CN107523015B - Preparation method of carbon nano tube-montmorillonite self-assembly nano powder grafted glass fiber reinforced resin composite material - Google Patents
Preparation method of carbon nano tube-montmorillonite self-assembly nano powder grafted glass fiber reinforced resin composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a carbon nano tube-montmorillonite self-assembly nano powder grafted glass fiber reinforced composite material, which comprises the following steps: dispersing carbon nanotubes in an aprotic organic solvent, and sequentially carrying out organic amine modification and hydrochloric acid salt-forming reaction to obtain carbon nanotube ammonium salt; ultrasonically dispersing montmorillonite and carbon nano tube ammonium salt in water, filtering, repeatedly washing with water, and spray drying to obtain carbon nano tube-montmorillonite self-assembly nano powder; ultrasonically dispersing the nano powder in a silane coupling agent solution, uniformly spraying the solution on the surface of the glass fiber, and performing vacuum drying to obtain a nano powder grafted glass fiber preform; and then compounding the resin with the prefabricated body through a composite material molding process to obtain the composite material. The invention can effectively improve the dispersibility of the carbon nano tube and the interlayer spacing of the montmorillonite, and the nano powder is grafted on the glass fiber, thereby further improving the dispersibility of the nano powder in the composite material and improving the interface adhesion of resin and fiber, thereby improving the mechanical property and the heat resistance of the fiber composite material.
Description
Technical Field
The invention belongs to the technical field of fiber reinforced polymer composite materials, and particularly relates to a preparation method of a carbon nano tube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material.
Background
The glass fiber reinforced composite material has the excellent characteristics of high strength, high modulus, good formability, fatigue damage resistance and the like, and is widely applied to the fields of aviation, traffic, new energy and the like. The properties of fiber-reinforced composites depend not only on the properties of the fibers and the resin matrix, but also to a large extent on the strength of the interfacial bond. In order to improve the interfacial adhesion of conventional glass fiber reinforced composites, surface modification of the glass fibers is often required. However, the traditional surface modification such as organic modification and surface etching can only improve the mechanical properties of the glass fiber reinforced composite material singly or limitedly, but cannot improve the conductivity, heat resistance and the like of the composite material, so that the further development and application of the glass fiber reinforced composite material are limited.
In recent years, the development of nano materials brings a new development opportunity for improving the interface adhesive property of glass fiber reinforced composite materials, wherein the application reports of montmorillonite (MMT) and Carbon Nanotubes (CNTs) are more. MMT is an inorganic layered silicate material, has strong rigidity, dimensional stability, thermal stability, ion exchange property and the like, can be used for reinforcing and stiffening polymer composite materials, and improves heat resistance, barrier property and the like. The CNTs have excellent mechanical, electrical and thermal properties and the like, have ultrahigh elastic toughness, and are ideal reinforcing and toughening materials for polymer composite materials. At present, some researchers mix and disperse the MMT and the CNTs in the polymer by means of stirring, ultrasound, three-roll grinding and the like so as to improve the mechanical property, the thermal property and the like of the polymer composite material, but the research of mixing the MMT and the CNTs and introducing the MMT and the CNTs into the fiber reinforced composite material is less. For example, Hesami et al [ Hesami M, Bagheri R, Masomi M.combination effects of carbon nanotubes, MMT and hosporos flame retardant on fire and thermal resistance of fire-reinformance composites [ J ]. Iranian Polymer Journal,2014,23(6):469-476 ] disperse MMT and CNTs in epoxy resin by high speed stirring and ultrasonic treatment and prepare glass fiber composites by a hand lay-up process; the ultimate oxygen index of the resulting hybrid reinforced composite is increased by about 8% over that without the addition of MMT and CNTs. However, the natural MMT has smaller interlayer spacing, and the surface is hydrophilic and oleophobic and has poor compatibility with polymers; and the CNTs have higher length-diameter ratio and larger specific surface area, and strong van der Waals force among the tubes is easy to wind and agglomerate. Therefore, secondary agglomeration of MMT and CNTs during polymer resin mixing is unavoidable and the viscosity of the resin system increases. In order to improve the dispersibility of MMT and CNTs in resin, the MMT and the CNTs can be hybridized to form a nano-scale one-dimensional/two-dimensional structure carbon nano tube-montmorillonite (CNTs-MMT) nano composite, and the nano composite is dispersed in the resin. Roy et al [ Roy S, Srivastava S K, Pionteck J, et al, Montmorillonite-multiwalled carbon nanotube nanoarchitecture re-establishment for thermal plastic polyurethane [ J ] Polymer Composites,2016,37(6): 1775-. The obtained nano composite material is researched and found that the tensile strength and the glass transition temperature of the nano composite material are improved by about 57 percent and 10 ℃ compared with the modified thermoplastic polyurethane. However, the preparation of fiber composite materials by pre-dispersing the CNTs-MMT nano composite in resin has not been reported.
