CN113846489B - Conductive modified basalt fiber cloth, low-insulativity basalt fiber reinforced polymer composite material and preparation method thereof - Google Patents

Conductive modified basalt fiber cloth, low-insulativity basalt fiber reinforced polymer composite material and preparation method thereof Download PDF

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CN113846489B
CN113846489B CN202111000433.3A CN202111000433A CN113846489B CN 113846489 B CN113846489 B CN 113846489B CN 202111000433 A CN202111000433 A CN 202111000433A CN 113846489 B CN113846489 B CN 113846489B
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fiber cloth
basalt fiber
composite material
conductive modified
cloth
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CN113846489A (en
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谭文军
郑直
何伟伟
陈益峰
蔡锟
郭超峰
许志红
张志立
李鹏飞
刘安康
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Xuchang University
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    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
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    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
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    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Abstract

A conductive modified basalt fiber cloth, a low-insulation basalt fiber reinforced polymer composite material and a preparation method thereof are provided, wherein heteropolyacid doped polyaniline grows on the surface of the conductive modified basalt fiber cloth in situ, the composite material is obtained by combining a fiber laminated body and a resin matrix and then curing and forming, the fiber laminated body is composed of two carbon fiber cloth layers and the conductive modified basalt fiber cloth layers, the carbon fiber cloth layers are laminated bodies of one-layer carbon fiber cloth or D-layer carbon fiber cloth, and the conductive modified basalt fiber cloth layers are laminated bodies of one-layer conductive modified basalt fiber cloth or S-layer conductive modified basalt fiber cloth. The invention adopts the laying mode of sandwich type reinforced fiber lamination body to construct a continuous plane conductive network in the composite material, has strong operability and strong laying design controllability, and can adjust the conductivity and mechanical property of the material simultaneously by adjusting the proportion of carbon fiber cloth-modified basalt fiber/cloth.

Description

Conductive modified basalt fiber cloth, low-insulativity basalt fiber reinforced polymer composite material and preparation method thereof
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a conductive modified basalt fiber cloth, a low-insulativity basalt fiber reinforced polymer composite material and a preparation method thereof.
Background
The basalt fiber reinforced polymer composite material has excellent mechanical properties, light weight and corrosion resistance, and is widely applied to the fields of fire protection, military industry, civil engineering, traffic, and the like, and even is used as a novel civil bridge material to gradually replace the traditional metal cable bridge material. However, there are few patent applications in the field of high-end bridges for high-current and high-fidelity signal density transmission of basalt fiber reinforced composite materials, and the reason is that when the basalt fiber reinforced composite materials are used in military aerospace, nuclear power stations and high-voltage substations, the volume resistance of the traditional basalt fiber reinforced polymer composite materials is relatively high, and the traditional basalt fiber reinforced polymer composite materials can still maintain a high insulation level even after being immersed in water. According to the specification of acceptance of construction quality of building electrical engineering, GB50303-2002, the whole length of a cable bridge is guaranteed to be well conducted, if no grounding wire (flat steel or bare copper wire) is laid on the cable bridge, the bridge connection part should be guaranteed to be well conducted, namely, good low resistance and antistatic performance become the primary problems faced by the novel cable bridge material, and the important problem that the high-end polymer bridge material replaces the traditional metal material under the novel caustic condition is also realized.
To reduce the resistivity of the material, patent application publication No. CN101376712B proposes a "method for improving the conductive thermal stability of polyaniline/inorganic nano-conductive composite": mixing polyaniline and inorganic nano powder under the condition of protonic acid to obtain a composite material filter cake, and then dehydrating the composite material by adopting an azeotropic distillation treatment mode and transferring the dehydrated composite material into an organic phase to obtain the polyaniline/inorganic nano conductive composite material. However, the method is only suitable for powder materials due to the processes of suction filtration, distillation, condensation and the like, and can not be used as a reinforcement of a resin matrix composite material for heating, curing and forming for fiber cloth materials with high flatness requirements, and meanwhile, the process is complex and has high equipment requirements.
