CN114292113A - Ceramic nanofiber low-temperature calcination forming device - Google Patents
Ceramic nanofiber low-temperature calcination forming device Download PDFInfo
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- CN114292113A CN114292113A CN202111376345.3A CN202111376345A CN114292113A CN 114292113 A CN114292113 A CN 114292113A CN 202111376345 A CN202111376345 A CN 202111376345A CN 114292113 A CN114292113 A CN 114292113A
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Abstract
The invention relates to a low-temperature calcination forming device for ceramic nanofibers, which comprises: an analysis mechanism: comprises an analysis cabin, a spraying component and a negative pressure suction component which are positioned in the analysis cabin; solvent gradient displacement mechanism: the device comprises a displacement cabin positioned behind the analysis cabin, and an alcohol-water bath tank, a displacement bath tank and an alcohol bath tank which are sequentially arranged in the displacement cabin along the advancing direction of the ceramic nano fibers; a drying mechanism: the device comprises a drying cabin positioned behind a replacing cabin and a drying component which is arranged in the drying cabin and used for heating and drying the ceramic nano-fibers; atmosphere-variable calcining mechanism: the device comprises a pre-sintering cabin, a constant temperature cabin and a cooling cabin which are positioned behind a drying cabin, are sequentially arranged along the advancing direction of the ceramic nano fibers and are mutually independent; a winding mechanism. Compared with the prior art, the invention realizes the high-purity, high-efficiency and large-scale preparation of the ceramic fiber.
Description
Technical Field
The invention belongs to the technical field of electrostatic spinning devices, and relates to a low-temperature calcination forming device for ceramic nanofibers.
Background
The ceramic nanofiber has high temperature resistance and good photoelectric characteristics of ceramic, the small-size effect and the dielectric confinement effect of a nanomaterial and the excellent heat/electric transport characteristics of the fiber, and is a key functional material in the fields of aerospace, environmental catalysis, electronic information, clean energy and the like. As a new ceramic material, the material has the advantages of high ion/electron transmission rate, high photoelectric conversion efficiency, good high-temperature/chemical stability, light weight, flexibility and the like, and can be used for guiding the ceramic material to realize the leap of application performance in various fields. At present, the preparation methods of ceramic nanofibers mainly include a self-assembly method, a vapor deposition method, a template synthesis method, an electrostatic spinning method and the like, wherein electrostatic spinning is the only method capable of realizing large-scale preparation. However, at present, electrostatic spinning needs to introduce a polymer template to form the inorganic sol into the nanofiber, and since the introduction of the polymer usually needs to be calcined at a high temperature (above 600 ℃) to remove organic polymer components, not only can serious environmental pollution be caused, but also the ceramic nanofiber has a large grain size, a micro-defect structure is generated inside the fiber, and the low-temperature crystalline ceramic nanofiber has poor flexibility and is easy to brittle fracture.
The applicant synthesizes linear inorganic polymer sol with low branching degree and high polymerization degree in the earlier stage, and utilizes the characteristics of high viscosity and easy entanglement of molecular chains to directly carry out electrostatic spinning to form fibers under the condition of not adding polymers. However, in the process from the step of forming inorganic polymer sol into fibers through electrostatic spinning gelation to the step of finally obtaining the ceramic nanofibers, although no polymer is added, a small amount of micromolecular organic ligands still exist on the molecular chains of the gel fibers, organic components on the inorganic gel nanofibers are removed through nondestructive deep analysis of ultrasonic spraying-negative pressure suction, the inorganic gel nanofibers are pre-shrunk by combining solvent gradient replacement and reduced pressure drying, the inorganic gel nanofibers are subjected to ceramization at a lower temperature through variable-atmosphere microwave calcination, and finally the flexible ceramic nanofiber material is obtained.
The patent "a low-temperature sintering microwave dielectric ceramic and its sintering method" (CN201110233645.6) discloses a low-temperature sintering microwave dielectric ceramic and its sintering method, the method adopts microwave sintering preparation technology, adds low-melting point sintering auxiliary agent to reduce sintering temperature, in the heating process, the internal temperature gradient of the material is very small, the thermal stress is also very small, even under the condition of very high heating rate, the cracking of the material can not be caused generally. However, the method aims at the powder, and the polymer polyvinyl alcohol is added into the mixture, so that the temperature in the implementation process also reaches 800-950 ℃, and the subsequent decomposition process of the polymer also brings serious environmental pollution and energy waste. The patent "a binder and bonding method for cutting silica fume pressed brick" (CN201910385601.1) discloses a binder for cutting silica fume pressed brick, the bonding method comprises the following steps in sequence: uniformly mixing the brick pressing base material, the binder and the water ingredient, and pressing into a green brick; naturally drying and then carrying out low-temperature calcination treatment; and (4) performing high-temperature calcination treatment to obtain a water permeable brick finished product. However, the low-temperature calcination temperature after natural drying in this method is 850 ℃, and the subsequent high-temperature calcination temperature is even up to 1250 ℃, and thus it is not a true low-temperature calcination, and a large amount of pollutants may still be present during combustion.
Disclosure of Invention
The invention aims to provide a low-temperature calcination forming device for ceramic nanofibers, which is used for further processing electrostatic spinning ceramic gel nanofibers, wherein a small amount of micromolecule organic ligands on the fibers are subjected to nondestructive deep desorption through ultrasonic spraying-negative pressure suction, and then subjected to solvent gradient replacement, reduced pressure drying and variable atmosphere microwave calcination to enable the inorganic gel nanofibers to be ceramized at a lower temperature, so that flexible ceramic nanofiber materials are finally obtained, and high-purity, high-efficiency and large-scale preparation of the ceramic fibers is realized.
