CN113831581A - High-elasticity anti-radiation nanofiber aerogel material and preparation method thereof - Google Patents

High-elasticity anti-radiation nanofiber aerogel material and preparation method thereof Download PDF

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CN113831581A
CN113831581A CN202111112759.5A CN202111112759A CN113831581A CN 113831581 A CN113831581 A CN 113831581A CN 202111112759 A CN202111112759 A CN 202111112759A CN 113831581 A CN113831581 A CN 113831581A
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hydrolysate
stirring
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radiation
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CN113831581B (en
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张恩爽
李文静
刘圆圆
张昊
黄红岩
张凡
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

The invention relates to a high-elasticity anti-radiation nanofiber aerogel material and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing tetraethoxysilane, phosphoric acid and water, stirring for 1-24 h, adding titanium dioxide nano powder, continuously stirring for 1-12h, and performing ultrasonic treatment to obtain a composite hydrolysate; uniformly mixing the polyvinyl alcohol aqueous solution and the composite hydrolysate with water, stirring for 1-12h, and then performing electrostatic spinning on the precursor solution to obtain a hybrid nanofiber membrane; carrying out heat treatment on the hybrid nanofiber membrane; adding the hybrid nanofiber membrane subjected to heat treatment, ethyl orthosilicate, boric acid and aluminum chloride into water, and adding a graphene oxide solution into the water to perform high-speed stirring to obtain a homogeneous dispersion liquid; and then sequentially freezing, freeze-drying and post-treating the homogeneous dispersion to prepare the high-elasticity anti-radiation nanofiber aerogel material. The material prepared by the invention has high elasticity, and has excellent radiation resistance, temperature resistance and high-temperature heat insulation performance.

Description

High-elasticity anti-radiation nanofiber aerogel material and preparation method thereof
Technical Field
The invention relates to the technical field of aerogel preparation, in particular to a high-elasticity anti-radiation nanofiber aerogel material and a preparation method thereof.
Background
The nano porous aerogel material is a gel material with a dispersion medium of gas, is a nano porous solid material with a network structure formed by mutually accumulating colloidal particles or high polymer molecules, and the size of pores in the material is in the order of nanometers. The porosity of the porous ceramic is as high as 80-99.8%, the typical size of the pores is 1-100 nm, and the specific surface area is 200-1000 m2A density of as low as 3kg/m3The heat conductivity coefficient at room temperature can be as low as 0.012W/m.K. Due to the characteristics, the aerogel material has wide application potential in the aspects of thermal, acoustic, optical, microelectronic and particle detection. Currently, the widest field of application of aerogels is still the field of thermal insulation, since the unique nanostructure of aerogels can effectively reduce convection conduction, solid phase conduction and thermal radiation. The existing research proves that aerogel is an effective heat insulation material, but most of aerogel materials reported at present are rigid aerogel materials with a nanometer skeleton in a nanometer pearl necklace structure. Aerogel materials with high elasticity are often considered as properties unique to organic aerogels,the preparation of elastic inorganic aerogels is difficult. In recent years, the preparation of inorganic nanofiber aerogel materials has become a focus of attention of researchers, and the elasticity characteristics of the inorganic nanofibers with high aspect ratio can be utilized to endow the inorganic nanofiber aerogel with high elasticity. However, despite the elasticity of the nanofiber aerogel, the thermal insulation performance of the nanofiber aerogel is far from the traditional aerogel materials. Chinese patent application CN201910202661.5 discloses a preparation method of modified silica powder/silica nanofiber composite aerogel material, which combines electrostatic spinning silica nanofibers with silica aerogel powder to prepare the modified silica powder/silica nanofiber composite aerogel material, the compression resilience can reach 85%, and through the uniform stable dispersion of the nanoscale aerogel powder, the heat insulation performance of pure nanofiber aerogel is improved, but the nanofibers in the patent application are pure silica phase, the radiation resistance at high temperature is not good, the thermal conductivity coefficient at high temperature is large, and the problem of insufficient heat insulation performance at high temperature is solved.
In addition, the nano-fiber aerogel has larger pores and more continuous framework, which determines that the nano-fiber aerogel has larger solid phase heat conduction and gas phase heat conduction, and the single component structure causes the nano-fiber aerogel to have poorer radiation resistance. A small amount of research work relates to the preparation of silicon carbide nanofiber aerogel materials with anti-radiation effects, however, pure silicon carbide nanofibers are prone to oxidation in air and poor in temperature resistance.
With the development of science and technology, various fields put higher demands on the temperature resistance, compression resilience, high-temperature heat-insulating property and the like of aerogel materials, so that an effective method for preparing a high-elasticity radiation-resistant nanofiber aerogel material is very needed.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a high-elasticity radiation-resistant nanofiber aerogel material and a preparation method thereof. The high-elasticity radiation-resistant nanofiber aerogel material prepared by the invention has high elasticity and excellent radiation resistance, temperature resistance and high-temperature heat insulation performance.
The invention provides a preparation method of a high-elasticity radiation-resistant nanofiber aerogel material in a first aspect, which comprises the following steps:
(1) uniformly mixing tetraethoxysilane, phosphoric acid and water to obtain a mixed solution, stirring the mixed solution for 1-24 hours to obtain a hydrolysate, adding titanium dioxide nano powder into the hydrolysate, continuously stirring for 1-12 hours, and finally performing ultrasonic treatment for 0.5-2 hours to obtain a composite hydrolysate;
(2) uniformly mixing a polyvinyl alcohol aqueous solution and the composite hydrolysate obtained in the step (1) with water, stirring for 1-12 hours to obtain a precursor solution, and then performing electrostatic spinning by using the precursor solution as an electrostatic spinning solution to obtain a hybrid nanofiber membrane;
(3) carrying out heat treatment on the hybrid nanofiber membrane obtained in the step (2) in an inert atmosphere; the heat treatment comprises the following steps: firstly, carrying out heat treatment at 300-600 ℃ for 1-10 h, then carrying out heat treatment at 600-900 ℃ for 1-5 h, and then naturally cooling to room temperature;
(4) adding the hybrid nanofiber membrane subjected to heat treatment in the step (3), ethyl orthosilicate, boric acid and aluminum chloride into water to obtain a to-be-dispersed solution, and then adding a graphene oxide solution into the to-be-dispersed solution and stirring at a high speed to obtain a homogeneous phase dispersed solution;
(5) sequentially freezing and freeze-drying the homogeneous dispersion liquid obtained in the step (4) to obtain a nanofiber aerogel material;
(6) and (5) carrying out post-treatment on the nanofiber aerogel material obtained in the step (5) in an inert atmosphere to obtain the high-elasticity anti-radiation nanofiber aerogel material.
Preferably, in step (1): the molar ratio of the ethyl orthosilicate to the phosphoric acid to the water is (0.5-1): (0.005-0.05): (1 to 20), preferably 1: (0.015 to 0.025): (8-15), more preferably 1:0.02: 10; and/or the amount of the titanium dioxide nano powder is 0.4-10% of the mass of the hydrolysate, preferably 0.5-5%, and more preferably 0.8-2.5%.
Preferably, in step (2): the mass fraction of polyvinyl alcohol contained in the polyvinyl alcohol aqueous solution is 1-20%; the mass ratio of the composite hydrolysate to the polyvinyl alcohol aqueous solution to the water is (1-5): (1-5): (0.5 to 5), preferably (2.5 to 3.5): (2.5-3.5): 2, more preferably 3:3: 2; and/or the stirring time is 3-6 h.