Disclosure of Invention
The invention aims to solve the defects of the technical problems and provides a conductive modified basalt fiber cloth, a low-insulativity basalt fiber reinforced polymer composite material and a preparation method thereof.
The invention solves the technical problems, and adopts the following technical scheme:
the surface of the conductive modified basalt fiber cloth is in-situ grown with heteropoly acid doped polyaniline.
Further optimizing the conductive modified basalt fiber cloth: the heteropolyacid is a mixed acid of phenyl phosphoric acid and perchloric acid.
A preparation method of conductive modified basalt fiber cloth comprises the following steps: the method comprises the steps of taking basalt fiber cloth as a matrix, and generating heteropoly acid doped polyaniline on the surface of the basalt fiber cloth by an in-situ growth method under an acidic condition.
As a further optimization of the above preparation method: the method comprises the following steps:
a. surface pretreatment of basalt fiber cloth;
b. adding an aniline monomer into the heteropoly acid solution to obtain an aniline suspension, and arranging basalt fibers with pretreated surfaces into the aniline suspension;
c. and adding the heteropoly acid solution of ammonium persulfate into the aniline suspension, and polymerizing and drying to obtain the conductive modified basalt fiber cloth.
As a further optimization of the above preparation method: the heteropoly acid solution is mixed acid with the molar ratio of phenylphosphoric acid to perchloric acid of 0.15-0.25:1.
As a further optimization of the above preparation method: the molar concentration of the phenyl phosphoric acid in the heteropoly acid solution in the step b is 0.075-0.375mol/L, the molar concentration of the perchloric acid is 0.5-1.5mol/L, the molar concentration of the phenyl phosphoric acid in the heteropoly acid solution of ammonium persulfate in the step c is 0.075-0.375mol/L, the molar concentration of the perchloric acid is 0.5-1.5mol/L, and the molar concentration of the ammonium persulfate is 0.04-0.12mol/L.
As a further optimization of the above preparation method: the molar concentration of aniline in the aniline suspension of the step b is 0.04-0.12mol/L, and the molar concentration ratio of the aniline in the aniline suspension of the step c to the ammonium persulfate in the heteropoly acid solution of the ammonium persulfate is 1:1.05.
As a further optimization of the above preparation method: the step a specifically comprises the following steps: and (3) placing basalt fibers in HNO3 for soaking treatment, then placing the basalt fibers in a hydrolysis solution of a silane coupling agent after ultrasonic flushing by deionized water, and performing ultrasonic soaking treatment to obtain the basalt fiber cloth subjected to surface pretreatment.
As a further optimization of the above preparation method: the hydrolysis solution of the silane coupling agent is obtained by dissolving the silane coupling agent in absolute ethyl alcohol/distilled water solution, wherein the silane coupling agent is KH-550, KBM903 or KH-792, and the mass percentage of the silane coupling agent in the hydrolysis solution is 0.3-2%.
The basalt fiber reinforced polymer composite material with low insulativity is obtained by combining and curing and forming a fiber laminated body and a resin matrix, wherein the fiber laminated body accounts for 45-75% of the total mass of the composite material, and the fiber laminated body is composed of two carbon fiber cloth layers and conductive modified basalt fiber cloth layers which are clamped between the two carbon fiber cloth layers; the carbon fiber cloth layer is a layer of carbon fiber cloth or a laminate of D layers of carbon fiber cloth, and D is a natural number greater than 1; the conductive modified basalt fiber cloth layer is a layer of conductive modified basalt fiber cloth or a laminate of S layers of conductive modified basalt fiber cloth, S is a natural number greater than 1, and the conductive modified basalt fiber cloth is the conductive modified basalt fiber cloth of claim 1 or 2.
Further optimization as the composite material described above: the resin matrix is phenolic resin, epoxy resin, unsaturated polyester, polyester resin, styrene resin, polyamide resin, polyurethane thermoplastic elastomer, polyether resin or polycarbonate resin.
A preparation method of a basalt fiber reinforced polymer composite material with low insulativity comprises the following steps: and (3) alternately and uniformly layering the conductive modified basalt fiber cloth and the carbon fiber cloth to obtain a fiber laminate with the top layer and the bottom layer of the carbon fiber cloth and the middle of the conductive modified basalt fiber cloth, filling a resin matrix into the fiber laminate, and finally, carrying out heating curing molding to obtain the low-insulation basalt fiber reinforced polymer composite material.