In addition, when the fiber composite material is prepared by using resin transfer molding processes such as resin transfer molding and vacuum-assisted resin infusion, the nano-filler is often blocked or filtered by fiber fabrics and is unevenly dispersed. E.g., Elisabete et al [ Elisabete F., Reiada costa. RTM processing and electrical performance of carbon nodes modified epoxy/fiber Composites [ J ]. Composites Part A,2012, 43 (4): 593-. The mixed filler of MMT and CNTs in the resin is even more unavoidable for the above problems. Therefore, a method for preparing a composite material which can improve the dispersibility of the MMT and the CNTs in the composite material and can avoid the MMT and the CNTs from being filtered by fiber fabrics is urgently needed to be searched, so that the excellent performances of the MMT and the CNTs are exerted to a great extent, and the application of the glass fiber reinforced composite material is widened.
Disclosure of Invention
The purpose of the invention is as follows: (1) the CNTs-MMT self-assembly nano powder with excellent MMT and CNTs characteristics is prepared, the MMT interlamellar spacing is effectively improved, and the problems that the CNTs are easy to agglomerate and wind and are not easy to disperse are solved; (2) providing a CNTs-MMT self-assembly nano powder grafted glass fiber preform for preventing or solving the aggregation problem caused by blocking or filtering of nano powder by fiber fabrics in the composite material forming process and realizing stable performance of the composite material; (3) the excellent characteristics of MMT and CNTs are fully utilized, and the interface adhesion of the fiber reinforced composite material is improved, so that the glass fiber composite material is reinforced and toughened.
The technical scheme is as follows: in order to realize the technical purpose, the invention provides a preparation method of a carbon nano tube-montmorillonite self-assembly nano powder grafted glass fiber reinforced composite material, which comprises the following steps:
(1) aminated carbon nanotubes: dispersing carbon nano tubes in an aprotic organic solvent, adding a dehydration condensing agent and an activating agent, and stirring and ultrasonically treating to obtain 1-50 g/L of carbon nano tube dispersion liquid; keeping stirring, preferably keeping the rotating speed of 100 r/min-800 r/min, adding organic amine into the carbon nano tube dispersion liquid for reaction, preferably reacting for 5 h-72 h at room temperature-80 ℃, washing with deionized water, washing with alcohol, and filtering to obtain an aminated carbon nano tube;
(2) preparing carbon nano tube ammonium salt: dispersing the aminated carbon nano tube obtained in the step (1) in deionized water to obtain dispersion liquid of the carbon nano tube of 10 g/L-50 g/L; then hydrochloric acid is used for adjusting the pH value to 3.5-6.5, after stirring for 5-48 h, preferably at the rotating speed of 100-800 r/min, water washing and filtering are carried out to obtain carbon nano tube ammonium salt;
(3) preparing carbon nano tube-montmorillonite self-assembly nano powder: adding montmorillonite into deionized water, stirring and carrying out ultrasonic treatment, preferably stirring for 1-3 h at 500-1000 r/min, and carrying out ultrasonic treatment to obtain 10-150 g/L montmorillonite suspension; adding the carbon nano tube ammonium salt in the step (2) into the montmorillonite suspension, preferably adding the ammonium salt into the montmorillonite suspension at the speed of 0.05-2 g/min, continuously stirring, preferably continuously stirring at the rotating speed of 100-800 r/min for 1-5 h, filtering, washing for 3-5 times, and spray drying to obtain the carbon nano tube-montmorillonite nano powder, wherein the adding amount of the montmorillonite is 100-1000 wt% of the mass of the carbon nano tube;
(4) preparing a nano powder grafted glass fiber preform: dissolving a silane coupling agent in a solvent, and uniformly stirring to obtain a silane coupling agent solution, or adjusting the pH value to 3.5-5.5 by using acetic acid; dispersing the nano powder in the step (3) in a silane coupling agent solution, uniformly spraying the solution on the surface of a glass fiber material after ultrasonic treatment, and performing vacuum drying at 100 +/-20 ℃ to obtain a nano powder grafted glass fiber reinforcement; the surface content of the carbon nano tube-montmorillonite nano powder on the surface of the glass fiber is 0.1-50 g/m2；
(5) Preparing a composite material: and (4) compounding the prefabricated body in the step (4) with a resin matrix by adopting a composite material forming process to obtain the carbon nano tube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material.