Preferably, the parameters for electrospinning are as follows: the voltage is 10-30 kV, the filling speed is 0.5-2 mL/h, the receiving distance is 10-25 cm, and/or the temperature in the spinning room is 15-35 ℃.
Preferably, in the step (2), the obtained hybrid nanofiber membrane is also subjected to vacuum drying; preferably, the obtained hybrid nanofiber membrane is dried in a vacuum drying oven at 60-120 ℃ for 1-3 h.
Preferably, in step (4): the graphene oxide solution is a graphene oxide aqueous solution with the concentration of 15-25 g/L; the amount of the graphene oxide solution is 0.5-2% of the mass of the to-be-dispersed solution; and/or the mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.4-0.6%, the mass fraction of ethyl orthosilicate contained in the liquid to be dispersed is 0.4-0.6%, the mass fraction of boric acid contained in the liquid to be dispersed is 0.05-0.2%, and the mass fraction of aluminum chloride contained in the liquid to be dispersed is 0.1-0.3%.
Preferably, in step (4): the rotating speed of the high-speed stirring is 5000-20000 r/min, and the time of the high-speed stirring is 5-30 min.
Preferably, in step (5): the freezing is performed for 10-60 min under liquid nitrogen; the freezing is carried out in a mould, the top and the side surfaces of the mould are made of materials with lower heat conductivity, the bottom of the mould is made of materials with higher heat conductivity, preferably, the top and the side surfaces of the mould are made of polytetrafluoroethylene, and the bottom of the mould is made of copper materials; and/or the freeze drying is vacuum freeze drying, preferably the vacuum freeze drying is carried out for 2-5 d under the conditions that the vacuum degree is 0.5-10 Pa and the temperature is-50 to-70 ℃.
Preferably, in step (6): the temperature of the post-treatment is 800-1000 ℃, and the time of the post-treatment is 0.1-12 h.
In a second aspect, the invention provides a high-elasticity radiation-resistant nanofiber aerogel material prepared by the preparation method in the first aspect of the invention.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the method of the invention carries out the doping of the anti-radiation agent in the composite hydrolysate, and realizes the in-situ doping of the anti-radiation agent after the heat treatment process, so that the anti-radiation agent can be embedded in the nano-fiber in situ; compared with single-component nanofiber aerogel (silicon dioxide, zirconium oxide and mullite), the high-elasticity radiation-resistant nanofiber aerogel material has excellent radiation resistance, the radiation-resistant agent (titanium dioxide nano powder) is embedded in the interior of the nanofibers in situ and can be uniformly dispersed, agglomeration among particles is avoided, a good radiation resistance effect can be realized, the high-elasticity radiation-resistant nanofiber aerogel material has good high-temperature heat insulation performance, and the thermal conductivity coefficient of the high-elasticity radiation-resistant nanofiber aerogel material prepared by the method is low at the high temperature of 800 ℃.
(2) According to the invention, the composite hydrolysate is doped with titanium dioxide nano powder to prepare a hybrid nanofiber membrane (composite nanofiber), the composite nanofiber is used as an aerogel basic unit, the self-assembly of the composite nanofiber is realized, and the preparation of the nanofiber aerogel material with good elasticity is realized by utilizing the bendable characteristic of the nanofiber with high length-diameter ratio.
(3) According to the invention, the silicon-aluminum composite component is adopted as the basic composition of the aerogel to obtain the aerogel material of the composite component, and the composite component can form a more temperature-resistant phase in the high-temperature use process, so that the temperature resistance of the material can be effectively improved.
(4) According to the nanofiber aerogel material, the anti-radiation nanoparticles are embedded in the nanofibers, so that the preparation of the core-shell structure porous network aerogel is realized, the titanium dioxide nanopowder can be effectively and uniformly distributed in the nanofiber aerogel material, and the anti-radiation performance of the aerogel material is improved.
(5) The invention adopts the freeze drying process to replace the supercritical drying process, reduces the cost and the period in the material preparation process, and simultaneously improves the environmental protection of the preparation method.
(6) The high-elasticity radiation-resistant nanofiber aerogel material prepared by the method disclosed by the invention has excellent elasticity on the premise of keeping low thermal conductivity not more than 0.032W/m.K, can realize temperature resistance of over 1100 ℃ for a short time, has a low thermal conductivity coefficient at a high temperature of 800 ℃, has excellent high-temperature heat-insulating property and excellent radiation-resistant property.
(7) The high-elasticity anti-radiation nanofiber aerogel material prepared by the method disclosed by the invention has the porosity of more than 90%, the pore size of 5-500 nm, the diameter of the nanofiber of 100-500 nm, the compression rebound rate of not less than 80% and the heat-resistant temperature of more than 1100 ℃.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention.
FIG. 2 is a schematic diagram showing the structural change of the material in the process of preparing a high-elasticity radiation-resistant nanofiber aerogel material according to the invention.
FIG. 3 shows the PVA/SiO after heat treatment prepared in example 1 of the present invention2/TiO2SEM image of hybrid nanofiber membrane. As can be seen from FIG. 3, PVA/SiO2/TiO2The surface of the hybrid nanofiber membrane is not distributed with titanium dioxide nanopowder.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a high-elasticity radiation-resistant nanofiber aerogel material in a first aspect, which comprises the following steps:
(1) mixing Tetraethoxysilane (TEOS) and phosphoric acid (H)3PO4) And water (e.g. toIonized water) to obtain a mixed solution, stirring the mixed solution for 1-24 h (for example, 1, 6, 12 or 24h) to obtain a hydrolysate, adding titanium dioxide nano powder into the hydrolysate, continuously stirring for 1-12h (for example, 1, 3, 6, 8, 10 or 12h), and finally performing ultrasonic treatment for 0.5-2 h (for example, 0.5, 1, 1.5 or 2h) to obtain a composite hydrolysate (also called TEOS composite hydrolysate); specifically, the step (1) is as follows: at room temperature, taking TEOS and H with certain mass3PO4And deionized water as per n (teos): n (H)3PO4)：n(H2O) ═ 0.5 to 1: (0.005-0.05): (1 to 20), preferably 1: (0.015 to 0.025): (8-15) more preferably mixing at a molar ratio of 1:0.02:10, and stirring on a magnetic stirrer for 1-12 hours, preferably 12 hours to obtain a hydrolysate; then adding titanium dioxide nano powder into the hydrolysate to ensure that the using amount of the titanium dioxide nano powder (anti-radiation agent) is 0.4-10% and preferably 0.8-2.5% of the mass of the hydrolysate, stirring for 1-12h, and carrying out ultrasonic treatment for 0.5-2 h to uniformly disperse the titanium dioxide nano powder in the hydrolysate to obtain a composite hydrolysate; in the present invention, the particle size of the titanium dioxide nanopowder is not particularly limited, and the titanium dioxide nanopowder with a nanometer size may be adopted, and in some specific embodiments, the titanium dioxide nanopowder is preferably the titanium dioxide nanopowder with a particle size range of 40-100 nm; the working frequency of the ultrasonic treatment is not particularly limited, and the ultrasonic treatment can be carried out by adopting a conventional frequency, for example, the frequency can be 25-40 kHz; in the invention, ethyl orthosilicate (TEOS) and phosphoric acid (H) are firstly required to be prepared3PO4) The mixed solution formed by mixing the nano-titanium dioxide powder with water is firstly hydrolyzed, then the nano-titanium dioxide powder is added into the hydrolysate and is stirred and ultrasonically treated, so that the nano-titanium dioxide powder can be uniformly dispersed in the hydrolysate, uniform doping of the nano-titanium dioxide powder in the subsequent electrostatic spinning process and uniform in-situ doping of the nano-titanium dioxide