CN113308764A - Silicon-based ceramic micro-nanofiber heat insulation felt and preparation method thereof - Google Patents
Silicon-based ceramic micro-nanofiber heat insulation felt and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon-based ceramic micro-nanofiber heat insulation felt and a preparation method thereof, wherein the preparation method comprises the following steps: preparing a raw material mixed solution, wherein the raw material mixed solution comprises an organic salt, a high molecular polymer and a solvent; spinning the raw material mixed solution into a silicon-based ceramic micro-nano fiber material precursor by using a centrifugal spinning device; collecting silicon-based ceramic micro-nanofiber material precursors, and stacking to form a felt state to obtain a silicon-based ceramic micro-nanofiber felt precursor; and sintering the silicon-based ceramic micro-nanofiber felt precursor at a high temperature to obtain the silicon-based ceramic micro-nanofiber heat insulation felt. The silicon-based ceramic micro-nanofiber heat insulation felt prepared by the method has the characteristics of low density, high temperature resistance and the like, and can be used in the field of heat preservation and heat insulation.
Description
Technical Field
The invention relates to the field of material science and engineering, and mainly relates to a silicon-based ceramic micro-nanofiber heat-insulation felt and a preparation method thereof.
Background
Heat insulating materials used in the construction field are classified into inorganic heat insulating materials and organic heat insulating materials. The organic heat-insulating material has poor high-heat resistance, can be decomposed when exposed to open fire, releases a large amount of heat and toxic gases, and can emit harmful gases such as formaldehyde and the like in the application process. Compared with an organic heat-insulating material, the inorganic heat-insulating material has strong high-temperature resistance and relatively stable thermochemical property. Organic insulation materials are being gradually replaced by inorganic insulation materials for safe production life and environmental protection. Common inorganic heat-insulating materials in the market at present, such as short fiber materials of rock wool, glass wool, aluminum silicate fiber, asbestos and the like, the diameters of the cross sections of the fibers are only micron-sized, organic binders such as phenolic resin or urea resin and the like are required to be added, and then the heat setting is carried out to prepare the heat-insulating material.
The inorganic heat insulating materials in the market at present generally have the following problems: 1. the short fiber material must be added with organic binder, and the mechanical strength of the short fiber material is enhanced by heat setting; 2. resin organic binders contained in the material can release gases such as formaldehyde and the like, so that the health of human bodies is harmed; 3. the organic binder contained in the material is decomposed when meeting high temperature or open fire (fire and other conditions), and simultaneously releases a large amount of heat and toxic gas; 4. after the binder in the material is decomposed, the material becomes loose and is easy to fall off, which is not beneficial to safe production and life; 5. the short-fiber heat-insulating material produced at present needs to be treated by a short-cut and elastic loosening process, and the manufacturing process is complicated; 6. the fiber heat-insulating material with the micron-sized cross section diameter has high density and low porosity, so that the material has high heat conductivity and poor heat-insulating effect.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a silicon-based ceramic micro-nanofiber heat insulation felt and a preparation method thereof, and aims to solve the problem that the existing inorganic heat insulation material needs a binder.
The technical scheme of the invention is as follows:
a preparation method of a silicon-based ceramic micro-nanofiber heat insulation felt comprises the following steps:
the method comprises the following steps: preparing a raw material mixed solution, wherein the raw material mixed solution comprises an organic salt, a high molecular polymer and a solvent;
step two: spinning the raw material mixed solution into a silicon-based ceramic micro-nano fiber material precursor by using a centrifugal spinning device;
step three: collecting silicon-based ceramic micro-nanofiber material precursors, and stacking to form a felt state to obtain a silicon-based ceramic micro-nanofiber felt precursor;
step four: and sintering the silicon-based ceramic micro-nanofiber felt precursor at a high temperature to obtain the silicon-based ceramic micro-nanofiber heat insulation felt.
The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt comprises the steps that organic salt is tetraethyl silicate and at least one of tin tetrachloride or tetrabutyl titanate, and the mass ratio of the tetraethyl silicate to the tin tetrachloride or tetrabutyl titanate is 1: 0.2-0.5.
The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt is characterized in that the mass ratio of organic salt to solvent in a raw material mixed solution is 1.2-3: 5-11; the high molecular polymer accounts for 6-30% of the total weight of the raw material mixed solution.