Preferably, the carbon nanotubes in step (1) are single-walled, double-walled or multi-walled carbon nanotubes. More preferably, the surface of the carbon nano tube is provided with any one or more functional groups of carboxyl, acyl halide, acid anhydride and aldehyde group.
Preferably, the aprotic organic solvent in step (1) has little or no tendency to undergo proton autodelivery, and the aprotic organic solvent is any one of carbon tetrachloride, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, acetone, and diethyl ether; the solvent in the step (4) is a mixture of any one of 75% ethanol aqueous solution, 75% methanol aqueous solution and 75% isopropanol aqueous solution.
The dehydration condensing agent in the step (1) is any one of carbodiimide type condensing agent, phosphorus cationic type condensing agent and urea cationic type condensing agent, including but not limited to N, N '-dicyclohexylcarbodiimide, N, N' -diisopropylcarbodiimide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate, trispyrrolidinylphosphonium bromide hexafluorophosphate, O- (7-azabenzotriazole) -N, N, N ', N' -tetramethylurea hexafluorophosphate, benzotriazol-N, N, N ', N' -tetramethylurea hexafluorophosphate, O-benzotriazol-N, N, N ', N' -tetramethylurea tetrafluoroborate, urea tetrafluoroborate, 6-chlorobenzotriazole-1, 1,3, 3-tetramethylurea hexafluorophosphate O- (1, 2-dihydro-2-oxo-pyridyl) -1,1,3, 3-tetramethylurea tetrafluoroborate, wherein the dehydration condensing agent accounts for 0-5 wt% of the mass of the carbon nano tube; the activating agent in the step (1) can activate carbonyl in carboxyl to inhibit the generation of byproducts in a reaction system, the activating agent is any one of N-hydroxysuccinimide, N-hydroxyphthalimide, 1-hydroxybenzotriazole, 1-hydroxy-7-azobenzotriazol, 4-dimethylaminopyridine and 4-pyrrolidinylpyridine, and the using amount of the activating agent is 0-5 wt% of the mass of the carbon nano tube.
Preferably, the organic amine in the step (1) is any one or a mixture of several of ethylenediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-diaminopentane, 1, 6-hexanediamine, 1, 8-octanediamine, 1, 10-decanediamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, N- (3-aminopropyl) -1, 4-butanediamine, 2-furanmethanamine, 5-methylfurfurylamine, 2-thiophenemethylamine, thiophene- α -sulfonamide, 5-bromothiophene-2-sulfonamide, 3-aminopropene, acrylamide and 9-octadecenylamine, wherein the amount of the organic amine is 0.5-10 wt% of the mass of the carbon nanotube.
Exchangeable cations in the montmorillonite in the step (3) are any one or a mixture of more of sodium, calcium, magnesium and iron, the cation exchange capacity of the montmorillonite is 60-120 mmol/100g, and the addition amount of the montmorillonite is 100-1000 wt% of the mass of the carbon nano tube.
The silane coupling agent in the step (4) is any one of an amino silane coupling agent, an epoxy silane coupling agent or a vinyl silane coupling agent, the silane coupling agent has a reactive group and comprises any one of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, diethylenetriamine propyl methyldimethoxysilane, 3- (2, 3-epoxypropoxy) propyl trimethoxysilane, 3- (2, 3-epoxypropoxy) propyl triethoxysilane, vinyl trimethoxysilane and vinyl tris- (2-methoxyethoxy) -silane, the dosage of the silane coupling agent is 0.1wt% -2 wt% of the mass of the nano powder.
The glass fiber material in the step (4) is any one of a unidirectional fabric, a multi-axial stitch-bonded fabric, a check fabric, a plain fabric, a twill fabric and a fiber felt; the surface density of the glass fiber material is 100-1500 g/m2。
The composite material forming process in the step (5) is any one of a pultrusion process, a hot pressing process, a vacuum auxiliary resin infusion process, a resin transfer molding process, a vacuum auxiliary resin transfer molding process, a resin impregnation molding process, a structural reaction injection molding process, a liquid resin wetting molding process, a resin film infiltration process and a vacuum bag method forming process.
The resin in the step (5) is any one of epoxy resin, unsaturated polyester resin, vinyl ester resin, bismaleimide resin and polyurethane resin.
