CN112457629A - Carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material and preparation method thereof - Google Patents
Carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material and a preparation method thereof, belonging to the technical field of carbon fiber reinforced polymer matrix composite materials. According to the invention, diazotization reaction is utilized to functionalize the surface of the carbon fiber (graft amino), active functional groups are introduced on the surface of the carbon fiber under the premise of not damaging the strength and integrity of the carbon fiber, so that the polarity and activity of the surface of the carbon fiber are increased, and then silicon dioxide nanowires and aminated graphene are grafted on the surface of the carbon fiber through covalent bond action to form the carbon fiber containing a two-dimensional interpenetrating network structure, so that the surface polarity and roughness of the carbon fiber are improved, the interface strength of the CF/PEEK composite material can be improved, and the problem of infirm combination of the nano particles and the surface of the fiber is solved.
Description
Technical Field
The invention relates to the technical field of carbon fiber reinforced polymer matrix composite materials, in particular to a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material and a preparation method thereof.
Background
The Polyetheretherketone (PEEK) has a regular structure, is a linear high-molecular polymer containing benzene rings, ether bonds and ketone bonds, and has good chemical stability and high strength and rigidity due to a large number of benzene rings in a main chain; the ether bond on the main chain is flexible and can rotate, so that the modified polyether polyol has certain flexibility, can be melted and crystallized, and has good processing performance. In addition, PEEK has high temperature resistance, fatigue resistance, chemical resistance, wear resistance, hydrolysis resistance and excellent mechanical properties, and is currently applied to the industries of aerospace, automobiles, machinery, petrochemical industry, nuclear power, rail transit, biomedical materials and the like. The Carbon Fiber (CF) reinforced PEEK composite material has the advantages of high modulus, high strength, high toughness, excellent corrosion resistance and the like, is one of the materials with the greatest development prospect at present, and has wide application prospect in the fields of automobiles, medical instruments, aerospace and the like. However, a significant obstacle limiting the widespread use of CF reinforced PEEK composites is the weak interfacial properties of the composite, such that the out-of-plane properties of CF reinforced PEEK composites, such as tensile properties, bending properties, interfacial shear strength (IFSS), are insufficient, limiting their further use. This is not only because CFs have a stable non-polar structure and a smooth graphite surface, but also because of the chemical inertness and high viscosity of the PEEK melt. Therefore, interfacial modification of CF-PEEK composite materials has attracted great attention in both academic and industrial fields.
In current research, researchers developed a series of interfacial modification methods in order to improve the mechanical properties of CF reinforced PEEK composites. Chunrui et al (Ploymers 11(2019)753) use plasma to treat CF, but these treatments destroy the CF's own strength. Chinese invention patent (CN109796725A) discloses a carbon fiber surface chemical grafting nano SiO2The reinforced polyether-ether-ketone composite material and the preparation method thereof, but the method uses concentrated nitric acid treatment to damage the surface of the fiber, and the used coupling agent has low temperature resistance and is easy to form defects in the composite material. Hansong Liu et al (J MATER RES TECHNONL 8(2019) 6289-. Elwathig A et al (Composites Part A112 (2018)155-160) introduce a polyether ketone (PEKK) interface layer on the activated CF of Meldrum's acid to improve the fiber matrix interface interaction of the CF-PEEK composite material, but the interface bonding problem of the CF and the thermoplastic sizing agent and the poor interface bonding caused by uneven coating can influence the strength enhancement effect of the CF reinforced PEEK composite material.
In the above series of interfacial modification methods for CF/PEEK composite materials, it is more suitable to modify the interface by roughening the CF surface, because the main chain of the PEEK molecular chain contains benzene ring, ether bond and ketone bond, while the CF surface has no reactive functional group and no polarity, so PEEK cannot form strong chemical action with the CF surface. In the current research methods, the CF surface roughening method still has some disadvantages: the strength of CF itself is destroyed by using CF surface treatment methods such as strong acid oxidation; by dipping the nanoparticle solution and depositing the particles on the CF surface, the interaction between CF and the nanoparticles is weak, and the degree of CF/PEEK composite interfacial modification is limited.
Disclosure of Invention
The invention aims to provide a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material, which comprises the following steps:
mixing carbon fiber, p-phenylenediamine, nitrite and concentrated hydrochloric acid, and performing diazotization reaction to obtain aminated carbon fiber;
mixing biphenyl dianhydride, an aminosilane coupling agent and a first solvent, and modifying to obtain a modified silane coupling agent;
mixing the dispersion liquid of the silicon dioxide nanowires with a modified silane coupling agent, and modifying to obtain modified silicon dioxide nanowires;
mixing the modified silicon dioxide nanowires, the aminated graphene, the aminated carbon fibers and a second solvent, and grafting to obtain two-dimensional network structure grafted carbon fibers;
and mixing the two-dimensional network structure grafted carbon fiber and the polyether-ether-ketone, and sequentially extruding and molding to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material.
Preferably, the carbon fibers are sizing agent-free carbon fibers, and the carbon fibers are chopped carbon fibers, long-cut carbon fibers or continuous carbon fibers.