The purpose of the invention can be realized by the following technical scheme:
a low-temperature calcination forming device for ceramic nanofibers comprises:
an analysis mechanism: the analysis device comprises an analysis cabin, a spraying assembly and a negative pressure suction assembly, wherein the spraying assembly and the negative pressure suction assembly are positioned in the analysis cabin, the spraying assembly is positioned above the negative pressure suction assembly, and after entering the analysis cabin, the ceramic nano fibers penetrate through the space between the spraying assembly and the negative pressure suction assembly and are soaked with analysis liquid sprayed by the spraying assembly;
solvent gradient displacement mechanism: the device comprises a displacement cabin positioned behind the analysis cabin, and an alcohol-water bath tank, a displacement bath tank and an alcohol bath tank which are sequentially arranged in the displacement cabin along the advancing direction of the ceramic nano fibers;
a drying mechanism: the device comprises a drying cabin positioned behind a replacing cabin and a drying component which is arranged in the drying cabin and used for heating and drying the ceramic nano-fibers;
atmosphere-variable calcining mechanism: the device comprises a pre-burning cabin, a sintering cabin, a constant temperature cabin and a cooling cabin which are positioned behind a drying cabin, sequentially arranged along the advancing direction of ceramic nano fibers and mutually independent, wherein the pre-burning cabin, the sintering cabin, the constant temperature cabin and the cooling cabin are respectively connected with external oxygen supply equipment and/or inert gas supply equipment through independent pipelines;
and the winding mechanism is positioned behind the variable atmosphere calcining mechanism and is used for winding the formed ceramic nano fibers.
Furthermore, the spray assembly comprises a spray head arranged in the analysis cabin, a liquid storage tank, a liquid pump and an analysis liquid tank which are sequentially connected with the spray head, the liquid storage tank is also connected with an ultrasonic generator, and an energy converter is also arranged between the liquid storage tank and the spray head. Here: 1. an ultrasonic generator, also called an ultrasonic driving power supply, an electronic box and an ultrasonic controller, is an important component of a high-power ultrasonic system. The ultrasonic generator is used for converting commercial power into a high-frequency alternating current signal matched with the ultrasonic transducer and driving the ultrasonic transducer to work. 2. The transducer is used for converting input electric power into mechanical power (namely ultrasonic waves) and transmitting the mechanical power, and consumes a small part of power. 3. During operation, compressed air forms high-speed airflow through the fine nozzle, the generated negative pressure drives liquid or other fluid to be sprayed onto the obstacle together, and the liquid drops splash to the periphery under high-speed impact to be changed into mist-shaped particles to be sprayed out of the air outlet pipe. The working principle of the ultrasonic atomization spraying device is the same as that of the current ultrasonic atomization spraying device, and the ultrasonic atomization spraying device belongs to the common knowledge in the industry.
Further, the negative pressure suction assembly comprises a hollow tray arranged in the analysis cabin and positioned below the conveyor belt for conveying the ceramic nanofibers, and a negative pressure suction pump connected with the hollow tray through a suction pipeline, wherein the plane of the hollow tray is just parallel to the plane of the conveyor belt.
Further, the analysis solution is an alkali alcohol solution, wherein the alkali is sodium hydroxide or potassium hydroxide, and the alcohol solvent is ethanol, propanol, n-butanol or tert-butanol.
Furthermore, the vacuum degree of the analysis cabin during working is-0.098 to-0.01 MPa.
Further, the alcohol-water bath tank is also connected with an alcohol-water bath preparation kettle for providing an alcohol-water mixed solution, the displacement bath tank is also connected with a displacement bath preparation kettle for providing a displacement solvent, and the alcohol bath tank is also connected with an alcohol bath preparation kettle for providing an alcohol solvent.
Furthermore, the temperature of the alcohol-water mixed solution in the alcohol-water bath is 10-30 ℃, the temperature of the replacement solvent in the replacement bath is 60-80 ℃, and the temperature of the alcohol solvent in the alcohol bath is 10-30 ℃.
Furthermore, the alcohol-water mixed solution is prepared from alcohol and water, wherein the alcohol is one or a combination of ethanol, propanol, n-butanol and tert-butanol.
Further, the replacement solvent is one or more of carbon tetrachloride, benzene, toluene, dichloroethane, dichloromethane, chloroform, diethyl ether, diphenyl ether, ethyl acetate, acetone, tetrahydrofuran, N-methylpyrrolidone and N, N-dimethylformamide.
Further, the alcohol solvent is one or more of ethanol, propanol, n-butanol and tert-butanol.
Further, the drying assembly comprises an infrared heating unit positioned in the drying chamber, and a vacuum generating device connected with the drying chamber through a pipeline, wherein the drying chamber is a substantially sealed chamber body.
Furthermore, the working temperature in the drying cabin is 60-80 ℃, and the vacuum degree is-0.1-0.098 MPa.
Furthermore, the pre-burning cabin and the cooling cabin are respectively connected with oxygen supply equipment through gas pipelines.
Furthermore, the sintering chamber and the constant temperature chamber are both connected with an oxygen supply device and an inert gas supply device through gas pipelines.
Furthermore, the pre-sintering cabin, the constant temperature cabin and the cooling cabin are respectively connected with an external microwave generator through waveguide tubes.
Further, the working atmosphere of the pre-sintering cabin and the cooling cabin is oxygen atmosphere, and the working atmosphere of the sintering cabin and the constant temperature cabin is mixed atmosphere of oxygen and inert gas.
Further, the working temperature in the pre-sintering cabin is set to be 100-150 ℃, the working temperature in the sintering cabin is set to be 200-500 ℃, the working temperature in the constant-temperature cabin is set to be 200-500 ℃, and the working temperature in the cooling cabin is set to be 60-80 ℃.