The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt comprises the following steps of mixing a raw material mixed solution with a nano graphene oxide sheet and liquid sodium silicate; the nano graphene oxide sheet accounts for 3-5% of the weight of the organic salt, and the liquid sodium silicate accounts for 2-3% of the weight of the organic salt.
The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt is characterized in that acetic acid is further included in the raw material mixed solution, and the mass ratio of organic salt to acetic acid is 1.2-3: 0.01.
the preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt is characterized in that the high polymer adopts at least one of PEO, PVA and PAN; the solvent is at least one of water, absolute ethyl alcohol, acetonitrile, acetone and dimethyl amide.
The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt comprises the steps that in the spinning process of the centrifugal spinning device, the electromechanical rotating speed is set to 4000 plus 10000 rpm, the aperture of the fine-hole needle head is 0.1-0.4 mm, and the collection distance of the collection device is 30-50 cm.
The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt is characterized in that the stacking mode can be winding stacking or zigzag stacking.
The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt comprises the following steps of heating the temperature from 50 ℃ to 1000 ℃ at a heating rate of 2 ℃/min, keeping the temperature in an environment of 1000 ℃ for sintering for 1h, and then cooling the temperature from 1000 ℃ to 50 ℃ at a cooling rate of 5 ℃/min.
The silicon-based ceramic micro-nanofiber heat insulation felt is prepared by the preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt.
Has the advantages that: the preparation method of the silicon-based ceramic micro-nanofiber heat-insulation felt provided by the invention has the characteristics of high speed, high efficiency, environmental friendliness, energy conservation, low cost, easiness for large-scale industrial production and the like, and overcomes the defects of difficulty in preparation, low yield, high energy consumption, large raw material demand and the like in the prior art. Moreover, the silicon-based ceramic micro-nanofiber heat insulation felt prepared by the method has the characteristics of low density, high temperature resistance and the like, and can be used in the field of heat preservation and heat insulation.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a silicon-based ceramic micro-nanofiber felt.
Fig. 2 is a schematic diagram of a process for preparing a precursor of the silicon-based ceramic micro-nanofiber felt through a silicon-based ceramic micro-nanofiber felt raw material solution in the invention.
Fig. 3 is a real object diagram of the single-layer silicon-based ceramic micro-nanofiber according to the embodiment of the invention.
Fig. 4 is an SEM image of the silicon-based ceramic micro-nanofiber precursor of embodiment 1 of the present invention.
Fig. 5 is a real object diagram of a silica-based ceramic micro-nanofiber felt precursor in embodiment 1 of the present invention.
Fig. 6 is a real object diagram of the silicon-based ceramic micro-nanofiber felt in embodiment 1 of the present invention.
Fig. 7 is an SEM image of the silicon-based ceramic micro-nanofiber according to embodiment 1 of the present invention.
Detailed Description
The invention provides a silicon-based ceramic micro-nanofiber heat insulation felt and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The centrifugal spinning method has the advantages of high yield, low energy consumption, low cost, wide application range and the like as a method for preparing the micro-nano fibers, and is easy to realize industrial production. At present, the raw materials for preparing the micro-nano fibers by a centrifugal spinning method mainly focus on the aspects of high molecular polymers, metal materials, carbon materials and the like, and are mainly used in the fields of biological medicines, nano sensors, environmental pollution treatment and the like. The micro-nano fiber material prepared by the centrifugal spinning method has the characteristics of fluffiness, porosity, ultralight weight and the like, and naturally meets the physical structure characteristics of super heat-insulating materials. Based on the structural characteristics of the micro-nano fiber material prepared by the centrifugal spinning method, through intensive research, the inventor finds that a silicon-based ceramic micro-nano fiber material precursor can be prepared by utilizing a centrifugal spinning technology, the precursor is stacked to form a silicon-based ceramic micro-nano fiber precursor material in a felt state, and a three-dimensional elastic felt consisting of silicon-based ceramic micro-nano fibers is obtained through high-temperature calcination.
Specifically, as shown in fig. 1, the invention provides a preparation method of a silicon-based ceramic micro-nanofiber heat insulation felt, which comprises the following steps:
the method comprises the following steps: preparing a raw material mixed solution, wherein the raw material mixed solution comprises an organic salt, a high molecular polymer and a solvent.