Preferably, the mass ratio of the carbon fiber to the p-phenylenediamine is (10-30): (0.1-0.5).
Preferably, the diazotization reaction has a pH value of 0-2, a temperature of 0-5 ℃ and a time of 6-10 h.
Preferably, the aminosilane coupling agent comprises KH550, KH540 or KH 792; the mass ratio of the aminosilane coupling agent to the biphenyl dianhydride is (0.1-0.5): (0.1-0.5).
Preferably, the modification temperature is room temperature, and the modification time is 4-6 h.
Preferably, the diameter of the silicon dioxide nanowire is 10-20 nm, and the length of the silicon dioxide nanowire is 5-15 μm; the temperature of the modification is 40-60 ℃, and the time is 6-8 h.
Preferably, the transverse size of the aminated graphene is 200-1000 nm, and the thickness of the aminated graphene is 0.6-5 nm; the mass ratio of the carbon fibers to the silicon dioxide nanowires to the amino silane coupling agent to the aminated graphene is (10-30): (0.5-2): (0.1-0.5): (0.5 to 2); the mass ratio of the polyether-ether-ketone to the carbon fiber is 100: (10-30).
Preferably, the grafting temperature is room temperature, and the grafting time is 6-8 h.
The invention provides a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material prepared by the preparation method in the technical scheme, which comprises polyether-ether-ketone and modified carbon fibers bonded on the polyether-ether-ketone, wherein the surface of the modified carbon fibers is grafted with silica nanowires and aminated graphene, and the silica nanowires and the aminated graphene are connected into a two-dimensional network structure through covalent bonds.
The invention provides a preparation method of a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material, which comprises the following steps: mixing carbon fiber, p-phenylenediamine, nitrite and concentrated hydrochloric acid, and performing diazotization reaction to obtain aminated carbon fiber; mixing biphenyl dianhydride, an aminosilane coupling agent and a first solvent, and modifying to obtain a modified silane coupling agent; mixing the dispersion liquid of the silicon dioxide nanowires with a modified silane coupling agent, and modifying to obtain modified silicon dioxide nanowires; mixing the modified silicon dioxide nanowires, the aminated graphene, the aminated carbon fibers and a second solvent, and grafting to obtain two-dimensional network structure grafted carbon fibers; and mixing the two-dimensional network structure grafted carbon fiber and the polyether-ether-ketone, and sequentially extruding and molding to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material. According to the invention, diazotization reaction is utilized to functionalize the surface of the carbon fiber (graft amino), active functional groups are introduced on the surface of the carbon fiber under the premise of not damaging the autogenous strength and integrity of the carbon fiber, so that the polarity and activity of the surface of the carbon fiber are increased, and then silicon dioxide nanowires and aminated graphene are grafted on the surface of the carbon fiber through covalent bond action to form the carbon fiber with a two-dimensional interpenetrating network structure, so that the surface polarity and roughness of the carbon fiber are improved, the CF/PEEK interface strength can be improved, and the problem of infirm combination of nano particles and the surface of the fiber is solved.
The microstructure of the silicon dioxide nanowire used in the invention is of a flocculent nanowire structure, and the special structure enables the silicon dioxide nanowire to have unique properties: the silicon dioxide nanowires have a large specific surface area, the aminated graphene also has a large specific surface area, and the silicon dioxide nanowires and the aminated graphene are introduced into a carbon fiber interface, so that the contact area between the fibers and the polyether-ether-ketone matrix is increased to a great extent.
According to the invention, amido bond is introduced into the amino silane coupling agent, and imine ring can be formed in the preparation process of the composite material, so that the heat resistance of the coupling agent is improved; meanwhile, the imine ring is utilized to connect the silicon dioxide nanowires and the carbon fibers together, and the imine ring is utilized to form a two-dimensional network, so that the carbon fibers, the silicon dioxide nanowires and the aminated graphene are firmly combined together, and the defect of the material caused by the separation of the nano particles from the surface of the fibers is prevented.
According to the invention, the silicon dioxide nanowires and the aminated graphene are connected into a two-dimensional network structure through covalent bonds, the roughness of the surface of the carbon fiber is improved by the network structure, and benzene rings, imine rings and amino groups in the two-dimensional network structure of the surface of the carbon fiber and a PEEK resin matrix form a strong non-covalent bond effect, so that the interface combination effect of the fiber and the resin matrix is increased; on the other hand, the PEEK resin matrix can permeate into a two-dimensional network structure in the melting process, the toughness of the silicon dioxide nanowires and the high strength of the aminated graphene are integrated, the mechanical interlocking effect of the carbon fibers and the resin matrix is increased through the synergistic effect of the silicon dioxide nanowires and the aminated graphene, the toughness and the rigidity of the composite material interface are increased, and further the mechanical strength and the toughness of the CF/PEEK composite material are improved.
