CN116240748B - Basalt fiber/aramid fiber nanofiber composite paper with self-assembled layered structure and preparation method thereof - Google Patents
Basalt fiber/aramid fiber nanofiber composite paper with self-assembled layered structure and preparation method thereof Download PDFInfo
- Publication number
- CN116240748B CN116240748B CN202211717269.2A CN202211717269A CN116240748B CN 116240748 B CN116240748 B CN 116240748B CN 202211717269 A CN202211717269 A CN 202211717269A CN 116240748 B CN116240748 B CN 116240748B
- Authority
- CN
- China
- Prior art keywords
- anfs
- composite paper
- basalt fiber
- dmso
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 142
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 239000002121 nanofiber Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920006231 aramid fiber Polymers 0.000 title claims description 23
- 239000004760 aramid Substances 0.000 claims abstract description 64
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 63
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 172
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000000725 suspension Substances 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 230000000694 effects Effects 0.000 claims description 21
- 230000009471 action Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 238000010292 electrical insulation Methods 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 2
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000012784 inorganic fiber Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000005588 protonation Effects 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
The invention discloses basalt fiber/aramid nanofiber composite paper with a self-assembled layered structure and a preparation method thereof, and belongs to the field of new materials. The basalt fiber/aramid nanofiber composite paper with the shell-like layered structure is formed by taking green and environment-friendly basalt fiber as a base material, taking aramid nanofiber as a construction module of composite paper, preparing uniformly dispersed mixed solution with a core-shell structure system by coating the basalt fiber in situ with the aramid nanofiber, and performing vacuum suction filtration and self-assembly. The basalt fiber/aramid nanofiber composite paper prepared by the invention has low heat conductivity, excellent flame retardance and electrical insulation, can be used in the fields of electronic heat management, construction and the like, and has extremely high use value.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to basalt fiber/aramid fiber nanofiber composite paper with a self-assembled layered structure and a preparation method thereof.
Background
The shell is a perfect structure created in the long-term evolution process of the nature, is formed by biological macromolecules, and comprises typical collagen, keratin and chitin, and accounts for 1-5%; and another part of inorganic mineral, usually organic-inorganic natural layered structure material composed of calcium phosphate, calcium carbonate and amorphous silica. The special multistage ordered 'brick-mud' assembled structure of the shell endows the shell with excellent mechanical properties of light weight, high strength and good toughness. Inspired by the 'brick-mud' structure of the natural shell, researchers prepare a series of bionic high-strength super-toughness layered composite materials by using different methods.
The basalt fiber is a product such as continuous fiber, rock wool and the like produced by taking specific basalt formed by volcanic eruption as a raw material, no toxic substances are generated in the production process, and no waste gas, waste water and waste residue are discharged, so that the basalt fiber is a green industrial material, and is known as a green industrial material in twenty-first century. As a high-performance inorganic fiber, basalt has the characteristics of higher strength performance, excellent thermal stability, good dielectric property and good chemical stability, and also has the characteristics of radiation resistance, heat insulation and sound insulation, and has wide application prospects in the fields of fireproof heat insulation, filtration and environmental protection, building materials, electronic technology, electrical insulation and the like. In recent years, scientific researchers have received a great deal of attention.
The aramid fiber has excellent mechanical, temperature-resistant, acid-base-resistant, chemical stability and other performances, but has smooth surface, lacks active groups, is difficult to generate physical or chemical action with the aramid fiber or other materials, and seriously hinders the development and application of the aramid fiber in the fields of hybridization and composite materials. The aramid nanofiber is a novel polymer nanofiber prepared from aramid fibers by a top-down strategy through a deprotonation method. The preparation method not only maintains most of the performances of the aramid fiber, including the performances of thermal stability, high crystallinity and the like; meanwhile, the nano-scale aramid nanofibers bring excellent mechanical properties and optical properties to the same. In addition, the active groups, the large length-diameter ratio and the specific surface area of the aramid nanofiber are rich in the surface of the aramid nanofiber, and the excellent characteristics of the nanomaterial are further provided. The aramid nano paper/film formed by the hydrogen bonding between the aramid nano fibers has the advantages of excellent performance, such as high strength, high temperature resistance, transparency, good flexibility and the like. The aramid nanofibers with high length-diameter ratio are preferentially arranged in the plane in the z direction under the action of vacuum suction filtration, so that the aramid nanofibers exhibit a bionic hierarchical structure, and the mechanical property and the insulation property of the aramid nanopaper are improved. Therefore, the aramid nanofiber has great application potential in the fields of electric insulation materials, battery diaphragms and the like.
