CN113999495B - Structural-function-integrated carbon fiber/epoxy composite material and preparation method thereof - Google Patents
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Abstract
The invention relates to a carbon fiber/epoxy composite material with integrated structure and function and a preparation method thereof, wherein the composite material comprises a carbon fiber fabric reinforcing material, an epoxy resin matrix material and a nano-scale transition metal sulfide modified on the surface of carbon fiber; the transition metal sulfide is petal-shaped tungsten sulfide synthesized by a hydrothermal method. According to the invention, the dense nano flower microstructure is introduced on the surface of the carbon fiber through the compounded surfactant by adopting a hydrothermal method, so that the contact area of the fiber and the epoxy resin matrix is increased, the interface between the matrix resin and the carbon fiber is more tightly combined, and the composite material has excellent interlaminar shear performance. And due to the introduction of the tungsten sulfide nanoflower, a certain electromagnetic absorption function of the composite material is provided.
Description
Technical Field
The invention belongs to the field of preparation of polymer matrix composite materials, and particularly relates to a structural-function integrated carbon fiber/epoxy composite material and a preparation method thereof.
Background
Carbon fiber/epoxy composite (Carbon Fiber Reinforced Epoxy Resin Composites, CFRERC) is a type of advanced composite that uses epoxy as a matrix and carbon fiber as a reinforcement material. Besides the main performance of advanced composite material, high specific strength and specific modulus, it has a series of excellent performances of high fatigue strength, small thermal expansion coefficient, corrosion resistance, stable structural dimension, designable material performance, etc. As a novel advanced composite material, the EP/CF composite material can be used as a structural material for bearing load, can meet the fields with strict requirements on weight, strength, rigidity, fatigue characteristics and the like, and can also be used as a functional material due to the high temperature and chemical stability of the EP/CF composite material. The method is widely applied to various high and new technical fields and civil fields such as cultural and physical equipment, medical machinery, automobiles, traffic, energy, construction, machinery, chemical industry and the like.
Carbon fiber/epoxy composite materials have been in the past for over sixty years, but research and application will be deeper with the development of high and new science and technology, the designability of the structure and performance of the carbon fiber/epoxy composite materials is continuously pushing the appearance and performance of new materials to be improved, and the application field of the carbon fiber/epoxy composite materials will be more and more extensive. The structural integrated functional material is a main development direction of a high-performance carbon fiber/epoxy resin composite material, and the material is required to have the characteristics of light weight, high strength, high toughness, high temperature resistance, corrosion resistance, abrasion resistance, low cost and structural function integration, and can adapt to special environment requirements. Wang Ting of Shandong university is separated from the conventional interlayer structure and adopts carbon fiber, aramid fiber, multi-wall carbon nanotubes (MWCNTs) and nitrogen carbide (C) 3 N 4 ) The filler designs a series of hybrid structures, so that not only the interlaminar shear strength (ILSS), tensile modulus, flexural modulus and other mechanical properties of the carbon fiber/epoxy composite material are improved, but also the damping performance of the material is greatly improved. Hu Tao of the university of martial arts improves the absorption loss of the CF/EP composite material while improving the density of fiber yarn bundles by adding carbonyl iron powder into carbon fiber cloth, so that the material has a more stable sandwich structure and has shielding performance with controllable interlayer direction.
The prior art has the case of improving interlayer performance and electromagnetic shielding performance by depositing CNTs on the surface of carbon fiber, but has the disadvantages of poor dispersibility, complex preparation, high price and the like. The transition metal sulfide with controllable morphology can more conveniently regulate and control the electromagnetic shielding performance of the whole material.
However, a considerable number of products in carbon fiber composites are laminate structures, microscopically a typical "three-phase" structure, comprising a carbon fiber reinforcement phase, a resin matrix phase, and an interfacial phase, wherein the interfacial phase is a tie and bridge that transfers load from the resin to the carbon fibers. The structure, composition, property, bonding mode and interfacial bonding strength of the interfacial phase play a vital role in the mechanical properties of the carbon fiber resin matrix composite. The carbon fiber has smooth surface, small specific surface area, few active groups and poor wettability with the resin matrix, so that the bonding between the carbon fiber layers is completely dependent on the resin, the interface phase becomes the weakest link of the composite material, and the phenomena of cracking and stripping between the layers of the material are easily caused in the use process. Therefore, how to improve the interfacial bonding between the carbon fiber and the epoxy matrix is a key to improve the interlaminar shear performance of the composite material.