As a further optimization of the above preparation method: the resin matrix is a resin matrix subjected to blending modification, and the modification method comprises the following steps: slowly adding the single-wall carbon nano tube, graphite powder, chopped carbon fiber and a diluent into a resin matrix, stirring at normal temperature, adding a flame retardant and an anti-aging agent, stirring and dispersing uniformly, and removing bubbles in vacuum.
As a further optimization of the above preparation method: the adding proportion of each raw material in the modification process is as follows: the mass ratio of the single-wall carbon nano tube, the graphite powder, the chopped carbon fiber, the diluent and the resin matrix is as follows: 0.5-1:10-30:1-5:3-10:100; the diameter of the single-wall carbon nano tube is 1.0-2.5nm, and the length is more than or equal to 5 mu m; the graphite powder is one or any mixture of artificial graphite powder, flake graphite powder and high-orientation graphite powder; the length of the chopped carbon fiber is 3-6mm, and the diameter of the chopped carbon fiber monofilament is 5-15 mu m.
As a further optimization of the above preparation method: the heating, solidifying and forming method is vacuum pouring, hot press forming or pultrusion forming.
As a further optimization of the above preparation method: the method of the heat curing molding is hot press molding, and the fiber cloth used in the fiber laminated body is pre-impregnated and semi-cured at low temperature before hot press molding.
The technical scheme of the invention has the following beneficial effects:
1. according to the invention, the micro-nano intrinsic conductive polymer layer is deposited on the surface of the basalt fiber cloth by an in-situ growth method, so that the operation is simple, continuous industrial production can be realized, the conductive modification effect is obvious, and the basalt fiber cloth is converted from a strong insulating material to a low insulating material;
2. the invention adopts the laying mode of the sandwich-type reinforced fiber laminate of carbon fiber cloth-modified basalt fiber cloth-carbon fiber cloth to construct a continuous plane conductive network in the composite material, has strong operability and strong laying design controllability, and can adjust the conductivity and mechanical property of the material simultaneously by adjusting the proportion of the carbon fiber cloth-modified basalt fiber/cloth;
3. according to the invention, a 'single-wall carbon nano tube', 'graphite powder', 'chopped carbon fiber' compound conductive system is added into a resin matrix, and a 'dot+line' multi-size combined conductive network is constructed in the matrix, so that the conductive network is communicated with a smaller addition amount, and compared with the traditional metal conductive agents such as micro-nano silver powder, copper powder and the like, the carbon conductive system has the advantages of oxidation resistance, low price and more stable service time, and the carbon conductive system has a lubricating function in the forming process, so that the friction force between the material and a die in the pultrusion process of the composite material is reduced, and the surface smoothness and the product quality of the material are improved.
Drawings
FIG. 1 is a cross-sectional morphology diagram of a basalt fiber reinforced polymer composite material with low insulativity prepared by the method;
FIG. 2 is a surface topography diagram of the basalt fiber reinforced polymer composite material with low insulativity prepared by the invention;
FIG. 3 is a photograph of resistance measurements of the modified basalt fiber prepared in example 1;
fig. 4 is a photograph of resistance measurements of basalt fiber of comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention.
A preparation method of conductive modified basalt fiber cloth comprises the following steps:
a. surface pretreatment of basalt fiber cloth: placing basalt fibers in HNO3 for soaking treatment, then placing the basalt fibers in a hydrolysis solution of a silane coupling agent after ultrasonic flushing by deionized water, and performing ultrasonic soaking treatment to obtain basalt fiber cloth subjected to surface pretreatment;
wherein the hydrolysis solution of the silane coupling agent is obtained by dissolving the silane coupling agent in absolute ethyl alcohol/distilled water solution, the silane coupling agent is KH-550, KBM903 or KH-792, and the mass percentage of the silane coupling agent in the hydrolysis solution is 0.3-2%.
b. Adding an aniline monomer into the heteropoly acid solution to obtain an aniline suspension, and arranging basalt fibers with pretreated surfaces into the aniline suspension;
wherein the molar concentration of phenyl phosphoric acid in the heteropoly acid solution is 0.075-0.375mol/L, the molar concentration of perchloric acid is 0.5-1.5mol/L, and the molar concentration of aniline in the aniline suspension is 0.04-0.12mol/L.
c. And adding the heteropoly acid solution of ammonium persulfate into the aniline suspension, and polymerizing and drying to obtain the conductive modified basalt fiber cloth.