The basic principle of the invention is as follows: the invention carries out organic amine modification and protonic acid salifying reaction on the carbon nano tube to obtain carbon nano tube ammonium salt, and then exchanges with montmorillonite cations to obtain the carbon nano tube-montmorillonite self-assembled nano powder with a one-dimensional/two-dimensional structure. The self-assembly nano powder has the excellent performances of both montmorillonite and carbon nano tube, and the intercalation of the carbon nano tube on one hand can improve the interlayer spacing of the montmorillonite and can replace the traditional long-chain alkyl quaternary ammonium salt with low thermal stability; on the other hand, the sheet structure of the montmorillonite can obstruct and weaken the winding of the carbon nano tube. Meanwhile, the carbon nano tube-montmorillonite self-assembly nano powder is grafted on the surface of the glass fiber, so that the problem that the nano powder is blocked or filtered by fiber fabrics in the forming process of the composite material is solved, the dispersibility of the nano powder in the composite material is further improved, and the interfacial adhesion between the fiber and resin can be improved, thereby enhancing and toughening the glass fiber composite material.
Has the advantages that: compared with the prior art, the invention has the following technical effects:
(1) the blocking of the lamellar montmorillonite in the carbon nano tube-montmorillonite nano powder can effectively improve the dispersibility of the carbon nano tube and reduce or avoid the phenomena of easy winding and agglomeration of the carbon nano tube;
(2) the carbon nano tube-montmorillonite nano powder improves the interlayer spacing of the montmorillonite by carbon nano tube intercalation, so that the excellent performance of the montmorillonite can be exerted, and the carbon nano tube-montmorillonite nano powder can partially or completely replace the traditional long-chain alkyl modifier with low thermal stability;
(3) the carbon nanotube-montmorillonite nano powder grafted glass fiber preform can effectively solve the aggregation problem caused by the blocking or filtering of nano powder by fiber fabrics in the composite material forming process, and effectively improve the interface adhesion of the glass fiber composite material;
(4) the carbon nano tube-montmorillonite nano powder grafted glass fiber preform has the advantages of simple preparation process, easiness in large-scale production, environmental friendliness and wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the composite nano-powder of carbon nanotube intercalated montmorillonite;
FIG. 2 is a microscopic morphology (SEM) of the carbon nanotube-montmorillonite self-assembled nano-powder grafted glass fiber preform in example 1;
FIG. 3 is a thermogravimetric plot (TG) of carbon nanotube-montmorillonite self-assembled nano-powder grafted glass fiber reinforced composite in examples 1 and 2;
Detailed Description
The above-mentioned aspects of the present invention are explained in further detail by specific examples below. This should not be construed as limiting the disclosure to only the following examples.
Example 1
A preparation method of a carbon nano tube-montmorillonite self-assembly nano powder grafted glass fiber reinforced composite material comprises the following specific steps:
(1) aminated carbon nanotubes: weighing 0.2g of carboxyl multi-walled carbon nano-tube, adding the carboxyl multi-walled carbon nano-tube into 0.02L of N, N '-dimethylformamide solvent, then respectively adding 0.005g of N, N' -diisopropylcarbodiimide and 1-hydroxybenzotriazole, stirring for 5min, performing ultrasonic treatment for 30min to obtain 10g/L of carbon nano-tube dispersion liquid, and magnetically stirring the carbon nano-tube dispersion liquid at the rotating speed of 200 r/min; weighing 0.01g of diethylenetriamine, adding the diethylenetriamine into the carbon nano tube dispersion liquid, reacting for 24 hours at room temperature, washing with deionized water and alcohol for 2 times respectively, and filtering to obtain a diethylenetriamine modified carbon nano tube;
(2) preparing carbon nano tube ammonium salt: stirring the diethylenetriamine modified carbon nano tube in the step (1) in 0.02L deionized water for 5min, performing ultrasonic treatment for 30min to obtain 10g/L amino carbon nano tube dispersion liquid, adjusting the pH to be about 4.5 by using hydrochloric acid (protonic acid), and stirring for 24h at the rotating speed of 300r/min to obtain carbon nano tube ammonium salt for later use;
(3) intercalation of the carbon nano tube with montmorillonite: dissolving 1g of montmorillonite (the cation exchange capacity is 90mmol/100g) in 50ml of deionized water, stirring for 1.5h, performing ultrasonic treatment for 0.5h to obtain 20g/L montmorillonite suspension, adding the carbon nano tube ammonium salt in the step (2) at the speed of 0.05g/min, and magnetically stirring for 3h at the rotating speed of 400 r/min; and standing, settling, washing with deionized water, filtering for 3-5 times, and spray drying to obtain the carbon nanotube intercalated montmorillonite nanopowder.
