CN113002024A - Method for toughening carbon fiber prepreg between nano-particle polymer composite nano-fiber film layers - Google Patents
Method for toughening carbon fiber prepreg between nano-particle polymer composite nano-fiber film layers Download PDFInfo
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
Abstract
The invention belongs to the field of composite materials, and relates to a method for toughening carbon fiber prepreg between nano-particle polymer composite nano-fiber film layers. The invention utilizes the nano-particle thermoplastic polymer composite nanofiber membrane as an interlayer reinforcing and toughening material, and directly spins the composite nanofiber membrane on the prepreg through electrostatic spinning to form the nanofiber membrane toughening layer. The film has a porous structure which facilitates the flow of the resin in the prepreg when heated. Meanwhile, the reinforcing and toughening nano particles can be uniformly dispersed among the layers of the composite material, so that the composite material and the nano particles are organically combined, the reinforcing and toughening effects of the nano particles are fully exerted, and the mechanical property of the material is further improved. The method can be suitable for interlaminar toughening on the basis of the commercially available finished prepreg, and avoids the change of the synthesis preparation process of the finished prepreg in industrial production.
Description
Technical Field
The invention relates to a method for toughening carbon fiber prepreg between nano-particle polymer composite nano-fiber film layers, belonging to the field of composite materials.
Background
The carbon fiber resin matrix composite material has the outstanding characteristics of light weight, excellent mechanical property and the like, and is widely applied to the field of aerospace. However, the layered carbon fiber/epoxy composite material still has a weak ability to resist the load in the thickness direction and is easily "delaminated", so that the application of such a high-performance composite material is severely limited. Therefore, how to effectively inhibit the delamination damage of the composite material and improve the interlaminar fracture toughness is a research hotspot in the field for a long time.
The first generation of composite material matrix is single thermosetting resin, the material brittleness is large due to high internal crosslinking density, the interlayer bonding force of the resin matrix composite material laminated plate is poor, and the inner part is easy to be delaminated and damaged after the resin matrix composite material laminated plate is subjected to impact load. In view of the damage tolerance requirements of composite materials, researchers have developed second generation composite materials by incorporating thermoplastic resins with superior properties into the thermoset resin matrix to form a particulate composite matrix composite material during the thermal reaction process, with significantly improved fracture toughness. However, when the thermoplastic resin is mixed with the epoxy resin, the viscosity of the resin increases, the resin is not easy to process and mold, and the improvement of the fracture toughness of the matrix resin cannot be expressed as the improvement of the toughness of the resin matrix composite. With the progress of interlaminar toughening technology, the composite material is developed from a first generation material and a second generation material into a third generation interlaminar toughening composite material. The interlayer toughening is realized by inserting the tough material between the layers of the composite material in a certain form, and the interlayer plasticity area is improved to hinder the propagation of interlayer cracks, so that the interlayer fracture toughness and the impact resistance of the composite material are improved.
In the traditional interlaminar toughening method, a thermoplastic film is laid between layers of a reinforced fabric, so that the CAI of the toughened composite material is obviously improved. However, the interlayer toughening of the film structure can limit the elimination of air bubbles, redistribution of resin between layers, and the like during the molding process of the composite material. The toughening materials are used as an independent individual and are inserted into the reinforcing material layers by methods such as manual laying and the like, the process is complicated, the efficiency is low, the toughening materials are mainly thermoplastic resin components, the spreadability is poor, and the process performance in the preparation process of the composite material is seriously influenced.
Disclosure of Invention
The invention aims to provide
In order to achieve the purpose, the method for toughening the carbon fiber prepreg between the nano particle polymer composite nano fiber film layers comprises the following steps:
(1) preparing a nanoparticle thermoplastic polymer spinning solution, and dissolving the nanoparticles and the thermoplastic polymer in an organic solvent to form the spinning solution.
(2) And (2) putting the nano-particle polymer spinning solution into an injector of an electrostatic spinning machine, taking the carbon fiber prepreg as a receiver of electrostatic spinning, and directly spinning the composite nano-fibers on the prepreg at a liquid inlet speed of 0.2-10.0ml/h and under the voltage of 8-30KV to form a nano-fiber film toughening layer. The thickness and uniformity of the nanofiber membrane toughening layer can be adjusted by adjusting the liquid inlet speed of electrostatic spinning and the conveying speed of the prepreg.
(3) And (3) carrying out hot pressing on the carbon fiber prepreg loaded with the toughening layer on the surface by a hot roller to enable the toughening layer and the prepreg to form a whole, namely the interlaminar toughening prepreg.
(4) And (3) passing the interlayer toughened prepreg through a drying oven to completely volatilize the solvent in the toughened layer.
