CN110181917B - Hybrid film modified carbon fiber composite material and preparation method thereof - Google Patents

Hybrid film modified carbon fiber composite material and preparation method thereof Download PDF

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CN110181917B
CN110181917B CN201910454943.4A CN201910454943A CN110181917B CN 110181917 B CN110181917 B CN 110181917B CN 201910454943 A CN201910454943 A CN 201910454943A CN 110181917 B CN110181917 B CN 110181917B
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hybrid film
composite material
carbon fiber
hybrid
heating
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CN110181917A (en
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向东
李维
李云涛
赵春霞
王斌
李辉
王平
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Southwest Petroleum University
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    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
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    • C08K3/041—Carbon nanotubes

Abstract

The invention discloses a hybrid film modified carbon fiber composite material, which is a composite material laminated board prepared by inserting a hybrid film between prepreg layers; the hybrid film is a composite filler hybrid polyether sulfone resin film consisting of carbon nanotubes and silver nanoparticles. The preparation method of the carbon fiber composite material comprises the following steps: s1, preparing the CNT/AgNP composite filler: mixing a silver nitrate aqueous solution, a carbon nano tube and a sodium citrate aqueous solution, heating and stirring in an oil bath until the solution becomes gray, and performing centrifugal separation to obtain a composite filler; s2, adding the composite filler and the polyether sulfone resin powder into an organic solvent, heating in an oil bath, and stirring to obtain a mixed feed liquid; s3, pouring the mixed liquid into a glass mold and drying in an oven to obtain a hybrid film; and S4, inserting the hybrid film between prepreg layers, and heating and curing to obtain the composite material laminated board. The carbon fiber composite material prepared by the method has the advantages of obviously improved conductivity, impact damage resistance and fracture toughness.

Description

Hybrid film modified carbon fiber composite material and preparation method thereof
Technical Field
The invention relates to the field of high-performance carbon fiber composite materials, in particular to a preparation method of a carbon nanotube/silver nanoparticle composite filler hybrid polyethersulfone resin film toughened resistance-reducing carbon fiber composite material.
Background
The carbon fiber composite material is a new-generation emerging material compounded by carbon fibers and an epoxy resin matrix, and has the advantages of light weight (1/3 or less of metal), high strength (equivalent to metal), excellent corrosion resistance, excellent heat resistance, structural dimensional stability, integral design and manufacture and the like, and can replace the traditional metal material to rapidly develop in the fields of aerospace, automobile lightweight technology, sports and the like. Especially, the consumption of the material on the plane is continuously increased, compared with the traditional metal material, the material can reduce the fuel consumption during flying and improve the cruising speed. On the latest Boeing B787 "fantasy" aircraft, the amount of composite material used is already over 50% of the weight of the aircraft body. However, due to the limitation of intrinsic brittleness of the thermosetting resin matrix of the carbon fiber reinforced resin matrix composite material, how to improve the damage resistance and damage tolerance (low-speed impact strength, post-impact compression strength, interlaminar fracture toughness and the like) of the thermosetting resin matrix composite material is always a main problem faced by the aeronautical composite material. In recent years, in order to meet the requirements of both high damage tolerance and a proper carbon fiber composite material production process, an interlayer toughening method is provided, wherein a toughening phase is separated from a matrix, compounded with a reinforcing phase and generated during epoxy resin curingThe second phase toughening phase is formed after cooling and solidification, and has the original solid performance to toughen the composite material. The impact damage resistance of the composite material is greatly improved while the in-plane mechanical property is maintained. The Doeny company of Japan developed a thermoplastic particle-intercalated prepreg (T800H/3900-2) that had been applied to a Boeing 777 airliner and had excellent impact resistance and three times the initial fracture toughness value (G)IC) Is improved. The american company cyanogen engineering materials used nylon for the first time as a toughening agent in the 977-3 prepreg system produced.
