CN115819921B - Preparation method and application of interface modified aramid fiber/epoxy resin composite material - Google Patents
Preparation method and application of interface modified aramid fiber/epoxy resin composite material Download PDFInfo
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Abstract
The invention discloses a preparation method for improving the performance of an aramid fiber/epoxy resin composite material. According to the method, active groups are introduced to the surface of the aramid fiber through plasma surface treatment, and then the number of the active groups is further increased through surface treatment combined with a silane coupling agent, so that more combining sites are provided, and the interface combining capability of the aramid fiber woven cloth of the fiber reinforced material and the epoxy resin of the matrix material is realized. The invention also introduces hollow Al of particle reinforced material 2 O 3 The microsphere is uniformly mixed with the matrix material, so that the structural stability of the matrix material is maintained, the mechanical property of the microsphere is improved, and the shock absorbing effect and the insulating property of the microsphere are enhanced. The method disclosed by the invention is based on the actual production process of the aramid fiber-resin composite material, starts improvement from improving the interface characteristic of the composite material, has the advantages of simple implementation, convenient operation and stronger industrial applicability, and can be applied to gas-insulated metal-enclosed switchgear.
Description
Technical Field
The invention relates to an epoxy resin composite material, in particular to an aramid fiber reinforced epoxy resin composite material modified by a plasma interface and application thereof in ultra-high voltage power transmission and transformation equipment.
Background
The extra-high voltage refers to voltage levels of +/-800 kilovolts of direct current and more than 1000 kilovolts of alternating current, and according to research data, the transmission capacity of +/-800 kilovolts of direct current engineering is 2-3 times that of +/-500 kilovolts of direct current engineering, and the economic transmission distance is increased to 2-2.5 times. Therefore, the research and the application of the ultra-high voltage power transmission and transformation engineering have wide economic benefits.
As the voltage increases, higher demands are placed on the insulation, safety and reliability of the device. The gas-insulated metal-enclosed switchgear (GIS) has the characteristics of compact structure, high reliability, strong safety, strong environment adaptability and the like, and is widely applied to the field of extra-high voltage.
The insulating pull rod is an extremely important component in the ultra-high voltage GIS breaker, and the main application is that the connecting grounding part is transmitted to the high potential part to play a role in electrical connection on-off. Because the insulating pull rod structure is thin and long, the impact voltage of tensile and compressive loads to a certain extent is needed to bear in electric operation, and the times of closing and opening in operation are more, the structural design and the quality of the insulating pull rod are very severely required. The design of the insulating pull rod is particularly focused on the electrical insulating performance and mechanical performance: breakdown or surface flashover cannot occur, and the insulation performance of the insulation material cannot be reduced under the long-term action of mechanical force and heat; and has high standard requirement on fatigue property for manufacturing materials. According to the requirements and characteristics of the insulating pull rod product, the key point of development is mainly to solve the technologies of withstand voltage, mechanical tensile strength, interfacial shear strength and the like.
At present, the insulating pull rod for the GIS breaker is almost entirely made of fiber reinforced epoxy materials, and glass fibers, polyester fibers and the like are more commonly used. The manufacturing processes adopted in the early stage of research and development mainly comprise a mould pressing method, a hand pasting method, a spraying method and a winding method, and a drawing forming method. However, the product produced by the manufacturing process has some defects, has more air gaps, has poor high-voltage tolerance and is easy to generate free discharge to cause insulation breakdown. With the technical progress and the maturity of the manufacturing process, a process route of vacuum pressure impregnation is formed in China, and the effect of practical application is greatly improved.