(5) And covering a polyethylene film as a protective layer on the hot-pressed and dried interlayer toughening prepreg through a hot pressing process, and finally rolling to obtain the interlayer toughening prepreg.
(6) And cutting and laying the interlayer toughened prepreg, and curing according to the process system of the prepreg resin matrix to prepare the composite material plate.
Thermoplastic polymer, including one or more of polyester, polyamide, polyether sulfone, polysulfone, polyether imide, polyether ketone; the thermoplastic polymer is dissolved in one or more solvents of dimethylformamide, dimethylacetamide, acetone, dichloromethane, trichloroethane, dimethyl sulfoxide and tetrahydrofuran to prepare a solution, and then electrostatic spinning is carried out.
The carbon fiber prepreg is a commercially available unidirectional carbon fiber prepreg; warp knitting, weft knitting and axial or multidirectional carbon fiber reinforced prepreg thereof; a carbon fiber prepreg of a two-dimensional or two-dimensional three-dimensional woven fabric.
The carbon fiber prepreg resin matrix is one of the following resins: the epoxy resin matrix and the blend of the epoxy resin matrix and the thermoplastic resin, the bismaleimide resin matrix and the blend of the bismaleimide resin matrix and the thermoplastic resin, the polyimide resin matrix and the blend of the polyimide resin matrix and the thermoplastic resin, the phenolic resin matrix and the blend of the phenolic resin matrix and the thermoplastic resin, the benzoxazine resin matrix and the blend of the benzoxazine resin matrix and the thermoplastic resin, and the cyanate resin matrix and the blend of the cyanate resin matrix and the thermoplastic resin.
Toughened nanoparticles include, but are not limited to, nano-CaCO3Particle, nano TiO2Particle, nano SiO2Particles, nanoclay particles, graphene, carbon nanotubes, and the like, and functionalized modified particles thereof.
The composite nanofiber membrane accounts for 1-5% of the weight of the resin matrix in the prepreg.
According to the invention, by utilizing the processability of the carbon fiber prepreg and the good conductivity of the carbon fiber, the carbon fiber prepreg can be used as a receiver of electrostatic spinning to prepare a nano-particle thermoplastic polymer spinning solution with good dispersibility, a composite nano-fiber film is directly spun on the prepreg to form a nano-fiber toughening layer compounded by the nano-particle thermoplastic polymer, and the nano-fiber toughening layer and the carbon fiber prepreg form a whole through a hot rolling process, so that a toughened prepreg product is obtained.
The method for preparing the interlayer toughened prepreg has the following advantages: firstly, the nanofiber membrane toughening layer prepared by the electrostatic spinning technology is of a uniform porous structure, and does not influence the exhaust process in curing molding and the redistribution of resin between layers; secondly, the nano particles added into the toughening material by the method can be uniformly dispersed among the layers of the composite material, so that the composite material and the nano particles are organically combined, the toughening and reinforcing effects of the nano particles are fully exerted, and the mechanical property of the composite material is further improved; and thirdly, the invention can simplify the process operation, greatly improve the preparation efficiency of the toughened prepreg and realize continuous industrial production. In addition, the method can be suitable for interlaminar toughening on the basis of the finished prepreg, and avoids the change of the synthesis preparation process of the finished prepreg in industrial production.
Drawings
FIG. 1 is a schematic view of an apparatus for interlaminar toughening of carbon fiber prepreg by electrospinning and a process thereof.
The reference numbers are as follows:
1. an electrostatic spinning device; 2. an injector; 3. spinning solution; 4. a high voltage power supply; 5. a prepreg unwinding roller; 6. a nanofiber layer; 7. a hot press roll; 8. drying the oven; 9. a polyethylene film unwinding roller; 10. and (5) a prepreg winding roller.
Detailed Description
The invention will be further explained with reference to the drawings
According to the scheme shown in the figure 1, firstly, commercially available carbon fiber prepreg is placed on an unreeling roller, the roller is grounded as a negative electrode, and the carbon fiber prepreg is used as an electrostatic spinning receiver; dissolving nanoparticles and a thermoplastic polymer in a proper organic solvent to form a spinning solution with good dispersibility, directly spinning nanoparticle polymer composite nanofibers on a carbon fiber prepreg to form a uniform nanofiber toughening layer, and forming the toughening layer and the prepreg into a whole through a hot pressing roller; drying the interlayer toughened prepreg in an oven to completely volatilize the solvent in the toughened layer; and finally, covering a polyethylene film as a protective layer on the surface of the intermediate toughening prepreg through a hot pressing process, and rolling to obtain the interlayer toughening prepreg.