Drawings
FIG. 1 is a schematic diagram of the modification process of the aminosilane coupling agent and the modification process of the silica nanowires of the present invention;
FIG. 2 is a schematic view of a process for producing a two-dimensional network-structured carbon fiber according to the present invention;
fig. 3 is a diagram illustrating a process of preparing a continuous carbon fiber having a two-dimensional network structure according to the present invention.
Detailed Description
The invention provides a preparation method of a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material, which comprises the following steps:
mixing carbon fiber, p-phenylenediamine, nitrite and concentrated hydrochloric acid, and performing diazotization reaction to obtain aminated carbon fiber;
mixing biphenyl dianhydride, an aminosilane coupling agent and a first solvent, and modifying to obtain a modified silane coupling agent;
mixing the dispersion liquid of the silicon dioxide nanowires with the modified silane coupling agent, and modifying to obtain modified silicon dioxide nanowires;
mixing the modified silicon dioxide nanowires, the aminated graphene, the aminated carbon fibers and a second solvent, and grafting to obtain two-dimensional network structure grafted carbon fibers;
and mixing the two-dimensional network structure grafted carbon fiber and the polyether-ether-ketone, and sequentially extruding and molding to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
According to the invention, carbon fiber, p-phenylenediamine, nitrite and concentrated hydrochloric acid are mixed and subjected to diazotization reaction to obtain the aminated carbon fiber. In the present invention, the carbon fiber is preferably a sizing-agent-free carbon fiber, and the carbon fiber is preferably a short carbon fiber, a long cut carbon fiber, or a Continuous Carbon Fiber (CCF); the length of the chopped carbon fiber (SCF) is preferably 3-10 mm, and more preferably 5-8 mm; the length of the long-cut carbon fiber (LCF) is preferably 20-100 mm, and more preferably 50-80 mm. In the present invention, the nitrite is preferably sodium nitrite; the mass concentration of the concentrated hydrochloric acid is preferably 31-38%, and more preferably 35%.
In the invention, the mass ratio of the carbon fiber to the p-phenylenediamine is preferably (10-30): (0.1-0.5), more preferably (15-25): 0.2-0.4); the mass ratio of the nitrite to the p-phenylenediamine is preferably (0.1-0.5) to (0.1-0.5), more preferably (0.2-0.4): (0.2-0.4). The dosage of the concentrated hydrochloric acid is not specially limited, and the condition of the pH value of the diazotization reaction can be achieved.
In the present invention, the process of mixing the carbon fiber, the para-phenylenediamine, the nitrite, and the concentrated hydrochloric acid is preferably a process of adding the carbon fiber to a diazotization solution formed by the para-phenylenediamine, the nitrite, and the concentrated hydrochloric acid.
In the invention, the pH value of the diazotization reaction is preferably 0-2, and more preferably 0.5-1.5; the temperature is preferably 0-5 ℃, and more preferably 2-4 ℃; the time is preferably 6 to 10 hours, and more preferably 7 to 8 hours. In the diazotization reaction process, p-phenylenediamine and nitrite form diazonium salt (NH) under the action of hydrochloric acid2ArN2Cl), diazonium salt to remove N2And forming an aniline free radical, wherein the aniline free radical is combined with the graphitized surface of the carbon fiber by a C-C single bond to form the aminated carbon fiber.
After the diazotization reaction is completed, the invention preferably washes and dries the obtained product system to obtain the aminated carbon fiber. The washing and drying process is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The invention mixes biphenyl dianhydride, amino silane coupling agent and first solvent for modification to obtain the modified silane coupling agent. In the present invention, the aminosilane coupling agent preferably comprises KH550, KH540 or KH 792; the mass ratio of the aminosilane coupling agent to the biphenyl dianhydride is preferably (0.1-0.5): (0.1 to 0.5), more preferably (0.2 to 0.4): (0.2 to 0.4); the first solvent is preferably dimethylacetamide (DMAc); in the present invention, the amount of the first solvent is not particularly limited, and the raw material can be completely dissolved. In the invention, the biphenyl dianhydride, the aminosilane coupling agent and the first solvent are preferably mixed in a process of dissolving the biphenyl dianhydride in the first solvent under the protection of nitrogen, and after the biphenyl dianhydride is completely dissolved, the aminosilane coupling agent is added into the obtained solution dropwise. The rate of the dropwise addition is not particularly limited in the present invention and may be carried out according to a procedure well known in the art.
In the invention, the modification temperature is preferably room temperature, and the modification time is preferably 4-6 h, and more preferably 4.5-5.5 h. In the modification process, amino on the aminosilane coupling agent reacts with biphenyl dianhydride to open the ring of anhydride, the amino reacts with the anhydride to form an amido bond, and the biphenyl dianhydride is connected with the aminosilane coupling agent through a covalent bond to form the modified silane coupling agent (the principle process is shown in figure 1).
After the modification is completed, the obtained product system is preferably subjected to separation, purification and drying in sequence to obtain the modified silane coupling agent. The separation, purification and drying processes are not particularly limited in the present invention, and may be performed according to processes well known in the art; in the examples of the present invention, the separation was carried out by distillation under reduced pressure (removal of solvent), followed by washing with anhydrous methanol and purification by multiple recrystallization with ethanol.