In the step, organic salt corresponding to the silicon-based ceramic micro-nanofiber heat insulation felt needs to be prepared into a spinnable mixed solution. In the process of preparing the solution, a proper solvent is required to be selected to dissolve the organic salt; meanwhile, high molecular polymers are required to be added, and the viscosity of the mixed solution is increased, so that the solution has spinnability; in addition, if necessary, a solvent such as a surfactant is added to improve the built-in property of the mixed solution. In a preferred embodiment of the invention, the raw material mixed solution further comprises acetic acid, and the mass ratio of the organic salt to the acetic acid is 1.2-3: 0.01, acetic acid is used as an organic salt catalyst and a colloid stabilizer, so that the liquid organic salt in the raw material mixed solution can be fully hydrolyzed and is uniformly mixed with the high molecular polymer solution, thereby improving the spinnability of the solution.
Wherein the organic salt can be tetraethyl silicate plus at least one of tin tetrachloride or tetrabutyl titanate. In the scheme of the preferred embodiment of the invention, the mass ratio of the tetraethyl silicate to the tin tetrachloride or the tetrabutyl titanate is 1: 0.2-0.5. The method is characterized in that a mixed solution of tetraethyl silicate and tin tetrachloride or tetraethyl silicate and tetrabutyl titanate organic salt is centrifugally spun and stacked into a felt and then calcined, and the obtained silicon-based ceramic micro-nanofiber felt is of a three-dimensional structure and has the characteristics of high temperature resistance, good elasticity, firm and stable felt fiber structure, low probability of breakage, no powder falling and the like.
In the invention, the solution is spun into the fiber by using a centrifugal spinning device only if the silicon-based ceramic micro-nano fiber felt raw material mixed solution has good spinnability, so that a high molecular polymer needs to be added into the raw material mixed solution to ensure that the raw material mixed solution has spinnability. In the embodiment of the present invention, the high molecular polymer to be used is not limited as long as it can make the raw material mixed solution spinnable. In some embodiments of the present invention, the high molecular polymer may be at least one of PEO, PVA, and PAN. After the high molecular polymer is added, the raw material mixed solution has certain viscosity and spinnability, so that the subsequent steps can be favorably carried out, and the silicon-based ceramic micro-nanofiber with excellent performance is collected.
In the present invention, it is necessary to select an appropriate solvent to dissolve the organic salt and the high molecular polymer in the raw material mixed solution, so that a sufficiently soluble raw material mixed solution having spinnability can be obtained. According to the embodiment of the present invention, the kind of the solvent used is not particularly limited, and those skilled in the art can select and formulate the solvent according to actual needs. In the embodiment of the present invention, the solvent may use at least one of water, absolute ethanol, acetonitrile, acetone, and dimethyl formamide (DMF) as a solvent to promote complete dissolution of different solutes in the mixed solution. In the present invention, the content and kind of the solvent in the raw material mixed solution are not particularly limited as long as the spinnability requirement can be satisfied. The solvent used in the embodiment of the present invention preferably has a certain volatility, so that the mixed solution can be rapidly volatilized during the process of preparing the fiber through centrifugal spinning, thereby obtaining the solid fiber.
In the scheme of the invention, the concentration of the solute in the raw material mixed solution is not particularly limited as long as the spinnability requirement can be met, and a person skilled in the art can flexibly select the solute according to the actual requirement. In the embodiment of the present invention, the mass percentage of the organic salt in the raw material mixed solution is generally not more than 40%, and the mass percentage of the high molecular polymer is generally not more than 35%.
Preferably, the mass ratio of the organic salt to the solvent in the raw material mixed solution is 1.2-3: 5-11; the high molecular polymer accounts for 6-30% of the total weight of the raw material mixed solution.
Furthermore, the raw material mixed solution further comprises nano graphene oxide sheets and liquid sodium silicate; the nano graphene oxide sheet accounts for 3-5% of the weight of the organic salt, and the liquid sodium silicate accounts for 2-3% of the weight of the organic salt. The nano graphene oxide sheets are added into the raw material mixed solution, and the nano graphene oxide sheets can become graphene fibers and are distributed in the felt fiber structure after spinning and sintering, so that the toughness and the strength of the heat-insulating felt are greatly improved, the brittleness and the stability of the heat-insulating felt are further improved, the felt fiber network is complete, the heat-insulating felt is flexible, and powder falling is avoided.