In recent years, the modification of carbon fibers themselves by researchers has been mainly focused on improving the surface roughness and polarity thereof. Wherein, the surface roughness of the carbon fiber is improved to form a strong mechanical locking effect between the fiber and the resin matrix, when the material is loaded, the concave-convex points on the surface of the fiber can more strongly grasp the resin matrix, thereby achieving the aim that the fiber is not easy to be pulled out from the resin matrix.
Disclosure of Invention
In order to overcome the defect that the carbon fiber/epoxy resin composite material in the prior art has poor interfacial phase affinity and is a weak link of the composite material, the nano microstructure of petal-shaped transition metal sulfide is introduced into the surface of the carbon fiber, and the method has three purposes: 1, the roughness of the interface is improved, so that the epoxy infiltration is facilitated, and the contact area of two phases of the interface is increased; 2, providing a mechanical interlocking effect, so that when the material is loaded, the fracture and peeling phenomena between layers are more difficult to occur, and excellent interlayer shearing performance is shown; and 3, the tungsten disulfide nano-sheet with high specific surface area and high dielectric loss is introduced to be compounded with the carbon fiber, so that the electromagnetic wave attenuation capability of the material is improved, the electromagnetic shielding performance is improved, and a certain electromagnetic absorption function is provided for the composite material. Research for improving interlayer shearing performance of carbon fiber/epoxy composite materials and simultaneously introducing electromagnetic absorption function by growing petal-shaped tungsten sulfide on the surface of carbon fiber has not been reported.
In order to solve the technical problems, the invention provides the following technical scheme:
the structural-function integrated carbon fiber/epoxy composite material comprises the following raw materials: carbon fiber cloth with nano-scale transition metal sulfide modified on the surface, epoxy resin and curing agent.
The mass ratio of the carbon fiber cloth to the epoxy resin to the curing agent is 1:2-5:0.2-0.3.
The gram weight of the carbon fiber cloth is 200-300.
The epoxy resin is bisphenol type epoxy resin, such as bisphenol A epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin, and has an epoxy value of 0.30-0.51. Specifically, for example, bisphenol A epoxy resin is at least one selected from the group consisting of E-51, E-44, E-42, and E-35.
The curing agent is at least one selected from 593 and 591.
The transition metal sulfide is at least one selected from tungsten sulfide, molybdenum sulfide, chromium sulfide and nickel sulfide.
The transition metal sulfide is in a nano flower shape and is formed by stacking two-dimensional sheet structures with diameters of about 3-5 mu m.
The transition metal sulfide is obtained by in-situ growth on the surface of the carbon fiber cloth reinforced material through hydrothermal reaction, and specifically is obtained by reacting the carbon fiber material with the surface cleaned and the precursor solution of the transition metal sulfide at 150-200 ℃ for 12-36 hours.
The transition metal sulfide precursor solution is obtained by uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant.
Further, the source of the transition metal element is a salt of at least one of tungsten, molybdenum, chromium, and nickel, such as sodium, potassium/ammonium salt of an oxo acid of the transition metal (A) 2 MO 4 A is Na, K or NH 4 M is W, mo, ni or Cr), a halide of a transition Metal (MX) n M is W, mo, ni or Cr, X is a halogen atom, and n is an integer of 2 to 6).
The sulfur source is selected from thiourea and/or thioacetamide, and provides sulfur ions; the reducing agent is at least one selected from hydroxylamine hydrochloride and oxalic acid.
The surfactant is quaternary ammonium salt cationThe surfactant and fatty alcohol sodium isethionate are compounded according to the mass ratio of 3-5:1, and the general formula of the quaternary ammonium salt cationic surfactant can be expressed as [ AB ] 3 N] + X - Wherein A is a long-chain alkyl group having 12 to 20 carbon atoms, B is a methyl group or an ethyl group, and X is a halogen atom such as chlorine or bromine; preferably, the quaternary ammonium salt cationic surfactant is selected from at least one of cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide.