After the modified silane coupling agent is obtained, the dispersion liquid of the silicon dioxide nanowire is mixed with the modified silane coupling agent for modification, and the modified silicon dioxide nanowire is obtained. In the invention, the diameter of the silicon dioxide nanowire (SNF) is preferably 10-20 nm, more preferably 15nm, and the length of the silicon dioxide nanowire is preferably 5-15 μm, more preferably 10 μm. In the present invention, the preparation process of the dispersion of silica nanowires is preferably: ultrasonically dispersing the silicon dioxide nanowires in ethanol to obtain a dispersion liquid of the silicon dioxide nanowires; the time for ultrasonic dispersion is preferably 1-2 h, and more preferably 1.5 h; the power of the ultrasonic dispersion is not particularly limited in the present invention, and the ultrasonic dispersion may be performed according to a power well known in the art.
The modified silane coupling agent is preferably rapidly added to the dispersion of silica nanowires and mixed, and the rapid addition process is not particularly limited in the present invention and may be performed according to procedures well known in the art.
In the invention, the modification temperature is preferably 40-60 ℃, and more preferably 45-60 ℃; the time is preferably 6 to 8 hours, and more preferably 6.5 to 7.5 hours. In the modification process, ethoxy on the aminosilane coupling agent reacts with hydroxyl of the silica nanowire, ethanol is removed to form a Si-O-Si bond, and the modified silane coupling agent is connected with SNF by the Si-O-Si bond to form the modified silica nanowire (the principle process is shown in figure 1).
After finishing the modification, the obtained materials are preferably washed and dried in sequence to obtain the modified silicon dioxide nanowire which is marked as the SNF-g-silane coupling agent. The washing and drying processes are not particularly limited in the present invention and may be performed according to processes well known in the art.
After the modified silicon dioxide nanowire is obtained, the modified silicon dioxide nanowire, the aminated graphene, the aminated carbon fiber and a second solvent are mixed and grafted to obtain the two-dimensional network structure grafted carbon fiber. In the invention, the transverse size of the Aminated Graphene (AGP) is preferably 200-1000 nm, and more preferably 400-800 nm; the thickness is preferably 0.6 to 5nm, and more preferably 1 to 3 nm. In the invention, the mass ratio of the carbon fibers, the silicon dioxide nanowires, the aminosilane coupling agent and the aminated graphene is preferably (10-30): (0.5-2): (0.1-0.5): (0.5-2), more preferably (15-25): (1-1.5): (0.2-0.4): (1.0-1.5). In the present invention, the second solvent is preferably dimethylacetamide (DMAc); in the present invention, the amount of the second solvent is not particularly limited, and the raw material can be sufficiently dissolved.
In the present invention, the process of mixing the modified silica nanowires, the aminated graphene, the aminated carbon fibers and the second solvent is preferably to disperse the modified silica nanowires and the aminated graphene in the second solvent to obtain a suspension (SNF-g-silane coupling agent/AGP suspension), and to place the aminated carbon fibers in the suspension; the dispersion is preferably carried out under ultrasonic conditions, and the dispersion time is preferably 1-2 h, and more preferably 1.5 h. The conditions of the ultrasound are not particularly limited in the present invention, and may be performed according to a procedure well known in the art.
In the invention, the grafting temperature is preferably room temperature, and the grafting time is preferably 6-8 h, and more preferably 7.5 h. In the grafting process, acid anhydride on the surface of the modified silicon dioxide nanowire and amino on the surface of the aminated carbon fiber form an amido bond, the carbon fiber and the silicon dioxide nanowire are connected together, meanwhile, the aminated graphene and the acid anhydride group of the modified silicon dioxide nanowire also form an amido bond, the aminated graphene and the silicon dioxide nanowire are connected together, the aminated graphene and the surface of the aminated carbon fiber form a hydrogen bond effect and can also form a hydrogen bond effect with the modified silicon dioxide nanowire, and the silicon dioxide nanowire and the aminated graphite form a two-dimensional network structure on the surface of the carbon fiber in the forms of the amido bond and the hydrogen bond.
In the invention, the preparation principle and process of the two-dimensional network structure grafted carbon fiber are shown in figure 2, and the carbon fiber, p-phenylenediamine and nitrite are subjected to diazotization reaction to obtain aminated carbon fiber; grafting the aminated carbon fiber with the anhydride-modified silicon dioxide nanowire to obtain the carbon fiber with the two-dimensional network structure.
After the grafting is finished, the obtained product is washed and dried in sequence to obtain the grafted carbon fiber with the two-dimensional network structure. The washing and drying processes are not particularly limited in the present invention and may be performed according to processes well known in the art.