(4) Preparing a nano powder grafted glass fiber preform: weighing 0.01g of aminopropyltriethoxysilane, dissolving in a solvent, and uniformly stirring to obtain an aminosilane coupling agent solution; dispersing 1g of the nano powder obtained in the step (3) in an aminosilane coupling agent solution, performing ultrasonic treatment, and uniformly spraying the solution on 1m2Has an areal density of 1200g/m2The surface of the unidirectional glass fiber fabric is dried in vacuum at 100 +/-20 ℃ to obtain the nano-powder grafted glass fiber reinforcement, wherein the 3-aminopropyltriethoxysilane accounts for 1wt% of the nano-powder by mass, and the surface content of the nano-powder on the surface of the unidirectional glass fiber fabric is 1g/m2。
(5) Preparing a composite material: and (3) compounding the prefabricated body in the step (4) with an epoxy resin matrix (LY1564 SP/3486, Hensmei company) by adopting a vacuum bag method forming process to obtain the carbon nano tube-montmorillonite self-assembly nano powder grafted glass fiber reinforced epoxy composite material.
Fig. 1, curve (b) is the XRD chart of the carbon nanotube-montmorillonite self-assembled nano-powder prepared in this example. As can be seen from fig. 1, the 2 θ angle is reduced from 7.08 ° to 5.66 °. It can be known from the calculation of bragg equation (2dsin θ ═ n λ) that the interlayer spacing of montmorillonite is increased after the intercalation of carbon nanotubes. Fig. 2 is an SEM image of the carbon nanotube-montmorillonite self-assembled nano-powder grafted glass fiber preform prepared in this example, wherein fig. 2(b) is a partially enlarged view of fig. 2 (a). As can be seen from FIG. 2, the carbon nanotube-montmorillonite nanopowder is uniformly dispersed on the surface of the glass fiber. In table 1, example 1 is a result of mechanical property test of the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced epoxy composite material prepared in this example, and it can be seen from table 1 that the tensile strength and modulus of the carbon nanotube-montmorillonite self-assembled nano powder-containing composite material are respectively improved by 13.8% and 15.5% compared with the pure glass fiber reinforced epoxy composite material (comparative example 1, as shown in table 1); the bending strength and the modulus are respectively improved by 21.1 percent and 23.4 percent; the interlaminar shear strength is improved by about 23.2 percent. The mechanical property of the composite material is improved mainly due to the uniform dispersion of the carbon nano tube-montmorillonite nano powder on the surface of the glass fiber and the good interface adhesion between the fiber and the resin. Fig. 3 shows a thermogravimetric analysis curve of example 1 in this example for preparing a carbon nanotube-montmorillonite self-assembled nano-powder grafted glass fiber reinforced epoxy composite material, and it can be seen from fig. 3 that when the carbon nanotube-montmorillonite self-assembled nano-powder composite material loses 5% of heat weight, the decomposition temperature is increased from 294.6 ℃ to 306.6 ℃ compared with the pure glass fiber reinforced epoxy composite material (comparative example 1, as shown in fig. 3). The heat resistance of the composite material is improved mainly due to the improvement of the interfacial adhesion of the composite material and the enhancement of the carbon nano tube-montmorillonite nano powder.
Example 2
A carbon nanotube-montmorillonite self-assembled nano-powder and a preparation method thereof, which are different from the embodiment 1 in that the carboxyl carbon nanotube in the step (1) is changed to 1g, the N, N' -diisopropylcarbodiimide and 1-hydroxybenzotriazole are respectively changed to 0.02g, and the organic amine is changed to 0.2g triethylene tetramine; adjusting the pH value of the solution in the step (2) to 4; adding 10g of montmorillonite into 100mL of deionized water in the step (3), stirring for 3h at 1000r/min, and performing ultrasonic treatment for 1 h; stirring the carbon nano tube ammonium salt in the montmorillonite suspension at the stirring speed of 800r/min for 5 hours; changing the silane coupling agent in the step (4) into 0.03g of 3- (2, 3-epoxypropoxy) propyl triethoxysilane, and adjusting the pH of the silane coupling agent solution to 4.0 by using acetic acid; the mass of the nano powder is changed into 3 g; and (5) changing the composite material forming process into a vacuum-assisted resin transfer molding process.
