CN112934128A - Core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer and preparation and application thereof - Google Patents
Core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer and preparation and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
Abstract
The invention relates to an organic-inorganic hybrid nanofiber aerogel elastomer with a core-shell structure and preparation and application thereof. The elastomer is organic-inorganic hybrid nano fiber which takes high-crystallinity nano long fiber as a core layer and takes an organopolysiloxane nano layer as a shell layer. The method comprises the following steps: mixing organic siloxane containing hydrophobic groups with an acid-containing aqueous solution for hydrolysis, then mixing with a high-crystallinity nano long fiber aqueous dispersion, stirring, freezing, freeze-drying, dehydrating and polycondensing. The elastomer has the advantages of excellent resilience, low density, low thermal conductivity, excellent hydrophobicity and heat resistance. The method has the advantages of easily available raw materials, low cost, and easy large-scale production.
Description
Technical Field
The invention belongs to the field of nanofiber aerogel and preparation and application thereof, and particularly relates to an organic-inorganic hybrid nanofiber aerogel elastomer with a core-shell structure and preparation and application thereof.
Background
The heat insulation material can play a role in protection, energy conservation and emission reduction in various fields such as national defense and military industry, aerospace, civil use, industry and the like, and has wide application requirements. There are a wide variety of thermal insulation materials, with highly porous, lightweight nano-aerogel materials being the most promising "super-insulation materials". However, the traditional dimeric siloxane aerogel skeleton structure is formed by connecting dimeric siloxane nanoparticles, has poor mechanical strength, large brittleness and easy breakage under stress, and greatly limits the application of the dimeric siloxane aerogel skeleton structure in the field of high-performance flexible heat insulation. The novel nanofiber aerogel is a light solid material taking high-length-diameter ratio nanofibers which are intertwined with one another as a framework, has excellent characteristics of the traditional aerogel and simultaneously integrates excellent flexibility of the nanofiber material, and has wide application prospects in the field of flexible heat-insulation clothes, such as space suits, individual combat uniforms, polar exploration clothes, factory high-temperature environment working clothes and the like.
Organic nanofiber aerogels have a greater advantage in flexibility than more brittle inorganic nanofiber aerogels, however organic nanofiber aerogels are generally prone to collapse in compressive structures due to lack of proper structural design and strong interfacial bonding. In addition, in practical applications, highly porous hydrophilic aerogel materials tend to cause severe degradation of mechanical and thermal insulation properties after absorbing water, and therefore additional post-treatment processes are usually required to improve the hydrophobic properties of the aerogel materials. Finally, in practical application, the heat resistance of the aerogel thermal insulation material needs to be considered so as to meet the requirements of different application scenarios. The light flexible nanofiber aerogel with excellent resilience, hydrophobicity and heat resistance is designed and prepared by a simple integrated method, and is very important for expanding the practical application of the aerogel in the field of high-performance flexible clothes. CN108031447A discloses that soaking a cellulose nanofiber three-dimensional network in a tetrafunctional silica sol, and performing alkali-catalyzed sol gelation reaction and post-treatment surface hydrophobic modification to improve the resilience and hydrophobic property of aerogel materials to a certain extent, but the obtained composite aerogel elastomer can recover elastic deformation up to 40%, which cannot meet the application requirements in the field of flexible heat insulation such as the field of clothing, and the technical route is relatively long, and the preparation process is tedious.
Disclosure of Invention
The invention aims to solve the technical problem of providing a core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer, and a preparation method and an application thereof, so as to overcome the defects that the existing flexible organic nanofiber aerogel has insufficient resilience, poor thermal stability, the surface of the aerogel needs to be subjected to hydrophobic treatment, the production cost is high, and the like.
The invention provides an organic-inorganic hybrid nanofiber aerogel elastomer with a core-shell structure, which is organic-inorganic hybrid nanofiber with a high-crystallinity nano long fiber as a core layer and an organopolysiloxane nanolayer as a shell layer, wherein the high-crystallinity nano long fiber and organopolysiloxane are connected through hydrogen bond interaction and chemical bonding.
Preferably, in the elastomer, the mass fraction of the organopolysiloxane in the elastomer is 10 to 60%, and the mass fraction of the high-crystallinity long nano-fiber is 90 to 40%.