powder after the heat treatment process can be realized, the nano-titanium dioxide powder can be uniformly embedded in the nano-fibers and can be uniformly dispersed, the agglomeration among particles is avoided, and thus, the nano-titanium dioxide powder can be effectively ensured to realize excellent performanceThe anti-radiation effect of the aerogel material improves the thermal stability of the aerogel material and reduces the high-temperature thermal conductivity of the aerogel material; the invention discovers that the ethyl orthosilicate and the water are in a phase-splitting state before hydrolysis, and the addition of the titanium dioxide nano powder can cause adsorption, thus influencing the hydrolysis effect and the dispersion effect of the titanium dioxide nano powder; after the tetraethoxysilane is completely hydrolyzed, the titanium dioxide nano powder is added to be dispersed more uniformly, and homogeneous composite hydrolysate can be formed; the invention discovers that if the Tetraethoxysilane (TEOS) and the phosphoric acid (H) are directly mixed3PO4) Mixing and hydrolyzing titanium dioxide nano powder and water or directly mixing and stirring a polyvinyl alcohol aqueous solution, the titanium dioxide nano powder and a hydrolysate without the titanium dioxide nano powder by using water in the subsequent step (2) to obtain a precursor solution, wherein the two modes can not realize uniform dispersion of the titanium dioxide nano powder, and finally, only a small part of the titanium dioxide nano powder can be embedded in the nano fibers, and the titanium dioxide nano powder is obviously distributed unevenly; in addition, the invention discovers that the dispersing mode of the titanium dioxide nano powder in the invention is directly compared with the dispersing mode of Tetraethoxysilane (TEOS) and phosphoric acid (H)3PO4) The titanium dioxide nano powder and water are mixed and hydrolyzed or directly in the subsequent step (2), the polyvinyl alcohol aqueous solution, the titanium dioxide nano powder and the hydrolysate without the titanium dioxide nano powder are mixed and stirred by water in a dispersing mode, and the compression resilience of the high-elasticity radiation-resistant nanofiber aerogel material can be obviously improved.
(2) Uniformly mixing a polyvinyl alcohol aqueous solution with the composite hydrolysate obtained in the step (1) by using water, stirring for 1-12h (for example, 1, 2, 4, 5, 6, 8, 10 or 12h) to obtain a precursor solution, and then performing electrostatic spinning by using the precursor solution as an electrostatic spinning solution to obtain a hybrid nanofiber membrane (also called as PVA/SiO)2/TiO2Hybrid nanofiber membranes); in the present invention, the polyvinyl alcohol aqueous solution (PVA aqueous solution) may be prepared, for example, by: weighing a certain mass of polyvinyl alcohol powder, adding the polyvinyl alcohol powder into deionized water, stirring for 1-12h, and heating and dissolving at 60-120 ℃; taking out after stirring, placing on a magnetic stirrer, stirring at room temperature, and cooling to room temperatureWarming; the mass fraction of the prepared PVA aqueous solution is 1-20 wt%; specifically, the step (2) is as follows: and (3) mixing TEOS composite hydrolysate, PVA aqueous solution and deionized water according to the ratio of (1-5): (1-5): (0.5-5), placing the mixture on a magnetic stirrer at room temperature, and stirring for 1-12 hours to obtain a uniform and clear precursor solution; then extracting the precursor solution by using an injector, and preparing PVA/SiO by using an electrostatic spinning machine2/TiO2A hybrid nanofiber membrane; the invention discovers that compared with a mode of directly mixing tetraethoxysilane and polymer and then hydrolyzing, the mode of preparing TEOS composite hydrolysate and polyvinyl alcohol aqueous solution into precursor solution by using water can obviously improve the high-temperature heat-insulating property of the nano-fiber aerogel material; the invention discovers that if TEOS, titanium dioxide nano powder and polyvinyl alcohol are directly mixed and hydrolyzed, on one hand, the polyvinyl alcohol can be dissolved more uniformly under the heating condition, the heating condition can lead to the acceleration of the hydrolysis speed and the generation of partial condensation reaction, which leads to the growth of single particles of silica sol, which is not beneficial to the formation of a small-particle homogeneous dispersion system, thus obviously influencing the effect of the hydrolyzed TEOS and finally the high-temperature heat-insulating property of the prepared aerogel material, on the other hand, the titanium dioxide nano powder is added before the hydrolysis of tetraethoxysilane, which also leads to the adsorption effect, thus influencing the hydrolysis effect and the dispersion effect of the titanium dioxide nano powder, and finally also obviously influencing the high-temperature heat-insulating property and compression resilience of the prepared aerogel material.
(3) Carrying out heat treatment on the hybrid nanofiber membrane obtained in the step (2) in an inert atmosphere (for example, nitrogen, argon or a mixed atmosphere of nitrogen and argon); the heat treatment comprises the following steps: heat-treating at 300-600 deg.C (e.g. 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C or 600 deg.C) for 1-10 h (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10h), then heat-treating at 600-900 deg.C (e.g. 600 deg.C, 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, 850 deg.C or 900 deg.C) for 1-5 h (e.g. 1, 2, 3, 4 or 5h), and naturally cooling to room temperature; in some specific embodiments, step (3) is: placing the hybrid nanofiber membrane obtained in the step (2) in an inert atmosphere furnace, setting the heating rate to be 1-6 ℃/min, preferably 3-6 ℃/min, more preferably 5 ℃/min, heating to 500 ℃ for heat treatment for 2h, then heating to 800 ℃, performing heat treatment for 3h, and then naturally cooling to room temperature; the invention discovers that the heat treatment process in the step (3) is crucial in order to obtain the high-elasticity (high compression resilience) radiation-resistant nanofiber aerogel material with high elasticity, and if the heat treatment process is not carried out or the calcination is carried out only at 300-600 ℃, the temperature resistance and the high-temperature resilience characteristic of the material can be obviously reduced.
(4) Adding the hybrid nanofiber membrane subjected to heat treatment in the step (3), ethyl orthosilicate, boric acid and aluminum chloride into water to obtain a to-be-dispersed solution, and then adding a graphene oxide solution into the to-be-dispersed solution and stirring at a high speed to obtain a homogeneous phase dispersed solution; in some specific embodiments, the hybrid nanofiber membrane subjected to the heat treatment in the step (3), ethyl orthosilicate, boric acid and aluminum chloride are added into water to obtain a to-be-dispersed solution, and then a graphene oxide solution is added into the to-be-dispersed solution and stirred at a high speed of 5000-20000 r/min, preferably 10000r/min, for 5-30 min, preferably 20min by using a high-speed shearing machine to obtain a homogeneous phase dispersion solution; the invention discovers that the addition of the ethyl orthosilicate and the aluminum chloride can form a silicon-aluminum compound at the node of the nano-fiber, and the addition of the boric acid can bond the fibers by forming boron oxide at high temperature to form continuous boron oxide phase, so that the nodes between the nano-fibers are ensured to be firm; the invention discovers that the high-elasticity anti-radiation nanofiber aerogel material with high elasticity, room-temperature thermal conductivity coefficient and lower high-temperature thermal conductivity coefficient can be prepared only by adding tetraethoxysilane, boric acid and aluminum chloride; the invention discovers that the flexibility of the nano-fiber is improved by adding the graphene oxide solution, the flexibility of the nano-fiber is improved by using the graphene sheet layer as a toughening agent, the compression resilience of the nano-fiber aerogel material is improved to a certain extent, the radiation resistance of the nano-fiber aerogel material is improved, and the heat insulation performance of the nano-fiber aerogel material at high temperature is improved.