In the scheme of the invention, the raw material mixed solution can be obtained by uniformly stirring the added solvent and solute by means of mechanical stirring, magnetic stirring, ultrasound and the like, and the preparation and the addition of the raw material mixed solution are not particularly limited.
Step two: and spinning the raw material mixed solution into a precursor of the silicon-based ceramic micro-nano fiber material by using a centrifugal spinning device.
In this step, the raw material mixed solution is poured into a liquid storage tank 1 of a centrifugal spinning apparatus, the liquid storage tank is driven by a motor to rotate at a high speed to generate a huge centrifugal force, and the mixed solution is driven by the centrifugal force to eject solution filaments 3 through a fine needle 2 installed on the liquid storage tank and is drawn to form fibers 4 which are collected by a collector 5, as shown in fig. 2. Compared with the existing fiber preparation methods such as an electrostatic spinning method, a chemical liquid phase method, an air flow spinning method, a template method and the like, the centrifugal spinning method used in the invention has the advantages of high production efficiency, high solvent utilization rate, low energy consumption, good safety and the like, and is easy to realize industrial production.
In the scheme of the invention, the process of spinning the raw material mixed solution into the precursor of the silicon-based ceramic micro-nano fiber material by using the centrifugal spinning device can be specifically divided into three stages: stage one, an initial stage of solution yarn formation; stage two, solution silk stretching stage; and a third stage of solvent volatilization. And in the first stage, under the drive of centrifugal force, the solution flows from the central position of the liquid storage tank to the direction of normal force, rapidly enters the fine-hole needle head, and is sprayed out from a spinning nozzle of the needle head under the action of the centrifugal force, solution viscosity, solution surface tension and the like in the fine-hole needle head. And in the second stage, the sprayed solution filaments can rotate together with the liquid storage tank rotating at a high speed to form huge drawing force on the solution filaments. The solution yarn continuously flies out beyond the normal force direction under the common action of the stretching force, the inertia force, the air resistance and the elastic viscous force, and is rapidly stretched by the common force, so that the solution yarn is rapidly thinned. And step three, after the solution yarn is stretched and rapidly thinned, the specific surface area of the solution yarn is greatly increased, so that the volatilization rate of the solvent is rapidly increased, and after the solvent is volatilized, the solid micro-nano fiber is finally formed, referring to fig. 3 and 4.
In the scheme of the present invention, the specific type of the motor used in the centrifugal spinning device is not particularly limited, as long as it can provide sufficient rotation speed to drive the liquid storage tank to rotate at high speed, and details are not repeated herein. The range of the electromechanical rotating speed is generally 4000-10000 rpm, and in order to obtain the silicon-based ceramic micro-nanofiber material precursor with uniform and continuous fiber diameter distribution, the rotating speed of the motor needs to be continuously stabilized at a certain fixed value within the rotating speed range. The rotating speed value of the control motor can be matched with the viscosity of the solution, the shape of the needle head and the like, so that the solution yarn can be uniformly and stably sprayed out to form the micro-nano fiber.
In the scheme of the invention, the type, length, aperture size and cross-sectional shape of the fine-hole needle arranged on the liquid storage tank are not particularly limited as long as the solution filaments can be sprayed out from the spinning nozzle of the needle. In the scheme of the invention, the fine-hole needle can be a sharp-mouth needle, a flat-mouth needle or an elbow needle and the like, and the fine-hole needle can be selected by a person skilled in the art according to actual conditions. In the embodiment of the invention, the pore diameter of the fine-pore needle head is 0.1-0.4 mm, so that the diameter of the section of the initial elastic solution yarn sprayed by the spinnable solution is small enough, and finally, the micro-nano-grade superfine fiber can be obtained.
The collecting distance of the collecting device is 30-50 cm. The collecting distance is the distance between the fine-hole needle head and the collector, and the advantage of the collecting distance is that enough time is provided for volatilizing the solvent in the sprayed elastic solution thread, and the dried solid micro-nano fiber material is collected. If the solvent is not volatilized completely, the collected solution is still the solution, and finally a film is formed instead of the solid micro-nano fiber.