The amide group and benzene ring in the molecular structure of the Aramid Fiber (AF) have conjugate effect, the internal rotation potential in the molecular structure is higher, and the molecular chain of the aramid fiber presents a planar rigid extended chain, so that the orientation degree and the crystallinity degree of the aramid fiber are higher, and the linear structure enables the molecular arrangement to be more compact. Therefore, the aramid fiber has extremely high tensile strength, and has the advantages of good insulating property, good heat resistance, high wear resistance and low conductivity, and has wide prospect in preparing the ultra-high voltage GIS breaker. But its drawbacks are also apparent: the surface of the aramid fiber is smooth and inert, and the epoxy resin matrix has no meshing point of a physical layer, so that the wettability of the aramid fiber and the epoxy resin is poor, the interface adhesion is poor when the composite material is formed, and the comprehensive performance, particularly the insulation performance and the mechanical performance, of the aramid fiber/epoxy composite material are reduced.
Therefore, how to improve the combination property of the aramid fiber and the epoxy resin becomes the key of the ultra-high voltage GIS breaker with excellent preparation property. The surface modification method can effectively reduce the orientation degree of the molecular structure of the surface of the aramid fiber, increase active groups on the surface, further improve the surface roughness of the aramid fiber material, enhance the interface performance of the composite material and achieve the aim of improving the overall performance of the composite material.
Currently, surface modification methods for materials mainly include physical modification and chemical modification. Chemical methods mainly include chemical etching, chemical surface grafting, and the like. Studies have shown that the surface roughness, interfacial shear strength (IFSS) and other properties after chemical treatment are significantly improved. However, chemical treatments may corrode the aramid fibers and reduce their mechanical properties; in addition, chemical treatments require large amounts of water and chemicals, which are not environmentally friendly. The physical method comprises the steps of coating the surface of the aramid fiber material, modifying the surface by plasma, radiating the aramid fiber by using high-energy rays, dipping the aramid fiber by ultrasonic, and the like.
In recent years, plasma treatment has been greatly developed as a physical method of surface modification, and the plasma treatment not only causes physical and variation of the polymer surface, but also maintains the original bulk quality of the aramid to the maximum extent. In addition, it is a drying process and thus is environmentally friendly. However, the time of plasma treatment, the technological parameters such as discharge power and the like, and the compounding process of the modified aramid fiber and the epoxy resin have important influences on the mechanical property and the electrical property of the composite material. On the other hand, there is also a report of surface treatment of aramid fiber with a silane coupling agent to increase the number of active functional groups on the surface thereof.
Disclosure of Invention
Aiming at the problems of the aramid fiber in the application of the extra-high voltage GIS breaker, the invention improves the combination mode of the aramid fiber reinforced material and the epoxy resin matrix material by adjusting the plasma treatment process parameters and combining the silane coupling agent modification process, realizes the successful preparation of the resin matrix material reinforced by the fiber and the particles, and the obtained composite material has excellent mechanical property and electrical property and is hopeful to promote the application prospect of the aramid fiber in the extra-high voltage GIS breaker.
The first aspect of the invention provides a preparation method of an interface modified aramid fiber/epoxy resin composite material, which comprises the following detailed operation steps:
cleaning and drying the aramid fiber woven cloth, fixing the aramid fiber woven cloth on a substrate, and performing plasma modification treatment on the surface of the aramid fiber woven cloth in an air environment by taking a plasma brush as a high-voltage electrode;
soaking the aramid fiber woven cloth subjected to plasma modification treatment in KH550 or KH570 at 30-50 ℃ for 4-6h, and naturally air-drying for later use;
uniformly mixing epoxy resin, a curing agent, an accelerator and a particle reinforced material to obtain a blending system as a matrix material for standby;
coating a layer of matrix material on the inner die, then spreading a layer of aramid fiber woven cloth subjected to plasma modification treatment, and then sequentially repeating the steps of coating the matrix material and spreading a layer of aramid fiber woven cloth subjected to plasma modification treatment for a plurality of times to obtain a sandwich structure;
and combining the outer die and the inner die, applying pressure to carry out hot press curing, demoulding, and heating again to carry out post curing to obtain the interface modified aramid fiber/epoxy resin composite material laminated structure.