Fig. 1, curve (c) is the XRD chart of the carbon nanotube-montmorillonite self-assembled nano-powder prepared in this example. As can be seen from fig. 1, the 2 θ angle decreases from 7.08 ° to 5.57 °. It can be known from the calculation of bragg equation (2dsin θ ═ n λ) that the interlayer spacing of montmorillonite is increased after the intercalation of carbon nanotubes. In table 1, example 2 is a result of mechanical property test of the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced epoxy composite material prepared in this example, and it can be seen from table 1 that, compared with a pure glass fiber reinforced epoxy composite material (comparative example 1, as shown in table 1), the tensile strength and modulus of the carbon nanotube-montmorillonite self-assembled nano powder-containing composite material are respectively improved by 17.0% and 18.6%; the bending strength and the modulus are respectively improved by 25.8 percent and 27.2 percent; the interlaminar shear strength is improved by about 26.5 percent. Fig. 3 shows a thermogravimetric analysis curve of the carbon nanotube-montmorillonite self-assembled nano-powder grafted glass fiber reinforced epoxy composite prepared in this example, and it can be seen from fig. 3 that when the carbon nanotube-montmorillonite self-assembled nano-powder composite loses 5% of heat weight, the decomposition temperature is increased from 294.6 ℃ to 314.5 ℃ as compared with the pure glass fiber reinforced epoxy composite (comparative example 1, as shown in fig. 3).
Example 3
A carbon nanotube-montmorillonite self-assembled nano-powder and a method for preparing the same, which are different from example 1 in that the carboxyl carbon nanotube in step (1) is changed to 1g, the aprotic organic solvent is changed to carbon tetrachloride, the dehydration condensation agent is changed to ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS), and the organic amine is changed to 0.05g of tetraethylenepentamine; adjusting the pH value of the solution in the step (2) to 3.5 by hydrochloric acid, wherein the rotating speed is adjusted to 600 r/min; the mass of the montmorillonite in the step (3) is changed to 5g, the cation exchange capacity of the montmorillonite is changed to 100mmol/100g, and the ammonium salt of the carbon nano tube is in the montmorilloniteThe stirring speed in the soil removal suspension is 600 r/min. Changing the silane coupling agent in the step (4) into N- (2-aminoethyl) -3-aminopropyltriethoxysilane; the glass fiber material has the surface density of 400g/m2The check cloth of (1); the composite material molding process in the step (5) is changed into a compression molding process; the resin is polyurethane resin (78BD075/44CP20, Bayer materials science and technology Co., Ltd.).
Fig. 1 is a graph (d) showing the XRD pattern of the carbon nanotube-montmorillonite self-assembled nano-powder prepared in this example. As can be seen from fig. 1, the 2 θ angle of the nano-powder in this embodiment is reduced from 7.08 ° to 5.5 °, which indicates that the interlayer spacing of the montmorillonite is increased after the carbon nanotube intercalation, and the carbon nanotube intercalation of the montmorillonite is successful.
Example 4
A carbon nanotube-montmorillonite self-assembled nano-powder and a preparation method thereof, which are different from example 1 in that the aprotic organic solvent in step (1) is changed to an acetone solvent, the organic amine substance is changed to 0.02g of 1, 8-octanediamine, and the dehydration condensation agent is changed to 0.01g of benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate (PyBOP); regulating the pH value to 3.5 by using hydrochloric acid in the step (2), and stirring for 12 hours at the speed of 800 r/min; the montmorillonite in the step (3) is changed into 4g of montmorillonite, the cation exchange capacity of the montmorillonite is changed into 70mmol/100g, and the stirring speed of the carbon nano tube ammonium salt in the montmorillonite suspension is 600 r/min. Changing the silane coupling agent in the step (4) into vinyl triethoxysilane, and adjusting the pH of the silane coupling agent solution to 3.5 by using acetic acid; the glass fiber material has the surface density of 400g/m2The check cloth of (1); the composite material forming process in the step (5) is changed into a resin transfer molding process; the resin is 191 unsaturated polyester resin.
Fig. 1 is a graph (e) showing the XRD pattern of the carbon nanotube-montmorillonite self-assembled nano-powder prepared in this example. As can be seen from fig. 1, the 2 θ angle of the nano-powder in this embodiment is reduced from 7.08 ° to 5.46 °, which shows that the interlayer distance of the montmorillonite is increased after the carbon nanotube intercalation, and the carbon nanotube intercalation succeeds.