(5) Sequentially freezing and freeze-drying the homogeneous dispersion liquid obtained in the step (4) to obtain a nanofiber aerogel material; the invention finds that the high-elasticity radiation-resistant nanofiber aerogel material with excellent comprehensive performance can be obtained only by sequentially freezing and freeze-drying, and if the obtained homogeneous phase dispersion liquid is sequentially subjected to freezing and normal-pressure drying, the density, the room-temperature thermal conductivity and the high-temperature thermal conductivity of the material are increased, and the material does not have compression resilience.
(6) Carrying out post-treatment (cracking) on the nanofiber aerogel material obtained in the step (5) in an inert atmosphere to prepare a high-elasticity anti-radiation nanofiber aerogel material; the invention discovers that after the nanofiber aerogel material obtained in the step (5) is subjected to post-treatment in an inert atmosphere, the compression resilience and the high-temperature heat-insulating property of the finally prepared high-elasticity radiation-resistant nanofiber aerogel material can be effectively ensured, and the high-temperature heat conductivity coefficient of the material is obviously reduced.
According to the method, the anti-radiation agent is doped in the composite hydrolysate, and after the heat treatment process, the in-situ doping of the anti-radiation agent is realized, so that the anti-radiation agent can be embedded in the nano-fibers in situ, the uniform dispersion of the anti-radiation agent can be ensured, and the agglomeration among particles is avoided; the components and the structure of the composite nanofiber are specially designed for high-elasticity radiation-resistant heat-insulating performance, and the high-elasticity radiation-resistant nanofiber aerogel material prepared by the method has high elasticity and simultaneously has excellent radiation-resistant performance, temperature-resistant performance and high-temperature heat-insulating performance.
The invention adopts an electrostatic spinning method to prepare the pearl beaded nanofiber material with the nanometer skeleton, and prepares the three-dimensional nanofiber aerogel material with the anti-radiation effect through an assembly process. Because the cladding effect of nanofiber, inside nanometer titanium dioxide can evenly distributed in nanofiber aerogel material's inside, can realize effectual radioresistance effect. Finally, the preparation of the nanofiber aerogel material with the characteristics of high temperature resistance, high temperature heat insulation performance, radiation resistance and high elasticity is realized.
According to some preferred embodiments, in step (1): the molar ratio of the ethyl orthosilicate to the phosphoric acid to the water is (0.5-1): (0.005-0.05): (1 to 20), preferably 1: (0.015 to 0.025): (8-15), more preferably 1:0.02: 10; and/or the titanium dioxide nanopowder is used in an amount of 0.4-10% (e.g., 0.4%, 0.8%, 1%, 1.5%, 2%, 5%, 8% or 10%), preferably 0.5-5% (e.g., 0.5%, 0.8%, 1%, 1.5%, 2%, 3%, 4% or 5%), more preferably 0.8-2.5% (e.g., 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2% or 2.5%) by mass of the hydrolysate; in the invention, the dosage of the titanium dioxide nano powder is more preferably 0.8-2.5% of the mass of the hydrolysate, and the invention finds that if the dosage of the titanium dioxide nano powder is too small, the radiation resistance of the material is insufficient, and if the dosage of the titanium dioxide nano powder is too large, the titanium dioxide nano powder is not easy to disperse, the titanium dioxide nano powder is seriously agglomerated, and too much titanium dioxide nano powder causes the fibers formed in the electrostatic spinning process to be discontinuous, so that the compression resilience and the overall strength of the prepared high-elasticity radiation-resistant nanofiber aerogel material are obviously reduced.
According to some preferred embodiments, in step (2): the mass fraction of polyvinyl alcohol contained in the polyvinyl alcohol aqueous solution is 1-20% (for example, 1, 5, 8, 10, 12, 15, 18 or 20%), and preferably 8-12% (for example, 8%, 9%, 10%, 11% or 12%); the mass ratio of the composite hydrolysate to the polyvinyl alcohol aqueous solution to the water is (1-5): (1-5): (0.5 to 5), preferably (2.5 to 3.5): (2.5-3.5): 2, more preferably 3:3: 2; in the invention, firstly, the polyvinyl alcohol can adjust the viscosity of the spinning solution, the fiber diameter in the spinning process is greatly influenced, and the fiber diameter determines the thermal conductivity of the nano-fiber aerogel material; and secondly, the polyvinyl alcohol is decomposed in the subsequent heat treatment process, the diameter of the obtained fiber is smaller when the content of the polyvinyl alcohol is higher, and the discontinuity of inorganic components of the fiber in the heat treatment process is caused by the overhigh content of the polyvinyl alcohol, so that the diameter of the fiber of the nanofiber aerogel material is as small as possible under the condition that the fiber diameter of the nanofiber aerogel material is kept continuous by proper mass ratio of the composite hydrolysate, the polyvinyl alcohol aqueous solution and the water, and the heat insulation performance of the finally prepared aerogel material is favorably ensured.
According to some preferred embodiments, in step (2): the stirring time is 3-6 h (for example, 3, 4, 5 or 6 h).
According to some preferred embodiments, the parameters for electrospinning are as follows: the voltage is 10-30 kV, the filling speed is 0.5-2 mL/h, the receiving distance is 10-25 cm, and/or the temperature in a spinning room (namely the ambient temperature) is 15-35 ℃; in the present invention, the perfusion speed refers to the flow rate of the electrospinning liquid.
According to some preferred embodiments, in step (2), the obtained hybrid nanofiber membrane is also subjected to vacuum drying; preferably, the obtained hybrid nanofiber membrane is dried in a vacuum drying oven at 60-120 ℃ for 1-3 h in vacuum, so as to remove water and residual solvent in the hybrid nanofiber membrane.
According to some preferred embodiments, in step (4): the graphene oxide solution is a graphene oxide aqueous solution with the concentration of 15-25 g/L (such as 15, 20 or 25 g/L); and/or the amount of the graphene oxide solution is 0.5-2% (e.g., 0.5%, 1%, 1.5%, or 2%) of the mass of the solution to be dispersed; the invention finds that the addition of the graphene oxide solution with a proper content can further improve the compression resilience of the high-elasticity radiation-resistant nanofiber aerogel material, if the mass fraction of the graphene oxide contained in the homogeneous dispersion liquid is too small, the effect of improving the compression resilience of the high-elasticity radiation-resistant nanofiber aerogel material is not obvious, and if the mass fraction of the graphene oxide contained in the homogeneous dispersion liquid is too high, the adverse effect on the temperature resistance of the material can be generated.