According to the scheme, the aramid fiber woven cloth is preferably Kevlar aramid fiber woven cloth, the thickness is generally between 0.3 and 0.5mm, and the requirements of moderate thickness and standard performance of the sandwich structure obtained after multi-layer stacking are met.
The substrate may be a glass substrate, and it is required to have a flat surface and no foreign matter. The glass substrate can be dried after being cleaned in alcohol in advance.
According to the scheme, the mass ratio of epoxy resin, curing agent, accelerator and particle reinforced material in the matrix material is 100 (65-80): (1-6): (0.3-8), wherein the epoxy resin is DGEBA, the curing agent is anhydride curing agent, the accelerator is methyl diethanol amine or aminophenol, and the particle reinforced material is hollow Al with the particle diameter of 30-70 mu m 2 O 3 Microspheres with a wall thickness of 10-25 μm.
The invention selects and adds proper hollow Al 2 O 3 The microballoons are used as particle reinforced materials and are used together with aramid fiber woven cloth to improve the strength of resin-based materials. The hollow structure of the particle reinforced material is beneficial to improving the insulating property of the composite material, and the formed cavity structure can realize the light weight of the material and improve the effect of reducing vibration. Through screening, hollow spheres with the particle size of 30-70 mu m (the wall thickness is about 10-25 mu m) are selected, the reinforcing effect on the composite material is optimal, and the particles are uniformly dispersed in the matrix to form uniformly distributed cavities, so that the insulating property is improved.
According to the scheme, the parameters of the plasma modification treatment are as follows: the high voltage output voltage is 3-7kV, the frequency is 50+/-1 kHz, the discharge power is 80W, the moving speed of the plasma brush is 1mm/s, and the treatment time is 600-900s.
According to the scheme, the die used in the invention is preferably made of stainless steel and comprises an inner die and an outer die. The mould can be designed into different shapes according to the needs, for example, when the insulating pull rod is prepared, the inner mould can be a mandrel and is shaped by the outer mould. The inner mold and the outer mold are cleaned by alcohol before use, and thermosetting epoxy resin high temperature resistant release agent is evenly sprayed on the surfaces of the inner mold and the outer mold.
According to the scheme, the mass ratio of the aramid fiber woven cloth to the matrix material is 1:3-5. In the invention, the resin is used as a matrix material in the composite material, the usage amount of the aramid fiber woven cloth is relatively obviously less than that of the matrix material, and the aramid fiber woven cloth is used as a reinforcing material.
According to the scheme, in the sandwich structure, the preferable matrix material is 2-5 layers, and the number of layers of the aramid fiber woven cloth is 1 less than that of the matrix material. The matrix material and the aramid fiber woven cloth are alternately laminated, the first layer is the matrix material, and the number of layers of the aramid fiber woven cloth is 1 less than that of the matrix material, so that the last layer is also the matrix material. After the matrix material is paved each time, the matrix material is fully soaked in the aramid fiber woven cloth and then is laminated again.
According to the scheme, if the number of layers of the aramid fiber woven cloth in the sandwich structure is larger than 1, the aramid fiber woven cloth is required to keep the same direction (namely, the warp direction is kept the same), so that the directivity of the mechanical and electrical properties of the composite material is improved.
According to the scheme, the preferable hot press curing conditions are that the pressure of 1-2MPa is applied at 120-165 ℃ and kept for 2 hours, so that the curing of the resin is realized; and then post-curing is carried out for 12-16 hours under the condition of 140-160 ℃, the stability of the integral structure of the material is further improved through high-temperature treatment, the effect of heat treatment on the aramid fiber and the particle reinforced material is realized, fusion occurs between interfaces of different groups, and the mechanical property of the material is obviously improved.
In a second aspect, the invention provides an application of the interface modified aramid fiber/epoxy resin composite material in gas-insulated metal-enclosed switchgear. By selecting a proper mold, winding the core shaft serving as an inner mold to obtain a sandwich structure, and curing and demolding to obtain the insulating pull rod with good mechanical property and insulativity.