In the prior art, the basalt fibers have strong surface static effect and poor bonding force, so that the fibers cannot be uniformly dispersed in water, and the paper strength is poor. In addition, the surface of basalt fiber is smooth and chemically inert, and the surface roughness of the fiber is increased by a surface oxidation and etching method to improve the binding force, however, the method can damage the fiber itself, thereby affecting the strength of the fiber and the composite material. The basalt fiber and the aramid fiber are compounded together, so that the excellent performance of the basalt fiber and the aramid fiber can be comprehensively exerted. Basalt fiber/aramid nanofiber composite paper and a preparation method thereof do not appear so far.
Therefore, the problems of poor binding force and poor dispersibility among basalt fibers are needed to be solved at present.
Disclosure of Invention
In order to solve the problems of poor binding force and poor dispersibility among basalt fibers, the invention provides basalt fiber/aramid nanofiber composite paper with a self-assembled layered structure and a preparation method thereof, and the activity and dispersibility of groups on the surface of basalt fibers are improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A preparation method of basalt fiber/aramid fiber nanofiber composite paper with a self-assembled layered structure comprises the following steps:
Step one: preparing an aramid nanofiber/dimethyl sulfoxide solution;
mixing PPTA fiber, KOH, deionized water and DMSO to form a mixed solution, and stirring the mixed solution to prepare ANFs/DMSO solution;
Step two: preparing basalt fiber dispersion liquid coated with aramid fiber nano-fibers in situ;
Heat treatment is carried out on basalt fibers, and surface sizing agents are removed, so that BF with high surface activity and water dispersibility is obtained; mixing BF with ANFs/DMSO solution and dispersing under ultrasonic action to form BF/ANFs/DMSO suspension, and injecting deionized water into BF/ANFs/DMSO suspension for protonic reduction to obtain ANFs@BF-DMSO dispersion;
step three: preparing basalt fiber/aramid nanofiber composite paper;
Washing the ANFs@BF-DMSO dispersion liquid prepared in the second step by deionized water to remove the DMSO solvent in the dispersion liquid, and then carrying out vacuum suction filtration and drying to obtain the ANFs@BFs composite paper with the self-assembled lamellar structure.
Further, the mixed solution in the first step is specifically obtained by mixing 1.0gPPTA fibers, 1.5g KOH and 20mL deionized water in 500mL of the mixed solution.
Further, the stirring in the first step was performed by using a magnetic stirrer at 1000rpm/min for 4 hours.
Further, the heat treatment in the second step is specifically to put basalt fiber into a muffle furnace to heat up to 300-500 ℃ and keep the temperature for 1-3 hours.
Further, the dispersing time under the ultrasonic action in the second step is 10min.
Further, in the second step, the volume ratio of the BF/ANFs/DMSO suspension to deionized water is 1:2.
Further, the injecting deionized water into the BF/ANFs/DMSO suspension in the second step specifically comprises: after the BF/ANFs/DMSO suspension was placed on a magnetic stirrer and brought to a rotational speed of 1500rmp to obtain a shearing action for the BF/ANFs/DMSO suspension, deionized water was measured into the BF/ANFs/DMSO suspension using a single-use pump syringe.
Further, in the third step, the mass of basalt fiber in the ANFs@BFs composite paper accounts for 50% -75% of the mass of the ANFs@BFs composite paper.
Further, the washing in the third step is performed 3 to 5 times, and the drying is specifically vacuum drying at 105 ℃ for 6min.
Basalt fiber/aramid nanofiber composite paper with self-assembled layered structure is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
According to the preparation method of the basalt fiber/aramid nanofiber composite paper with the self-assembled layered structure, aramid nanofibers and basalt fibers are compounded, and the activity and the dispersibility of the basalt fiber surface groups are improved through heat treatment of the basalt fibers and ultrasonic synergism in ANFs/DMSO solvents in the preparation process of the aramid nanofibers, so that a uniformly dispersed suspension is obtained. In-situ cladding basalt fiber in ANFs protonizing reduction process to prepare uniform dispersion liquid with core-shell structure system, and self-assembling by vacuum suction filtration method to make the obtained composite paper have clear organic fiber-inorganic fiber alternately arranged layered structure.