Compared with the prior art, the invention has the following advantages:
(1) according to the low-temperature calcination forming device for the ceramic nanofibers, the nondestructive deep desorption mechanism of ultrasonic spraying-negative pressure suction is used for realizing mild and efficient removal of organic micromolecule ligands on the ceramic gel nanofiber membrane, and the nanofiber membrane cannot be damaged;
(2) according to the low-temperature calcination forming device for the ceramic nanofiber, microwave plasma sintering of the ceramic gel nanofiber membrane is realized through the variable-atmosphere microwave calcination device, the microwave heating temperature field is uniform, the thermal stress is small, the sintering speed is high, in addition, the crystal grains in the ceramic fiber are further refined by matching with the change of gas atmosphere in different cabin bodies, the abnormal growth of the crystal grains is effectively inhibited, and the mechanical property of the finally obtained finished product is improved;
(3) the low-temperature calcination forming device for the ceramic nanofibers can realize efficient, rapid and nondestructive acquisition from ceramic gel nanofiber membranes to pure ceramic nanofiber membranes, becomes an indispensable important part in the post-treatment process of electrostatic spinning and fiber formation of linear inorganic polymer sol, and provides a new scheme for a large-scale preparation device for the ceramic nanofibers.
Drawings
FIG. 1 is a schematic view of a low-temperature calcination forming device for ceramic nanofibers according to the present invention;
FIG. 2 is a schematic diagram of the analytic mechanism of the ceramic nanofiber low-temperature calcination forming device of the present invention;
FIG. 3 is a schematic view of a solvent gradient displacement device of the ceramic nanofiber low-temperature calcination forming device according to the present invention;
FIG. 4 is a schematic view of a vacuum drying device and a variable-atmosphere microwave calcining device of the low-temperature calcining and forming device for ceramic nanofibers according to the present invention;
the notation in the figure is:
10-an ultrasonic generator, 11-an analysis liquid tank, 12-a liquid pump, 13-a liquid storage tank, 14-an energy converter, 15-a spray head, 16-a negative pressure suction pump, 17-a hollow tray, 18-an analysis cabin and 19-a first heat preservation layer;
20-alcohol water bath preparation kettle, 21-replacement bath preparation kettle, 22-alcohol bath preparation kettle, 23-alcohol water bath, 24-replacement bath, 25-alcohol bath, 26-second heat insulation layer and 27-second heat insulation shell;
30-a drying cabin, 31-a vacuum pump and 32-an infrared heating unit;
40-an oxygen cylinder, 41-an inert gas cylinder, 42-a pre-burning cabin, 43-a sintering cabin, 44-a constant temperature cabin, 45-a cooling cabin, 46-a microwave generator, 47-a third heat insulation layer and 48-a third heat insulation shell;
and 50-a winding mechanism.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In the following embodiments or examples, functional components or structures that are not specifically described are all conventional components or structures that are adopted in the art to achieve the corresponding functions.
In order to realize high-purity, high-efficiency and large-scale preparation of ceramic fibers and the like, the invention provides a low-temperature calcination forming device for ceramic nanofibers, the structure of which is shown in figures 1 to 4 and comprises the following components:
an analysis mechanism: the device comprises an analysis cabin 18, and a spraying assembly and a negative pressure suction assembly which are positioned in the analysis cabin 18, wherein the spraying assembly is positioned above the negative pressure suction assembly, and after entering the analysis cabin 18, the ceramic nano fibers pass through the space between the spraying assembly and the negative pressure suction assembly and are soaked with analysis liquid sprayed by the spraying assembly;
solvent gradient displacement mechanism: the device comprises a replacement cabin positioned behind the analysis cabin 18, and an alcohol-water bath 23, a replacement bath 24 and an alcohol bath 25 which are sequentially arranged in the replacement cabin along the advancing direction of the ceramic nano fibers;
a drying mechanism: comprises a drying cabin 30 positioned behind a replacing cabin and a drying component which is arranged in the drying cabin 30 and used for heating and drying the ceramic nano-fiber;
atmosphere-variable calcining mechanism: the device comprises a pre-sintering cabin 42, a sintering cabin 43, a constant temperature cabin 44 and a cooling cabin 45 which are positioned behind a drying cabin 30 and are sequentially arranged along the advancing direction of ceramic nano fibers and are mutually independent, wherein the pre-sintering cabin 42, the sintering cabin 43, the constant temperature cabin 44 and the cooling cabin 45 are respectively connected with external oxygen supply equipment and/or inert gas supply equipment through independent pipelines;
and the winding mechanism is positioned behind the variable atmosphere calcining mechanism and is used for winding the formed ceramic nano fibers.
In some specific embodiments, referring to fig. 1 and the like again, the spray assembly includes a spray header 15 disposed in the analysis chamber 18, and a liquid storage tank 13, a liquid pump 12 and an analysis liquid tank 11 sequentially connected to the spray header 15, the liquid storage tank 13 is further connected to an ultrasonic generator 10, and a transducer 14 is further disposed between the liquid storage tank 13 and the spray header 15. Here: (1) an ultrasonic generator, also called an ultrasonic driving power supply, an electronic box and an ultrasonic controller, is an important component of a high-power ultrasonic system. The ultrasonic generator is used for converting commercial power into a high-frequency alternating current signal matched with the ultrasonic transducer and driving the ultrasonic transducer to work. (2) The transducer is used for converting input electric power into mechanical power (namely ultrasonic waves) and transmitting the mechanical power, and consumes a small part of power. (3) During operation, compressed air forms high-speed airflow through the fine nozzle, the generated negative pressure drives liquid or other fluid to be sprayed onto the obstacle together, and the liquid drops splash to the periphery under high-speed impact to be changed into mist-shaped particles to be sprayed out of the air outlet pipe. The working principle of the ultrasonic atomization spraying device is the same as that of the current ultrasonic atomization spraying device, and the ultrasonic atomization spraying device belongs to the common knowledge in the industry.