According to some preferred embodiments, the mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.4 to 0.6%, the mass fraction of the tetraethoxysilane contained in the liquid to be dispersed is 0.4 to 0.6%, the mass fraction of the boric acid contained in the liquid to be dispersed is 0.05 to 0.2%, and the mass fraction of the aluminum chloride contained in the liquid to be dispersed is 0.1 to 0.3%; in some preferred embodiments, the mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.53%, the mass fraction of the tetraethoxysilane contained in the liquid to be dispersed is 0.5%, the mass fraction of the boric acid contained in the liquid to be dispersed is 0.1%, and the mass fraction of the aluminum chloride contained in the liquid to be dispersed is 0.15%.
According to some preferred embodiments, in step (4): the high-speed stirring speed is 5000-20000 r/min (such as 5000, 10000, 15000 or 20000r/min), and the high-speed stirring time is 5-30 min (such as 5, 10, 15, 20, 25 or 30 min); in some preferred embodiments, the rotation speed of the high-speed stirring is 10000r/min, and the time of the high-speed stirring is 20 min.
According to some preferred embodiments, in step (5): the freezing is performed under liquid nitrogen for 10-60 min (for example, 10, 20, 30, 40, 50 or 60min), preferably 10-30 min; the freezing is carried out in a mould, the top and the side surfaces of the mould are made of materials with lower heat conductivity, the bottom of the mould is made of materials with higher heat conductivity, preferably, the top and the side surfaces of the mould are made of polytetrafluoroethylene, and the bottom of the mould is made of copper materials; and/or the freeze-drying is vacuum freeze-drying, preferably, the vacuum freeze-drying is carried out for 2-5 d (for example, 2, 3, 4 or 5 days) under the conditions that the vacuum degree is 0.5-10 Pa and the temperature is-50 to-70 ℃.
According to some preferred embodiments, in step (6): the temperature of the post-treatment is 800-1000 ℃ (such as 800, 850, 900, 950 or 1000 ℃), and the time of the post-treatment is 0.1-12h, preferably 3-8 h (such as 3, 4, 5, 6, 7 or 8 h).
According to some specific embodiments, the preparation of the high elasticity radiation resistant nanofiber aerogel material comprises the following steps:
preparation of hybrid nanofiber membranes
Preparing TEOS composite hydrolysate: at room temperature, taking TEOS and H with certain mass3PO4And deionized water as per n (teos): n (H)3PO4)：n(H2O) ═ 0.5 to 1: (0.005-0.05): (1-20), and placing the mixture on a magnetic stirrer to stir for 1-24 hours to obtain a hydrolysate; then adding titanium dioxide nano-particles into the hydrolysateAnd (3) powder, wherein the titanium dioxide nano powder accounts for 0.4-10% of the mass of the hydrolysate, stirring for 1-12h, and performing ultrasonic treatment for 0.5-2 h to uniformly disperse the titanium dioxide nano powder in the hydrolysate to obtain the TEOS composite hydrolysate.
Preparation of aqueous PVA solution: weighing a certain mass of polyvinyl alcohol powder, adding the polyvinyl alcohol powder into deionized water, heating and dissolving at 60-120 ℃, and stirring for 1-12 hours; taking out after stirring, placing on a magnetic stirrer, stirring at room temperature, and cooling to room temperature; the mass fraction of the prepared PVA aqueous solution is 1-20 wt%.
Preparation of precursor solution for electrospinning: and (3) mixing TEOS composite hydrolysate, PVA aqueous solution and deionized water according to the ratio of (1-5): (1-5): (0.5-5), placing the mixture on a magnetic stirrer at room temperature, and stirring for 1-12 hours to obtain a uniform and clear precursor solution.
Extracting the precursor solution by an injector to be used as electrostatic spinning solution, and preparing PVA/SiO by using an electrostatic spinning machine2/TiO2A hybrid nanofiber membrane. The electrostatic spinning process parameters comprise voltage of 5-40 kV, perfusion speed of 0.5-2 mL/h, receiving distance of 10-25 cm and temperature in a spinning chamber of 25 +/-10 ℃. After the test is finished, collecting the hybrid nanofiber membrane (PVA/SiO)2/TiO2Hybrid nanofiber membrane), and drying in a vacuum drying oven at 60-120 ℃ for 2h to remove water and residual solvent in the hybrid nanofiber membrane.
② heat treatment process
PVA/SiO prepared by electrostatic spinning2/TiO2Putting the hybrid nanofiber membrane into an atmosphere furnace, setting the heating rate to be 1-6 ℃/min and preferably 3-6 ℃/min, setting the temperature to be 300-600 ℃, keeping for 1-10 h, then heating to 600-900 ℃, keeping for 1-5 h, and then naturally cooling to room temperature; the room temperature in the invention is the environment temperature for carrying out the invention, and can be, for example, 15-35 ℃.
③ homogeneous dispersion process
And (3) adding the hybrid nanofiber membrane subjected to the heat treatment in the step two, tetraethoxysilane, boric acid and aluminum chloride into water to obtain a to-be-dispersed solution, then adding a graphene oxide solution into the to-be-dispersed solution, and stirring for 5-30 min by adopting a high-speed shearing machine under the condition that the rotating speed is 5000-20000 r/min to obtain a homogeneous dispersion solution.
Fourthly, freezing process: adding the homogeneous dispersion liquid into a mold with a fixed shape, wherein the top and the side of the mold are made of a material (polytetrafluoroethylene) with low thermal conductivity, the bottom of the mold is made of a copper sheet with good thermal conductivity (high thermal conductivity), and the sealed mold is placed in liquid nitrogen for 10-60 min of freezing.
A freeze drying process: and after the homogeneous dispersion liquid is completely frozen and formed, transferring the homogeneous dispersion liquid to a freeze dryer for vacuum freeze drying, wherein the freeze drying temperature is-50 to-70 ℃, the freeze drying time is 2 to 5 days, and the vacuum degree of freeze drying is 0.5 to 10 Pa.
Sixthly, post-treatment process: and (4) carrying out post-treatment (cracking) on the nanofiber aerogel material prepared in the fifth step in a protective atmosphere (in a nitrogen, argon or argon-hydrogen mixed gas), carrying out post-treatment at 900 ℃ for 0.1-12h, and stabilizing the lap joint between the nanofibers to prepare the high-elasticity anti-radiation nanofiber aerogel material.
In a second aspect, the invention provides a high-elasticity radiation-resistant nanofiber aerogel material prepared by the preparation method in the first aspect of the invention.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
Preparation of hybrid nanofiber membranes
Preparing TEOS composite hydrolysate: at room temperature, TEOS (tetraethyl orthosilicate) and H are taken3PO4(phosphoric acid) and deionized water as per n (teos): n (H)3PO4)：n(H2Mixing O) in a molar ratio of 1:0.02:10, and stirring for 12 hours on a magnetic stirrer to obtain hydrolysate; and then adding titanium dioxide nano powder into the hydrolysate to ensure that the titanium dioxide nano powder accounts for 2% of the mass of the hydrolysate, stirring for 5h, and performing ultrasonic treatment for 1h to uniformly disperse the titanium dioxide nano powder in the hydrolysate to obtain the TEOS composite hydrolysate.