Example 1
Selecting a commercially available carbon fiber/epoxy resin prepreg, dissolving graphene and polysulfone resin in dichloroethane, and uniformly stirring to prepare a mixed solution with the concentration of 20 wt%, wherein the mass fraction of the graphene is 3 wt%. And adding the mixed solution into electrostatic spinning equipment, and spinning resin on the surface of the prepreg by using an electrostatic spinning method to form a nanofiber toughening layer. The spinning voltage is 12kV, the working distance is 15cm, and the liquid inlet speed is 1.5 ml/h. The diameter of the prepared nanofiber is 200-700nm, and the mass part of the nanofiber is 2% by weight. And (2) carrying out hot pressing on the carbon fiber prepreg loaded with the toughening layer on the surface by a hot roller at 80 ℃ to enable the nanofiber toughening layer and the carbon fiber impregnated material to form a whole, removing the solvent from the toughened prepreg by a drying oven at 80 ℃, finally covering a polyethylene film on the surface of the prepreg as a protective layer, and rolling to obtain the interlaminar toughened prepreg.
And cutting and laying the interlayer toughened prepreg, and preparing the graphene polysulfone toughened epoxy resin-based carbon fiber composite material by adopting a hot press molding process. Compared with the composite material toughened by the composite fiber film without the added graphene polymer, the compression strength after impact of the composite material prepared by the embodiment is improved from 163MPa to 247 MPa.
Example 2
Selecting commercially available carbon fiber/bismaleimide resin prepreg, and grafting epoxy resin monomer micromolecules on carbon nanotubes after mixed acid treatment to obtain the modified carbon nanotubes. And dissolving the modified carbon nano tube and polyetherimide in a mixed solvent of dichloromethane and chloroform to prepare a solution with the concentration of 25 wt%, wherein the mass fraction of the carbon nano tube is 5 wt%. And adding the mixed solution into electrostatic spinning equipment, and spinning resin on the surface of the prepreg by using an electrostatic spinning method to form a nanofiber toughening layer. The spinning voltage is 18kV, the working distance is 20cm, and the liquid inlet speed is 2 ml/h. The diameter of the prepared nanofiber is 300-1000nm, and the mass part of the nanofiber is 4% by weight. And (2) carrying out hot pressing on the carbon fiber prepreg loaded with the toughening layer on the surface by a hot roller at 80 ℃ to enable the nanofiber toughening layer and the carbon fiber impregnated material to form a whole, removing the solvent from the toughened prepreg by a drying oven at 80 ℃, finally covering a polyethylene film on the surface of the prepreg as a protective layer, and rolling to obtain the interlaminar toughened prepreg.
And cutting and laying the interlayer toughened prepreg, and preparing the carbon nanotube polyetherimide toughened bismaleimide resin-based carbon fiber composite material by adopting a hot press molding process. Compared with the composite material toughened by the composite fiber film without the carbon nano tube polymer, the compression strength of the composite material prepared by the embodiment after impact is improved from 224MPa to 315 MPa.
Example 3
Selecting commercially available carbon fiber/epoxy resin prepreg, and grafting epoxy resin monomer micromolecules to the carbon nano tube after mixed acid treatment to obtain the modified carbon nano tube. And dissolving the modified carbon nano tube and PA66 in a mixed solvent of dichloromethane and formic acid to prepare a solution with the concentration of 15 wt%, wherein the mass fraction of the carbon nano tube is 3 wt%. And adding the mixed solution into electrostatic spinning equipment, and spinning resin on the surface of the prepreg by using an electrostatic spinning method to form a nanofiber toughening layer. The spinning voltage is 15kV, the working distance is 20cm, and the liquid inlet speed is 3 ml/h. The diameter of the prepared nanofiber is 400-100nm, and the nanofiber accounts for 3% by weight through weighing calculation. And (2) carrying out hot pressing on the carbon fiber prepreg loaded with the toughening layer on the surface by a hot roller at 80 ℃ to enable the nanofiber toughening layer and the carbon fiber impregnated material to form a whole, removing the solvent from the toughened prepreg by a drying oven at 80 ℃, finally covering a polyethylene film on the surface of the prepreg as a protective layer, and rolling to obtain the interlaminar toughened prepreg.
And cutting and laying the interlayer toughened prepreg, and preparing the carbon nanotube PA66 toughened epoxy resin-based carbon fiber composite material by adopting a hot press molding process. Compared with the composite material toughened by the composite fiber film without the carbon nanotube polymer, the compression strength of the composite material prepared by the embodiment after impact is improved from 218MPa to 286 MPa.