Further, basalt fiber is used as a physical barrier in the layered structure, has a microporous structure for preventing combustible from volatilizing, and therefore reduces the heat conductivity of the composite paper.
Further, BF and ANFs/DMSO solution are mixed and dispersed under the action of ultrasound, so that the physical and chemical effect regulation and control on the length and the dispersibility of the fiber are realized.
Further, the preparation method of the aramid nanofiber by utilizing the proton donor coupling proton removing method shortens the preparation period of the aramid nanofiber from the traditional 7 days to 4 hours, and is simple, time-saving and efficient.
The basalt fiber/aramid fiber nanofiber composite paper with the self-assembled layered structure provided by the invention forms the high-performance fiber composite paper ANFs@BFs with the organic fiber-inorganic fiber alternating layered structure through the self-assembly of the aramid fiber nanofiber membrane and the basalt fiber after coating modification. The shell-structure-imitated basalt fiber/aramid nanofiber composite paper has excellent mechanical properties, flame retardance and extremely low thermal conductivity, and the excellent fireproof flame retardance can be used in the fields of electronic heat management systems, buildings and the like, so that the application field of basalt fibers is expanded.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an electron photograph of the dispersion effect of basalt fiber after heat treatment and ultrasound in the preparation process of example 1, wherein (a) is the dispersion effect of basalt fiber in ANFs/DMSO solution without any treatment, (b) is the dispersion effect of basalt fiber after heat treatment in ANFs/DMSO solution after ultrasound synergism, and (c) is the preparation of ANFs coated BF (ANFs@BF-DMSO) dispersion.
FIG. 2 is an electronic photograph of ANFs@2BFs composite paper prepared in example 1.
Fig. 3 is an electronic photograph of the flame retardant test and the flame retardant test result of the anfs@2bfs composite paper prepared in example 1, wherein (a) is an electronic photograph of the flame burning of the anfs@2bfs composite paper prepared in example 1, and (b) is an electronic photograph of the flame retardant test result of the anfs@2bfs composite paper prepared in example 1.
Fig. 4 is an SEM image of the preparation process of example 1 and comparative example 1, in which (a) is an SEM image of the anfs@2bfs composite paper prepared in example 1, (b) is an SEM image of ANFs/2BFs composite paper prepared in comparative example 1, and (c) is an SEM image of the aramid nanofiber in-situ coated basalt fiber prepared in example 1.
FIG. 5 is a thermal weight graph of ANFs@2BFs composite paper prepared in example 1.
Detailed Description
The present invention is described in further detail below:
A preparation method of basalt fiber/aramid fiber nanofiber composite paper with a self-assembled layered structure comprises the following steps:
Step one: preparing an aramid nanofiber/dimethyl sulfoxide solution;
Mixing 1.0gPPTA fiber, 1.5g KOH, 20mL deionized water and 500mL LDMSO to form a mixed solution, stirring the mixed solution, and stirring at 1000rpm/min for 4 hours by using a magnetic stirrer to prepare ANFs/DMSO solution;
Step two: preparing basalt fiber dispersion liquid coated with aramid fiber nano-fibers in situ;
Heat treatment is carried out on basalt fibers, specifically, the basalt fibers are placed in a muffle furnace at 300-500 ℃ and kept for 1-3 hours, surface impregnating compound is removed, and BF with high surface activity and water dispersibility is obtained; mixing BF and ANFs/DMSO solution and dispersing for 10min under the action of ultrasound to form BF/ANFs/DMSO suspension, injecting deionized water into the BF/ANFs/DMSO suspension for protonizing reduction, wherein the volume ratio of the BF/ANFs/DMSO suspension to the deionized water is 1:2, placing the BF/ANFs/DMSO suspension on a magnetic stirrer and adjusting the rotating speed to 1500rmp to enable the BF/ANFs/DMSO suspension to obtain shearing action, and measuring the deionized water with a disposable pump to inject the BF/ANFs/DMSO suspension to obtain ANFs@BF-DMSO dispersion;
step three: preparing basalt fiber/aramid nanofiber composite paper;
Washing the ANFs@BF-DMSO dispersion liquid prepared in the second step with deionized water for 3 to 5 times, removing DMSO solvent in the dispersion liquid, performing vacuum filtration, and drying, wherein the drying is specifically performed under the condition of 105 ℃ for 6 minutes, so as to obtain the ANFs@BFs composite paper with the self-assembled lamellar structure. The mass of basalt fiber in the ANFs@BFs composite paper accounts for 50% -75% of the mass of the ANFs@BFs composite paper.