The technical scheme of the invention provides a preparation method for improving the performance of an aramid fiber/epoxy resin composite material. According to the method, active groups are introduced to the surface of the aramid fiber through plasma surface treatment, and then the number of the active groups is further increased through surface treatment combined with a silane coupling agent, so that more combining sites are provided, the interface combining capability of the aramid fiber woven cloth of the fiber reinforced material and the epoxy resin of the matrix material is realized, and the performances such as the breakdown strength of the aramid fiber/epoxy resin composite material are improved. Wherein the mass of the matrix material is at least 3 times that of the aramid fiber woven cloth, and the matrix material needs to be ensured to fully infiltrate the aramid fiber woven cloth in the lamination process.
On the other hand, the invention also introduces particle reinforced materials, and finally determines the hollow Al with the particle diameter of 30-70 mu m and the wall thickness of 10-25 mu m through multiple orthogonal experiment comparison screening 2 O 3 The microsphere has optimal effect, is uniformly mixed with the matrix material, maintains the structural stability of the matrix material, improves the mechanical property of the matrix material, and enhances the shock absorbing effect and the insulating property.
In summary, the method disclosed by the invention is based on the actual production process of the aramid fiber-resin composite material, starts from improving the interface characteristic of the composite material, has the advantages of simple implementation, convenient operation and stronger industrial applicability, and can be applied to gas-insulated metal-enclosed switchgear.
Drawings
FIG. 1 is a process flow diagram of example 1 for preparing an interface modified aramid fiber/epoxy resin composite;
FIG. 2 is an SEM image of the interface-modified aramid fiber/epoxy resin composite obtained in example 1;
FIG. 3 is an SEM image of the interface-modified aramid fiber/epoxy resin composite obtained in example 2;
FIG. 4 is an SEM image of the interface-modified aramid fiber/epoxy resin composite obtained in comparative example 1;
FIG. 5 is an SEM image of the interface-modified aramid fiber/epoxy resin composite obtained in comparative example 2;
FIG. 6 is an SEM image of the aramid fibers stripped from the composite material of example 1;
FIG. 7 is an SEM image of the aramid fibers stripped from the composite material of example 2;
FIG. 8 is an SEM image of the aramid fibers exfoliated from the composite material of comparative example 1;
FIG. 9 is an SEM image of the aramid fibers exfoliated from the composite material of comparative example 2;
FIG. 10 is a graph showing the results of the shear strength at the filament drawing interface of the interface-modified aramid fiber/epoxy resin composite material obtained in example 3 and comparative examples 3 to 6.
Detailed Description
The invention is illustrated and described by the following detailed description of the invention for better explaining the invention.
Example 1
As shown in fig. 1, the preparation method of the interface modified aramid fiber/epoxy resin composite material is characterized in that the obtained material is applied to an insulating pull rod in the field of ultra-high voltage power transmission and transformation. The method comprises the following steps:
firstly, alternately cleaning a 0.3mm thick Kevlar aramid fiber woven cloth with acetone and deionized water for 12 hours, then placing the cloth in a vacuum drying oven for drying with hot air at 110 ℃, and fixing the cloth on the surface of a clean and flat glass substrate. Wherein the size of the Kevlar aramid fiber woven cloth is equal to the size of the glass substrate. Plasma brush is used as a high-voltage electrode to carry out plasma modification treatment on the surface of the aramid fiber woven cloth in an air environment, and the treatment conditions are as follows: the high voltage output voltage is 7kV, the frequency is 50kHz, the discharge power is 80W, the moving speed of the plasma brush is 1mm/s, and the treatment time is 600s.
Secondly, soaking the Kevlar aramid fiber woven cloth subjected to the plasma modification treatment for 4 hours at 50 ℃ by KH550, and naturally air-drying for later use.