The inventors have unexpectedly found that by using a combination of a long-chain alkyl quaternary ammonium surfactant and sodium fatty alcohol isethionate as the surfactant, a stable microemulsion system can be obtained when the combination ratio is suitable, although both surfactants carry head groups with different charges, precipitation can be generated due to electrostatic action or liquid crystals greatly limit the application thereof. And because of the strong electrostatic attraction of anions and cations, the electric property in the adsorption layer is partially neutralized, the electrostatic repulsion between charge ions in the surface adsorption layer is weakened, the surface interface property is greatly changed, the surface energy is reduced, the anion-cation surfactant compound system can obtain lower surface interface tension compared with a single component, the efficiency of reducing the surface tension is improved, the use amount of the surfactant is reduced, and meanwhile, the overall synergy and the stability are higher. In addition, the anionic and cationic surfactant compound system can form abundant microstructures such as spherical, rod-shaped micelles, lamellar liquid crystals, vesicles and the like in aqueous solution. Therefore, the long-chain alkyl quaternary ammonium salt surfactant and the organic anion surfactant with proper proportion are adopted as the surfactant, so that the morphology of the transition metal sulfide crystal can be effectively controlled and obtained. Wherein the quaternary ammonium salt in the excess quaternary ammonium salt cationic surfactant is combined with MS 4 2+ The electron pair is formed, the crystal growth unit is transported, the transition metal sulfide can be uniformly and stably grown, the Critical Micelle Concentration (CMC) and the surface tension (IFT) value are effectively reduced, more stable micelle is obtained, and the formed micelle is used as a microreactor and a template to control the crystal shape of the transition metal sulfide and simultaneously cover the surface of the formed transition metal sulfide, so that agglomeration is prevented.
Wherein the mass ratio of the transition metal source (calculated as transition metal), the sulfur source (calculated as sulfur), the reducing agent and the surfactant is 1:1-10:1-5:0.1-0.5, preferably 1:3-5:2-3:0.1-0.2.
The structural-functional integrated carbon fiber/epoxy composite material provided by the invention is characterized in that a petal-shaped tungsten sulfide microstructure is grown on the surface of carbon fiber cloth by a hydrothermal method, the modified carbon fiber cloth is used as a reinforcement, epoxy resin is used as a polymer matrix, the epoxy resin matrix and the carbon fiber cloth are compounded together, and finally, the composite material product is obtained by curing.
The invention provides a preparation method of a structural-functional integrated carbon fiber/epoxy composite material, which comprises the following steps:
1) Growing transition metal sulfide on the surface of the carbon fiber cloth: uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant in water according to a certain proportion, adding a transition metal sulfide precursor solution, desizing, reacting the carbon fiber cloth with the surface cleaned at 150-200 ℃ for 12-36h, cooling, washing and drying to obtain the carbon fiber cloth with the surface grown transition metal sulfide;
2) Compounding of carbon fiber and epoxy resin: and (3) compounding the carbon fiber cloth with the transition metal sulfide grown on the surface obtained in the step (1) with an epoxy resin matrix material by a vacuum assisted resin transfer molding method, and finally curing to obtain a carbon fiber/epoxy composite material product.
Vacuum Assisted Resin Transfer Molding (VARTM) is a process in which resin is injected into a closed mold to impregnate the reinforcing material and cure. The technology is suitable for products with high quality requirements, small batch and larger size, and compared with the traditional autoclave molding process, the technology has the outstanding characteristics of low cost of a die, room-temperature curing of resin, almost unlimited product size and the like, and is one of the most extensive molding methods for manufacturing composite material parts.
The pretreatment of carbon fiber cloth and the post-treatment of carbon fiber cloth with surface growing transition metal sulfide are well known in the art, specifically, the carbon fiber cloth cut into proper size is soaked in an organic solvent, the slurry removal treatment is carried out for 48 hours under the room temperature condition, then the carbon fiber cloth after the slurry removal is repeatedly washed by ethanol and deionized water, the slurry and acetone remained on the surface of the carbon fiber cloth are washed off, and the carbon fiber cloth is dried; and the post-treatment is to take out the carbon fiber cloth after naturally cooling to room temperature, wash the carbon fiber cloth with ethanol and deionized water for a plurality of times, wash off the tungsten sulfide powder remained on the surface of the carbon fiber cloth, and dry the carbon fiber cloth in an oven at 60-80 ℃ to obtain the carbon fiber cloth with the tungsten sulfide nanoflower on the surface.