Specifically, the surface of the spray header 15 is hollowed with circular spray holes, the aperture of each spray hole is 1-8 mm, and the distribution density is 16-64 cm2。
In some embodiments, referring to fig. 1 and the like, the negative pressure suction assembly includes a hollow tray 17 disposed in the analysis chamber 18 and below the conveyor belt for conveying the ceramic nanofibers, and a negative pressure suction pump 16 connected to the hollow tray 17 through a suction pipe, wherein a plane of the hollow tray 17 is parallel to a plane of the conveyor belt. In addition, the shape of the hollow on the hollow tray 17 is one or a combination of a circle, a triangle, a quadrangle, a polygon and other irregular figures, and the hollow area of the tray accounts for 60-90% of the whole area.
In some specific embodiments, the resolving solution is an alcohol solution of an alkali, and the concentration of the alcohol solution may be 0.1 to 5mol/L, specifically, the alkali may be sodium hydroxide or potassium hydroxide, and the alcohol solvent may be one or a combination of ethanol, propanol, n-butanol, or tert-butanol.
In some specific embodiments, the vacuum degree of the analysis cabin 18 during operation is-0.098 MPa to-0.01 MPa, the temperature is controlled at 60 ℃ to 100 ℃, and the analysis can be realized by heating with a resistance wire.
In some specific embodiments, referring to fig. 1 and the like, the alcohol-water bath 23 is further connected to an alcohol-water bath preparation kettle 20 for providing an alcohol-water mixed solution, the substitution bath 24 is further connected to a substitution bath preparation kettle 21 for providing a substitution solvent, and the alcohol bath 25 is further connected to an alcohol bath preparation kettle 22 for providing an alcohol solvent.
In a more specific embodiment, the temperature of the alcohol-water mixture in the alcohol-water bath 23 is 10 to 30 ℃, the temperature of the substitution solvent in the substitution bath 24 is 60 to 80 ℃, and the temperature of the alcohol solvent in the alcohol bath 25 is 10 to 30 ℃.
In a more specific embodiment, the alcohol-water mixed solution is prepared from alcohol and water, and specifically can be composed of 95 wt% of alcohol and 5 wt% of water, wherein the alcohol can be one or a combination of ethanol, propanol, n-butanol and tert-butanol.
In a more specific embodiment, the displacement solvent may be one or a combination of more of carbon tetrachloride, benzene, toluene, dichloroethane, dichloromethane, chloroform, diethyl ether, diphenyl ether, ethyl acetate, acetone, tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide.
In a more specific embodiment, the alcohol solvent may be one or a combination of ethanol, propanol, n-butanol, and t-butanol.
In some embodiments, referring again to fig. 1 and the like, the drying assembly includes an infrared heating unit 32 located in the drying chamber 30, and a vacuum generating device (such as a vacuum pump and the like) connected to the drying chamber 30 through a pipe, and the drying chamber 30 is a substantially sealed chamber. Here, the infrared heating unit 32 may be an infrared heating pipe, and the power thereof may range from 300W to 3500W.
In some embodiments, the working temperature in the drying chamber 30 is 60-80 deg.C, and the vacuum degree is-0.1-0.098 MPa.
In some embodiments, referring again to fig. 1 and the like, the burn-in compartment 42 and the cooling compartment 45 are connected to an oxygen supply device (which may be an oxygen cylinder 40) through gas pipes.
In some embodiments, the sintering chamber 43 and the constant temperature chamber 44 are connected to an oxygen supply device and an inert gas supply device (which may be an inert gas bottle 41) through gas pipes.
In some specific embodiments, referring to fig. 1 and the like again, the pre-sintering chamber 42, the sintering chamber 43, the constant temperature chamber 44 and the cooling chamber 45 are respectively connected to an external microwave generator 46 through a waveguide, a plasma is formed by ionizing gas with microwave, and then the plasma heats the gel ceramic nanofiber film to obtain a dense nanofiber film. The microwave plasma heating is adopted in the invention, which is different from the conventional microwave heating, and the microwave sintering is that alternating electromagnetism can repeatedly adjust dipoles in the material to generate strong vibration and friction, so that the material is heated, and the purpose of heating and sintering is achieved. The essence of microwave plasma sintering is that microwave energy is used to excite gas discharge to generate plasma, and the green body is heated by the plasma to obtain a dense ceramic sintered body. It is noted that during the sintering of the ceramic, some of the energy also heats the sample in the form of microwaves, accompanied by the heating of the high temperature plasma. The microwave plasma sintering method overcomes the defects that selective heating is realized during simple microwave sintering of ceramics, and all materials cannot be effectively heated, and simultaneously, the problems of large temperature gradient and uneven heating of a plasma space are reduced to a certain extent.
In some specific embodiments, the working atmosphere of the pre-sintering chamber 42 and the cooling chamber 45 is an oxygen atmosphere, and the working atmosphere of the sintering chamber 43 and the constant temperature chamber 44 are both a mixed atmosphere of oxygen and an inert gas, and are generally controlled to have an oxygen gas content of 80-95% and an inert gas content of 5-20% (both by volume fraction). The inert gas may include one or more combinations of nitrogen, helium, neon, argon, and the like.
In some specific embodiments, the working temperature in the pre-sintering chamber 42 is set to be 100-150 ℃, the working temperature in the sintering chamber 43 is set to be 200-500 ℃, the working temperature in the constant temperature chamber 44 is set to be 200-500 ℃, and the working temperature in the cooling chamber 45 is set to be 60-80 ℃. In addition, during specific work, according to actual conditions, the gel nanofiber membrane can keep differential drafting and proper tension compensation in the whole process from the moment when the gel nanofiber membrane does not enter the pre-burning chamber 42 to the moment when the gel nanofiber membrane leaves the cooling chamber 45, wherein the differential speed between the inlet and the outlet of the pre-burning chamber 42 is 20%, the differential speed between the inlet and the outlet of the sintering chamber 43 is 30%, the differential speed between the inlet and the outlet of the constant temperature chamber 44 is 30%, and the differential speed between the inlet and the outlet of the cooling chamber 45 is 5%. The above can be routinely adjusted empirically.