It is reported that an aircraft is struck by lightning 3000 hours per flight, and the composite material applied to the aircraft is struck by lightning because of its insufficient electrical conductivity (10)-3～100S/m, conductivity of the metal is about 106S/m) cannot easily safely conduct the extreme current (about 200000A) generated by a lightning strike, which would vaporize the resin in the area of the lightning strike and burn through the laminate. The traditional method for increasing the conductivity of the composite material is to bond an aluminum or copper mesh on the surface of the structure or embed the aluminum or copper mesh in a matrix to form a conductive path so as to safely conduct the current generated by lightning stroke. However, this increases the total weight of the system, and the process is complicated, expensive to maintain and inefficient. Both Carbon Nanotubes (CNTs) and silver nanoparticles have excellent electrical conductivity, high specific strength and specific modulus, and are ideal fillers for toughening and resistance reduction of composite materials. However, the carbon nanofiller has a large aspect ratio and a large specific surface area, and is easily agglomerated, resulting in low bonding strength with the matrix interface, thereby reducing the mechanical properties of the composite material. Acidification of the carbon nanofiller improves agglomeration and increases its dispersion in the resin phase, but will damage the overall structure and reduce the electrical conductivity and mechanical properties of the structure. Carbon nanofillers also present practical problems when applied to the production of aerospace composite structural members. Dispersing the nano filler in the resin matrix will obviously increase the viscosity of the resin, and the filtering effect of the reinforcing fiber is not favorable for filling the mold cavity with the resin in the molding process, so that the nano filler cannot be uniformly distributed in the composite material system.
Disclosure of Invention
The invention aims to provide a carbon fiber composite material with modified, toughened and resistance-reduced hybrid film, aiming at the current situation that the toughness and the conductivity of the existing carbon fiber composite material are poor.
The invention also aims to provide a preparation method of the hybrid film modified toughened resistance-reducing carbon fiber composite material.
The hybrid film modified toughened resistance-reducing carbon fiber composite material provided by the invention is a composite material laminated plate prepared by inserting a hybrid film between prepreg layers. The hybrid film is a composite filler hybrid polyether sulfone resin film consisting of carbon nanotubes and silver nanoparticles.
Preferably, the amount by weight ratio of the carbon nanotubes to the silver nanoparticles in the composite filler is 10: 1-5. The preparation method of the composite filler comprises the following steps: mixing a silver nitrate aqueous solution, a carbon nano tube and a sodium citrate aqueous solution, heating in an oil bath, stirring and reacting for 1h at the temperature of 120 ℃ until the solution becomes grey, and performing centrifugal separation to obtain a precipitate, namely the CNT/AgNP composite filler.
Adding the composite filler and the polyether sulfone resin powder into an N-N dimethylformamide solvent, heating and stirring to completely dissolve the polyether sulfone resin to obtain a mixed feed liquid, and then preparing the mixed feed liquid into a hybrid film. Preferably, the weight ratio of the polyether sulfone resin to the carbon nanotubes in the mixed feed liquid is 1: 0.03-1: 0.15.
The preparation method of the hybrid film modified carbon fiber composite material comprises the following steps:
s1, preparing the CNT/AgNP composite filler: sequentially putting a silver nitrate aqueous solution, a carbon nano tube and a sodium citrate aqueous solution flask into an oil bath pot, heating the flask in the oil bath, stirring and reacting for 1-2h at the temperature of 110-; storing the composite filler in absolute ethyl alcohol for later use;
s2, adding the CNT/AgNP composite filler and the polyether sulfone resin powder into a flask, then adding an organic solvent, wherein the organic solvent is N-N dimethylformamide or tetrahydrofuran or a mixed solvent of the N-N dimethylformamide and the tetrahydrofuran, placing the flask in an oil bath pot, heating the oil bath, stirring for 1-2h at the temperature of 190 ℃ until the polyether sulfone resin is completely dissolved, ensuring that all components are uniformly mixed through violent mechanical stirring, and then cooling to room temperature to obtain a mixed material liquid; the mass fraction of the polyether sulfone resin in the mixed feed liquid is 10-20%;
s3, pouring the mixed liquid into a self-made glass mold (150mm multiplied by 8mm), then placing the mixture into a blast oven, firstly drying the mixture for 10 to 12 hours at the temperature of 80 to 100 ℃, and then drying the mixture for 3 to 5 hours at the temperature of 120 to 140 ℃ to obtain the hybrid film of the CNT/AgNP composite filler hybrid polyethersulfone; the thickness of the hybrid film is 10-20 μm;
s4, inserting the hybrid film between prepreg layers, heating and curing, firstly heating to 180 ℃ at a heating rate of 4 ℃/min under the pressure of 0MPa, preserving heat for 30min, then boosting to 15MPa, heating to 200 ℃ at a heating rate of 8 ℃/min, and finally cooling to room temperature under the pressure of 15MPa to obtain the composite laminated board.