The invention has the advantages and characteristics that:
a layer of functional tungsten sulfide nanoflower grows on the surface of the carbon fiber cloth through hydrothermal reaction, so that the interface between the matrix resin and the carbon fiber is combined more tightly while the contact area between the carbon fiber and the epoxy resin matrix is increased by utilizing the microstructure of the nanoflower. Thereby the composite material shows excellent interlaminar shear performance. And due to the existence of the tungsten sulfide nanoflower, the composite material has a certain electromagnetic absorption function, reduces or avoids the influence caused by electromagnetic radiation, such as a protective material for reducing the harm of electromagnetic waves, or a material for preventing electromagnetic waves is needed, so that the prepared carbon fiber/epoxy composite material has excellent mechanical property and electromagnetic shielding functionality, and can be applied and made to invisible aircrafts, radioactive medical instruments, electronic equipment shells (shielding covers and shielding darkrooms), electromagnetic pollution reduction (the energy carried by the electromagnetic waves influences sensitive organs of human bodies), electromagnetic stealth (stealth aircrafts or ships), special communication (high transmittance in specific wave bands and shielding in other wave bands).
Drawings
FIG. 1 is an SEM image of a carbon fiber composite material prepared in example 1;
FIG. 2 is an SEM image of the carbon fiber composite material prepared in example 2;
FIG. 3 is an SEM image of a carbon fiber composite material prepared in example 3;
fig. 4 is an SEM image of the carbon fiber composite material prepared in example 4.
Detailed Description
Example 1
1) Soaking the carbon fiber cloth cut into the size of 7 multiplied by 3cm in an acetone solution, maintaining the solution at room temperature for 48 hours for desizing treatment, repeatedly washing the desized carbon fiber cloth with ethanol and deionized water, washing off residual slurry and acetone on the surface of the desized carbon fiber cloth, and drying to obtain desized carbon fiber cloth; soaking the desized carbon fiber cloth in an ethanol solution, ultrasonically cleaning the carbon fiber cloth for 1 hour by using ultrasonic equipment with the power of 600W, repeatedly flushing the carbon fiber cloth by using ethanol and deionized water, washing off impurities and dust remained on the surface of the carbon fiber cloth, and drying; respectively weighing 10mmol, 40mmol and 20mmol of sodium tungstate hexahydrate, thiourea and hydroxylamine hydrochloride, dissolving in 40mL of deionized water to prepare a mixed solution A, weighing 0.375g of cetyltrimethylammonium bromide (CTAB) and 0.125g of fatty alcohol sodium isethionate, dissolving in 40mL of deionized water to prepare a mixed solution B, magnetically stirring for 30 minutes to ensure that solutes in A and B are completely dissolved and uniformly mixed, pouring A, B of the uniformly mixed solution into a 100mL of hydrothermal kettle lining, adding ultrasonic cleaned and dried carbon fiber cloth, placing the lining into the hydrothermal kettle, screwing, placing in a baking oven at 180 ℃ to react for 24 hours, naturally cooling to room temperature, taking out the carbon fiber cloth, washing with ethanol and deionized water for a plurality of times, cleaning tungsten sulfide powder remained on the surface of the carbon fiber cloth, and drying in the baking oven at 80 ℃ to obtain the carbon fiber cloth with tungsten sulfide nanoflower on the surface;
2) Taking out 8 pieces of carbon fiber cloth (WS) with tungsten sulfide nanoflower 2 @ CF) and weighed to determine a mass of 5g of carbon cloth. Coating release agent on glass plate, and coating 8 WS blocks 2 The @ CF is tiled and a vacuum resin transfer molding device is built, so that the tightness of the whole system is good. 10g of epoxy resin and 3g of 593 curing agent are weighed, mixed with the epoxy resin and stirred uniformly to obtain a mixed solution. Removing bubbles in the mixed solution by using a vacuum pump, pumping the solution after removing the bubbles into a built resin transfer molding device by using the vacuum pump, sealing ports at two ends after the solution is completely soaked in 8 layers of carbon cloth, and curing for 5 hours at room temperature to obtain WS 2 @ CF/EP composite laminate. Cutting and sawing each carbon plate into test bars with the thickness of 6 multiplied by 20mm, and carrying out subsequent interlayer shearing test; cutting into 22.86×10.16mm test bars, and performing subsequent electromagnetic shielding test.