In some specific embodiments, heat insulating shells and heat insulating layers may be disposed outside the analysis cabin 18, the replacement cabin, the drying cabin 30, the pre-burning cabin 42, the sintering cabin 43, the constant temperature cabin 44, the cooling cabin 45, and the like, that is, the first heat insulating layer 19 and the first heat insulating shell are disposed outside the analysis cabin 18, and the second heat insulating layer 26 and the second heat insulating shell 27 are disposed outside the replacement cabin; the drying chamber 30, the pre-burning chamber 42, the sintering chamber 43, the constant temperature chamber 44 and the cooling chamber 45 can be collectively arranged in the same large-scale chamber body, and thus, a third heat-insulating layer 47 and a third heat-insulating shell 48 are uniformly arranged.
In summary, the technical problems to be solved by the present invention are that currently, electrostatic spinning ceramic nanofibers can be normally spun only by adding a polymer to a precursor solution to adjust spinnability, but introduction of the polymer usually requires high-temperature calcination (above 600 ℃) to remove organic polymer components, which not only causes serious environmental pollution, but also causes oversize crystal grains of finally obtained ceramic nanofibers and micro-defect structures in the fibers, so that finally obtained pure ceramic nanofibers have poor flexibility and serious mechanical properties. The method is characterized in that linear inorganic polymer sol is synthesized in the early stage, the sol can be normally spun under the condition that no high molecular polymer is added in a precursor solution, and on the basis, an electrostatic spinning device for preparing the flexible ceramic nanofiber in a large scale is developed, so that the ceramic gel nanofiber is industrially prepared from the linear inorganic polymer sol through an electrostatic spinning process. However, in the process of obtaining ceramic gel nanofibers from inorganic polymer sols through electrostatic spinning, although no polymer is added, a small amount of small-molecule organic ligands still exist on the molecular chains of the gel fibers, so that the temperature for removing the organic ligands subsequently is also high, and in addition, the crystal grain growth speed also exists in the conventional air atmosphere calcination process treatment, and the quality of the subsequent finished products is also seriously influenced. According to the invention, through the matching use of the analysis mechanism, the solvent gradient displacement mechanism, the decompression drying mechanism and the variable-atmosphere microwave calcining mechanism, the mild removal of the micromolecule organic ligand can be realized, the inhibition effect on the grain growth of the ceramic gel fiber is obvious, and the mechanical property of the final pure ceramic fiber is obviously improved. The specific mechanism is as follows:
on the one hand, a small part of organic ligands on the ceramic gel fiber are formed by chelating polydentate ligands on metal alkoxide in the process of preparing spinning sol for limiting the reactivity of the metal alkoxide (particularly, zirconium and titanium atoms have high electropositivity, the metal alkoxide formed by the ligands has severe hydrolysis reaction, and the local gelation phenomenon is very easy to occur rapidly when water is encountered). Therefore, the organic ligand on the gel fiber needs to be removed by using a related method to obtain pure ceramic fiber, and the calcination temperature of the fiber after the ligand is removed can be greatly reduced.
The following takes a linear zirconium sol prepared by chelating zirconium metal alkoxide with acetic acid as an example to illustrate the chemical reaction of zirconium gel nanofibers obtained by zirconium sol electrospinning in an analytical mechanism:
however, it should be noted that, compared with the traditional woven fabric and knitted fabric, the strength of the electrospun nanofiber membrane in the longitudinal and transverse directions is inferior, so the developed analysis mechanism adopts an ultrasonic spray-negative pressure suction method, for example, an ethanol solution of sodium hydroxide is used as an analysis solution to be ultrasonically sprayed on the surface of the nanofiber membrane, and then the spray solution is immersed into the fiber membrane by the negative pressure suction method, so that the spray solution is sufficiently soaked to achieve the effect of deep analysis. However, if the soaking treatment similar to the conventional fabric is adopted, not only the process is time-consuming and energy-consuming, but also the strength of the fiber membrane is greatly impaired (the strength of the fiber membrane in a wet state is poor).
On the other hand, the ceramic gel nanofiber membrane is treated by adopting a variable-atmosphere microwave calcining mechanism, mainly because the microwave heating mode is different from the conventional heating mode, the microwave heating mode is that the microwave interacts with a dielectric material in a rapidly-changing high-frequency electromagnetic field, the microwave is absorbed by the dielectric material to generate body heating, the heating starts from the inside and the outside of an object at the same time, and the inside and the outside can be simultaneously heated, so that the microwave heating temperature field is uniform, the thermal stress is small, and the ceramic gel nanofiber membrane is suitable for rapid sintering. In addition, the microwave electromagnetic field promotes diffusion, accelerates the sintering process, can refine the grains of the ceramic material, effectively inhibits the abnormal growth of the grains, and improves the uniformity of the microstructure of the material. More importantly, different gas atmospheres of the cabin body are set (the pre-sintering stage is an oxygen atmosphere, the sintering and constant temperature stage is controlled to be a mixed atmosphere of oxygen and inert gas, wherein the oxygen content is 80-95%, the inert gas content is 5-20%, and the cooling stage is an oxygen atmosphere), microwave ionized gas is further utilized to form plasma, and then the plasma heats the gel ceramic nanofiber membrane to obtain the compact nanofiber membrane. Due to rapid heating, the coarsening of crystal grains caused by surface diffusion (mainly occurring in the low-temperature stage of traditional sintering) is reduced, and a strong driving force and a short diffusion path are provided for grain boundary diffusion and volume diffusion, so that the microstructure of the ceramic is refined, and the rapid densification of the fiber membrane is promoted. This is because there is an extremely small amount of residual carbon in the environment of incomplete oxygen during the sintering stage, which can be trapped at the grain boundaries, inhibiting grain growth, and the resulting increase in densification of the ceramic fiber is associated with smaller grain size and more additional oxygen vacancies created during the reducing atmosphere heat treatment.