In addition, 100 parts by mass of DGEBA, 70 parts by mass of MTHPA curing agent, 6 parts by mass of methyldiethanolamine, 4 parts by mass of hollow Al 2 O 3 The microspheres are uniformly mixed to obtain a blending system as a matrix material for standby. Hollow Al 2 O 3 The D50 particle size of the microspheres is 65 μm,the wall thickness averages 16 μm.
Then, according to 1 part by mass of Kevlar aramid fiber woven cloth and 3 parts by mass of matrix material, taking an insulating pull rod mandrel as an inner mold, coating a layer of thermosetting epoxy resin high-temperature resistant release agent after alcohol cleaning, then coating a layer of matrix material (the mesh cloth is not contacted with the mandrel after soaking the aramid fiber woven cloth), then tightly winding a layer of treated Kevlar aramid fiber woven cloth, then coating a layer of matrix material, ensuring that the matrix material is fully soaked and then tightly wound with a layer of treated Kevlar aramid fiber woven cloth, repeatedly operating, coating three layers of matrix materials altogether, winding two layers of Kevlar aramid fiber woven cloth, and obtaining a cylindrical sandwich structure (the mandrel is not removed at this time), wherein the warp directions of the two layers of Kevlar fiber woven cloth are kept consistent (the weaving trend of the woven cloth is consistent).
Finally, sheathing an outer mold on the outer surface of the sandwich structure, tightly packing, applying pressure of 2MPa, carrying out hot pressing and curing for 2 hours at 165 ℃, demoulding after the hot pressing and curing for 12 hours at 140 ℃ again, and obtaining the insulating pull rod made of the interface modified aramid fiber/epoxy resin composite material.
Example 2
The preparation method of the interface modified aramid fiber/epoxy resin composite material comprises the following steps:
firstly, alternately cleaning a 0.5mm thick Kevlar aramid fiber woven cloth with acetone and deionized water for 8 hours, then placing the woven cloth in a vacuum drying oven for hot air drying at 120 ℃, and fixing the woven cloth on the surface of a glass substrate, wherein the glass substrate is dried after being cleaned with alcohol in advance. The size of the Kevlar aramid fiber woven cloth is slightly smaller than the size of the glass substrate.
Plasma brush is used as a high-voltage electrode to carry out plasma modification treatment on the surface of the aramid fiber woven cloth in an air environment, and the treatment conditions are as follows: the high-voltage output voltage is 7kV, the frequency is 50kHz, the discharge power is 80W, the moving speed of the plasma brush is 1mm/s, and the treatment time is 900s for standby.
Secondly, soaking the Kevlar aramid fiber woven cloth subjected to the plasma modification treatment for 6 hours at 30 ℃ by using KH570, and naturally air-drying for later use.
In addition, 100 parts by mass of DGEBA, 80 parts by mass of MTHPA curing agent, 1 part by mass of aminophenol and 1 part by mass of hollow Al 2 O 3 The microspheres are uniformly mixed to obtain a blending system as a matrix material for standby. Hollow Al 2 O 3 The D50 particle size of the microspheres was 30 μm and the wall thickness was 10 μm on average.
Then, according to 1 part by mass of Kevlar aramid fiber woven cloth and 5 parts by mass of matrix material, cleaning the surface of a stainless steel inner die with alcohol, coating a layer of thermosetting epoxy resin high-temperature resistant release agent, drying at 70 ℃ for 15min, coating a layer of matrix material (the situation that the woven cloth is not contacted with the inner die after the aramid fiber woven cloth is soaked), then spreading a layer of treated Kevlar aramid fiber woven cloth, and then coating a layer of matrix material, ensuring that the matrix material fully wets the aramid fiber woven cloth, spreading a layer of treated Kevlar aramid fiber woven cloth, repeatedly operating, spreading 5 layers of matrix material altogether, spreading 4 layers of Kevlar aramid fiber woven cloth, and obtaining a platy sandwich structure, wherein the warp direction of the 4 layers of Kevlar fiber woven cloth is kept consistent (the warp direction of the woven cloth is consistent).
