functional polymer fibers prepared using the same
CN104465121A (en) * 2014-11-28 2015-03-25 天津大学 Graphene oxide-polyaniline composite electrode material with three-dimensional structure and manufacturing method thereof
US20160348283A1 (en) * 2015-05-26 2016-12-01 Korea Institute Of Science And Technology Nanocarbon composite carbon fiber with low cost and high performance and their preparation method
CN105552399A (en) * 2015-12-15 2016-05-04 湖北大学 Graphene-doping conductive polymer modified metal bipolar plate of proton exchange membrane fuel cell and preparation method of metal bipolar plate
CN108755126A (en) * 2018-05-08 2018-11-06 中国科学院宁波材料技术与工程研究所 The method and carbon fibre composite of electrochemical polymerization modified surface Treatment of Carbon
CN112323482A (en) * 2020-11-02 2021-02-05 四川大学 Carbon fiber obtained by electrophoretic deposition-electropolymerization combined modification and resin matrix composite material thereof
CN113564913A (en) * 2021-07-02 2021-10-29 北京化工大学 Modification treatment method for surface of high-performance carbon fiber

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115491784A (en) * 2022-08-24 2022-12-20 凯盛石墨碳材料有限公司 Preparation method of graphene/carbon fiber/polypropylene fiber with excellent conductivity
CN115477816A (en) * 2022-09-06 2022-12-16 湖北合聚新材料有限公司 Dielectric composite material and preparation method thereof
CN115477816B (en) * 2022-09-06 2023-08-18 湖北合聚高分子材料有限公司 Dielectric composite material and preparation method thereof
CN115584066A (en) * 2022-09-30 2023-01-10 上海熹贾精密技术有限公司 Wear-resistant butyronitrile material with high vulcanization speed and preparation method thereof
CN115584066B (en) * 2022-09-30 2024-05-07 上海熹贾精密技术有限公司 Wear-resistant butyronitrile material with high vulcanization speed and preparation method thereof

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