Example 5
Carbon nano tube-montmorillonite self-assembly nanoRice flour and a preparation method thereof, which are different from the embodiment 1, in that the surface of the carbon nano tube in the step (1) has no active functional group, the mass of the carbon nano tube is changed to 0.5g, the aprotic organic solvent is changed to dimethyl sulfoxide solvent, the dehydration condensing agent is changed to 0g, the organic amine substance is changed to 0.02g of 2-furanmethanamine, and the reaction is carried out for 48 hours at 50 ℃; adjusting the pH value to 5.5 in the step (2); and (4) stirring the ammonium salt of the carbon nano tube in the montmorillonite suspension for 8 hours at a rotating speed of 300 r/min. Changing the silane coupling agent in the step (4) into vinyl trimethoxy silane, and adjusting the pH value of a silane coupling agent solution to 3.5 by using acetic acid; the glass fiber material has the surface density of 400g/m2The plain weave fabric of (1); the composite material forming process in the step (5) is changed into a vacuum-assisted resin transfer molding process; the resin is 3201 vinyl ester resin.
Fig. 1 is a graph (f) showing the XRD pattern of the carbon nanotube-montmorillonite self-assembled nano-powder prepared in this example. As can be seen from fig. 1, the 2 θ angle of the nano-powder of this example is reduced from 7.08 ° to 5.68 °, which indicates that the interlayer spacing of montmorillonite is increased after intercalation of carbon nanotubes.
Example 6
A carbon nanotube-montmorillonite self-assembly nano powder and a preparation method thereof are different from the embodiment 1 in that the surface of the carbon nanotube in the step (1) has no active functional group, the mass of the carbon nanotube is changed to 1g, the aprotic organic solvent is changed to hexamethylphosphoric triamide, the dehydration condensation agent is changed to 0g, the organic amine substance is changed to 0.04g of 3-amino propylene, and the reaction is carried out for 36h at 50 ℃; converting the protonic acid in the step (2) into nitric acid, and adjusting the pH value to 5; the stirring speed of the carbon nano tube ammonium salt in the montmorillonite suspension in the step (3) is changed to 200r/min, and the stirring time is changed to 6 h; the silane coupling agent described in the step (4) was changed to 0.02g of N- (2-aminoethyl) -3-aminopropyltriethoxysilane; the glass fiber material has the surface density of 1500g/m2S-glass fiber unidirectional fabric of (a); the mass of the nano powder becomes 1.5 g; the composite material forming process in the step (5) is changed into a vacuum-assisted resin transfer molding process; the resin is 5406 bismaleimide resin.
Fig. 1 is a graph (g) showing the XRD pattern of the carbon nanotube-montmorillonite self-assembled nano-powder prepared in this example. As can be seen from fig. 1, the 2 θ angle of the nano-powder in this embodiment is reduced from 7.08 ° to 5.56 °, and the interlayer spacing of montmorillonite is increased after the intercalation of the carbon nanotube.
Comparative example 1
1200g/m2The unidirectional glass fiber fabric is laid in a vacuum bag for standby; and uniformly mixing an epoxy resin matrix (LY1564 SP/3486, Hensmei company) and injecting into a vacuum bag, and curing to obtain the glass fiber reinforced epoxy composite material prepared by the vacuum bag forming process.