The above embodiments may be implemented individually, or in any combination of two or more.
The above embodiments will be described in more detail with reference to specific examples.
Example 1:
a low-temperature calcination forming device for ceramic nanofibers is shown in figure 1 and comprises an analysis mechanism, a solvent gradient displacement mechanism, a reduced-pressure drying mechanism, a variable-atmosphere microwave calcination mechanism and a winding mechanism. Wherein, the schematic diagram of the analysis mechanism is shown in fig. 2, the schematic diagram of the solvent gradient displacement mechanism is shown in fig. 3, and the schematic diagram of the reduced pressure drying mechanism and the variable atmosphere microwave calcination mechanism is shown in fig. 4.
The analysis mechanism mainly comprises an ultrasonic generator 10, an analysis liquid tank 11, a liquid pump 12, a liquid storage tank 13, a transducer 14, a spray header 15, a negative pressure suction pump 16, a hollow tray 17 and an analysis cabin 18;
The analytic solution contained in the analytic solution tank 11 is an aqueous alkali solution of alcohol with the concentration of 0.1-5 mol/L, wherein the alkali solute is sodium hydroxide or potassium hydroxide, and the alcohol solvent is ethanol, propanol, n-butanol or tert-butanol; the surface of the spray head 15 is hollowed with circular spray holes, the aperture of each spray hole is 1-8 mm, and the distribution density is 16-64 cm 2; the hollowed-out tray 17 is hollowed out to be circular, triangular, quadrilateral, polygonal or other irregular figures, and the hollowed-out area accounts for 60-90% of the whole area; the hollow tray 17 is driven by a negative pressure suction pump 16 to perform nondestructive deep analysis on the inorganic gel fiber membrane sprayed by ultrasonic waves on the conveyor belt, the vacuum degree in the analysis cabin 18 is-0.098 to-0.01 MPa, the analysis mechanism is heated by a resistance wire, and the temperature is 60-100 ℃.
The solvent gradient displacement mechanism mainly comprises an alcohol water bath preparation kettle 20, a displacement bath preparation kettle 21, an alcohol bath preparation kettle 22, an alcohol water bath tank 23, a displacement bath tank 24 and an alcohol bath tank 25;
the alcohol water bath preparation kettle 20 is used for preparing alcohol and water mixed liquor, the mixed liquor is composed of 95 wt% of alcohol and 5 wt% of water, wherein the alcohol solvent is ethanol, propanol, n-butanol or tert-butanol; the displacement bath preparation kettle 21 is used for preparing a displacement solvent, and the low surface tension solvent is one or a combination of carbon tetrachloride, benzene, toluene, dichloroethane, dichloromethane, chloroform, diethyl ether, diphenyl ether, ethyl acetate, acetone, tetrahydrofuran, N-methylpyrrolidone and N, N-dimethylformamide; the alcohol bath preparation kettle 22 is used for preparing alcohol solvent, wherein the mass fraction of the alcohol is higher than 99 wt%, and the alcohol solvent is ethanol, propanol, n-butanol or tert-butanol. The solvent gradient replacement mechanism sets the temperature of the solution in the preparation kettle, and conveys the prepared solution at a certain temperature to a corresponding tank through a pipeline after the preparation is finished, wherein the temperature of the solution in the alcohol water bath preparation kettle 20 is 10-30 ℃, the temperature of the solution in the replacement bath preparation kettle 21 is 60-80 ℃, and the temperature of the solution in the alcohol bath preparation kettle 22 is 10-30 ℃.
The decompression drying mechanism mainly comprises a drying cabin 30, a vacuum pump 31 and an infrared heating mechanism;
the decompression drying mechanism utilizes a quartz glass infrared heating tube to dry the gel nanofiber membrane subjected to solvent gradient displacement to complete pre-shrinkage treatment, the power range of the heating tube is 300W-3500W, the vacuum degree in the decompression drying process is set to be-0.1 to-0.098 MPa, and the temperature is set to be 60-80 ℃.
The variable atmosphere microwave calcining mechanism consists of an oxygen cylinder 40, an inert gas cylinder 41, a pre-sintering cabin 42, a sintering cabin 43, a constant temperature cabin 44, a cooling cabin 45 and a microwave generator 46;
the oxygen cylinder 40 and the inert gas cylinder 41 are arranged outside the drying chamber 30, and a pre-burning chamber 42, a sintering chamber 43, a constant temperature chamber 44 and a cooling chamber 45 are sequentially arranged from a position close to the drying chamber 30, wherein the oxygen cylinder 40 is respectively connected to the pre-burning chamber 42 and the cooling chamber 45 through gas pipelines, the mixed gas of the oxygen cylinder 40 and the inert gas cylinder 41 is respectively connected to the sintering chamber 43 and the constant temperature chamber 44 through gas pipelines, and the gas input into the pre-burning chamber 42, the sintering chamber 43, the constant temperature chamber 44 and the cooling chamber 45 is subjected to variable gas atmosphere microwave plasma sintering under the action of a microwave generator 46.