Preparation of aqueous PVA solution: weighing polyvinyl alcohol powder, adding the polyvinyl alcohol powder into deionized water, heating and dissolving at 80 ℃, and stirring for 5 hours; taking out after stirring, placing on a magnetic stirrer, stirring at room temperature, and cooling to room temperature; the mass fraction of the prepared PVA aqueous solution is 10 wt%.
Preparation of precursor solution for electrospinning: mixing TEOS composite hydrolysate, PVA aqueous solution and deionized water according to the mass ratio of 3:3:2, placing the mixture on a magnetic stirrer at room temperature, and stirring the mixture for 4 hours to obtain uniform and clear precursor solution.
Extracting the precursor solution by an injector to be used as electrostatic spinning solution, and preparing PVA/SiO by using an electrostatic spinning machine2/TiO2A hybrid nanofiber membrane. The technological parameters of electrostatic spinning are that the voltage is 20kV, the perfusion speed is 1.5mL/h, the receiving distance is 15cm, and the temperature in the spinning chamber is 25 ℃. After the test is finished, collecting the hybrid nanofiber membrane (PVA/SiO)2/TiO2Hybrid nanofiber membrane) was dried in a vacuum oven at 80 ℃ for 2h to remove moisture and residual solvent in the hybrid nanofiber membrane.
② heat treatment process
PVA/SiO prepared by electrostatic spinning2/TiO2Putting the hybrid nanofiber membrane into an atmosphere furnace, setting the heating rate to be 5 ℃/min by taking nitrogen as inert protective gas, firstly heating to 500 ℃ for heat treatment for 2h, then heating to 800 ℃ for heat treatment for 3h, and then naturally cooling to room temperature.
③ homogeneous dispersion process
Adding the hybrid nanofiber membrane subjected to the heat treatment in the step two, ethyl orthosilicate, boric acid and aluminum chloride into water (deionized water) to obtain a to-be-dispersed solution, then adding a graphene oxide solution into the to-be-dispersed solution, and stirring at a high speed for 20min by using a high-speed shearing machine under the condition that the rotating speed is 10000r/min to obtain a homogeneous dispersion solution; the graphene oxide solution is a graphene oxide aqueous solution with the concentration of 20 g/L; the adding amount of the graphene oxide solution is 1% of the mass of the to-be-dispersed solution; the mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.53%, the mass fraction of the tetraethoxysilane contained in the liquid to be dispersed is 0.5%, the mass fraction of the boric acid contained in the liquid to be dispersed is 0.1%, the mass fraction of the aluminum chloride contained in the liquid to be dispersed is 0.15%, and the mass fraction of the water contained in the liquid to be dispersed is 98.72%.
Fourthly, freezing process: adding the homogeneous dispersion liquid into a mold with a fixed shape, wherein the top and the side of the mold are made of a material (polytetrafluoroethylene) with lower thermal conductivity, the bottom of the mold is made of a copper sheet with good thermal conductivity (higher thermal conductivity), and the sealed mold is placed in liquid nitrogen for 20min of freezing process.
A freeze drying process: and after the homogeneous dispersion liquid is completely frozen and molded, transferring the homogeneous dispersion liquid into a freeze dryer for vacuum freeze drying, wherein the freeze drying temperature is-70 ℃, the freeze drying time is 3d, and the vacuum degree of freeze drying is 5 Pa.
Sixthly, post-treatment process: and (4) carrying out post-treatment (pyrolysis) on the nanofiber aerogel material prepared in the fifth step for 5 hours at the temperature of 900 ℃ in an inert protective atmosphere (nitrogen), so as to stabilize the lap joint between the nanofibers and prepare the high-elasticity anti-radiation nanofiber aerogel material.
The performance test of the high-elasticity radiation-resistant nanofiber aerogel material in example 1 is carried out, and the results are shown in table 1.
The density of the high-elasticity radiation-resistant nanofiber aerogel material prepared in example 1 is 0.06g/cm3The porosity was 95%, the average nanofiber diameter was 200nm, the compression recovery was 90%, the linear shrinkage at 1100 ℃ was 0.5%, the thermal conductivity at room temperature was 0.030W/mK, and the thermal conductivity at 800 ℃ was 0.050W/mK.
The linear shrinkage of the high-elasticity radiation-resistant nanofiber aerogel material prepared in the embodiment is only 0.5% after the aerogel material is used at 1100 ℃ for 1200s, which shows that the aerogel material can resist the temperature of more than 1100 ℃. In particular, the linear shrinkage at 1100 ℃ in Table 1 of the present invention is the linear shrinkage results of the materials prepared in the examples and comparative examples after being used at 1100 ℃ for 1200 s; the higher the linear shrinkage of the material at 1100 ℃, the poorer the effect of the material on 1100 ℃ resistance.
Example 2
Example 2 is essentially the same as example 1, except that:
in the step I, the preparation of the TEOS composite hydrolysate comprises the following steps: at room temperature, take TEOS, H3PO4And deionized water as per n (teos): n (H)3PO4)：n(H2Mixing O) in a molar ratio of 1:0.02:10, and stirring for 12 hours on a magnetic stirrer to obtain hydrolysate; and then adding titanium dioxide nano powder into the hydrolysate to ensure that the titanium dioxide nano powder accounts for 1% of the mass of the hydrolysate, stirring for 6 hours, and performing ultrasonic treatment for 1 hour to uniformly disperse the titanium dioxide nano powder in the hydrolysate to obtain the TEOS composite hydrolysate.
The performance test of the high elasticity radiation resistant nanofiber aerogel material in example 2 is performed, and the results are shown in table 1.
Example 3
Example 3 is essentially the same as example 1, except that:
the homogeneous dispersion process comprises: adding the hybrid nanofiber membrane subjected to the heat treatment in the step two, tetraethoxysilane, boric acid and aluminum chloride into water to obtain a to-be-dispersed solution, and then stirring the to-be-dispersed solution at a high speed for 20min by using a high-speed shearing machine under the condition that the rotating speed is 10000r/min to obtain a homogeneous dispersion solution; the mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.53%, the mass fraction of the tetraethoxysilane contained in the liquid to be dispersed is 0.5%, the mass fraction of the boric acid contained in the liquid to be dispersed is 0.1%, the mass fraction of the aluminum chloride contained in the liquid to be dispersed is 0.15%, and the mass fraction of the water contained in the liquid to be dispersed is 98.72%.
The material obtained in example 3 was subjected to the performance test, and the results are shown in table 1.
Example 4
Example 4 is essentially the same as example 1, except that:
PVA/SiO produced without electrostatic spinning2/TiO2The hybrid nanofiber membrane was subjected to a heat treatment process, and directly subjected to the same homogeneous dispersion process, freezing process, freeze-drying process and post-treatment process as in example 1.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 5
Example 5 is essentially the same as example 1, except that:
in the third step, the liquid to be dispersed is stirred for 20min by a high-speed shearing machine under the condition that the rotating speed is 1000r/min, and homogeneous dispersion liquid is obtained.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 6
Example 6 is essentially the same as example 1, except that:
in the third step, the homogeneous dispersion process is as follows: adding the hybrid nanofiber membrane subjected to the heat treatment in the step two into water to obtain a to-be-dispersed solution; then adding a graphene oxide solution into the to-be-dispersed solution, and stirring for 20min by adopting a high-speed shearing machine under the condition that the rotating speed is 10000r/min to obtain a homogeneous dispersion solution; the graphene oxide solution is a graphene oxide aqueous solution with the concentration of 20 g/L; the using amount of the graphene oxide solution is 1% of the mass of the to-be-dispersed solution; the mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.53%, and the mass fraction of the water contained in the liquid to be dispersed is 99.47%.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 7
Example 7 is essentially the same as example 1, except that:
the fifth step is that the normal pressure drying process: and after the homogeneous dispersion liquid is completely frozen and molded, transferring the homogeneous dispersion liquid to dry for 144 hours at normal temperature and normal pressure.