Preferably, in the above elastomer, the elastomer has a three-dimensional nanofiber network structure.
Preferably, in the elastomer, the high-crystallinity long nanofiber is a native wet unmodified bacterial cellulose nanofiber or a wet unmodified kevlar nanofiber.
Preferably, in the elastomer, the diameter of the high-crystallinity long nanofiber is 2 to 100 nm; the thickness of the organopolysiloxane nano-layer is 1-10 nm.
The invention also provides a preparation method of the core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer, which comprises the following steps:
(1) mixing organic siloxane containing hydrophobic groups with an acid-containing aqueous solution for hydrolysis, mixing the obtained silica sol with a high-crystallinity long nano-fiber aqueous dispersion, and stirring to obtain a mixed dispersion, wherein the mass ratio of the organic siloxane containing hydrophobic groups to the high-crystallinity long nano-fiber is (3-30): 1-10;
(2) transferring the mixed water dispersion liquid obtained in the step (1) into a mold, freezing, then carrying out vacuum freeze drying, gradually dehydrating and self-polymerizing hydrophilic silica sol wrapped on the surface of hydrophilic nanofibers, and preliminarily forming an organopolysiloxane nano-coating layer on the surface of the nanofibers to obtain the hybrid nanofiber aerogel with the core-shell structure;
(3) and (3) drying, dehydrating and polycondensing the hybrid nanofiber aerogel with the core-shell structure in the step (2) to obtain the core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer.
Preferably, in the above method, the organosiloxane having a hydrophobic group in step (1) is at least one of methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane and propyltrimethoxysilane.
Preferably, in the above method, the acid-containing aqueous solution in step (1) is: acetic acid, oxalic acid or hydrochloric acid with the concentration of 0.01-6 mmol/L.
Preferably, in the above method, the mass fraction of the high-crystallinity long nanofibers in the aqueous dispersion of high-crystallinity long nanofibers in step (1) is 0.05 to 0.5%.
Preferably, in the method, the hydrolysis time in the step (1) is 15-30 min; the stirring time is 1-3 h.
Preferably, in the above method, the freezing in step (2) is freezing in liquid nitrogen.
Preferably, in the above method, the vacuum freeze-drying process in step (2) includes: and freeze-drying and polymerizing for 2-3 days in a vacuum environment with the vacuum degree lower than 30 Pa.
Preferably, in the method, the drying, dehydrating and polycondensation treatment in the step (3) is carried out at the temperature of 40-90 ℃ for 8-48 h.
The invention also provides application of the core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer in heat insulation materials, sound insulation materials, vibration absorption materials, catalytic materials, oil absorption materials, flexible functional material three-dimensional frameworks, pressure sensing materials or magnetic response materials.
Preferably, in the above application, the core-shell structure organic-inorganic hybrid conductive, catalytic or magnetic response nanofiber aerogel elastomer is prepared by introducing conductive nanoparticles, metal catalytic active nanoparticles or magnetic functional nanoparticles by in-situ addition or after-loading based on the core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer material.
According to the invention, organic nano-fiber is used as a framework unit, organic siloxane is used as a precursor, and an organic polysiloxane nano-coating layer is formed on the surface of an organic nano-fiber network by freeze drying and vacuum driving silica sol self-polymerization and further post-treatment self-polymerization, so that the organic-inorganic hybrid nano-fiber aerogel elastomer with a core-shell structure is obtained.
According to the invention, the hydrophilic silica sol is self-polymerized on the surface of the hydrophilic organic nanofiber network to form the uniform organic polysiloxane nano coating layer by utilizing a freeze drying vacuum condition, so that strong interface combination and soft and strong framework units among organic nanofibers are endowed, the highly porous hybrid nanofiber aerogel has excellent stability (the structure is not collapsed after compression and can be rebounded), and meanwhile, the hydrophobic property and the heat resistance of the material are improved by the organic polysiloxane coating layer.
The high crystallinity of the high-crystallinity unmodified hydrophilic organic nano long fiber refers to the crystallinity of 85-99%.