The interlayer shear strength of the carbon fiber composite material obtained in the embodiment is 55.3MPa, and the minimum reflection loss value of electromagnetic absorption of 4GHz reaches-23 dB.
Example 2
Other conditions and operations were the same as in example 1 except that in step 1), the amount of the surfactant was changed to 0.42g of cetyltrimethylammonium bromide and 0.08g of sodium isethionate fatty alcohol. The interlayer shear strength of the carbon fiber composite material obtained in the embodiment is 52.4MPa, and the minimum reflection loss value of electromagnetic absorption of 4GHz reaches-22 dB.
Example 3
Other conditions and operations were the same as in example 1 except that in step 1), the amount of the surfactant was changed to 0.25g of cetyltrimethylammonium bromide and 0.25g of sodium isethionate fatty alcohol.
The interlayer shear strength of the carbon fiber composite material obtained in the embodiment is 48.2MPa, and the minimum reflection loss value of electromagnetic absorption of 4GHz reaches-21 dB.
Example 4
Other conditions and operations were the same as in example 1 except that in step 1), the amount of the surfactant was changed to 0.5g of cetyltrimethylammonium bromide.
The interlayer shear strength of the carbon fiber composite material obtained in the embodiment is 41.7MPa, and the minimum reflection loss value of electromagnetic absorption of 4GHz reaches-20 dB.
FIGS. 1 to 4 are SEM images of carbon fiber composites obtained in examples 1 to 4, respectively. The composite materials obtained in the examples 1 and 2 can be seen to form nanoflower nanosheets, the size and structure between the nanosheets are uniform and stable, no obvious agglomeration and accumulation phenomenon exists except for a small amount of impurities, and the fact that under a proper proportion, CTAB and fatty alcohol sodium isethionate are compounded to form more stable micelles provides more favorable conditions for subsequent reactions. In example 3, the surfactant ratio was not within the preferred range, so that the anions and cations did not form stable micelles due to electrostatic adsorption, and thus part of WS2 did not form a lamellar nano-flower structure. Example 4 used a single cationic quaternary ammonium salt surfactant, which did not form a uniform and stable nanoflower structure, indicating that a single cationic surfactant was difficult to form a stable textbook, and further was unable to form a uniform and stable nanoflower structure, resulting in reduced interlaminar shear strength.
Comparative example 1
Other conditions and operations are the same as in example 1, except that the carbon fiber cloth is not subjected to surface growth of tungsten sulfide nanoflower, and the step 2) and the epoxy resin are directly compounded after desizing and cleaning.
The interlayer shear strength of the obtained carbon fiber composite material is 35.8MPa, and the minimum reflection loss value of electromagnetic absorption of 4GHz reaches-12 dB.
Claims (10)
1. The carbon fiber/epoxy composite material with integrated structural function is characterized by comprising the following raw materials: carbon fiber cloth with nano-scale transition metal sulfide modified on the surface, epoxy resin and curing agent;
the transition metal sulfide is tungsten sulfide;
the transition metal sulfide is in a nano flower shape and is formed by stacking two-dimensional sheet structures with diameters of 3-5 mu m;
the transition metal sulfide is obtained by in-situ growth on the surface of the carbon fiber cloth reinforced material through hydrothermal reaction, and is obtained by reacting the carbon fiber material with the surface cleaned with a transition metal sulfide precursor solution at 150-200 ℃ for 12-36 hours; the transition metal sulfide precursor solution is obtained by uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant; the surfactant is a compound of quaternary ammonium salt cationic surfactant and fatty alcohol sodium isethionate according to a mass ratio of 3-5:1.