Wherein the molar concentration of phenyl phosphoric acid in the heteropoly acid solution of ammonium persulfate is 0.075-0.375mol/L, the molar concentration of perchloric acid is 0.5-1.5mol/L, the molar concentration of ammonium persulfate is 0.04-0.12mol/L, and the molar concentration ratio of ammonium persulfate in the heteropoly acid solution of ammonium persulfate is 1:1.05.
Wherein the heteropolyacid solution used in the steps is mixed acid of phenyl phosphoric acid and perchloric acid in a molar ratio of 0.15-0.25:1.
A preparation method of a basalt fiber reinforced polymer composite material with low insulativity comprises the following steps: and (3) alternately and uniformly layering the conductive modified basalt fiber cloth and the carbon fiber cloth to obtain a fiber laminate with the top layer and the bottom layer of the carbon fiber cloth and the middle of the conductive modified basalt fiber cloth, filling a resin matrix into the fiber laminate, and finally, carrying out heating curing molding to obtain the low-insulation basalt fiber reinforced polymer composite material.
Wherein, the resin matrix is a resin matrix subjected to blending modification, and the modification method comprises the following steps: slowly adding the single-wall carbon nano tube, graphite powder, chopped carbon fiber and a diluent into a resin matrix, stirring at normal temperature, adding a flame retardant and an anti-aging agent, stirring and dispersing uniformly, and removing bubbles in vacuum.
The adding proportion of the raw materials is as follows: the mass ratio of the single-wall carbon nano tube, the graphite powder, the chopped carbon fiber, the diluent and the resin matrix is as follows: 0.5-1:10-30:1-5:3-10:100; the diameter of the single-wall carbon nano tube is 1.0-2.5nm, and the length is more than or equal to 5 mu m; the graphite powder is one or any mixture of artificial graphite powder, flake graphite powder and high-orientation graphite powder; the length of the chopped carbon fiber is 3-6mm, and the diameter of the chopped carbon fiber monofilament is 5-15 mu m.
The single-wall carbon nano tube is formed by winding a layer of graphene sheets, the diameter range is 0.75-3nm, the multi-wall carbon nano tube is formed by two or more layers of coaxial round tubular graphene sheets, the number of layers is 2-50, the diameter is 2-30nm, the dispersion in a resin matrix is difficult, the agglomeration phenomenon is easy to cause, and the material processing and forming are not facilitated. Moreover, trap centers are easy to form between layers of the multi-wall carbon nano tube, so that the tube wall is often distributed with small hole defects, which is not beneficial to the improvement of the mechanical properties of materials.
In comparison, the single-walled carbon nanotube has larger length-diameter ratio, is easier to be uniformly dispersed in the matrix, has fewer surface defects and is relatively low in price, so that the invention selects the single-walled carbon nanotube, the graphite powder and the chopped carbon fiber as the compound conductive agent, builds a multi-dimensional conductive network of 'point+line' in the resin matrix, and reduces the resistivity of the composite material.
The method of heating, solidifying and forming is vacuum pouring, hot press forming or pultrusion forming.
The selected method of heat curing molding is hot press molding, and the fiber cloth used in the fiber laminate is pre-impregnated and low-temperature semi-cured before hot press molding.
First embodiment
A preparation method of conductive modified basalt fiber cloth comprises the following steps:
125g of distilled water is added to 2375g of absolute ethyl alcohol, 50g of silane coupling agent KH550 is added, and the mixture is stirred at room temperature for 5min to obtain a hydrolysis solution of the silane coupling agent. 200g of plain basalt fiber is arranged on HNO with the concentration of 1mol/L 3 And (3) performing medium treatment for 45min, then repeatedly performing ultrasonic flushing with deionized water, and then placing the solution in a hydrolysis solution of a silane coupling agent, and performing ultrasonic impregnation for 30min to obtain the basalt fiber cloth (GBPC) subjected to surface pretreatment.