The basalt fiber/aramid fiber nanofiber composite paper with the self-assembled layered structure is characterized by being prepared by the preparation method.
The invention is further illustrated by the following examples:
example 1
The preparation method of the basalt fiber/aramid nanofiber composite paper imitating the shell structure in the embodiment comprises the following steps:
step one: preparation of aramid nanofiber/dimethyl sulfoxide solution
1.0GPPTA fiber, 1.5g KOH, 20mL deionized water and 500mL dimethyl sulfoxide (DMSO) were placed in an conical flask, and then stirred with a magnetic stirrer at 1000rpm/min for 4 hours until the mixture became uniformly transparent and dark red, thus obtaining an aramid nanofiber/dimethyl sulfoxide (ANFs/DMSO) solution.
Step two: preparation of basalt fiber dispersion liquid coated with aramid fiber nano-fibers in situ
And (3) placing the basalt fiber in a muffle furnace, heating to 500 ℃, preserving heat for 3 hours, and removing the surface impregnating compound to obtain the Basalt Fiber (BF) with high surface activity and water dispersibility. Then mixing 0.253gBF mL of ANFs/DMSO solution with 63.5mL of the solution to form a mixed solution, and dispersing for 10min under the ultrasonic action to finally obtain BF/ANFs/DMSO suspension with good dispersing effect. Further, 127mL of deionized water was injected into the BF/ANFs/DMSO suspension for protonation reduction, the BF/ANF/DMSO suspension was placed on a magnetic stirrer and the rotation speed was adjusted to 1500rmp to obtain a shearing action on the BF/ANF/DMSO suspension, and then the deionized water was injected into the BF/ANFs/DMSO suspension by measuring with a single-use pump syringe to obtain ANFs coated BF (ANFs@BF-DMSO) dispersion.
Step three: preparation of basalt fiber/aramid nanofiber composite paper with shell-like structure
Pouring the basalt fiber dispersion liquid coated with the aramid nanofibers in situ, which is prepared in the second step, into a sand core funnel, connecting a vacuum pump, controlling the vacuum degree to be higher than-0.1 MPa, continuously performing suction filtration, ensuring that the moisture above the paper is completely pumped, stopping vacuumizing, taking the filter paper adhered with the composite paper off the filter, performing vacuum drying for 6min at 105 ℃, and finally removing the composite paper from the filter paper to finally obtain the shell-like layered basalt fiber/aramid nanofiber composite paper, wherein the label is ANFs@2BFs. Wherein the basalt fiber accounts for 67% of the mass of the ANFs@2BFs composite paper. An electronic photograph of the composite paper is shown in fig. 2.
An electron photograph of the dispersion effect of basalt fiber after heat treatment and ultrasonic synergy in the preparation process of example 1 is shown in fig. 1. Fig. 1 (a) shows the dispersion effect of basalt fibers in ANFs/DMSO solution without any treatment, and fig. 1 (b) shows the dispersion effect of heat-treated basalt fibers in ANFs/DMSO solution after ultrasonic synergism, so that basalt fibers are uniformly dispersed in ANFs/DMSO solution, and BF/ANFs/DMSO suspension with good dispersion effect is obtained. FIG. 1 (c) shows that ANFs coated BF (ANFs@BF-DMSO) dispersion was prepared, and that basalt fibers also showed good dispersibility in the dispersion. The composite paper ANFs@2BFs prepared in example 1 is shown in FIG. 2. The flame-retardant effect was observed by placing it on a flame for 1min as shown in FIG. 3 (a) and as shown in FIG. 3 (b).