In the invention, when the carbon fiber is continuous carbon fiber, the two-dimensional network structure grafted carbon fiber is prepared according to the process shown in figure 3, the continuous carbon fiber is drawn by a round roller to pass through a diazotization solution for diazotization reaction, after drying, the obtained aminated carbon fiber is grafted by SNF-g-silane coupling agent/AGP suspension, and the two-dimensional network structure grafted continuous carbon fiber is obtained after washing, drying and filament collection. The present invention is not particularly limited to the device shown in fig. 3, and devices known in the art may be used; the process of washing, drying and collecting the filaments is not particularly limited in the present invention, and may be performed according to a process well known in the art.
After the two-dimensional network structure grafted carbon fiber is obtained, the two-dimensional network structure grafted carbon fiber and polyether-ether-ketone are mixed, and then the mixture is extruded and molded in sequence to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material. In the present invention, the form of the polyether ether ketone is preferably a powder; the invention has no special limitation on the parameters of the polyether-ether-ketone, and the polyether-ether-ketone can be obtained from commercial products well known in the field; in the embodiment of the invention, the melt index of the polyether-ether-ketone is specifically 47 g/min; the mass ratio of the polyetheretherketone to the carbon fibers is preferably 100: (10 to 30), more preferably 100: (15-25), more preferably 100: 20.
before the two-dimensional network structure grafted carbon fiber and the polyether-ether-ketone are mixed, the PEEK and the two-dimensional network structure grafted carbon fiber are preferably dried in a drying oven, the drying temperature is preferably 120 ℃, and the drying time is preferably 5 hours.
In the present invention, the extrusion is preferably carried out in an extruder; the invention preferably adds the powder of the polyether-ether-ketone into an extruder, and the two-dimensional network structure grafted carbon fiber is added into the extruder at a constant speed through side feeding, and then is subjected to extrusion granulation and cooling to obtain the granular material. In the invention, the melting temperature range of each feeding section of the extruder is preferably 350-380 ℃, the screw rotating speed is preferably 100r/min, and the screw rotating speed of side feeding is preferably 20 r/min. In the embodiment of the invention, the temperature of each feeding section is specifically 360 ℃ in one section, 365 ℃ in two sections, 370 ℃ in three sections, 375 ℃ in four sections and 380 ℃ in five sections. The extruder is not particularly limited in the present invention, and any type of extruder known in the art can satisfy the above-mentioned condition parameters.
After the particles are obtained, the particles are preferably added into an injection molding machine for injection molding, so that the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material is obtained. In the invention, the temperature range of each section of the charging barrel of the injection molding machine is preferably 360-390 ℃, in the embodiment of the invention, the temperature of the charging barrel is 360 ℃ at the first section, 370 ℃ at the second section, 380 ℃ at the third section and 390 ℃ at the injection nozzle; the mold temperature is preferably 200 ℃.
The invention provides a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material prepared by the preparation method in the technical scheme, which comprises polyether-ether-ketone and modified carbon fibers bonded on the polyether-ether-ketone, wherein the surface of the modified carbon fibers is grafted with silica nanowires and aminated graphene, and the silica nanowires and the aminated graphene are connected into a two-dimensional network structure through covalent bonds.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the chopped carbon fibers (SCF) have a length of 3 to 10 mm; the length of the long-cut carbon fiber (LCF) is 20-100 mm; the diameter of the silicon dioxide nanowire (SNF) is 10-20 nm, and the length of the silicon dioxide nanowire (SNF) is 5-15 mu m; the transverse dimension of the Aminated Graphene (AGP) is 200-1000 nm, and the thickness is 0.6-5 nm.
Example 1
Adding 20g of chopped carbon fiber (SCF) into concentrated hydrochloric acid solution (mass concentration is 38%) containing 0.25g of p-phenylenediamine and 0.25g of sodium nitrite, adjusting the pH value to 1, performing diazotization reaction at the temperature of 5 ℃ for 8h, washing the obtained product with deionized water to be neutral, and performing vacuum drying to obtain aminated carbon fiber (marked as NH)2-CF；
Dissolving 0.25g of biphenyl dianhydride in a DMAc solvent under the conditions of nitrogen protection and room temperature, dropwise adding 0.25gKH550 after dissolving, modifying for 5 hours, removing the solvent by reduced pressure distillation after the reaction is finished, washing with absolute methanol, recrystallizing with ethanol for multiple times, and drying to obtain modified KH550(g-KH 550);
ultrasonically dispersing 0.5g of SNF (silicon dioxide nanowire) in ethanol for 2h, quickly adding the g-KH550 at 60 ℃, modifying for 8h, washing with ethanol and deionized water to remove unreacted g-KH550, and vacuum drying to obtain a modified silicon dioxide nanowire, which is recorded as SNF-g-KH 550;
adding the SNF-g-KH550 and 0.5g of Aminated Graphene (AGP) into DMAc and ultrasonically dispersing for 2h to form a suspension; reacting NH2Placing CF in the suspension for grafting reaction for 8h at room temperature, washing the obtained product by using DMAc, and drying in vacuum to obtain the grafted carbon fiber with the two-dimensional network structure;
100g of PEEK powder (the melt index is 47g/min) and the two-dimensional network structure grafted carbon fiber are put into a drying oven to be dried for 5 hours at the temperature of 120 ℃;
adding the dried PEEK powder into an extruder, wherein the temperature of each feeding section is 360 ℃ at one section, 365 ℃ at two sections, 370 ℃ at three sections, 375 ℃ at four sections and 380 ℃ at five sections, the rotating speed of a screw is 100r/min, the two-dimensional network structure grafted carbon fibers are added into the extruder at constant speed through side feeding, the rotating speed of the side feeding screw is 20r/min, and carrying out extrusion granulation and cooling to obtain granules;
and adding the granules into an injection molding machine, and carrying out injection molding, wherein the temperature of the charging barrel is 360 ℃ in one section, 370 ℃ in two sections, 380 ℃ in three sections, 390 ℃ in a nozzle, and the temperature of the mold is 200 ℃, so as to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material, which is recorded as SCF/PEEK-1.