Fully mixing phenyl phosphoric acid solution with the molar concentration of 0.15mol/L and perchloric acid solution with the molar concentration of 1mol/L respectively to obtain heteropolyacid solution, adding 16.4ml of An monomer into 3L of heteropolyacid solution, adding basalt fiber cloth with the surface subjected to pretreatment, putting into a mechanical ultrasonic cleaner (with the power of 500 w), performing ultrasonic dispersion for 15min, and standing and preserving in ice water bath for 5min to obtain aniline suspension.
41g of Ammonium Persulfate (APS) is added into 3L of heteropoly acid solution, the solution is put into a mechanical ultrasonic cleaner for ultrasonic dispersion (the power is 500 w), ultrasonic dispersion is carried out for 5min, then the solution is kept stand in an ice water bath for 5min, then the solution is slowly dripped into an aniline suspension soaked with basalt fiber cloth at a speed of 10ml/min, ultrasonic polymerization is carried out for 40min under the ice water bath condition, and the basalt fiber cloth after conducting modification of polyaniline is obtained after drying.
Second embodiment
A preparation method of conductive modified basalt fiber cloth comprises the following steps:
125g of distilled water is added to 2375g of absolute ethyl alcohol, 60g of silane coupling agent KH550 is added, and the mixture is stirred for 5 minutes at room temperature to obtain a hydrolysis solution of the silane coupling agent. 200g of plain basalt fiber is arranged on HNO with the concentration of 1.2mol/L 3 And (3) performing treatment for 30min, then repeatedly performing ultrasonic flushing with deionized water, and then placing the treated basalt fiber cloth in a hydrolysis solution of a silane coupling agent for ultrasonic impregnation for 30min to obtain the basalt fiber cloth (GBPC) subjected to surface pretreatment.
Fully mixing phenyl phosphoric acid solution with the molar concentration of 0.25mol/L and perchloric acid solution with the molar concentration of 1mol/L respectively to obtain heteropolyacid solution, adding 21.90ml of An monomer into 3L of heteropolyacid solution, adding basalt fiber cloth with the surface subjected to pretreatment, putting into a mechanical ultrasonic cleaner (with the power of 500 w), performing ultrasonic dispersion for 20min, and standing and preserving in ice water bath for 5min to obtain aniline suspension.
Adding 55g of Ammonium Persulfate (APS) into 3L of heteropoly acid solution, putting into a mechanical ultrasonic cleaner for ultrasonic dispersion (with the power of 500 w), performing ultrasonic dispersion for 15min, standing in an ice water bath for preservation for 10min, slowly dripping the heteropoly acid solution into an aniline suspension soaked with basalt fiber cloth at the speed of 8ml/min, performing ultrasonic polymerization for 45min under the ice water bath condition, and drying to obtain the basalt fiber cloth subjected to conductive modification by polyaniline.
Third embodiment
A preparation method of conductive modified basalt fiber cloth comprises the following steps:
125g of distilled water is added to 2375g of absolute ethyl alcohol, 60g of silane coupling agent KH792 is added, and the mixture is stirred at room temperature for 5 minutes to obtain a hydrolysis solution of the silane coupling agent. 200g basalt unidirectional fiber was arranged in HNO with a concentration of 1.0mol/L 3 And (3) performing treatment for 25min, then repeatedly performing ultrasonic flushing with deionized water, and then placing the treated basalt fiber cloth in a hydrolysis solution of a silane coupling agent for ultrasonic dipping for 30min to obtain the basalt fiber cloth (GBPC) subjected to surface pretreatment.
Fully mixing phenyl phosphoric acid solution with the molar concentration of 0.20mol/L and perchloric acid solution with the molar concentration of 1mol/L respectively to obtain heteropolyacid solution, adding 21.90ml of An monomer into 3L of heteropolyacid solution, adding basalt fiber cloth with the surface subjected to pretreatment, putting into a mechanical ultrasonic cleaner (with the power of 500 w), performing ultrasonic dispersion for 20min, and standing and preserving in ice water bath for 5min to obtain aniline suspension.