In the scheme of the invention, after the raw material mixed solution is injected into the liquid storage tank, the supply rate of the solution is influenced by the rotation speed of the motor, the viscosity of the solution, the aperture size of the fine-hole needle head and other factors. Generally, the solution supply rate can reach more than 1mL/min, and a person skilled in the art can judge that the solution supply rate of the centrifugal spinning method is much higher than that of the electrostatic spinning method and the air spinning method, so that the production efficiency of the centrifugal spinning method for preparing the micro-nanofibers is high, and the industrial production is easier to realize.
In the scheme of the invention, the shape of the collector for collecting the silicon-based ceramic micro-nanofiber material precursor is not particularly limited, and a person skilled in the art can select the shape and the structure of the collector according to actual requirements.
Step three: and stacking the collected silicon-based ceramic micro-nanofiber material precursors to form a felt state, so as to obtain the silicon-based ceramic micro-nanofiber felt precursor.
In the step, the collected single-layer silicon-based ceramic micro-nanofiber material precursors shown in fig. 3 are stacked to form a felt state (shown in fig. 5), so that the silicon-based ceramic micro-nanofiber felt precursors are obtained.
The stacking manner may be a winding stack or a zigzag stack, etc. Preferably, in the scheme of the invention, the winding and stacking mode is adopted, so that the overall structural stability of the felt can be improved, and the felts with different densities can be obtained by controlling the winding speed, so that the pressing and shaping process flow is omitted.
According to the scheme of the invention, the single-layer silicon-based ceramic micro-nanofiber material precursor is subjected to stacking processing before sintering, so that the overall structure of the obtained silicon-based ceramic micro-nanofiber felt precursor is facilitated, the overall structure of the felt formed by stacking after sintering is more stable, and the phenomenon that the whole layer of fibers fall off is not easy to occur.
Step four: and sintering the silicon-based ceramic micro-nanofiber felt precursor at a high temperature to obtain the silicon-based ceramic micro-nanofiber heat insulation felt.
In the step, the silicon-based ceramic micro-nanofiber felt precursor is moved to a tube furnace for sintering, in the sintering process, the high molecular polymer is removed, organic salt is calcined at high temperature to generate oxidation reaction, and the oxidation reaction is converted into silicon-based oxide, so that the silicon-based ceramic micro-nanofiber felt is obtained, and reference is made to fig. 6 and 7.
In the scheme of the invention, the sintering temperature, time, heating rate and cooling rate are not particularly limited, and for the mass percentages of different organic salts and high molecular polymers, a person skilled in the art can adjust the sintering temperature, time, heating rate and cooling rate according to actual conditions, as long as the high molecular polymers can be completely removed and the organic salts can be completely converted into the silicon-based ceramic fiber material. In the scheme of the embodiment of the invention, the sintering temperature can be increased from 50 ℃ to 1000 ℃ at the temperature increase rate of 2 ℃/min, the sintering is kept for 1h at the environment of 1000 ℃, and then the temperature is reduced from 1000 ℃ to 50 ℃ at the temperature reduction rate of 5 ℃/min, so that the ultralight silicon-based ceramic micro-nano fiber heat-insulating felt with elastic performance is finally obtained.
The invention also provides the silicon-based ceramic micro-nanofiber heat insulation felt which is prepared by the preparation method.
In summary, in the first aspect, the invention provides a preparation method of a silicon-based ceramic micro-nanofiber heat insulation felt, which can be used for producing reboundable, ultra-light, high-temperature-resistant, non-fragile and low-cost silicon-based ceramic micro-nanofiber heat insulation materials in batches. The preparation method has the characteristics of high efficiency, low energy consumption, simple operation and the like, and has the potential of industrial mass production. In a second aspect, the invention provides a silicon-based ceramic micro-nanofiber heat insulation felt. The silicon-based ceramic micro-nanofiber heat insulation felt is prepared by the method. The silicon-based ceramic micro-nanofiber heat insulation felt has a three-dimensional structure with low density, high temperature resistance, resilience and other performances, and is suitable for multiple fields including building heat insulation.