FIG. 5 is a graph of the thermogravimetric profile of the ANFs@2BFs composite paper prepared in example 1, tested at temperatures ranging from room temperature to 800 ℃, at a heating rate of 10 ℃/min, and under an atmosphere of N 2. The residual weight value after TG measurement was 75.6% for the paper of example 1. The obvious weight loss temperature of the paper is higher than 500 ℃, which indicates that the ANFs@2BFs composite paper has higher thermal stability.
Comparative example 1
Basalt fiber/aramid fiber nanofiber composite paper prepared by different mixing methods
Step one: preparing an aramid nanofiber dispersion liquid: 1.0gPPTA fiber, 1.5g KOH, 20mL deionized water and 500mL dimethyl sulfoxide are placed in an conical flask, and after sealing, the mixture is stirred for 4 hours at the rotating speed of 1000rpm by using a magnetic stirrer until the mixed solution in the conical flask is changed from the original macroscopic PPTA fiber to a uniform transparent dark red solution, thus obtaining the aramid nanofiber/dimethyl sulfoxide solution. 200ml of deionized water was then poured into the mixed solution for protonation reduction to give ANFs dispersion.
Step two: basalt fiber/aramid nanofiber composite paper: 0.253g basalt fiber is dispersed in ANFs dispersion liquid, and the dispersion is uniform under the actions of ultrasonic and magnetic stirring. Connecting a vacuum pump, controlling the vacuum degree to be higher than-0.1 MPa, continuously pumping and filtering for a certain time to ensure that the water above the paper is completely pumped, stopping pumping, taking the filter paper off the filter, vacuum drying for 6min at 105 ℃, and finally removing the basalt fiber/aramid nanofiber composite paper from the filter paper to finally obtain the basalt fiber/aramid nanofiber composite paper prepared by the different mixing methods, wherein the label is ANFs/2BFs.
Fig. 4 (a) is an SEM image of anfs@2bfs composite paper prepared in example 1, fig. 4 (b) is ANFs/2BFs composite paper prepared in comparative example 1, and fig. 4 (c) is an SEM image of aramid nanofiber in-situ coated basalt fiber prepared in example 1. The basalt fiber treated in the embodiment 1 is shown to increase the surface activity of the basalt fiber, so that the aramid nanofiber in-situ coating of the basalt fiber is realized. And the prepared ANFs@2BFs composite paper has a clearer layered structure with alternately arranged organic-inorganic fibers compared with other mixing methods. The basalt fiber is used as a physical barrier in the layered structure to prevent the micropore structure caused by the volatilization of combustible matters, so that the heat conductivity coefficient of the composite paper is reduced. Basalt fiber has excellent high temperature resistance, and plays a key role in the fireproof performance of composite paper.
Example 2
The preparation method of the basalt fiber/aramid nanofiber composite paper imitating the shell structure in the embodiment comprises the following steps:
step one: preparation of aramid nanofiber/dimethyl sulfoxide solution
1.0GPPTA fiber, 1.5g KOH, 20mL deionized water and 500mL dimethyl sulfoxide (DMSO) were placed in an conical flask, and then stirred with a magnetic stirrer at 1000rpm/min for 4 hours until the mixture became uniformly transparent and dark red, thus obtaining an aramid nanofiber/dimethyl sulfoxide (ANFs/DMSO) solution.
Step two: preparation of basalt fiber dispersion liquid coated with aramid fiber nano-fibers in situ
And (3) placing the basalt fiber in a muffle furnace, heating to 300 ℃ and preserving heat for 2 hours, and removing the surface impregnating compound to obtain the Basalt Fiber (BF) with high surface activity and water dispersibility. Then mixing 0.19gBF with 95mL ANFs/DMSO solution, and dispersing for 10min under the ultrasonic action, finally obtaining BF/ANFs/DMSO suspension with good dispersing effect. Further, 190mL of deionized water was injected into the BF/ANFs/DMSO suspension for protonation reduction, the BF/ANFs/DMSO suspension was placed on a magnetic stirrer and the rotation speed was adjusted to 1500rmp to obtain a shearing action on the BF/ANFs/DMSO suspension, and then the BF/ANFs/DMSO suspension was injected with deionized water by measuring with a single-use pump syringe to obtain ANFs coated BF (ANFs@BF-DMSO) dispersion.