Adding 68.75g of APS into 3L of heteropoly acid solution, putting into a mechanical ultrasonic cleaner for ultrasonic dispersion (with the power of 500 w), performing ultrasonic dispersion for 15min, standing in an ice water bath for preservation for 10min, slowly dripping the heteropoly acid solution into aniline suspension soaked with basalt fiber cloth at the speed of 8ml/min, performing ultrasonic polymerization for 45min under the ice water bath condition, and drying to obtain the basalt fiber cloth after conductive modification.
Fourth embodiment
A preparation method of a basalt fiber reinforced polymer composite material with low insulativity comprises the following steps:
wiping the stainless steel plate with acetone, drying, coating a release agent, respectively taking 4 layers of plain weave carbon cloth and 8 layers of basalt fiber plain weave cloth with the size of 200 x 200mm polyaniline after conducting modification, carrying out 45-degree layer-by-layer lamination, sequentially installing the release cloth, a flow guide net, a flow guide pipe, a metal tee joint, a spiral winding pipe and a high-temperature-resistant vacuum bag, standing for 2h, checking the air tightness of the device, and ensuring the good tightness of the device.
30g of single-wall carbon nano tube, 3000g of graphite powder and 30g of chopped carbon fiber are taken, 100g of absolute ethyl alcohol is slowly added into 5L of 2511-1A epoxy resin manufactured by Tianjin Shang-in wind power materials, inc., and stirred for 0.5h at a rotating speed of 300r/min, then 30g of aluminum hydroxide and 1.5L of resin curing agent manufactured by Tianjin Shang-in wind power materials, inc., with 2511-1BS resin are added, and the mixture is uniformly stirred, and bubbles are removed in vacuum. The vacuum pump is then started, resin is infused into the vacuum bag, and the vacuum pump is turned off after the resin completely submerges the fibers. Transferring the device into an oven for heating and solidifying, heating from room temperature to 60 ℃ for 3 hours, then heating to 90 ℃ for 3 hours, and cooling to obtain the basalt fiber reinforced composite material laminate, wherein the surface resistance of the basalt fiber reinforced composite material laminate is thatThe rate reaches 103 omega m -2 Grade, the mass of the reinforced fiber laminate accounts for 55% of the total mass of the composite material, and fig. 1 and 2 are electron microscope photographs of the prepared composite material.
Fifth embodiment
A preparation method of a basalt fiber reinforced polymer composite material with low insulativity comprises the following steps:
25g of single-wall carbon nano tube, 3000g of graphite powder and 40g of chopped carbon fiber are slowly added into 5L of epoxy resin auxiliary agent with the brand name SG-10A produced by Tianjin Si composite material Co., ltd and 2L of curing agent with the brand name SG-10B produced by Tianjin Si composite material Co., ltd, and then the mixture is stirred for 0.5h at the rotating speed of 300r/min, then 30g of aluminum hydroxide is added, the mixture is stirred uniformly, and bubbles are removed in vacuum and placed in a gum dipping tank.
And respectively arranging 2 layers of plain weave carbon cloth on the bottom layer and the top layer, and respectively arranging 4 layers of basalt fiber plain weave cloth subjected to polyaniline conductive modification on the middle layer and dipping sizing materials. The impregnated fiber cloth is stably sent into a grinding tool at 175 ℃, the traction speed is 3m/min, and naturally cooled, so that the basalt fiber reinforced composite material laminate is obtained, and the surface resistivity of the basalt fiber reinforced composite material laminate reaches 102 Ω & m -2 The grade, the reinforcing fiber laminate mass accounts for 65% of the total mass of the composite material.