Example 2
Adding 20g of chopped carbon fiber (SCF) into concentrated hydrochloric acid solution (mass concentration is 38%) containing 0.30g of p-phenylenediamine and 0.30g of sodium nitrite, adjusting the pH value to 1, performing diazotization reaction at the temperature of 5 ℃ for 8h, washing the obtained product with deionized water to be neutral, and performing vacuum drying to obtain aminated carbon fiber (marked as NH)2-CF；
Dissolving 0.30g of biphenyl dianhydride in a DMAc solvent under the conditions of nitrogen protection and room temperature, dropwise adding 0.30gKH550 after dissolving, modifying for 5 hours, removing the solvent by reduced pressure distillation after the reaction is finished, washing with absolute methanol, recrystallizing with ethanol for multiple times, and drying to obtain modified KH550(g-KH 550);
ultrasonically dispersing 1g of SNF in ethanol for 2h, quickly adding the g-KH550 at 60 ℃, modifying for 8h, washing with ethanol and deionized water to remove unreacted g-KH550, and vacuum drying to obtain modified silica nanowires, wherein the number of the modified silica nanowires is marked as SNF-g-KH 550;
adding SNF-g-KH550 and 1g of Aminated Graphene (AGP) into DMAc and ultrasonically dispersing for 2h to form a suspension; reacting NH2Placing CF in the suspension for grafting reaction for 8h at room temperature, washing the obtained product by using DMAc, and drying in vacuum to obtain the grafted carbon fiber with the two-dimensional network structure;
100g of PEEK powder (the melt index is 47g/min) and the two-dimensional network structure grafted carbon fiber are put into a drying oven to be dried for 5 hours at the temperature of 120 ℃;
adding the dried PEEK powder into an extruder, wherein the temperature of each feeding section is 360 ℃ at one section, 365 ℃ at two sections, 370 ℃ at three sections, 375 ℃ at four sections and 380 ℃ at five sections, the rotating speed of a screw is 100r/min, the two-dimensional network structure grafted carbon fibers are added into the extruder at constant speed through side feeding, the rotating speed of the side feeding screw is 20r/min, and carrying out extrusion granulation and cooling to obtain granules;
and adding the granules into an injection molding machine, and carrying out injection molding, wherein the temperature of the charging barrel is 360 ℃ in one section, 370 ℃ in two sections, 380 ℃ in three sections, 390 ℃ in a nozzle, and the temperature of the mold is 200 ℃, so as to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material, which is recorded as SCF/PEEK-2.
Example 3
Adding 20g of chopped carbon fiber (SCF) into concentrated hydrochloric acid solution (mass concentration is 38%) containing 0.35g of p-phenylenediamine and 0.35g of sodium nitrite, adjusting the pH value to 1, performing diazotization reaction at the temperature of 5 ℃ for 8h, washing the obtained product with deionized water to be neutral, and performing vacuum drying to obtain aminated carbon fiber (marked as NH)2-CF；
Dissolving 0.35g of biphenyl dianhydride in a DMAc solvent under the conditions of nitrogen protection and room temperature, dropwise adding 0.35gKH550 after dissolving, modifying for 5 hours, removing the solvent by reduced pressure distillation after the reaction is finished, washing with absolute methanol, recrystallizing with ethanol for multiple times, and drying to obtain modified KH550(g-KH 550);
ultrasonically dispersing 1.5g of SNF in ethanol for 2h, quickly adding the g-KH550 at 60 ℃, modifying for 8h, washing with ethanol and deionized water to remove unreacted g-KH550, and vacuum drying to obtain modified silica nanowires, wherein the number of the modified silica nanowires is marked as SNF-g-KH 550;
adding SNF-g-KH550 and 1.5g of Aminated Graphene (AGP) into DMAc and performing ultrasonic dispersion for 2h to form a suspension; reacting NH2Placing CF in the suspension for grafting reaction for 8h at room temperature, washing the obtained product by using DMAc, and drying in vacuum to obtain the grafted carbon fiber with the two-dimensional network structure;
100g of PEEK powder (the melt index is 47g/min) and the two-dimensional network structure grafted carbon fiber are put into a drying oven to be dried for 5 hours at the temperature of 120 ℃;
adding the dried PEEK powder into an extruder, wherein the temperature of each feeding section is 360 ℃ at one section, 365 ℃ at two sections, 370 ℃ at three sections, 375 ℃ at four sections and 380 ℃ at five sections, the rotating speed of a screw is 100r/min, the two-dimensional network structure grafted carbon fibers are added into the extruder at constant speed through side feeding, the rotating speed of the side feeding screw is 20r/min, and carrying out extrusion granulation and cooling to obtain granules;
and adding the granules into an injection molding machine, and carrying out injection molding, wherein the temperature of the charging barrel is 360 ℃ in one section, 370 ℃ in two sections, 380 ℃ in three sections, 390 ℃ in a nozzle, and the temperature of the mold is 200 ℃, so as to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material, which is recorded as SCF/PEEK-3.