Introducing the pre-shrunk gel nanofiber membrane to a variable-atmosphere microwave calcining mechanism through a traction roller, wherein a microwave generator 46 generates high-power microwave energy by utilizing an electric vacuum device, the electric vacuum device can comprise a magnetron, a multi-cavity klystron, a microwave triode, a microwave tetrode or a traveling wave tube, and the fiber membrane sequentially passes through a pre-sintering cabin 42, a sintering cabin 43, a constant-temperature cabin 44 and a cooling cabin 45; the temperature setting range of the pre-burning cabin 42 is 100-150 ℃, the temperature setting range of the sintering cabin 43 is 200-500 ℃, the temperature setting range of the constant temperature cabin 44 is 200-500 ℃, and the temperature setting of the cooling cabin 45 is 60-80 ℃; controlling the oxygen gas content to be 80-95% and the inert gas content to be 5-20% in the gas atmosphere in the sintering chamber 43 and the constant temperature chamber 44; the gas contained in the inert gas bottle 41 includes nitrogen, helium, neon, or argon. The gel nanofiber membrane keeps differential drafting and proper tension compensation in the whole process from not entering the pre-burning cabin 42 to leaving the cooling cabin 45, wherein the differential speed between the inlet and the outlet of the pre-burning cabin 42 is 20%, the differential speed between the inlet and the outlet of the sintering cabin 43 is 30%, the differential speed between the inlet and the outlet of the constant temperature cabin 44 is 30%, and the differential speed between the inlet and the outlet of the cooling cabin 45 is 5%; the analysis mechanism, the solvent gradient replacement mechanism, the reduced pressure drying mechanism and the variable atmosphere microwave calcination mechanism are all provided with heat preservation layers (a first heat preservation layer 19, a second heat preservation layer 26 and a third heat preservation layer 47 respectively) and heat preservation shells (a first heat preservation shell, a second heat preservation shell 27 and a third heat preservation shell 48 respectively) so as to maintain the temperature environment of the whole cabin body to be stable.
The ceramic nanofiber low-temperature calcination forming device is used in the post-treatment process of electrostatic spinning titanium oxide gel nanofiber membrane, and the process parameters are as follows: the resolving solution is ethanol solution of sodium hydroxide with concentration of 2mol/L, the diameter of circular spray holes on the surface of the spray header 15 is 4mm, and the distribution density is 32 cm2The negative pressure suction pump 16 is connected with the hollow tray 17, the hollow shape on the hollow tray 17 is circular, the hollow area accounts for 70% of the whole area, the vacuum degree in the analysis cabin 18 is-0.075 MPa, 95 wt% of ethanol and 5 wt% of water are contained in the alcohol-water bath preparation kettle 20, N-dimethylformamide is contained in the displacement bath preparation kettle 21, and ethanol with the mass fraction higher than 99 wt% is contained in the alcohol bath preparation kettle 22. The resolving mechanism is heated by a resistance wire, and the temperature is 60 ℃; the solution temperature of the alcohol water bath preparation kettle 20 is 30 ℃, the solution temperature of the replacement bath preparation kettle 21 is 60 ℃, and the solution temperature of the alcohol bath preparation kettle 22 is 30 ℃. The power of the quartz glass infrared heating tube is 1000W, the vacuum degree in the decompression drying process is set to be-0.08 MPa, and the temperature is set to be 60 ℃. The microwave generator 46 generates microwaves by using a magnetron, the temperature of the pre-sintering chamber 42 is set to be 100 ℃, the temperature of the sintering chamber 43 is set to be 400 ℃, the temperature of the constant temperature chamber 44 is set to be 400 ℃, the temperature of the cooling chamber 45 is set to be 80 ℃, and the oxygen gas content and the nitrogen gas content in the sintering chamber 43 and the constant temperature chamber 44 are controlled to be 90% and 10%, respectively. The electrostatic spinning titanium oxide gel fiber membrane keeps differential drafting and proper tension compensation in the whole process from the moment when the electrostatic spinning titanium oxide gel fiber membrane does not enter the pre-burning chamber 42 to the moment when the electrostatic spinning titanium oxide gel fiber membrane leaves the cooling chamber 45, wherein the differential speed between the inlet and the outlet of the pre-burning chamber 42 is 20 percent, the differential speed between the inlet and the outlet of the sintering chamber 43 is 30 percent, the differential speed between the inlet and the outlet of the constant temperature chamber 44 is 30 percent, and the differential speed between the inlet and the outlet of the cooling chamber 45 is 5 percent.
After passing through an analysis mechanism, the removal rate of the micromolecular organic ligand on the titanium oxide gel fiber is up to 99%, and the anatase phase appears in the finally obtained pure titanium oxide fiber at 400 ℃.
Comparative example 1
A conventional laboratory electric furnace calcining device is used for post-treatment of the titanium oxide gel nanofiber membrane in example 1, related process parameters are basically the same, the difference is that the obtained titanium oxide gel fiber is directly calcined without an analysis mechanism, a solvent gradient replacement mechanism, a reduced pressure drying mechanism and a variable atmosphere microwave calcining mechanism, and it can be found that more than 10% of organic ligands are not completely removed at 400 ℃, and no crystalline phase is generated at the time. This indicates that the titania gel fibers are not fully cerammed at this temperature, but require higher temperature treatment to cerammed, but result in grain coarsening. Comparing comparative example 1 with example 1, it can be seen that the fibers of example 1 are ceramized at a relatively low temperature (400 ℃) and the inorganic component has a high purity (> 99%) because example 1 removes most of the organic ligands on the gel fibers, so that the calcination temperature of the fibers is significantly reduced after removing the ligands, and also, a very small amount of carbon residues is present in the incomplete oxygen environment by microwave plasma sintering in a varying atmosphere, and the carbon residues are trapped at the grain boundaries, thereby inhibiting the grain growth. However, in comparative example 1, the gel fibers were directly calcined in a laboratory electric furnace, because the box of the electric furnace was an air environment, the oxygen content was limited and the external air could not be supplemented in time, resulting in insufficient calcination, the fiber film was dark black, indicating that the carbon deposition was severe and a large amount of organic ligands were not removed. In conclusion, these combined factors will play a decisive role in the low-temperature calcination and formation of ceramic nanofibers.