The material prepared in this example was subjected to a performance test, the results of which are shown in table 1; the material produced in this example had substantially no rebound resilience, and the compression rebound resilience was considered to be 0.
Example 8
Example 8 is essentially the same as example 1, except that:
this example does not include the post-treatment process of step (c).
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 9
Example 9 is essentially the same as example 1, except that:
in the step I, the preparation of the TEOS composite hydrolysate: at room temperature, take TEOS, H3PO4And deionized water as per n (teos): n (H)3PO4)：n(H2Mixing O) in a molar ratio of 1:0.02:10 to obtain a mixed solution; and then adding titanium dioxide nano powder which accounts for 2 percent of the mass of the mixed solution into the mixed solution, and placing the mixed solution on a magnetic stirrer to continuously stir for 18 hours to obtain TEOS composite hydrolysate.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 10
Example 10 is essentially the same as example 1, except that:
in the step (I), preparing TEOS hydrolysate: at room temperature, take TEOS, H3PO4And deionized water as per n (teos): n (H)3PO4)：n(H2Mixing O) in a molar ratio of 1:0.02:10, and continuously stirring for 12 hours on a magnetic stirrer to obtain TEOS hydrolysate; in this example, the TEOS hydrolysate was used instead of the TEOS composite hydrolysate in example 1 for subsequent experiments.
Preparation of aqueous PVA solution: weighing polyvinyl alcohol powder, adding the polyvinyl alcohol powder into deionized water, heating and dissolving at 80 ℃, and stirring for 5 hours; taking out after stirring, placing on a magnetic stirrer, stirring at room temperature, and cooling to room temperature; the mass fraction of the prepared PVA aqueous solution is 10 wt%.
The preparation of the precursor solution for electrospinning was: mixing TEOS hydrolysate, PVA aqueous solution and deionized water according to the mass ratio of 3:3:2 to obtain mixed solution; then adding titanium dioxide nano powder which accounts for 5 percent of the mixed solution in mass into the mixed solution, and then placing the mixed solution on a magnetic stirrer at room temperature for stirring for 4 hours to obtain a uniform and clear precursor solution.
Extracting the precursor solution by an injector to be used as electrostatic spinning solution, and preparing PVA/SiO by using an electrostatic spinning machine2/TiO2A hybrid nanofiber membrane. The technological parameters of electrostatic spinning are that the voltage is 20kV, the perfusion speed is 1.5mL/h, the receiving distance is 15cm, and the temperature in the spinning chamber is 25 ℃. After the test is finished, collecting the hybrid nanofiber membrane (PVA/SiO)2/TiO2Hybrid nanofiber membrane) was dried in a vacuum oven at 80 ℃ for 2h to remove moisture and residual solvent in the hybrid nanofiber membrane.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 11
Example 11 is essentially the same as example 1, except that:
in the step I, the preparation of the TEOS composite hydrolysate comprises the following steps: at room temperature, take TEOS, H3PO4And deionized water as per n (teos): n (H)3PO4)：n(H2Mixing O) in a molar ratio of 1:0.02:10, and stirring for 12 hours on a magnetic stirrer to obtain hydrolysate; and then adding titanium dioxide nano powder into the hydrolysate to ensure that the titanium dioxide nano powder accounts for 4% of the mass of the hydrolysate, stirring for 6h, and performing ultrasonic treatment for 1h to uniformly disperse the titanium dioxide nano powder in the hydrolysate to obtain the TEOS composite hydrolysate.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 12
Example 12 is essentially the same as example 1, except that:
the heat treatment process of the second step is as follows: PVA/SiO prepared by electrostatic spinning2/TiO2Putting the hybrid nanofiber membrane into an atmosphere furnace, setting the heating rate to be 5 ℃/min by taking the inert protective gas as nitrogen, heating to 500 ℃ for heat treatment for 5h, and then naturally cooling to room temperature.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 13
Example 13 is essentially the same as example 1, except that:
in the step (I), the preparation of the TEOS hydrolysate comprises the following steps: at room temperature, take TEOS, H3PO4And deionized water as per n (teos): n (H)3PO4)：n(H2Mixing O) in a molar ratio of 1:0.02:10, and continuously stirring for 12 hours on a magnetic stirrer to obtain TEOS hydrolysate; in the subsequent steps, TEOS hydrolysate is used to replace the TEOS composite hydrolysate in example 1 for experiment.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Example 14
Example 14 is essentially the same as example 1, except that:
the homogeneous dispersion process comprises: adding the hybrid nanofiber membrane subjected to the heat treatment in the step two, ethyl orthosilicate, boric acid and aluminum chloride into water to obtain a to-be-dispersed solution, then adding a graphene oxide solution into the to-be-dispersed solution, and stirring at a high speed for 20min by using a high-speed shearing machine under the condition that the rotating speed is 10000r/min to obtain a homogeneous dispersion solution; the graphene oxide solution is a graphene oxide aqueous solution with the concentration of 20 g/L; the addition amount of the graphene oxide solution is 4% of the mass of the to-be-dispersed solution; the mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.53%, the mass fraction of the tetraethoxysilane contained in the liquid to be dispersed is 0.5%, the mass fraction of the boric acid contained in the liquid to be dispersed is 0.1%, the mass fraction of the aluminum chloride contained in the liquid to be dispersed is 0.15%, and the mass fraction of the water contained in the liquid to be dispersed is 98.72%.
The material obtained in this example was subjected to a performance test, and the results are shown in table 1.
Comparative example 1
Preparing a nanofiber membrane: heating, stirring and dissolving polyvinyl alcohol and tetraethoxysilane in deionized water at 80 ℃ to obtain a precursor solution; the molar ratio of the ethyl orthosilicate to the water is 1: 20; the mass fraction of polyvinyl alcohol contained in the precursor solution is 10%. And extracting the precursor solution by using an injector to obtain an electrostatic spinning solution, and preparing the nanofiber membrane by using an electrostatic spinning machine. The technological parameters of electrostatic spinning are that the voltage is 20kV, the perfusion speed is 1.5mL/h, the receiving distance is 15cm, and the temperature in the spinning chamber is 25 ℃. And after the test is finished, collecting the nanofiber membrane, and drying the nanofiber membrane in a vacuum drying oven at 80 ℃ for 2h to remove water and residual solvent in the nanofiber membrane.
② heat treatment process
And (3) putting the nanofiber membrane prepared by electrostatic spinning into a muffle furnace, setting the heating rate to be 5 ℃/min, raising the temperature to 500 ℃, carrying out heat treatment for 5h, and then naturally cooling to room temperature.
③ homogeneous dispersion process
Collecting the nanofiber membrane subjected to heat treatment in the step three, adding the nanofiber membrane into deionized water to obtain a to-be-dispersed solution, and stirring the to-be-dispersed solution for 20min by adopting a high-speed shearing machine under the condition that the rotating speed is 10000r/min to obtain a homogeneous dispersion solution; the mass fraction of the nanofiber membrane contained in the liquid to be dispersed was 0.53%.