2. The carbon fiber/epoxy composite material according to claim 1, wherein the mass ratio of the carbon fiber cloth, the epoxy resin and the curing agent is 1:2-5:0.2-0.3.
3. The carbon fiber/epoxy composite material of claim 1, wherein the carbon fiber cloth has a grammage of 200-300; the epoxy resin is bisphenol epoxy resin, and the epoxy value is 0.30-0.51; the curing agent is at least one selected from 593 and 591.
4. A carbon fiber/epoxy composite material according to claim 3, wherein the bisphenol-type epoxy resin is selected from bisphenol a epoxy resin, bisphenol S epoxy resin, bisphenol F epoxy resin.
5. The carbon fiber/epoxy composite material of claim 1, wherein the source of transition metal elements is sodium, potassium, ammonium salts of tungsten transition metal oxyacids, halides of tungsten transition metals; the sulfur source is at least one of thiourea and thioacetamide; the reducing agent is at least one selected from hydroxylamine hydrochloride and oxalic acid.
6. The carbon fiber/epoxy composite of claim 1, wherein the quaternary ammonium salt cationic surfactant is represented by the general formula [ AB ] 3 N] + X - Wherein A is a long-chain alkyl group having 12 to 20 carbon atoms, B is a methyl group or an ethyl group, X is a halogen atom selected from chlorine and bromine.
7. The carbon fiber/epoxy composite material according to claim 6, wherein the quaternary ammonium salt cationic surfactant is at least one selected from cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide.
8. The carbon fiber/epoxy composite material of claim 6, wherein the mass ratio of transition metal source, sulfur source, reducing agent, surfactant is 1:1-10:1-5:0.1 to 0.5, a source of transition metal, calculated as transition metal; sulfur source, in terms of sulfur.
9. The carbon fiber/epoxy composite material according to claim 8, wherein the ratio of the amounts of the substances of the transition metal source, the sulfur source, the reducing agent, and the surfactant is 1:3-5:2-3:0.1-0.2.
10. A method for preparing a carbon fiber/epoxy composite material according to any one of claims 1 to 9, comprising the steps of:
1) Growing transition metal sulfide on the surface of the carbon fiber cloth: uniformly mixing a transition metal source, a sulfur source, a reducing agent and a surfactant in water to obtain a transition metal sulfide precursor solution, adding desized carbon fiber cloth with the surface cleaned, reacting at 150-200 ℃ for 12-36h, cooling, washing, and drying to obtain carbon fiber cloth with the surface growing transition metal sulfide;
2) Compounding of carbon fiber and epoxy resin: and (3) compounding the carbon fiber cloth with the transition metal sulfide grown on the surface obtained in the step (1) with an epoxy resin matrix material by a vacuum assisted resin transfer molding method, and finally curing to obtain a carbon fiber/epoxy composite material product.
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| CN105839398A (en) * | 2016-04-26 | 2016-08-10 | 复旦大学 | Nanosheet-layer tungsten disulfide reinforced carbon fiber sizing agent and preparation method thereof |
| CN107188232A (en) * | 2017-05-11 | 2017-09-22 | 苏州大学 | A kind of petal-shaped tungsten sulfide nanosphere, preparation method and applications |
| CN107459771A (en) * | 2016-06-03 | 2017-12-12 | 南京中赢纳米新材料有限公司 | The preparation method of Nano diamond and functionalized carbon fiber reinforced epoxy composite |
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| CN105803781A (en) * | 2016-04-26 | 2016-07-27 | 复旦大学 | Lubricant for carbon fiber sizing agent and preparation method |
| CN105839398A (en) * | 2016-04-26 | 2016-08-10 | 复旦大学 | Nanosheet-layer tungsten disulfide reinforced carbon fiber sizing agent and preparation method thereof |
| CN107459771A (en) * | 2016-06-03 | 2017-12-12 | 南京中赢纳米新材料有限公司 | The preparation method of Nano diamond and functionalized carbon fiber reinforced epoxy composite |
| CN107188232A (en) * | 2017-05-11 | 2017-09-22 | 苏州大学 | A kind of petal-shaped tungsten sulfide nanosphere, preparation method and applications |
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