Sixth embodiment
A preparation method of a basalt fiber reinforced polymer composite material with low insulativity comprises the following steps:
sequentially taking 40g of single-wall carbon nano tube, 3000g of graphite powder, 80g of chopped carbon fiber 120g of N, N-dimethylformamide, 1L of methyltetrahydrofuran and 0.8L of dodecenyl succinic anhydride, slowly adding into 5L of 3, 4-epoxy cyclohexyl formate, stirring at the rotating speed of 300r/min for 0.5h, then adding 30g of aluminum hydroxide, stirring uniformly, removing bubbles in vacuum, and standing in a gum dipping tank.
Impregnating sizing materials into 4 layers of unidirectional carbon cloth and 8 layers of basalt fiber unidirectional cloth (GBPAC) subjected to conductive modification by using polyaniline layer by layer, and curing for 1h at 90 ℃ to obtain the prepreg. Then coating a release agent on the surface of the die, paving 2 layers of unidirectional carbon cloth which is subjected to pre-impregnation treatment on the surface of the die, and sequentially and gradually coatingPaving 8 layers of GBPAC subjected to pre-impregnation treatment, paving 2 layers of unidirectional carbon cloth subjected to pre-impregnation treatment, clamping and pressurizing to 5MPa, solidifying for 2 hours at 130 ℃, solidifying for 3 hours at 160 ℃, naturally cooling to room temperature, and demolding to obtain the basalt fiber reinforced composite material laminate, wherein the surface resistivity of the basalt fiber reinforced composite material laminate is 103 omega-m -2 The quality of the reinforced fiber lamination body accounts for 55 percent of the total quality of the composite material.
< comparison of conductive Properties >
Comparative example 1
Commercial common basalt fiber is selected, and the fiber is not modified.
Comparative example 2
According to the preparation method of the first embodiment, the heteropolyacid solution is replaced by a pure perchloric acid solution, and other conditions are unchanged, so that the modified basalt fiber cloth is prepared.
Comparative example 3
According to the preparation method of the first embodiment, the heteropolyacid solution is replaced by a pure phenylphosphoric acid solution, and other conditions are unchanged, so that the modified basalt fiber cloth is prepared.
< conductivity contrast >
The basalt fiber cloth of example 1 and comparative examples 1 to 3 was used as a comparison object, and conductivity data thereof were measured, and the results were as follows:
< resistance contrast >
The basalt fiber cloths in example 1 and comparative example 1 were used as comparison objects, and their resistance data were measured, and the results were as follows (as shown in fig. 3 and 4):
sample species Comparative example 1 Example 1
Resistor Greater than 40MΩ 31.2Ω
From the above results, it can be seen that the unmodified basalt fiber is hardly conductive, and the conductivity of the basalt fiber modified by the invention is greatly improved.
This is due to: unlike single inorganic proton acid source, the present invention adopts heteropoly acid solution as reaction system, and inorganic perchloric acid is used mainly to provide required acidity for reaction, while organic phenyl phosphoric acid is used to provide proton source for reaction, and the organic phenyl phosphoric acid may enter polyaniline molecular skeleton in the form of doping agent.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.

Claims (8)

1. The utility model provides a conductive modified basalt fiber cloth which characterized in that: the surface of basalt fiber cloth grows in situ with heteropolyacid doped polyaniline, the heteropolyacid is mixed acid of phenyl phosphoric acid and perchloric acid, and the conductive modified basalt fiber cloth is prepared by the following method:
a. surface pretreatment of basalt fiber cloth;
basalt fiber is arranged on HNO 3 Soaking in deionized water, ultrasonic washing with deionized water, and adding into silane coupling agentUltrasonic dipping treatment is carried out in the hydrolysis solution to obtain basalt fiber cloth subjected to surface pretreatment;
b. adding an aniline monomer into the heteropoly acid solution to obtain an aniline suspension, and arranging basalt fibers with pretreated surfaces into the aniline suspension;
the heteropoly acid solution is mixed acid with the molar ratio of phenylphosphoric acid to perchloric acid of 0.15-0.25:1;
the molar concentration of phenyl phosphoric acid in the heteropoly acid solution is 0.075-0.375mol/L, and the molar concentration of perchloric acid is 0.5-1.5mol/L;
c. adding the heteropoly acid solution of ammonium persulfate into an aniline suspension, and polymerizing and drying to obtain conductive modified basalt fiber cloth;
the molar concentration of phenyl phosphoric acid in the heteropoly acid solution of ammonium persulfate is 0.075-0.375mol/L, the molar concentration of perchloric acid is 0.5-1.5mol/L, and the molar concentration of ammonium persulfate is 0.04-0.12mol/L;
the molar concentration of aniline in the aniline suspension of the step b is 0.04-0.12mol/L, and the molar concentration ratio of the aniline in the aniline suspension of the step c to the ammonium persulfate in the heteropoly acid solution of the ammonium persulfate is 1:1.05.