Advantageous effects
(1) The invention selects the high-crystallinity nano long fiber with a large amount of high-reactivity hydrophilic functional groups on the surface as a skeleton unit. The characteristics of high crystallinity and long fiber endow the aerogel skeleton unit with soft and tough characteristics, a highly entangled network structure is favorably constructed, the structural strength of the porous material is favorably improved, and in addition, compared with an amorphous structure, the organic nanofiber has higher heat resistance due to the high crystallinity structure; organic siloxane with hydrophobic groups is selected as an inorganic precursor, the organic siloxane is hydrolyzed by weak acid to obtain silica sol, a large number of silicon hydroxyl groups can react with hydroxyl groups or amino groups in a nano long fiber network with a large number of hydrophilic functional groups with high reaction activity to form strong hydrogen bond interaction or chemical bonding, and the structural strength and the stability of the porous material are favorably improved (the structure is not collapsed and can rebound after being compressed).
(2) The invention utilizes the characteristic that the silica sol is easy to dehydrate and self-condense, simultaneously realizes the formation of a three-dimensional nanofiber network and the self-polymerization of the silica sol on the surface of the nanofiber in the vacuum environment in the freeze drying process, the silica sol self-polymerizes to form a hard polysiloxane nano layer to cover the surface of a soft long nanofiber network to form the nanofiber network with a core-shell structure, the structure provides strong interface connection between organic nanofibers, and when the material is subjected to compressive strain, the hard inorganic component can effectively support the soft organic nanofiber network to recover deformation, so the core-shell structure can play a role in stabilizing the nanofiber network. Through proper 'soft-hard' component regulation, the nanofiber aerogel elastomer with excellent resilience performance can be obtained. The core-shell structure is beneficial to further improving the heat resistance of the organic nanofiber network, and the abundant hydrophobic groups on the polysiloxane shell layer endow the material with excellent hydrophobicity.
(3) The preparation method can directly prepare the hybrid nanofiber aerogel elastomer with excellent resilience, low density, low thermal conductivity, excellent hydrophobicity and heat resistance; the density of the hybrid nanofiber aerogel elastomer is 0.7-20 mg/cm-3The recoverable elastic deformation is 90-99%, the thermal conductivity is lower than 0.03W/(m.K), and the water contact angle is larger than or equal to 140 degrees. The preparation process is simple and efficient, the raw materials from the preparation process to the product are all green and pollution-free, the raw materials are easy to obtain, the cost is low, and the large-scale production is easy to realize.
Drawings
FIG. 1 is a cross-sectional focused ion beam-TEM (transmission electron microscope) photograph and a surface element distribution diagram of hybrid nanofibers in the organic-inorganic hybrid nanofiber aerogel elastomer in example 1;
FIG. 2 is a photograph of water contact angle of core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer in example 1;
FIG. 3 is a stress-strain curve of compression resilience and a photo of physical representation of the organic-inorganic hybrid nanofiber aerogel elastomer with a core-shell structure in example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The native wet unmodified bacterial cellulose nanofiber is purchased from Hainan coconut food Co., Ltd, the wet unmodified Kevlar nanofiber is obtained from Kevlar fiber (purchased from DuPont), the Kevlar fiber is peeled in a dimethyl sulfoxide solvent added with a small amount of sodium hydroxide to obtain the Kevlar nanofiber, and the organic siloxane containing hydrophobic groups and the acid catalyst are purchased from national medicine group chemical reagent Co., Ltd.
The test procedures and test conditions for the performance data in the examples are as follows: the elastic deformation of the material is recovered by an electronic universal material testing machine (compression rebound testing gauge length is 2cm, Instron 5969, Instron corporation, USA); the surface contact angle test adopts a full-automatic video microcosmic contact angle measuring instrument (the water drop size is 3ul, OCA40Micro, Germany dataphysics company), the thermal conductivity adopts a steady-state heat flow meter method national standard GB/T10295-2008 'heat insulation material steady-state thermal resistance and related characteristic measuring heat flow meter method' to test, and the heat-resisting temperature test adopts a thermal weight loss analyzer to test in an air atmosphere (the temperature rise speed is 10 ℃/min, TG209F1, Germany speed-resistant company).