Example 4
Adding 20g of chopped carbon fiber (SCF) into concentrated hydrochloric acid solution (mass concentration is 38%) containing 0.40g of p-phenylenediamine and 0.40g of sodium nitrite, adjusting the pH value to 1, performing diazotization reaction at the temperature of 5 ℃ for 8h, washing the obtained product with deionized water to be neutral, and performing vacuum drying to obtain aminated carbon fiber (marked as NH)2-CF；
Dissolving 0.40g of biphenyl dianhydride in a DMAc solvent under the conditions of nitrogen protection and room temperature, dropwise adding 0.40gKH550 after dissolving, modifying for 5 hours, removing the solvent by reduced pressure distillation after the reaction is finished, washing with absolute methanol, recrystallizing with ethanol for multiple times, and drying to obtain modified KH550(g-KH 550);
ultrasonically dispersing 2g of SNF in ethanol for 2h, quickly adding the g-KH550 at 60 ℃, modifying for 8h, washing with ethanol and deionized water to remove unreacted g-KH550, and vacuum drying to obtain modified silica nanowires, wherein the number of the modified silica nanowires is marked as SNF-g-KH 550;
adding SNF-g-KH550 and 2g of Aminated Graphene (AGP) into DMAc and ultrasonically dispersing for 2h to form a suspension; reacting NH2Placing CF in the suspension for grafting reaction for 8h at room temperature, washing the obtained product by using DMAc, and drying in vacuum to obtain the grafted carbon fiber with the two-dimensional network structure;
100g of PEEK powder (the melt index is 47g/min) and the two-dimensional network structure grafted carbon fiber are put into a drying oven to be dried for 5 hours at the temperature of 120 ℃;
adding the dried PEEK powder into an extruder, wherein the temperature of each feeding section is 360 ℃ at one section, 365 ℃ at two sections, 370 ℃ at three sections, 375 ℃ at four sections and 380 ℃ at five sections, the rotating speed of a screw is 100r/min, the two-dimensional network structure grafted carbon fibers are added into the extruder at constant speed through side feeding, the rotating speed of the side feeding screw is 20r/min, and carrying out extrusion granulation and cooling to obtain granules;
and adding the granules into an injection molding machine, and carrying out injection molding, wherein the temperature of the charging barrel is 360 ℃ in one section, 370 ℃ in two sections, 380 ℃ in three sections, 390 ℃ in a nozzle, and the temperature of the mold is 200 ℃, so as to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material, which is recorded as SCF/PEEK-4.
Example 5
The difference from example 1 is that: long-cut carbon fibers (LCF) were used in place of the short-cut carbon fibers of example 1, and the same procedure as in example 1 was followed and designated LCF/PEEK-1.
Example 6
The difference from example 2 is that: long-cut carbon fibers (LCF) were used in place of the short-cut carbon fibers of example 2, and the same as example 2 was designated LCF/PEEK-2.
Example 7
The difference from example 3 is that: long-cut carbon fibers (LCF) were used in place of the short-cut carbon fibers of example 3, and the same as example 3 was designated LCF/PEEK-3.
Example 8
The difference from example 4 is that: long-cut carbon fibers (LCF) were used in place of the short-cut carbon fibers of example 4, and the same as example 4 was labeled LCF/PEEK-4.
Example 9
The difference from example 1 is that: continuous Carbon Fiber (CCF) was used in place of chopped carbon fiber in example 1, otherwise the same as example 1, and is designated CCF/PEEK-1.
Example 10
The difference from example 2 is that: continuous Carbon Fiber (CCF) was used in place of chopped carbon fiber of example 2, otherwise the same as example 2, and is designated CCF/PEEK-2.
Example 11
The difference from example 3 is that: continuous Carbon Fiber (CCF) was used in place of chopped carbon fiber in example 3, otherwise the same as example 3, and is designated CCF/PEEK-3.
Example 12
The difference from example 4 is that: continuous Carbon Fiber (CCF) was used in place of chopped carbon fiber of example 4, otherwise the same as example 4, and is designated CCF/PEEK-4.