The invention has the advantages that:
(1) the invention prepares the hybrid film of the carbon nano tube-silver nano particle composite filler hybrid thermoplastic polyether sulfone resin by a simple solution casting method. The hybrid film is an organic-inorganic hybrid system. The addition of the silver nanoparticles improves the dispersibility of the carbon nanotubes and realizes the uniform distribution of the carbon nanotubes in the matrix under the condition of not damaging the conductive performance. The hybrid film is inserted between prepreg layers based on an intercalation method, the hybrid film is dissolved by utilizing the high temperature during the curing of the epoxy resin, and the composite filler is dispersed in the epoxy resin matrix to form a three-dimensional conductive structure, so that the conductivity of the system is obviously increased. And the seepage threshold can be obviously reduced due to the synergistic effect of the two fillers, namely, the dosage of the fillers can be reduced and the cost is reduced compared with the condition of only using one filler. The polyether sulfone resin and the epoxy resin have good reaction compatibility, a phase separation structure can be formed in an epoxy system, and the interlaminar fracture toughness of the system can be remarkably increased.
(2) The method of the invention solves the problems that the carbon nano-filler is not beneficial to filling the mold cavity with resin in the forming process due to the improved viscosity of the resin and the filtering effect (filtering effect) of the reinforcing fiber on the nano-filler in the Resin Transfer Molding (RTM) process when the carbon nano-filler is practically applied to the composite material, so that the carbon nano-filler cannot be uniformly distributed in a composite material system. The problems of dispersion and distribution of the carbon nano-filler in the resin phase are solved. Meanwhile, the influence on the viscosity of the resin can be reduced, and the performance of the product is not reduced. The method meets the preconditions of rapid molding, simple process and reasonable cost, and can be applied to the industrial production of carbon fiber composite materials.
(3) The dynamic performance, the impact damage resistance and the fracture toughness of the prepared carbon fiber composite material are obviously improved, and the electric conductivity of the carbon fiber composite material is also obviously improved. The cracking strength of the I-type layer of the 0-degree unidirectional laminated board can be improved by 50 percent, the cracking strength of the II-type layer can be improved by 50 percent, the drop hammer impact strength can be improved by 20 percent, and the conductivity can be improved by two orders of magnitude.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic structural diagram of an interlaminar fracture toughness test sample.
Fig. 2 is a schematic diagram of the structure of the conductivity test sample.