Example 1
Mixing 2ml of methyltrimethoxysilane and 6ml of acetic acid aqueous solution (the concentration is 5mM), stirring and hydrolyzing for 30min to obtain silica sol, mixing 200ul of silica sol and 8g of primary wet unmodified bacterial cellulose nanofiber aqueous dispersion with the mass fraction of 0.3%, stirring for 2h, pouring into a mold, freezing in liquid nitrogen, placing the frozen sample in a freeze dryer for drying and vacuum (0.8Pa) polymerization, and taking out after 3 daysAnd putting the sample in an oven at 80 ℃ for further self-polycondensation treatment for 8h to obtain the organic-inorganic hybrid nanofiber aerogel elastomer with the nano core-shell structure. The density of the prepared hybrid nanofiber aerogel elastomer is 5.7mg/cm-3The recoverable elastic deformation reaches 99 percent, the water contact angle reaches 167.5 degrees, the thermal conductivity value is 0.0289W/(m.K), and the thermal stability reaches 300 ℃.
FIG. 1 shows that: polysiloxane forms a nano shell structure and is tightly wrapped on the surface of the bacterial cellulose nanofiber to obtain the organic-inorganic hybrid nanofiber with the core-shell structure.
Example 2
Mixing 2ml of methyltrimethoxysilane and 6ml of oxalic acid aqueous solution (the concentration is 6mM), stirring and hydrolyzing for 30min to obtain silica sol, mixing 400ul of silica sol and 8g of wet unmodified Kevlar nanofiber aqueous dispersion with the mass fraction of 0.3%, stirring for 2h, pouring into a mold, freezing in liquid nitrogen, placing the frozen sample in a freeze dryer for drying vacuum (0.8Pa) polymerization, taking out after 3 days, placing the sample in a 60 ℃ oven for further self-polycondensation reaction for 12h, and obtaining the organic-inorganic hybrid nanofiber aerogel elastomer with the nano core-shell structure. The density of the prepared hybrid nanofiber aerogel elastomer is 8.1mg/cm-3The recoverable elastic deformation is up to 90 percent, the water contact angle is up to 150 degrees, the thermal conductivity value is 0.0281W/(m.K), and the thermal stability is up to 390 ℃.
Example 3
Mixing 2ml of vinyltrimethoxysilane and 6ml of hydrochloric acid aqueous solution (the concentration is 0.01mM), stirring and hydrolyzing for 15min to obtain silica sol, mixing 5ul of silica sol and 8g of primary wet unmodified bacterial cellulose nano long fiber aqueous dispersion with the mass fraction of 0.05 percent, stirring for 1h, pouring into a mold, freezing in liquid nitrogen, placing the frozen sample in a freeze dryer for freeze drying vacuum (0.8Pa) polymerization, taking out after 2 days, placing the sample in a40 ℃ oven for further self-polycondensation treatment for 48h, and obtaining the organic-inorganic hybrid nanofiber aerogel elastomer with the nano core-shell structure. The density of the prepared hybrid nanofiber aerogel elastomer is 0.7mg/cm-3The recoverable elastic deformation reaches 92 percent, and the water connection is carried outThe antenna is up to 140 degrees, the thermal conductivity value is 0.026W/(m.K), and the thermal stability is up to 350 ℃.
Example 4
Mixing 2ml of ethyl trimethoxy silane and 6ml of acetic acid aqueous solution (the concentration is 6mM), stirring and hydrolyzing for 30min to obtain silica sol, mixing 300ul of silica sol and 8g of primary wet unmodified bacterial cellulose nano long fiber aqueous dispersion with the mass fraction of 0.1%, stirring for 2h, pouring into a mold, freezing in liquid nitrogen, placing the frozen sample in a freeze dryer for freeze drying vacuum (0.8Pa) polymerization, taking out after 3 days, placing the sample in a 60 ℃ drying oven for further self-polycondensation reaction for 12h, and obtaining the organic-inorganic hybrid nanofiber aerogel elastomer with the nano core-shell structure. The density of the prepared hybrid nanofiber aerogel elastomer is 3.0mg/cm-3The recoverable elastic deformation reaches 91 percent, the water contact angle reaches 151 degrees, the thermal conductivity value is 0.0278W/(m.K), and the thermal stability reaches 330 ℃.
Example 5
Mixing 2ml of propyl trimethoxy silane and 6ml of hydrochloric acid aqueous solution (the concentration is 6mM), stirring and hydrolyzing for 30min to obtain silica sol, mixing 500ul of silica sol and 8g of native wet unmodified Kevlar long fiber aqueous dispersion with the mass fraction of 0.5%, stirring for 3h, pouring into a mold, freezing in liquid nitrogen, placing the frozen sample in a freeze dryer for freeze drying vacuum (0.8Pa) polymerization, taking out after 3 days, placing the sample in a 90 ℃ oven for further self-polycondensation treatment for 48h, and obtaining the organic-inorganic hybrid nanofiber aerogel elastomer with the nano core-shell structure. The density of the prepared hybrid nanofiber aerogel elastomer is 20.0mg/cm-3The recoverable elastic deformation is up to 90 percent, the water contact angle is up to 145 degrees, the thermal conductivity value is 0.0295W/(m.K), and the thermal stability is up to 370 ℃.
Comparative example 1
CN108031447A firstly adopts a biological synthesis method to prepare a cellulose three-dimensional network template frame, further immerses the frame into a solution containing a tetrafunctional silicon source and a surfactant cetyl trimethyl ammonium bromide, adds an alkali catalyst ammonia water to promote the hydrolysis and polycondensation of the silicon source to form a silicon dioxide gel network in the cellulose network, further immerses the cellulose/silicon dioxide gel into a long-chain alkyl silicate solution with hydrophobic groups to carry out surface hydrophobic modification, and obtains the cellulose/silicon oxide composite aerogel elastomer with certain elasticity and hydrophobic property after washing solvent replacement and normal-temperature drying. The elastic recovery deformation of the obtained composite aerogel elastomer can reach 40 percent at most, and the water contact angle is 151 degrees. Compared with CN108031447A, the invention adopts organosiloxane containing hydrophobic groups as a silicon source, adopts native wet organic long nanofiber as a construction unit, adopts a freeze-drying vacuum polymerization method to uniformly wrap polysilane on the surface of organic nanofiber to form stable cross-linking points, obtains the super-elastic and super-hydrophobic organic-inorganic hybrid nanofiber aerogel elastomer with a core-shell structure, can recover elastic deformation up to 99% at most, has a water contact angle up to 168 degrees, and has performance superior to that reported in CN 108031447A.
Claims (10)
1. The organic-inorganic hybrid nanofiber aerogel elastomer with the core-shell structure is characterized by being organic-inorganic hybrid nanofibers with high-crystallinity long nanofibers as core layers and organopolysiloxane nanolayers as shell layers, wherein the high-crystallinity long nanofibers are connected with organopolysiloxane through hydrogen bond interaction and chemical bonding.
2. The elastomer according to claim 1, wherein the mass fraction of the organopolysiloxane in the elastomer is 10-70%, and the mass fraction of the high-crystallinity long nano-fibers is 90-30%; the elastomer has a three-dimensional nanofiber network structure.
3. The elastomer of claim 1, wherein the high crystallinity nano long fibers are native wet unmodified bacterial cellulose nanofibers or wet unmodified kevlar nanofibers.
4. A preparation method of an organic-inorganic hybrid nanofiber aerogel elastomer with a core-shell structure comprises the following steps:
(1) mixing organic siloxane containing hydrophobic groups with an acid-containing aqueous solution for hydrolysis, mixing the obtained silica sol with a high-crystallinity long nano-fiber aqueous dispersion, and stirring to obtain a mixed dispersion, wherein the mass ratio of the organic siloxane containing hydrophobic groups to the high-crystallinity long nano-fiber is (3-30): 1-10;
(2) transferring the mixed dispersion liquid in the step (1) into a mold, freezing, and then carrying out vacuum freeze drying to obtain the hybrid nanofiber aerogel with the core-shell structure;
(3) and (3) drying, dehydrating and polycondensing the hybrid nanofiber aerogel with the core-shell structure in the step (2) to obtain the core-shell structure organic-inorganic hybrid nanofiber aerogel elastomer.
5. The method according to claim 4, wherein the organic siloxane containing hydrophobic group in step (1) is at least one of methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane and propyltrimethoxysilane; the acid-containing aqueous solution comprises: acetic acid, oxalic acid or hydrochloric acid with the concentration of 0.01-6 mmol/L.
6. The method according to claim 4, wherein the mass fraction of the high-crystallinity long nano-fibers in the aqueous dispersion of high-crystallinity long nano-fibers in step (1) is 0.05 to 0.5%.
7. The method according to claim 4, wherein the hydrolysis time in the step (1) is 15-30 min; the stirring time is 1-3 h.
8. The method according to claim 4, wherein the freezing in the step (2) is freezing in liquid nitrogen; the technological conditions of vacuum freeze drying are as follows: and freeze-drying and polymerizing for 2-3 days in a vacuum environment with the vacuum degree lower than 30 Pa.
9. The method according to claim 4, wherein the drying, dehydrating and polycondensing treatment in the step (3) is carried out at a temperature of 40 to 90 ℃ for 8 to 48 hours.
10. Use of the elastomer according to claim 1 in thermal insulation materials, sound insulation materials, vibration absorption materials, catalytic materials, oil absorption materials, flexible functional material three-dimensional frameworks, pressure sensing materials or magnetic response materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113648940A (en) * | 2021-09-23 | 2021-11-16 | 航天特种材料及工艺技术研究所 | Ultra-light high-elasticity radiation-resistant nanofiber aerogel material and preparation method thereof |
| CN114602394A (en) * | 2022-01-28 | 2022-06-10 | 西安理工大学 | Organic aerogel with surface compact layer removed and preparation method thereof |
| CN115155469A (en) * | 2022-07-26 | 2022-10-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Water-soluble IB group noble metal sub-10 nano colloidal particle, and preparation method and application thereof |
| CN116876253A (en) * | 2023-06-14 | 2023-10-13 | 哈尔滨工程大学 | Controllable preparation method of multifunctional aramid nanofiber wave-absorbing composite membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050192366A1 (en) * | 2004-01-06 | 2005-09-01 | Aspen Aerogels, Inc. | Ormosil aerogels containing silicon bonded polymethacrylate |
| CN107868270A (en) * | 2016-09-23 | 2018-04-03 | 中国科学院化学研究所 | A kind of aerogel material constructed by fiber and adhesive and its preparation method and application |
| CN109608686A (en) * | 2018-12-18 | 2019-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Kevlar aerogel, preparation method and application |
| CN111499919A (en) * | 2020-05-11 | 2020-08-07 | 江西理工大学 | Biomass fiber hybrid polysiloxane aerogel glass and preparation method thereof |
-
2021
- 2021-01-27 CN CN202110111854.7A patent/CN112934128A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050192366A1 (en) * | 2004-01-06 | 2005-09-01 | Aspen Aerogels, Inc. | Ormosil aerogels containing silicon bonded polymethacrylate |
| CN107868270A (en) * | 2016-09-23 | 2018-04-03 | 中国科学院化学研究所 | A kind of aerogel material constructed by fiber and adhesive and its preparation method and application |
| CN109608686A (en) * | 2018-12-18 | 2019-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Kevlar aerogel, preparation method and application |
| CN111499919A (en) * | 2020-05-11 | 2020-08-07 | 江西理工大学 | Biomass fiber hybrid polysiloxane aerogel glass and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XUEXIA ZHANG ET AL.: "Ultralight, hydrophobic, anisotropic bamboo-derived cellulose nanofibrils aerogels with excellent shape recovery via freeze-casting", 《CARBOHYDRATE POLYMERS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113648940A (en) * | 2021-09-23 | 2021-11-16 | 航天特种材料及工艺技术研究所 | Ultra-light high-elasticity radiation-resistant nanofiber aerogel material and preparation method thereof |
| CN113648940B (en) * | 2021-09-23 | 2023-05-05 | 航天特种材料及工艺技术研究所 | Ultra-light high-elasticity anti-radiation nanofiber aerogel material and preparation method thereof |
| CN114602394A (en) * | 2022-01-28 | 2022-06-10 | 西安理工大学 | Organic aerogel with surface compact layer removed and preparation method thereof |
| CN115155469A (en) * | 2022-07-26 | 2022-10-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Water-soluble IB group noble metal sub-10 nano colloidal particle, and preparation method and application thereof |
| CN115155469B (en) * | 2022-07-26 | 2023-10-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Water-soluble group IB noble metal sub-10 nanometer colloidal particle, preparation method and application thereof |
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