Comparative example 1
100g of PEEK powder (melt index 47g/min) is placed in a drying oven and dried for 5h at 120 ℃;
adding the dried PEEK powder into an extruder, wherein the temperature of each feeding section is 360 ℃, 365 ℃ at two sections, 370 ℃ at three sections, 375 ℃ at four sections and 380 ℃ at five sections, and the rotating speed of a screw is 100r/min, performing extrusion granulation, and cooling to obtain a granular material;
and adding the granules into an injection molding machine, and performing injection molding, wherein the temperature of the charging barrel is 360 ℃ in one section, 370 ℃ in two sections, 380 ℃ in three sections, 390 ℃ in a nozzle, the temperature of the mold is 200 ℃, and the obtained sample is marked as PEEK.
Performance testing
The performance of the polyetheretherketone materials prepared in examples 1 to 12 and comparative example 1 was tested, an electronic universal material testing machine was used to perform tensile and bending tests, and an interface meter was used to evaluate the interfacial shear strength of the carbon fibers and the polyetheretherketone matrix, and the results are shown in table 1.
TABLE 1 Performance data for PEEK materials prepared in examples 1-12 and comparative example 1
| Serial number | Tensile Strength (MPa) | Flexural Strength (MPa) | Interfacial shear strength (MPa) |
| PEEK | 94 | 144 | 56 |
| SCF/PEEK-1 | 106 | 159 | 59 |
| SCF/PEEK-2 | 112 | 163 | 61 |
| SCF/PEEK-3 | 119 | 171 | 63 |
| SCF/PEEK-4 | 125 | 180 | 67 |
| LCF/PEEK-1 | 109 | 164 | 61 |
| LCF/PEEK-2 | 114 | 173 | 64 |
| LCF/PEEK-3 | 121 | 181 | 65 |
| LCF/PEEK-4 | 127 | 190 | 69 |
| CCF/PEEK-1 | 113 | 173 | 60 |
| CCF/PEEK-2 | 120 | 187 | 62 |
| CCF/PEEK-3 | 128 | 194 | 68 |
| CCF/PEEK-4 | 139 | 207 | 70 |
As can be seen from Table 1, compared with pure PEEK, the carbon fiber surface grafted two-dimensional network structure reinforced polyetheretherketone composite material prepared by the method has higher interface shear strength and excellent mechanical properties.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material comprises the following steps:
mixing carbon fiber, p-phenylenediamine, nitrite and concentrated hydrochloric acid, and performing diazotization reaction to obtain aminated carbon fiber;
mixing biphenyl dianhydride, an aminosilane coupling agent and a first solvent, and modifying to obtain a modified silane coupling agent;
mixing the dispersion liquid of the silicon dioxide nanowires with a modified silane coupling agent, and modifying to obtain modified silicon dioxide nanowires;
mixing the modified silicon dioxide nanowires, the aminated graphene, the aminated carbon fibers and a second solvent, and grafting to obtain two-dimensional network structure grafted carbon fibers;
and mixing the two-dimensional network structure grafted carbon fiber and the polyether-ether-ketone, and sequentially extruding and molding to obtain the carbon fiber surface grafted two-dimensional network structure reinforced polyether-ether-ketone composite material.
2. The production method according to claim 1, wherein the carbon fiber is a sizing-agent-free carbon fiber, and the carbon fiber is a chopped carbon fiber, a long-cut carbon fiber, or a continuous carbon fiber.
3. The method according to claim 1, wherein the mass ratio of the carbon fiber to the p-phenylenediamine is (10-30) to (0.1-0.5).
4. The preparation method according to claim 1 or 3, wherein the diazotization reaction is carried out at a pH value of 0-2, a temperature of 0-5 ℃ and a time of 6-10 h.
5. The process of claim 1, wherein the aminosilane coupling agent comprises KH550, KH540, or KH 792; the mass ratio of the aminosilane coupling agent to the biphenyl dianhydride is (0.1-0.5): (0.1-0.5).
6. The preparation method according to claim 1 or 5, wherein the modification is carried out at room temperature for 4-6 h.
7. The preparation method according to claim 1, wherein the diameter of the silica nanowires is 10 to 20nm, and the length of the silica nanowires is 5 to 15 μm; the temperature of the modification is 40-60 ℃, and the time is 6-8 h.
8. The preparation method according to claim 1, wherein the aminated graphene has a transverse dimension of 200-1000 nm and a thickness of 0.6-5 nm; the mass ratio of the carbon fibers to the silicon dioxide nanowires to the amino silane coupling agent to the aminated graphene is (10-30): (0.5-2): (0.1-0.5): (0.5 to 2); the mass ratio of the polyether-ether-ketone to the carbon fiber is 100: (10-30).
9. The preparation method according to claim 1 or 8, wherein the grafting temperature is room temperature and the grafting time is 6-8 h.
10. The carbon fiber surface grafted two-dimensional network structure reinforced polyetheretherketone composite material prepared by the preparation method of any one of claims 1 to 9 comprises polyetheretherketone and modified carbon fibers bonded on the polyetheretherketone, wherein silica nanowires and aminated graphene are grafted on the surface of the modified carbon fibers, and the silica nanowires and the aminated graphene are connected into a two-dimensional network structure through covalent bonds.
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