Finally, assembling the outer die, applying a pressure of 1MPa to carry out hot press curing for 2 hours at 120 ℃, demoulding after completion, and heating to 160 ℃ again to cure for 16 hours to obtain the interface modified aramid fiber/epoxy resin composite material.
Comparative example 1
A method for preparing an interface modified aramid fiber/epoxy resin composite material, which is different from example 2 in that plasma treatment is not performed.
Comparative example 2
A method for preparing an interface modified aramid fiber/epoxy resin composite material, which is different from example 2 in that the plasma treatment time is 300s.
The chemical components of the surfaces of the aramid fibers are not changed greatly after the plasma treatment for 5min, the element peak is not changed, the functional groups of the aramid fibers are dominant, and the number of C=O on the surfaces of the aramid fibers is obviously improved. After the plasma treatment time is prolonged for 10min under the same plasma power, the surface of the aramid fiber is provided with-O-C=O bonds, which shows that the plasma modification of the aramid fiber is successful. When the plasma treatment time is 15min, the number of-O-c=o bonds on the surface of the aramid fiber continues to increase.
It can be determined from this that the number of c=o and the proportion of c=o increases in the case of a short processing time, at which time the-O-c=o bonds may already start to appear, but the number is particularly small. more-O-c=o bonds are produced with longer treatment times, but continued treatment times are accompanied by carbonization of the aramid fiber surface. A suitable plasma treatment time is 600-900s.
Fig. 2 to 5 are SEM images of the composite materials obtained in example 1, example 2, comparative example 1 and comparative example 2, respectively.
As can be seen from comparison of fig. 2 to 5, the etching effect of the plasma-treated aramid fiber strongly depends on the treatment time, and the surface roughness of the aramid fiber increases with the increase of the treatment time: the surface of the fiber treated for 15min is uneven, while the surface of the untreated aramid fiber is clean and smooth, and the surface of the aramid fiber treated by 5min plasma starts to generate etching marks, namely, the surface is slightly rough, and slight scratches and bulges appear.
From the surface morphology, the roughness and damage to the fiber surface become more severe with increasing plasma treatment time, and aramid fibers tend to "fibrillate" in the process of skin exfoliation. The fibrillation process can greatly improve the roughness of the aramid fiber, thereby improving the adhesiveness of the aramid fiber and the epoxy resin.
Further, fig. 6 to 9 are SEM images after the aramid fibers in the composite materials obtained in example 1, example 2, comparative example 1 and comparative example 2 were peeled off, respectively.
Comparing fig. 6-9, the aramid fiber of the peeling surface of the composite material formed by the aramid fiber which is not treated by the plasma treatment and the epoxy resin still presents a smooth interface, and the adhesion degree of the aramid fiber and the epoxy resin is weaker. However, when the treatment time was increased to 5min, the aramid fiber surface exhibited fiber damage to a lesser extent to the interstitial surface. The highest strength of bonding and fiber damage is achieved when the treatment time is increased to 10 and 15 min. This means that the "fibrillation" modification of the aramid fiber by the plasma can increase the surface roughness of the aramid fiber, thereby further enhancing the interfacial adhesion strength of the aramid fiber woven cloth and the epoxy resin matrix.
In contrast to the SEM images above, there is a better treatment time for plasma treatment of aramid fibers. In combination, a plasma treatment time of 15min was successful for the surface modification treatment of the aramid fiber.
Example 3
The preparation method of the interface modified aramid fiber/epoxy resin composite material comprises the following steps:
firstly, alternately cleaning a 0.3mm thick Kevlar aramid fiber woven cloth with acetone and deionized water for 6 hours, then placing the woven cloth in a vacuum drying oven for hot air drying at 100 ℃, and fixing the woven cloth on the surface of a glass substrate, wherein the glass substrate is dried after being cleaned with alcohol in advance. The size of the Kevlar aramid fiber woven cloth is equal to that of the glass substrate, and the four corners are fixed by heat-resistant glue.