FIG. 3 is a graph showing the temperature rise during curing.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
A preparation method of a hybrid film modified carbon fiber composite material comprises the following steps:
s1, preparing the CNT/AgNP composite filler: the composite weight ratio of CNT and AgNP is 10:1, the dosage of silver nitrate is 0.12mM (millimole), the dosage of carbon nano tube is 1mg, the dosage of sodium citrate aqueous solution is 10mL, and the mass fraction of the sodium citrate aqueous solution is 1 wt%. The carbon nano-tube has an average diameter of 9.5nm, an average length of 1.5 mu m and a specific surface area of 250-300m2(ii) in terms of/g. The method comprises the following specific operations: sequentially putting a silver nitrate aqueous solution, a carbon nano tube and a sodium citrate aqueous solution into a flask, heating the flask in an oil bath, stirring and reacting for 1h at 120 ℃ until the solution becomes grey, and performing centrifugal separation (the rotating speed of a centrifugal machine is 10000rpm) to obtain a precipitate, namely the CNT/AgNP composite filler; storing the composite filler in absolute ethyl alcohol for later use;
s2, adding the CNT/AgNP composite filler and polyether sulfone resin powder into a flask, then adding an organic solvent, wherein the organic solvent is N-N dimethylformamide or tetrahydrofuran or a mixed solvent of the N-N dimethylformamide and the tetrahydrofuran, placing the flask in an oil bath pot, heating the flask in an oil bath, stirring the flask at 180 ℃ for 1h until the polyether sulfone resin is completely dissolved, ensuring that all components are uniformly mixed by violent mechanical stirring, and then cooling the flask to room temperature to obtain a mixed feed liquid; the mass fraction of the polyether sulfone resin in the mixed feed liquid is 10-20%, and the weight ratio of the polyether sulfone resin to the carbon nano tube is 1: 0.03-1: 0.15;
s3, pouring the mixed liquid into a self-made glass mold (150mm multiplied by 8mm), then placing the mixture into a blast oven, firstly drying the mixture at 80 ℃ for 10h, and then drying the mixture at 120 ℃ for 3h to obtain the hybrid film of the CNT/AgNP composite filler hybrid polyethersulfone; the thickness of the hybrid film is 15 mu m;
s4 preparation of hybrid film modified carbon fiber composite laminated board
The prepreg was first cut into 150mm by 150mm prepregs. Preparing interlaminar fracture toughness test samples: as shown in FIG. 1, the prepreg lay-up sequence was [0 ° ]]24The prepared conductive film is inserted between the twelfth prepreg layer and the thirteenth prepreg layer, and a 13-micron-thick polytetrafluoroethylene film and the conductive film are inserted and laid adjacently on the same layer to generate an initial crack with the length of 50 mm. The upper and lower surfaces of the polytetrafluoroethylene film are coated with a release agent. The lengths of the conductive film and the polytetrafluoroethylene film were 95mm and 45mm, respectively. Preparation of conductivity test samples: as shown in FIG. 2, the prepreg lay-up sequence was [0 ° C ]]12With conductive films interposed between every two adjacent prepregs (i.e. a total of 11 conductive films and 12 prepregs), the top and bottom layers being prepregs.
The prepreg and hybrid film were stacked and placed in a steel mold and the temperature was raised according to the curing procedure shown in fig. 3. The curing process is divided into three steps, including three stages of pre-curing, curing and cooling. Firstly, heating to 180 ℃ at the heating rate of 4C/min under the pressure of 0MPa, preserving heat for 30min, then heating to 15MPa at the heating rate of 8C/min, heating to 200 ℃ at the same time, and finally cooling to room temperature under the pressure of 15MPa to prepare the composite material laminated board modified by the carbon nano tube/silver nano particle (CNT/AgNP) composite filler hybrid polyethersulfone film. The laminate was cut into strips of 140mm by 20mm by 4mm with a water knife for interlaminar fracture toughness testing. Conductivity test sample size was 10mm × 10mm × 2 mm.