Fourthly, freezing process: adding the homogeneous dispersion liquid into a mold with a fixed shape, wherein the top and the side of the mold are made of a material (polytetrafluoroethylene) with lower thermal conductivity, the bottom of the mold is made of a copper sheet with good thermal conductivity (higher thermal conductivity), and the sealed mold is placed in liquid nitrogen for 20min of freezing process.
A freeze drying process: and after the homogeneous dispersion liquid is completely frozen and molded, transferring the homogeneous dispersion liquid into a freeze dryer for vacuum freeze drying, wherein the freeze drying temperature is-70 ℃, the freeze drying time is 3d, and the vacuum degree of freeze drying is 5 Pa.
Sixthly, post-treatment process: and (4) carrying out post-treatment (cracking) on the material obtained in the step (sixthly) for 5 hours at the temperature of 900 ℃ in an inert protective atmosphere (nitrogen).
The material obtained in this comparative example was subjected to a performance test, and the results are shown in Table 1.
Comparative example 2
Comparative example 2 is substantially the same as comparative example 1 except that:
in the first step, polyvinyl alcohol, tetraethoxysilane and titanium dioxide nano powder are heated and stirred at 80 ℃ and uniformly dispersed in deionized water to obtain a precursor solution in which the polyvinyl alcohol and the titanium dioxide nano powder are dissolved; the molar ratio of the ethyl orthosilicate to the water is 1: 20; the mass fraction of polyvinyl alcohol contained in the precursor solution is 10%; the mass fraction of the titanium dioxide nano powder contained in the precursor solution is 2%. And extracting the precursor solution by using an injector to obtain an electrostatic spinning solution, and preparing the nanofiber membrane by using an electrostatic spinning machine. The technological parameters of electrostatic spinning are that the voltage is 20kV, the perfusion speed is 1.5mL/h, the receiving distance is 15cm, and the temperature in the spinning chamber is 25 ℃. And after the test is finished, collecting the nanofiber membrane, and drying the nanofiber membrane in a vacuum drying oven at 80 ℃ for 2h to remove water and residual solvent in the nanofiber membrane.
The material obtained in this comparative example was subjected to a performance test, and the results are shown in Table 1.
Figure BDA0003274360290000221
Figure BDA0003274360290000231
In particular, the symbol "-" in Table 1 indicates that the performance index was not tested.
The invention has not been described in detail and is in part known to those of skill in the art.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a high-elasticity radiation-resistant nanofiber aerogel material is characterized by comprising the following steps:
(1) uniformly mixing tetraethoxysilane, phosphoric acid and water to obtain a mixed solution, stirring the mixed solution for 1-24 hours to obtain a hydrolysate, adding titanium dioxide nano powder into the hydrolysate, continuously stirring for 1-12 hours, and finally performing ultrasonic treatment for 0.5-2 hours to obtain a composite hydrolysate;
(2) uniformly mixing a polyvinyl alcohol aqueous solution and the composite hydrolysate obtained in the step (1) with water, stirring for 1-12 hours to obtain a precursor solution, and then performing electrostatic spinning by using the precursor solution as an electrostatic spinning solution to obtain a hybrid nanofiber membrane;
(3) carrying out heat treatment on the hybrid nanofiber membrane obtained in the step (2) in an inert atmosphere; the heat treatment comprises the following steps: firstly, carrying out heat treatment at 300-600 ℃ for 1-10 h, then carrying out heat treatment at 600-900 ℃ for 1-5 h, and then naturally cooling to room temperature;
(4) adding the hybrid nanofiber membrane subjected to heat treatment in the step (3), ethyl orthosilicate, boric acid and aluminum chloride into water to obtain a to-be-dispersed solution, and then adding a graphene oxide solution into the to-be-dispersed solution and stirring at a high speed to obtain a homogeneous phase dispersed solution;
(5) sequentially freezing and freeze-drying the homogeneous dispersion liquid obtained in the step (4) to obtain a nanofiber aerogel material;
(6) and (5) carrying out post-treatment on the nanofiber aerogel material obtained in the step (5) in an inert atmosphere to obtain the high-elasticity anti-radiation nanofiber aerogel material.
2. The production method according to claim 1, wherein in step (1):
the molar ratio of the ethyl orthosilicate to the phosphoric acid to the water is (0.5-1): (0.005-0.05): (1 to 20), preferably 1: (0.015 to 0.025): (8-15), more preferably 1:0.02: 10; and/or
The amount of the titanium dioxide nano powder is 0.4-10% of the mass of the hydrolysate, preferably 0.5-5%, and more preferably 0.8-2.5%.
3. The production method according to claim 1, wherein in step (2):
the mass fraction of polyvinyl alcohol contained in the polyvinyl alcohol aqueous solution is 1-20%;
the mass ratio of the composite hydrolysate to the polyvinyl alcohol aqueous solution to the water is (1-5): (1-5): (0.5 to 5), preferably (2.5 to 3.5): (2.5-3.5): 2, more preferably 3:3: 2; and/or
The stirring time is 3-6 h.
4. The method of claim 1, wherein the electrospinning is carried out with the following parameters:
the voltage is 10-30 kV, the filling speed is 0.5-2 mL/h, the receiving distance is 10-25 cm, and/or the temperature in the spinning room is 15-35 ℃.
5. The method of claim 1, wherein:
in the step (2), the obtained hybrid nanofiber membrane is also subjected to vacuum drying; preferably, the obtained hybrid nanofiber membrane is dried in a vacuum drying oven at 60-120 ℃ for 1-3 h.
6. The production method according to claim 1, wherein in step (4):
the graphene oxide solution is a graphene oxide aqueous solution with the concentration of 15-25 g/L; the amount of the graphene oxide solution is 0.5-2% of the mass of the to-be-dispersed solution; and/or
The mass fraction of the hybrid nanofiber membrane contained in the liquid to be dispersed is 0.4-0.6%, the mass fraction of ethyl orthosilicate contained in the liquid to be dispersed is 0.4-0.6%, the mass fraction of boric acid contained in the liquid to be dispersed is 0.05-0.2%, and the mass fraction of aluminum chloride contained in the liquid to be dispersed is 0.1-0.3%.
7. The production method according to claim 1, wherein in step (4):
the rotating speed of the high-speed stirring is 5000-20000 r/min, and the time of the high-speed stirring is 5-30 min.
8. The production method according to claim 1, wherein in step (5):
the freezing is performed for 10-60 min under liquid nitrogen;
the freezing is carried out in a mould, the top and the side surfaces of the mould are made of materials with lower heat conductivity, the bottom of the mould is made of materials with higher heat conductivity, preferably, the top and the side surfaces of the mould are made of polytetrafluoroethylene, and the bottom of the mould is made of copper materials; and/or
The freeze drying is vacuum freeze drying, preferably the vacuum freeze drying is carried out for 2-5 d under the conditions that the vacuum degree is 0.5-10 Pa and the temperature is-50 to-70 ℃.
9. The production method according to claim 1, wherein in step (6):
the temperature of the post-treatment is 800-1000 ℃, and the time of the post-treatment is 0.1-12 h.
10. The high-elasticity radiation-resistant nanofiber aerogel material prepared by the preparation method of any one of claims 1 to 9.
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