TABLE 1 mechanical Property test results
Claims (8)
1. A preparation method of a carbon nano tube-montmorillonite self-assembly nano powder grafted glass fiber reinforced resin composite material is characterized by comprising the following steps:
(1) the amination carbon nano tube is prepared by dispersing the carbon nano tube in an aprotic organic solvent, adding a dehydration condensing agent and an activating agent, stirring and carrying out ultrasonic treatment to obtain 1 g/L-50 g/L of carbon nano tube dispersion liquid, keeping stirring, adding organic amine into the carbon nano tube dispersion liquid to react, washing with deionized water and carrying out alcohol washing to obtain the amination carbon nano tube, wherein the proton self-delivery reaction of the aprotic organic solvent in the step (1) is very weak or has no self-delivery tendency, the aprotic organic solvent is any one of carbon tetrachloride, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-2-imidazolidinone, acetone and diethyl ether, the organic amine is ethylenediamine, 1, 3-propanediamine, 1, 4-butanediamine, 1, 5-diaminopentane, 1, 6-hexanediamine, 1, 8-octanediamine, 1, 10-decanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N- (3-aminopropyl) -1, 4-butanediamine, 2-methylamine, 5-tetramethylenediamine, 5-2-butanediamine, 5-2-octadecylamide, 5-2-octadecylamide, 5-9-2-octylsulfamide, 5-10-octylsulfamide and a mixture of one of ethylene sulfamide, wherein the weight of the organic amine is one of ethylene sulfamide;
(2) preparing carbon nano tube ammonium salt: dispersing the aminated carbon nano tube obtained in the step (1) in deionized water to obtain dispersion liquid of the carbon nano tube of 10 g/L-50 g/L; adjusting the pH value to 3.5-6.5 by using hydrochloric acid, stirring for 5-48 h, washing with water, and filtering to obtain carbon nano tube ammonium salt;
(3) preparing carbon nano tube-montmorillonite self-assembly nano powder: adding montmorillonite into deionized water, stirring and carrying out ultrasonic treatment to obtain montmorillonite suspension of 10-150 g/L; adding the carbon nano tube ammonium salt obtained in the step (2) into the montmorillonite suspension for continuous stirring, filtering, washing, and performing spray drying to obtain carbon nano tube-montmorillonite nano powder, wherein the adding amount of the montmorillonite is 100 wt% -1000 wt% of the mass of the carbon nano tube;
(4) preparing a nano powder grafted glass fiber preform: dissolving a silane coupling agent in a solvent, and uniformly stirring to obtain a silane coupling agent solution, or adjusting the pH value to 3.5-5.5 by using acetic acid; dispersing the nano powder in the step (3) in a silane coupling agent solution, uniformly spraying the solution on the surface of a glass fiber material after ultrasonic treatment, and performing vacuum drying at 100 +/-20 ℃ to obtain a nano powder grafted glass fiber reinforcement; the surface content of the carbon nano tube-montmorillonite nano powder on the surface of the glass fiber is 0.1-50 g/m2(ii) a The solvent in the step (4) is any one or a mixture of more of 75% ethanol aqueous solution, 75% methanol aqueous solution and 75% isopropanol aqueous solution;
(5) preparing a composite material: and (4) compounding the prefabricated body in the step (4) with a resin matrix by adopting a composite material forming process to obtain the carbon nano tube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material.
2. The method for preparing carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material according to claim 1, wherein the carbon nanotubes in step (1) are single-walled, double-walled or multi-walled carbon nanotubes.
3. The method for preparing the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material as claimed in claim 1, wherein the dehydration condensation agent in the step (1) is any one of a carbodiimide type condensation agent, a phosphorus cationic type condensation agent and a urea cationic type condensation agent, and the dehydration condensation agent is 0-5 wt% of the mass of the carbon nanotube; the activating agent is any one of N-hydroxysuccinimide, N-hydroxyphthalimide, 1-hydroxybenzotriazole, 1-hydroxy-7-azobenzotriazol, 4-dimethylaminopyridine and 4-pyrrolidinylpyridine; the dosage of the activating agent is 0 wt% -5 wt% of the mass of the carbon nano tube.
4. The preparation method of the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material according to claim 1, wherein exchangeable cations in the montmorillonite in the step (3) are any one or a mixture of more of sodium, calcium, magnesium and iron, the cation exchange capacity of the montmorillonite is 60-120 mmol/100g, and the addition amount of the montmorillonite is 100 wt% -1000 wt% of the mass of the carbon nanotube.
5. The method for preparing the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material as claimed in claim 1, wherein the silane coupling agent in step (4) is any one of an aminosilane coupling agent, an epoxysilane coupling agent or a vinylsilane coupling agent, and the amount of the silane coupling agent is 0.1-2 wt% of the mass of the nano powder.
6. The method for preparing the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material according to claim 1, wherein the glass fiber material in the step (4) is any one of a unidirectional fabric, a multi-axial stitch-bonded fabric, a checkered fabric, a plain fabric, a twill fabric and a fiber mat; the surface density of the glass fiber material is100～1500 g/m2。
7. The method for preparing the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material according to claim 1, wherein the composite material forming process in the step (5) is any one of a pultrusion process, a hot pressing process, a vacuum-assisted resin infusion process, a resin transfer molding process, a vacuum-assisted resin transfer molding process, a resin impregnation molding process, a structural reaction injection molding process, a liquid resin wetting molding process, a resin film infiltration process and a vacuum bag method forming process.
8. The method for preparing the carbon nanotube-montmorillonite self-assembled nano powder grafted glass fiber reinforced resin composite material according to claim 1, wherein the resin in the step (5) is any one of epoxy resin, unsaturated polyester resin, vinyl ester resin, bismaleimide resin and polyurethane resin.
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