2. The electrically conductive modified basalt fiber cloth according to claim 1, wherein: the hydrolysis solution of the silane coupling agent is obtained by dissolving the silane coupling agent in absolute ethyl alcohol/distilled water solution, wherein the silane coupling agent is KH-550, KBM903 or KH-792, and the mass percentage of the silane coupling agent in the hydrolysis solution is 0.3-2%.
3. A basalt fiber reinforced polymer composite material with low insulativity is characterized in that: the composite material is obtained by combining a fiber laminated body and a resin matrix and then curing and forming, wherein the fiber laminated body accounts for 45-75% of the total mass of the composite material, and the fiber laminated body is composed of two carbon fiber cloth layers and a conductive modified basalt fiber cloth layer clamped between the two carbon fiber cloth layers; the carbon fiber cloth layer is a layer of carbon fiber cloth or a laminate of D layers of carbon fiber cloth, and D is a natural number greater than 1; the conductive modified basalt fiber cloth layer is a layer of conductive modified basalt fiber cloth or a laminate of S layers of conductive modified basalt fiber cloth, S is a natural number larger than 1, and the conductive modified basalt fiber cloth is the conductive modified basalt fiber cloth of claim 1.
4. The low insulation basalt fiber reinforced polymer composite according to claim 3, wherein: the resin matrix is phenolic resin, epoxy resin, polyester resin, styrene resin, polyamide resin, polyurethane thermoplastic elastomer, polyether resin or polycarbonate resin.
5. The method for preparing the basalt fiber reinforced polymer composite material with low insulation property according to claim 3, wherein the method comprises the following steps: the method comprises the steps of alternately and uniformly layering conductive modified basalt fiber cloth and carbon fiber cloth to obtain a fiber laminate with a top layer and a bottom layer of carbon fiber cloth and a middle layer of conductive modified basalt fiber cloth, filling a resin matrix into the fiber laminate, and finally, carrying out heating curing molding to obtain a low-insulation basalt fiber reinforced polymer composite material;
the resin matrix is a resin matrix subjected to blending modification, and the modification method comprises the following steps: slowly adding the single-wall carbon nano tube, graphite powder, chopped carbon fiber and a diluent into a resin matrix, stirring at normal temperature, adding a flame retardant and an anti-aging agent, stirring and dispersing uniformly, and removing bubbles in vacuum.
6. The method for preparing the basalt fiber reinforced polymer composite material with low insulation property according to claim 5, wherein the method comprises the following steps: the adding proportion of each raw material in the modification process is as follows: the mass ratio of the single-wall carbon nano tube, the graphite powder, the chopped carbon fiber, the diluent and the resin matrix is as follows: 0.5-1:10-30:1-5:3-10:100; the diameter of the single-wall carbon nano tube is 1.0-2.5nm, and the length is more than or equal to 5 mu m; the graphite powder is one or any mixture of artificial graphite powder, flake graphite powder and high-orientation graphite powder; the length of the chopped carbon fiber is 3-6mm, and the diameter of the chopped carbon fiber monofilament is 5-15 mu m.
7. The method for preparing the basalt fiber reinforced polymer composite material with low insulation property according to claim 5, wherein the method comprises the following steps: the heating, solidifying and forming method is vacuum pouring, hot press forming or pultrusion forming.
8. The method for preparing the basalt fiber reinforced polymer composite material with low insulation property according to claim 5, wherein the method comprises the following steps: the method of the heat curing molding is hot press molding, and the fiber cloth used in the fiber laminated body is pre-impregnated and semi-cured at low temperature before hot press molding.
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