Step three: preparation of basalt fiber/aramid nanofiber composite paper with shell-like structure
Pouring the basalt fiber dispersion liquid coated with the aramid nanofibers in situ, which is prepared in the second step, into a sand core funnel, connecting a vacuum pump, continuously performing suction filtration, ensuring that water above paper is completely pumped, stopping vacuum pumping, taking the filter paper adhered with the composite paper off the filter, performing vacuum drying for 6min at 105 ℃, and finally removing the composite paper from the filter paper to finally obtain the shell-like layered basalt fiber/aramid nanofiber composite paper, wherein the label is ANFs@1BFs. Wherein the basalt fiber accounts for 50% of the mass of the ANFs@1BFs composite paper.
Example 3
The preparation method of the basalt fiber/aramid nanofiber composite paper imitating the shell structure in the embodiment comprises the following steps:
step one: preparation of aramid nanofiber/dimethyl sulfoxide solution
1.0GPPTA fiber, 1.5g KOH, 20mL deionized water and 500mL dimethyl sulfoxide are placed in an conical flask, and after sealing, the mixture is stirred for 4 hours at the rotating speed of 1000rpm by using a magnetic stirrer until the mixed solution in the conical flask is changed from the original macroscopic PPTA fiber to a uniform transparent dark red solution, thus obtaining the aramid nanofiber/dimethyl sulfoxide solution.
Step two: preparation of basalt fiber dispersion liquid coated with aramid fiber nano-fibers in situ
And (3) placing the basalt fiber in a muffle furnace, heating to 400 ℃, preserving heat for 1 hour, and removing the surface impregnating compound to obtain the Basalt Fiber (BF) with high surface activity and water dispersibility. Then mixing 0.285, 0.285gBF and 47.5mL ANFs/DMSO solution, and dispersing for 10min under the ultrasonic action, finally obtaining BF/ANFs/DMSO suspension with good dispersing effect. Further, 95mL of deionized water was injected into the BF/ANFs/DMSO suspension for protonation reduction, the BF/ANFs/DMSO suspension was placed on a magnetic stirrer and the rotation speed was adjusted to 1500rmp to obtain a shearing action on the BF/ANFs/DMSO suspension, and then the BF/ANFs/DMSO suspension was injected with deionized water by measuring with a single-use pump syringe to obtain ANFs coated BF (ANFs@BF-DMSO) dispersion.
Step three: preparation of basalt fiber/aramid nanofiber composite paper with shell-like structure
Pouring the basalt fiber dispersion liquid coated with the aramid nanofibers in situ, which is prepared in the second step, into a sand core funnel, connecting a vacuum pump, continuously performing suction filtration, ensuring that water above paper is completely pumped, stopping vacuum pumping, taking the filter paper adhered with the composite paper off the filter, performing vacuum drying for 6min at 105 ℃, and finally removing the composite paper from the filter paper to finally obtain the shell-like layered basalt fiber/aramid nanofiber composite paper, wherein the label is ANFs@3BFs. Wherein the basalt fiber accounts for 75% of the mass of the ANFs@3BFs composite paper.
Table 1 shows the thermal conductivity coefficients and breakdown strength at room temperature of the samples prepared in examples 1-3. It can be seen that the anfs@1bfs composite paper prepared in example 2 has lower thermal conductivity and better breakdown strength.
TABLE 1
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of protection thereof, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: various changes, modifications, or equivalents may be made to the particular embodiments of the invention by those skilled in the art after reading the present disclosure, but such changes, modifications, or equivalents are within the scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the basalt fiber/aramid fiber nanofiber composite paper with the self-assembled layered structure is characterized by comprising the following steps of:
Step one: preparing an aramid nanofiber/dimethyl sulfoxide solution;
mixing PPTA fiber, KOH, deionized water and DMSO to form a mixed solution, and stirring the mixed solution to prepare ANFs/DMSO solution;
Step two: preparing basalt fiber dispersion liquid coated with aramid fiber nano-fibers in situ;
Heat treatment is carried out on basalt fibers, and surface sizing agents are removed, so that BF with high surface activity and water dispersibility is obtained; mixing BF with ANFs/DMSO solution and dispersing under ultrasonic action to form BF/ANFs/DMSO suspension, and injecting deionized water into BF/ANFs/DMSO suspension for protonic reduction to obtain ANFs@BF-DMSO dispersion; the volume ratio of the BF/ANFs/DMSO suspension to deionized water is 1:2;
step three: preparing basalt fiber/aramid nanofiber composite paper;
Washing the ANFs@BF-DMSO dispersion liquid prepared in the second step by deionized water to remove DMSO solvent in the dispersion liquid, and then carrying out vacuum suction filtration and drying to obtain ANFs@BFs composite paper with a self-assembled layered structure; the mass of basalt fiber in the ANFs@BFs composite paper accounts for 50% -75% of the mass of the ANFs@BFs composite paper.