Plasma brush is used as a high-voltage electrode to carry out plasma modification treatment on the surface of the aramid fiber woven cloth in an air environment, and the treatment conditions are as follows: the high-voltage output voltage is 3kV, the frequency is 50kHz, the discharge power is 80W, the moving speed of the plasma brush is 1mm/s, and the treatment time is 900s for standby.
Secondly, soaking the Kevlar aramid fiber woven cloth subjected to the plasma modification treatment for 5 hours at 30 ℃ by using KH550, and naturally air-drying for later use.
In addition, 100 parts by mass of DGEBA, 65 parts by mass of MTHPA curing agent, 3 parts by mass of aminophenol and 8 parts by mass of hollow Al 2 O 3 The microspheres are uniformly mixed to obtain a blending system as a matrix material for standby. Hollow Al 2 O 3 The D50 particle size of the microspheres was 50 μm and the wall thickness was 20 μm on average.
Then, according to 1 part by mass of Kevlar aramid fiber woven cloth and 4 parts by mass of matrix material, cleaning the surface of a stainless steel inner die with alcohol, coating a layer of thermosetting epoxy resin high-temperature resistant release agent, drying at 70 ℃ for 10min, coating a layer of matrix material (the situation that the woven cloth is not contacted with the inner die after the aramid fiber woven cloth is soaked), then spreading a layer of treated Kevlar aramid fiber woven cloth, and then coating a layer of matrix material, ensuring that the matrix material fully wets the aramid fiber woven cloth, spreading a layer of treated Kevlar aramid fiber woven cloth, repeatedly operating, spreading 4 layers of matrix material altogether, spreading 3 layers of Kevlar aramid fiber woven cloth, and obtaining a platy sandwich structure, wherein the warp directions of 3 layers of Kevlar aramid fiber woven cloth are kept consistent.
Finally, assembling the outer die, applying a pressure of 2MPa, carrying out hot press curing for 2 hours at 140 ℃, demoulding after completion, and heating to 150 ℃ again for curing for 16 hours to obtain the interface modified aramid fiber/epoxy resin composite material.
Comparative example 3
A method for preparing an interface modified aramid fiber/epoxy resin composite material is different from example 3 in that hollow Al is not added into a matrix material 2 O 3 And (3) microspheres.
Comparative example 4
The preparation method of the interface modified aramid fiber/epoxy resin composite material is different from that of the embodiment 3 in that the Kevlar aramid fiber woven cloth is not soaked in KH 550.
Comparative example 5
The preparation method of the interface modified aramid fiber/epoxy resin composite material is different from that of the embodiment 3 in that the Kevlar aramid fiber woven cloth is not subjected to plasma treatment.
Comparative example 6
Interface modified aramid fiber/ringThe preparation method of the oxygen resin composite material is different from that of the embodiment 3 in that the Kevlar aramid fiber woven cloth is not soaked in KH550, and hollow Al is not added into the matrix material 2 O 3 And (3) microspheres.
The mechanical properties of the interface modified aramid fiber/epoxy resin composite materials obtained in example 3 and comparative examples 3 to 6 were measured by a monofilament strength tester.
The force F at the moment of the adhesion removal of the epoxy resin microdroplets is recorded, the diameter d of the aramid fiber and the embedding length L of the epoxy microdroplets are measured through a microscope, the number of the required tests of each sample is 10, and the average value is obtained. The interfacial shear strength is calculated as follows:
τ in IFSS The interfacial shear strength of the aramid fiber monofilament-epoxy resin microdroplets is Pa; f is the force at the moment of epoxy microdroplet de-adhesion, N; d is the diameter of the fiber, m; l is the length of the fiber embedded in the resin, m. The results obtained are shown in FIG. 10.
As can be seen from FIG. 10, the filament drawing interface shear strength of the obtained aramid fiber is obviously better than that of other comparative examples, and is 25.4% higher than that of the fiber treated by plasma only.