The following examples of the present invention are described in detail, and specific techniques or conditions not specified in the examples are performed according to technical conditions described in documents in the art or according to product specifications. The materials and instruments used in the examples are not indicated by the manufacturer, and are conventional products available on the market.
Example 1
In this embodiment, the specific preparation method is as follows: firstly, preparing a raw material mixed solution, uniformly mixing tetraethyl silicate, tetrabutyl titanate, water and acetic acid in a sealed bottle according to the mass ratio of 1:0.5:9:0.01, adding PEO powder particles into the uniformly mixed solution, continuously sealing and stirring for 8 hours, wherein the mass percentage of PEO in the raw material mixed solution is 6%, and then adding nano graphene oxide sheets and liquid sodium silicate, wherein the nano graphene oxide sheets account for 3% of the weight of organic salt, and the liquid sodium silicate accounts for 2% of the weight of the organic salt. A certain amount of uniform raw material mixed solution is extracted and injected into a liquid storage tank, the rotating speed of a motor is controlled to 4000 rpm, the solution is sprayed out from a fine needle head arranged on the liquid storage tank by utilizing the centrifugal force generated by the high-speed rotation of the liquid storage tank, the sprayed solution is rapidly stretched in the air to form a viscous solution yarn, the solvent in the solution yarn is rapidly volatilized to form micro-nano fibers, the micro-nano fibers are collected on a collecting column which is 35cm away from a needle head nozzle, and the micro-nano fibers are mutually wound and stacked to form a layered felt precursor, as shown in figures 3 and 4. And finally, putting the collected silicon-based organic salt/PEO micro-nano fiber felt precursor into a tube furnace for sintering, heating to 1000 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1 hour at the temperature of 1000 ℃, and then cooling to 50 ℃ at the cooling rate of 10 ℃/min. The material obtained after sintering is a silicon-based ceramic micro-nanofiber felt as shown in fig. 6 and 7.
The thermal conductivity of the finally obtained silicon-based ceramic micro-nanofiber felt material is as follows: 0.026-0.036 (W/m.K), density: 21-116mg/cm3The maximum compression set is 90%.
Example 2
In this embodiment, the specific preparation method is as follows: firstly, preparing a raw material mixed solution, uniformly mixing tetraethyl silicate, stannic chloride, water and acetic acid in a sealed bottle according to the mass ratio of 1:0.3:11:0.01, adding PEO powder particles into the uniformly mixed solution, continuously sealing and stirring for 8 hours, adding nano graphene oxide sheets and liquid sodium silicate, wherein the nano graphene oxide sheets account for 4% of the weight of organic salt, and the liquid sodium silicate accounts for 3% of the weight of the organic salt. A certain amount of uniform raw material mixed solution is extracted and injected into a liquid storage tank, the rotating speed of a motor is controlled to 8000rpm, the solution is sprayed out from a fine needle head arranged on the liquid storage tank by utilizing the centrifugal force generated by the high-speed rotation of the liquid storage tank, the sprayed solution is rapidly stretched in the air to form a viscous solution yarn, the solvent in the solution yarn is rapidly volatilized to form micro-nano fibers, and the micro-nano fibers are collected on a collecting column which is 50cm away from a needle head nozzle, and are mutually wound and stacked to form a layered felt precursor. And finally, putting the collected silicon-based organic salt/PEO micro-nano fiber felt precursor into a tube furnace for sintering, heating to 1000 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1 hour at the temperature of 1000 ℃, and then cooling to 50 ℃ at the cooling rate of 10 ℃/min. The material obtained after sintering is a silicon-based ceramic micro-nanofiber felt.
The thermal conductivity of the finally obtained silicon-based ceramic micro-nanofiber felt material is as follows: 0.026-0.036 (W/m.K), density: 21-116mg/cm3The maximum compression set is 90%.