In the above embodiments or examples, the ceramic nanofibers enter and exit the respective compartments through the existing fully-closed belt conveyor to ensure the substantial sealing of the compartments such as the drying compartment, and specifically, the sealing structure of the closed reversible distribution belt conveyor [ J ] hoisting and transporting machinery, 1993(09):33-34, etc.) can be realized by the following prior art (1) has wide application to the roof and has rich the Hades.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A low-temperature calcination forming device for ceramic nanofibers is characterized by comprising:
an analysis mechanism: the analysis device comprises an analysis cabin, a spraying assembly and a negative pressure suction assembly, wherein the spraying assembly and the negative pressure suction assembly are positioned in the analysis cabin, the spraying assembly is positioned above the negative pressure suction assembly, and after entering the analysis cabin, the ceramic nano fibers penetrate through the space between the spraying assembly and the negative pressure suction assembly and are soaked with analysis liquid sprayed by the spraying assembly;
solvent gradient displacement mechanism: the device comprises a displacement cabin positioned behind the analysis cabin, and an alcohol-water bath tank, a displacement bath tank and an alcohol bath tank which are sequentially arranged in the displacement cabin along the advancing direction of the ceramic nano fibers;
a drying mechanism: the device comprises a drying cabin positioned behind a replacing cabin and a drying component which is arranged in the drying cabin and used for heating and drying the ceramic nano-fibers;
atmosphere-variable calcining mechanism: the device comprises a pre-burning cabin, a sintering cabin, a constant temperature cabin and a cooling cabin which are positioned behind a drying cabin, sequentially arranged along the advancing direction of ceramic nano fibers and mutually independent, wherein the pre-burning cabin, the sintering cabin, the constant temperature cabin and the cooling cabin are respectively connected with external oxygen supply equipment and/or inert gas supply equipment through independent pipelines;
and the winding mechanism is positioned behind the variable atmosphere calcining mechanism and is used for winding the formed ceramic nano fibers.
2. The low-temperature calcination forming device for the ceramic nanofibers according to claim 1, wherein the spray assembly comprises a spray header arranged in the desorption chamber, a liquid storage tank, a liquid pump and a desorption liquid tank which are sequentially connected with the spray header, the liquid storage tank is further connected with an ultrasonic generator, and an energy converter is further arranged between the liquid storage tank and the spray header;
the negative pressure suction assembly comprises a hollow tray arranged in the analysis cabin and positioned below the conveyor belt for conveying the ceramic nanofibers, and a negative pressure suction pump connected with the hollow tray through a suction pipeline, wherein the plane of the hollow tray is just parallel to the plane of the conveyor belt.
3. The low-temperature calcination forming device for the ceramic nanofibers according to claim 1, wherein the desorption solution is an alcohol solution of alkali, wherein the alkali is sodium hydroxide or potassium hydroxide, and the alcohol solvent is ethanol, propanol, n-butanol or tert-butanol;
the vacuum degree in the analysis cabin is-0.098 to-0.01 MPa when the analysis cabin works.
4. The low-temperature calcination forming device for ceramic nanofibers according to claim 1, wherein the alcohol water bath is further connected to an alcohol water bath preparation kettle for providing an alcohol water mixture, the substitution bath is further connected to a substitution bath preparation kettle for providing a substitution solvent, and the alcohol bath is further connected to an alcohol bath preparation kettle for providing an alcohol solvent.
5. The low-temperature calcination forming device for ceramic nanofibers according to claim 4, wherein the temperature of the alcohol-water mixed solution in the alcohol-water bath is 10 to 30 ℃, the temperature of the substitution solvent in the substitution bath is 60 to 80 ℃, and the temperature of the alcohol solvent in the alcohol bath is 10 to 30 ℃;
the alcohol-water mixed solution is prepared from alcohol and water, wherein the alcohol is one or more of ethanol, propanol, n-butanol and tert-butanol;
the replacement solvent is one or more of carbon tetrachloride, benzene, toluene, dichloroethane, dichloromethane, chloroform, diethyl ether, diphenyl ether, ethyl acetate, acetone, tetrahydrofuran, N-methylpyrrolidone and N, N-dimethylformamide;
the alcohol solvent is one or more of ethanol, propanol, n-butanol and tert-butanol.
6. The low-temperature calcination forming device for ceramic nanofibers according to claim 1, wherein the drying assembly comprises an infrared heating unit located in a drying chamber and a vacuum generating device connected to the drying chamber through a pipeline, and the drying chamber is a sealed chamber.
7. The low-temperature calcination forming device for the ceramic nanofibers according to claim 1, wherein the working temperature in the drying chamber is 60-80 ℃, and the vacuum degree is-0.1-0.098 MPa.
8. The low-temperature calcination forming device for ceramic nanofibers according to claim 1, wherein the pre-sintering chamber and the cooling chamber are respectively connected to an oxygen supply device through gas pipes;
the sintering chamber and the constant temperature chamber are both connected with an oxygen supply device and an inert gas supply device through gas pipelines.
9. The low-temperature calcination forming device for the ceramic nanofibers according to claim 1, wherein the pre-sintering chamber, the constant-temperature chamber and the cooling chamber are respectively connected with an external microwave generator through waveguides.
10. The low-temperature calcination forming device for the ceramic nanofibers according to claim 1, wherein the working atmosphere of the pre-sintering chamber and the cooling chamber is oxygen atmosphere, and the working atmosphere of the sintering chamber and the constant-temperature chamber is oxygen and inert gas mixed atmosphere;
the working temperature in the pre-sintering chamber is set to be 100-150 ℃, the working temperature in the sintering chamber is set to be 200-500 ℃, the working temperature in the constant-temperature chamber is set to be 200-500 ℃, and the working temperature in the cooling chamber is set to be 60-80 ℃.
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