Further, the applicant has also explored hollow Al 2 O 3 Influence of microsphere particle size. It was found that when the particle size exceeds 100 μm, it has a negative effect on the overall performance of the material, and it is suspected that the particle size is large, the effect of particle reinforcement is difficult to be exerted, and the large particle size affects the wetting effect of the resin and the aramid fiber. And selecting hollow Al of 30-70 μm 2 O 3 The microsphere has better promotion effect, and the strength is improved by 12.1 percent as can be seen from the example 3 and the comparative example 3.
Claims (8)
1. The preparation method of the interface modified aramid fiber/epoxy resin composite material is characterized by comprising the following steps of:
cleaning and drying the aramid fiber woven cloth, fixing the aramid fiber woven cloth on a substrate, and performing plasma modification treatment on the surface of the aramid fiber woven cloth in an air environment by taking a plasma brush as a high-voltage electrode;
soaking the aramid fiber woven cloth subjected to plasma modification treatment in KH550 or KH570 at 30-50 ℃ for 4-6h, and naturally air-drying for later use;
uniformly mixing epoxy resin, a curing agent, an accelerator and a particle reinforced material to obtain a blending system as a matrix material for standby;
coating a layer of the matrix material on the internal mold, then paving a layer of the aramid fiber woven cloth subjected to plasma modification treatment, and then sequentially repeating the steps of coating the matrix material and paving a layer of the aramid fiber woven cloth subjected to plasma modification treatment for a plurality of times to obtain a sandwich structure; the mass ratio of the aramid fiber woven cloth to the matrix material is 1:3-5;
combining the outer die and the inner die, applying pressure to carry out hot press curing, demoulding, and heating again to carry out post curing to obtain the interface modified aramid fiber/epoxy resin composite material laminated structure;
the mass ratio of epoxy resin, curing agent, accelerator and particle reinforced material in the matrix material is 100 (65-80): 1-6): 0.3-8; the particle reinforced material is hollow Al with the particle diameter of 30-70 mu m 2 O 3 A microsphere; the hollow Al 2 O 3 The wall thickness of the microsphere is 10-25 mu m;
the hot press curing condition is that 1-2MPa pressure is applied at 120-165 ℃ and kept for 2h, and the post curing condition is that the post curing is carried out at 140-160 ℃ for 12-16h;
the aramid fiber woven cloth is Kevlar aramid fiber woven cloth with the thickness of 0.3-0.5mm.
2. The method for preparing an interface-modified aramid fiber/epoxy resin composite material according to claim 1, wherein the substrate is a glass substrate.
3. The method for preparing the interface modified aramid fiber/epoxy resin composite material according to claim 1, wherein the epoxy resin is DGEBA, the curing agent is an anhydride curing agent, and the accelerator is methyl diethanol amine or aminophenol.
4. The method for preparing the interface modified aramid fiber/epoxy resin composite material according to claim 1, wherein parameters of the plasma modification treatment are as follows: the high voltage output voltage is 3-7kV, the frequency is 50+/-1 kHz, the discharge power is 80W, the moving speed of the plasma brush is 1mm/s, and the treatment time is 600-900s.
5. The method for preparing the interface modified aramid fiber/epoxy resin composite material according to claim 1, wherein the inner mold and the outer mold are made of stainless steel, are cleaned by alcohol before use, and are uniformly sprayed with a thermosetting epoxy resin high-temperature-resistant release agent on the surfaces of the inner mold and the outer mold.
6. The method for preparing the interface modified aramid fiber/epoxy resin composite material according to claim 1, wherein in the sandwich structure, the number of layers of the matrix material is 2-5, and the number of layers of the aramid fiber woven cloth is 1 less than that of the matrix material.
7. The method of claim 1, wherein the aramid fiber woven cloth in the plurality of layers in the sandwich structure has a consistent warp direction.
8. Use of an interface-modified aramid fiber/epoxy resin composite material obtained according to the preparation method of any one of claims 1 to 7 in a gas-insulated metal-enclosed switchgear.
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