Example 3
In this embodiment, the specific preparation method is as follows: firstly, preparing a raw material mixed solution, uniformly mixing tetraethyl silicate, water, ethanol and acetic acid in a sealed bottle according to the mass ratio of 1:0.2:11:1:0.01, then adding PVA powder particles into the uniformly mixed solution, and continuously stirring in a sealed manner for 2 hours in a water bath condition at 80 ℃, wherein the mass percentage of PVA in the raw material mixed solution is 30%, and then adding nano graphene oxide sheets and liquid sodium silicate, the nano graphene oxide sheets account for 4% of the weight of organic salt, and the liquid sodium silicate accounts for 5% of the weight of the organic salt. A certain amount of uniform raw material mixed solution is extracted and injected into a liquid storage tank, the rotating speed of a motor is controlled to 8000rpm, the solution is sprayed out from a fine needle head arranged on the liquid storage tank by utilizing the centrifugal force generated by the high-speed rotation of the liquid storage tank, the sprayed solution is rapidly stretched in the air to form a viscous solution yarn, the solvent in the solution yarn is rapidly volatilized to form micro-nano fibers, and the micro-nano fibers are collected on a collecting column which is 50cm away from a needle head nozzle, and are mutually wound and stacked to form a layered felt precursor. And finally, putting the collected silicon-based organic salt/PVA micro-nanofiber felt precursor into a tube furnace for sintering, heating to 1000 ℃ at the heating rate of 4 ℃/min, keeping the temperature for 1 hour at the temperature of 1000 ℃, and then cooling to room temperature at the cooling rate of 10 ℃/min. The material obtained after sintering is a silicon-based ceramic micro-nanofiber felt.
The thermal conductivity of the finally obtained silicon-based ceramic micro-nanofiber felt material is as follows: 0.026-0.036 (W/m.K), density: 21-116mg/cm3The maximum compression set is 90%.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a silicon-based ceramic micro-nanofiber heat insulation felt is characterized by comprising the following steps:
the method comprises the following steps: preparing a raw material mixed solution, wherein the raw material mixed solution comprises an organic salt, a high molecular polymer and a solvent;
step two: spinning the raw material mixed solution into a silicon-based ceramic micro-nano fiber material precursor by using a centrifugal spinning device;
step three: collecting silicon-based ceramic micro-nanofiber material precursors, and stacking to form a felt state to obtain a silicon-based ceramic micro-nanofiber felt precursor;
step four: and sintering the silicon-based ceramic micro-nanofiber felt precursor at a high temperature to obtain the silicon-based ceramic micro-nanofiber heat insulation felt.
2. The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, wherein the organic salt is tetraethyl silicate and at least one of tin tetrachloride or tetrabutyl titanate, and the mass ratio of the tetraethyl silicate to the tin tetrachloride or the tetrabutyl titanate is 1: 0.2-0.5.
3. The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, wherein the mass ratio of the organic salt to the solvent in the raw material mixed solution is 1.2-3: 5-11; the high molecular polymer accounts for 6-30% of the total weight of the raw material mixed solution.
4. The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, wherein the raw material mixed solution further comprises nano graphene oxide sheets and liquid sodium silicate; the nano graphene oxide sheet accounts for 3-5% of the weight of the organic salt, and the liquid sodium silicate accounts for 2-3% of the weight of the organic salt.
5. The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, characterized in that the raw material mixed solution further comprises acetic acid, and the mass ratio of the organic salt to the acetic acid is 1.2-3: 0.01.
6. the method for preparing the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, wherein the high polymer is at least one of PEO, PVA and PAN; the solvent is at least one of water, absolute ethyl alcohol, acetonitrile, acetone and dimethyl amide.
7. The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, wherein in the spinning process of a centrifugal spinning device, the electromechanical rotation speed is set to 4000-10000 rpm, the aperture of a fine-hole needle head is 0.1-0.4 mm, and the collection distance of a collection device is 30-50 cm.
8. The preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, wherein the stacking mode can be winding stacking or zigzag stacking.
9. The method for preparing the silicon-based ceramic micro-nanofiber heat insulation felt according to claim 1, wherein the sintering process is that the temperature is increased from 50 ℃ to 1000 ℃ at a temperature increase rate of 2 ℃/min, the sintering process is kept for 1h in an environment of 1000 ℃, and then the temperature is decreased from 1000 ℃ to 50 ℃ at a temperature decrease rate of 5 ℃/min.
10. A silicon-based ceramic micro-nanofiber heat insulation felt is characterized by being prepared by the preparation method of the silicon-based ceramic micro-nanofiber heat insulation felt according to any one of claims 1 to 9.
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