2. The method for preparing basalt fiber/aramid nanofiber composite paper with a self-assembled layered structure according to claim 1, wherein the mixed solution in the first step is specifically 1.0gPPTA fiber, 1.5g koh and 20mL deionized water mixed in 500mL of ldmso solution.
3. The method for preparing basalt fiber/aramid nanofiber composite paper having a self-assembled layered structure according to claim 1, wherein the stirring in the first step is performed for 4 hours at 1000rpm using a magnetic stirrer.
4. The method for preparing basalt fiber/aramid nanofiber composite paper with a self-assembled layered structure according to claim 1, wherein the heat treatment in the second step is specifically that basalt fiber is placed in a muffle furnace to be heated to 300-500 ℃ and kept for 1-3 hours.
5. The method for preparing basalt fiber/aramid nanofiber composite paper with a self-assembled layered structure according to claim 1, wherein the dispersing time under the ultrasonic action in the second step is 10min.
6. The method for preparing basalt fiber/aramid nanofiber composite paper with a self-assembled layered structure according to claim 1, wherein the injecting deionized water into BF/ANFs/DMSO suspension in the second step is specifically as follows: after the BF/ANFs/DMSO suspension was placed on a magnetic stirrer and the rotation speed was adjusted to 1500rpm to obtain a shearing action of the BF/ANFs/DMSO suspension, deionized water was measured into the BF/ANFs/DMSO suspension using a single-use pump syringe.
7. The method for preparing basalt fiber/aramid nanofiber composite paper with self-assembled layered structure according to claim 1, wherein the washing in the step three is performed 3 to 5 times, and the drying is specifically vacuum drying for 6min at 105 ℃.
8. Basalt fiber/aramid nanofiber composite paper with a self-assembled layered structure, characterized in that it is manufactured by the manufacturing method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211717269.2A CN116240748B (en) | 2022-12-29 | Basalt fiber/aramid fiber nanofiber composite paper with self-assembled layered structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211717269.2A CN116240748B (en) | 2022-12-29 | Basalt fiber/aramid fiber nanofiber composite paper with self-assembled layered structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116240748A CN116240748A (en) | 2023-06-09 |
| CN116240748B true CN116240748B (en) | 2024-06-07 |
Family
ID=
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106737A (en) * | 2019-06-10 | 2019-08-09 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber/mica composite-insulating paper |
| CN111188222A (en) * | 2020-02-20 | 2020-05-22 | 陕西科技大学 | Preparation method of few-glue/no-glue basalt fiber paper |
| CN112409613A (en) * | 2020-11-19 | 2021-02-26 | 陕西科技大学 | Preparation method of aramid nanofiber dispersion liquid |
| CN112759930A (en) * | 2020-12-30 | 2021-05-07 | 四川大学 | Liquid metal/aramid nano-fiber heat-conducting composite material, preparation method and application |
| CN113206345A (en) * | 2021-04-21 | 2021-08-03 | 陕西科技大学 | Para-aramid nanofiber/inorganic nanoparticle composite coating enhanced polyolefin battery diaphragm and preparation method thereof |
| CN113389080A (en) * | 2021-06-28 | 2021-09-14 | 陕西科技大学 | Aramid fiber modification method |
| CN113506949A (en) * | 2021-07-09 | 2021-10-15 | 陕西科技大学 | Preparation method of aramid nanofiber-based battery diaphragm with micro-nano porous structure |
| CN115044079A (en) * | 2022-06-30 | 2022-09-13 | 陕西科技大学 | Aramid nanofiber doped basalt nanosheet composite insulating film and preparation method thereof |
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106737A (en) * | 2019-06-10 | 2019-08-09 | 陕西科技大学 | A kind of preparation method of aramid nano-fiber/mica composite-insulating paper |
| CN111188222A (en) * | 2020-02-20 | 2020-05-22 | 陕西科技大学 | Preparation method of few-glue/no-glue basalt fiber paper |