Example 2
A preparation method of a hybrid film modified carbon fiber composite material comprises the following steps:
s1, preparing the CNT/AgNP composite filler: the composite weight ratio of CNT and AgNP is 5:1, the dosage of silver nitrate is 0.22mM (millimole), the dosage of carbon nano tube is 1mg, the dosage of sodium citrate aqueous solution is 10mL, and the mass fraction of the sodium citrate aqueous solution is 1 wt%. The carbon nano-tube has an average diameter of 9.5nm, an average length of 1.5 mu m and a specific surface area of 250-300 m2(ii) in terms of/g. The method comprises the following specific operations: sequentially putting a silver nitrate aqueous solution, a carbon nano tube and a sodium citrate aqueous solution into a flask, heating the flask in an oil bath, stirring and reacting for 2 hours at 110 ℃ until the solution becomes gray, and performing centrifugal separation (the rotating speed of a centrifugal machine is 10000rpm) to obtain a precipitate, namely the CNT/AgNP composite filler; storing the composite filler in absolute ethyl alcohol for later use;
s2, adding the CNT/AgNP composite filler and polyether sulfone resin powder into a flask, then adding an organic solvent, wherein the organic solvent is N-N dimethylformamide or tetrahydrofuran or a mixed solvent of the N-N dimethylformamide and the tetrahydrofuran, placing the flask in an oil bath pot, heating the flask in the oil bath, stirring the flask at 170 ℃ for 2 hours until the polyether sulfone resin is completely dissolved, ensuring that all components are uniformly mixed by violent mechanical stirring, and then cooling the flask to room temperature to obtain a mixed feed liquid; the mass fraction of the polyether sulfone resin in the mixed feed liquid is 10-20%; the weight ratio of the polyether sulfone resin to the carbon nano tube is 1: 0.03-1: 0.15;
s3, pouring the mixed liquid into a self-made glass mold (150mm multiplied by 8mm), then placing the mixture into a blast oven, firstly drying the mixture at 100 ℃ for 12h, and then drying the mixture at 140 ℃ for 5h to obtain the hybrid film of the CNT/AgNP composite filler hybrid polyethersulfone; the thickness of the hybrid film is 20 μm;
s4, preparation of the hybrid film modified carbon fiber composite laminated board: the same as in example 1.
Example 3
A preparation method of a hybrid film modified carbon fiber composite material comprises the following steps:
s1, preparing the CNT/AgNP composite filler: the composite weight ratio of CNT and AgNP is 2:1, the dosage of silver nitrate is 0.53mM (millimole), the dosage of carbon nano tube is 1mg, the dosage of sodium citrate aqueous solution is 10mL, and the mass fraction of the sodium citrate aqueous solution is 1 wt%. The carbon nano-tube has an average diameter of 9.5nm, an average length of 1.5 mu m and a specific surface area of 250-300 m2(ii) in terms of/g. The method comprises the following specific operations: sequentially putting a silver nitrate aqueous solution, a carbon nano tube and a sodium citrate aqueous solution into a flask, heating the flask in an oil bath, stirring and reacting for 2 hours at 110 ℃ until the solution becomes gray, and performing centrifugal separation (the rotating speed of a centrifugal machine is 10000rpm) to obtain a precipitate, namely the CNT/AgNP composite filler; storing the composite filler in absolute ethyl alcohol for later use;
s2, adding the CNT/AgNP composite filler and polyether sulfone resin powder into a flask, then adding an organic solvent, wherein the organic solvent is N-N dimethylformamide or tetrahydrofuran or a mixed solvent of the N-N dimethylformamide and the tetrahydrofuran, placing the flask in an oil bath pot, heating the flask in an oil bath, stirring the flask at 190 ℃ for 1h until the polyether sulfone resin is completely dissolved, ensuring that all components are uniformly mixed by violent mechanical stirring, and then cooling the flask to room temperature to obtain a mixed feed liquid; the mass fraction of the polyether sulfone resin in the mixed feed liquid is 10-20%;
s3, pouring the mixed liquid into a self-made glass mold (150mm multiplied by 8mm), then placing the mixture into a blast oven, firstly drying the mixture at 90 ℃ for 11h, and then drying the mixture at 130 ℃ for 4h to obtain the hybrid film of the CNT/AgNP composite filler hybrid polyethersulfone; the thickness of the hybrid film is 10 mu m;
s4, preparation of the hybrid film modified carbon fiber composite laminated board: the same as in example 1.
Preparation of comparative sample: a carbon fiber composite laminate not containing the hybrid film was prepared in a similar manner to step S4 in example 1. And respectively preparing an interlaminar fracture toughness test sample and a conductivity test sample.
The hybrid thin film modified carbon fiber composite laminates prepared in examples 1-3, and the comparative samples were each tested for interlaminar fracture toughness and electrical conductivity, with the results shown in table 1. Compared with a carbon fiber composite laminated board (a comparative sample) without the hybrid film intercalation, the hybrid film modified carbon fiber composite laminated board prepared by the embodiment of the invention has the advantages that the I-layer breaking strength of the 0-degree unidirectional laminated board can be improved by 50%, the II-layer breaking strength can be improved by 50%, the drop hammer impact strength can be improved by 20%, and the electrical conductivity can be improved by two orders of magnitude.
TABLE 1 Performance test data for hybrid film modified carbon fiber composite laminates prepared in examples 1-3 and comparative samples
Figure BDA0002076306510000061
In summary, the invention prepares an organic-inorganic hybrid system conductive film of carbon nanotube/silver nanoparticle composite filler hybrid thermoplastic polyethersulfone resin by a solution casting method, the hybrid conductive film is mixed into the interlayer of the carbon fiber composite material based on an intercalation method, a high-temperature dissolved fiber film generated during epoxy resin curing is utilized to form a second phase in an epoxy resin matrix, and the mechanical property and the electrical property of the carbon fiber composite material are simultaneously improved by the high toughness of the thermoplastic resin and the high conductivity of the carbon nanotube/silver nanoparticle. By compounding the carbon nano tube/silver nano particles, the dispersibility of the carbon nano tube is improved, and the conductivity and the stability of the carbon nano tube conductive network are further improved. The fiber membrane is uniformly distributed in the fiber, and is dispersed in the resin matrix to form a three-dimensional conductive structure while the fiber membrane is dissolved, so that the toughness is improved, and the conductivity of the composite material in different directions is improved.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (5)

1. A hybrid film modified carbon fiber composite material is characterized in that a composite material laminated board prepared by a hybrid film is inserted between prepreg layers, and the hybrid film is a composite filler hybrid polyether sulfone resin film consisting of carbon nanotubes and silver nanoparticles; the weight ratio of the carbon nano tube to the silver nano particle in the composite filler is 10: 1-5;
the preparation method of the hybrid film modified carbon fiber composite material comprises the following steps:
s1, preparing the CNT/AgNP composite filler: mixing a silver nitrate aqueous solution, a carbon nano tube and a sodium citrate aqueous solution, heating in an oil bath, stirring and reacting for 1-2h at the temperature of 110-; storing the composite filler in absolute ethyl alcohol for later use;
s2, adding the CNT/AgNP composite filler and the polyether sulfone resin powder into an organic solvent, heating in an oil bath, stirring for 1-2 hours at the temperature of 190 ℃ until the polyether sulfone resin is completely dissolved, uniformly mixing with the composite filler, and then cooling to room temperature to obtain a mixed feed liquid; the weight ratio of the polyether sulfone resin to the carbon nano tube is 1: 0.03-1: 0.15;
s3, pouring the mixed liquid into a glass mold, and then placing the glass mold into an oven for drying to obtain a hybrid film of CNT/AgNP composite filler hybrid polyethersulfone;
and S4, inserting the hybrid film between prepreg layers, and heating and curing to obtain the composite material laminated board.
2. The hybrid film modified carbon fiber composite material as claimed in claim 1, wherein in the step S1, the raw material addition sequence is in the order of: silver nitrate aqueous solution, carbon nano tube and sodium citrate aqueous solution.
3. The hybrid film modified carbon fiber composite of claim 1, wherein in step S2, the organic solvent is N-N dimethylformamide or tetrahydrofuran or a mixture thereof; the mass fraction of the polyether sulfone resin in the obtained mixed feed liquid is 10-20%.
4. The hybrid film modified carbon fiber composite material as claimed in claim 1, wherein in step S3, the drying operation is specifically: drying for 10-12h at 80-100 ℃, and then drying for 3-5 h at 120-140 ℃ to obtain the hybrid film with the thickness of 10-20 mu m.
5. The hybrid film modified carbon fiber composite material according to claim 1, wherein the temperature-raising curing process of step S4: firstly, heating to 180 ℃ at the heating rate of 4 ℃/min under the pressure of 0MPa, preserving heat for 30min, then boosting to 15MPa, heating to 200 ℃ at the heating rate of 8 ℃/min, and finally cooling to room temperature under the pressure of 15 MPa.
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