In order to realize the reinforcement and toughening of the composite material, the invention solves the problem of reinforcement and toughening of the carbon fiber composite material from an interlayer reinforcement and toughening method, mainly aims at an interlayer toughening technology of a finished carbon fiber prepreg, and solves the defects of poor manufacturability, complicated operation and reduced strength, modulus and heat resistance of the composite material of the traditional interlayer toughening method. The nano-particle thermoplastic polymer composite nanofiber membrane is used as an interlayer reinforcing and toughening material, and the composite nanofiber membrane is directly spun on the prepreg through an electrostatic spinning technology to form a nanofiber membrane toughening layer. The film has a porous structure, is good in air permeability and adhesive permeability, and is beneficial to the flowing of resin in the prepreg during heating. Meanwhile, the reinforcing and toughening nano particles can be uniformly dispersed among the layers of the composite material, so that the composite material and the nano particles are organically combined, the reinforcing and toughening effects of the nano particles are fully exerted, and the mechanical property of the material is further improved. The method can be suitable for interlaminar toughening on the basis of the commercially available finished prepreg, and avoids the change of the synthesis preparation process of the finished prepreg in industrial production. The interlayer toughening mechanism is that a toughening material is inserted between the layers of the composite material in a certain form, and the interlayer plastic area is improved to hinder the propagation of interlayer cracks, so that the interlayer fracture toughness and the impact resistance of the composite material are improved, and meanwhile, the thermosetting epoxy resin structure in the laminated plate layer is not changed.
Claims (7)
1. A method for toughening carbon fiber prepreg between nano-particle polymer composite nano-fiber film layers is characterized by comprising the following steps:
(1) preparing a nanoparticle thermoplastic polymer spinning solution, and dissolving nanoparticles and a thermoplastic polymer in an organic solvent to form a spinning solution;
(2) preparing nano-particle thermoplastic polymer composite nano-fibers by adopting an electrostatic spinning method, taking carbon fiber prepreg as a receiver of electrostatic spinning, and directly spinning the composite nano-fibers on the prepreg to form a nano-fiber film toughening layer;
(3) the carbon fiber prepreg loaded with the toughening layer on the surface is hot-pressed by a hot roller to enable the toughening layer and the prepreg to form a whole, namely the interlaminar toughening prepreg;
(4) drying the interlayer toughened prepreg in an oven to completely volatilize the solvent in the toughened layer;
(5) covering a polyethylene film as a protective layer on the hot-pressed and dried interlayer toughening prepreg through a hot pressing process, and finally rolling to prepare the interlayer toughening prepreg;
(6) and cutting and laying the interlayer toughened prepreg, and curing according to the process system of the prepreg resin matrix to prepare the composite material plate.
2. The method for toughening the carbon fiber prepreg between the nano-particle polymer composite nano-fiber film layers according to claim 1, wherein the carbon fiber prepreg is a commercially available prepreg of unidirectional carbon fibers; warp knitting, weft knitting and axial or multidirectional carbon fiber reinforced prepreg thereof; a carbon fiber prepreg of a two-dimensional or two-dimensional three-dimensional woven fabric.
3. The method of claim 1, wherein the toughening nanoparticles comprise nano CaCO3Particle, nano TiO2Particle, nano SiO2Particles, nanoclay particles, graphene, functionalized modified particles of carbon nanotubes.
4. The method for toughening a carbon fiber prepreg between nano-particle polymer composite nano-fiber film layers as claimed in claim 1, wherein the diameter of the nano-fiber is controlled between 100-5000 nm.
5. The method for toughening the carbon fiber prepreg between the nano-particle polymer composite nano-fiber film layers according to claim 1, wherein in the nano-particle thermoplastic polymer spinning solution, the thermoplastic polymer is one or more of polyester, polyamide, polyethersulfone, polysulfone, polyetherimide and polyetherketone; the thermoplastic polymer is dissolved in one or more solvents of dimethylformamide, dimethylacetamide, acetone, dichloromethane, trichloroethane, dimethyl sulfoxide and tetrahydrofuran to prepare a solution, and then electrostatic spinning is carried out.
6. The method of claim 1, wherein the prepreg resin matrix is one of the following resins: the epoxy resin matrix and the blend of the epoxy resin matrix and the thermoplastic resin, the bismaleimide resin matrix and the blend of the bismaleimide resin matrix and the thermoplastic resin, the polyimide resin matrix and the blend of the polyimide resin matrix and the thermoplastic resin, the phenolic resin matrix and the blend of the phenolic resin matrix and the thermoplastic resin, the benzoxazine resin matrix and the blend of the benzoxazine resin matrix and the thermoplastic resin, and the cyanate resin matrix and the blend of the cyanate resin matrix and the thermoplastic resin.
7. The method for toughening the carbon fiber prepreg between the nano-particle polymer composite nano-fiber film layers according to claim 1, wherein the mass fraction of the composite nano-fiber film relative to the resin matrix in the prepreg is 1-5%.
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