| CN112409613A (en) * | 2020-11-19 | 2021-02-26 | 陕西科技大学 | Preparation method of aramid nanofiber dispersion liquid |
| CN112759930A (en) * | 2020-12-30 | 2021-05-07 | 四川大学 | Liquid metal/aramid nano-fiber heat-conducting composite material, preparation method and application |
| CN113206345A (en) * | 2021-04-21 | 2021-08-03 | 陕西科技大学 | Para-aramid nanofiber/inorganic nanoparticle composite coating enhanced polyolefin battery diaphragm and preparation method thereof |
| CN113389080A (en) * | 2021-06-28 | 2021-09-14 | 陕西科技大学 | Aramid fiber modification method |
| CN113506949A (en) * | 2021-07-09 | 2021-10-15 | 陕西科技大学 | Preparation method of aramid nanofiber-based battery diaphragm with micro-nano porous structure |
| CN115044079A (en) * | 2022-06-30 | 2022-09-13 | 陕西科技大学 | Aramid nanofiber doped basalt nanosheet composite insulating film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | A nanocellulose polypyrrole composite based on tunicate cellulose | |
| Wu et al. | Synthesis of flexible aerogel composites reinforced with electrospun nanofibers and microparticles for thermal insulation | |
| US20120171488A1 (en) | Sheets including fibrous aerogel and method for producing the same | |
| CN1320181C (en) | Modification method of interface between carbon fiber and non-polar resin | |
| CN103483786B (en) | A kind of Fully-biodegradable composite membrane of filling nano-sliver/cellulosnanocrystalline nanocrystalline composite particle and preparation method thereof | |
| CN108187503B (en) | Preparation method of montmorillonite-reinforced chitosan composite cellulose acetate film | |
| CN103225126B (en) | Fibroin/sodium alginate composite nanofiber scaffold preparation method | |
| KR101804577B1 (en) | Carbon nanotube fibers and method of preparing the same | |
| CN113668139A (en) | Flexible high-temperature-resistant SiO2Preparation method of ceramic nanofiber membrane | |
| CN109864042A (en) | A kind of nano-graphene preparing high thermal conductivity silk freshens food and educates silkworm method and its product | |
| CN111285949B (en) | Polyacrylonitrile-coated graphene composite material and preparation method and application thereof | |
| CN108176256A (en) | A kind of high temperature resistant composite nano fiber filters membrane preparation method | |
| CN109942996A (en) | A kind of composite material and preparation method thereof and composite material | |
| KR100596543B1 (en) | Ag-Containing Silica Nano-Fibers and Method for Producing the Same | |
| CN116240748B (en) | Basalt fiber/aramid fiber nanofiber composite paper with self-assembled layered structure and preparation method thereof | |
| CN109853135B (en) | Polybenzimidazole coated polyimide nanofiber core-shell structure nanofiber membrane and preparation method thereof | |
| CN109369964B (en) | Composite antibacterial film and preparation method and application thereof | |
| CN110863349B (en) | Preparation method of centrifugal spinning nanofiber body material | |
| CN107475793A (en) | A kind of preparation method of graphene oxide parcel polyacrylonitrile composite nano fiber | |
| CN116240748A (en) | Basalt fiber/aramid fiber nanofiber composite paper with self-assembled layered structure and preparation method thereof | |
| CN105063805B (en) | The preparation method of loose structure calcium titanate nanobelt | |
| KR101801790B1 (en) | Microcapsule having self-healing and conducting property, self-healing fiber and method for preparing the same | |
| CN113235304B (en) | Aqueous solution sizing agent based on polyether-ether-ketone, preparation method thereof and preparation method of carbon fiber cloth reinforced polyether-ether-ketone composite material | |
| CN1170018C (en) | Method for preparing aluminium oxide-silicon oxide fibre | |
| CN113198434B (en) | Intelligent adsorption/release system based on excitation response polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |