CN114455573A - Ultralow-density solid material, preparation method and application thereof - Google Patents
Ultralow-density solid material, preparation method and application thereof Download PDFInfo
- Publication number
- CN114455573A CN114455573A CN202210144808.1A CN202210144808A CN114455573A CN 114455573 A CN114455573 A CN 114455573A CN 202210144808 A CN202210144808 A CN 202210144808A CN 114455573 A CN114455573 A CN 114455573A
- Authority
- CN
- China
- Prior art keywords
- solid material
- layered
- lauryl
- alcohol
- density
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/003—Phosphorus
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to an ultra-low density solid material, a preparation method and application thereof. The ultra-low density solid material has a porous structure with the aperture of 10 mu m-10mm, the porous structure is built by solid material building units, and the density of the ultra-low density solid material is 0.001mg/cm3～0.1mg/cm3. The invention mixes the materials by a vacuum foaming methodFoaming the slurry, freezing in situ for shaping, expanding the volume of the slurry mixture by 5-100 times, and drying to obtain the ultra-low density solid material with the density of 0.001mg/cm3～0.1mg/cm3The time can be adjusted and controlled. The density breaks through the density record of the lightest solid material in the world which is published and reported at present, and develops a new boundary for exploring low-density solids by human beings.
Description
Technical Field
The invention relates to the field of ultra-light materials, in particular to an ultra-low density solid material, a preparation method and application thereof.
Background
The ultra-low density solid material belongs to the ultra-light material, and is a type of material with extremely low density (the true density is usually lower than 10 mg/cm)3) The performance of the novel material mainly depends on the internal structure (pore structure and the distribution of solid components in space) and the performance (rigidity, strength and the like) of raw materials, the novel material is a unity of excellent physical and chemical properties and structural performance, has unique performance in the aspects of thermal, acoustic, electrical, magnetic, optical and the like, and has important functions in the fields of dampers, electrodes, heat insulation, heat preservation, separators, absorbents, tissue engineering supports, aerospace, electrode materials, sensors and the like.
The ultra-low density solid material mainly comprises aerogel, low density foam, micro-lattice material and the like according to different material structures. Common ultralight materials include silica aerogel, carbon nanotube aerogel, graphene aerogel, boron nitride aerogel, low-density metal foam, low-density polymer foam, micro-lattice metal, and the like. Common preparation methods mainly include self-assembly, foaming, 3D printing, precursor conversion, and the like.
The presently publicly reported lowest density solid material is a carbon nanotube/graphene aerogel, with a density of only about 0.12mg/cm3(DOI:10.1038/ncomms 6802). Due to the nature of solid materials and manufacturing techniques, it is currently a great challenge to produce lower density solid materials. The development of novel ultra-low density solid materials and preparation technology thereof has important significance for the development and application of ultra-light materials.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Object of the Invention
The invention aims to provide an ultralow-density solid material, a preparation method and application thereof, wherein the density of the ultralow-density solid material is 0.001mg/cm3～0.1mg/cm3The ultra-low density solid material breaks through the record of the lowest density solid material which is published and reported in the world at present.
Solution scheme
In order to achieve the purpose of the invention, the embodiment of the invention provides the following technical scheme.
The embodiment of the invention provides an ultralow-density solid material, which has a porous structure with the pore diameter of 10 mu m-10mm, and the density of the ultralow-density solid material is 0.001mg/cm3～0.1mg/cm3。
The density test method includes: cutting a sample into regular cuboids, measuring the size by using a ruler, and calculating the volume; the weight of the sample was measured with an electronic balance in a vacuum glove box and the density was determined by dividing the weight by the volume.
In one possible implementation of the ultra low density solid material, the density of the ultra low density solid material is 0.001mg/cm3～0.1mg/cm3Preferably 0.005mg/cm3～0.05mg/cm3。
In one possible implementation manner of the ultra-low density solid material, the pore diameter of the porous structure is preferably 100 μm to 5 mm.
In one possible implementation of the ultra-low density solid material, the solid material includes at least one of graphene oxide, graphene, graphite nanoplatelets, layered phosphates, layered hydroxides, layered double hydroxides, layered silicates, layered clays, layered chalcogenides, layered oxides, layered nitrides, layered carbides, layered silicides, layered borides, layered black phosphorus, layered elemental metals, layered covalent organic framework materials, layered metal organic framework materials, carbon nanotubes, carbon nanofibers, silicon carbide whiskers, copper nanowires, silver nanowires, titanium dioxide nanowires, fullerenes, quantum dots, nanoclusters, natural fibers, proteins, natural rubber, dextran, synthetic resins, synthetic fibers, or starch;
preferably, the solid material includes at least one of graphene oxide, layered phosphate, layered hydroxide, layered double hydroxide, layered silicate, layered oxide, carbon nanotube, carbon nanofiber, copper nanowire or silver nanowire.
The embodiment of the invention also provides a preparation method of the ultralow-density solid material, which comprises the following steps:
providing a solid material dispersion liquid, and adding a toughening agent into the solid material dispersion liquid to obtain a mixed dispersion liquid;
foaming the mixed dispersion liquid through vacuum foaming, and then freezing and shaping for 5-60 min at low temperature; and drying to obtain the ultra-low density solid material.
In one possible implementation of the preparation method of the present invention, the solid material is dispersed in a solvent to form a solid material dispersion.
In one possible implementation manner of the preparation method of the present invention, the solvent is any one of the following solvents:
(a) water; (b) a mixed solvent of water and an organic solvent.
In one possible implementation of the preparation method of the present invention, the mass fraction of the solid material in the solid material dispersion is 0.001% to 10%, for example, 0.1%, 0.2%, 0.5%, 1%, or 10%. If the content is less than 0.001 percent, the content of the solid materials in the solid material dispersion liquid is too low, so that the solid materials cannot be mutually overlapped to form a complete porous structure, or the finally formed porous solid material has poor mechanical property and is easy to collapse; if the content is more than 10%, the density of the finally formed porous solid material is too high, and the ultra-light target cannot be achieved. Preferably, the mass fraction of the solid material in the solid material dispersion is 0.005% to 5%.
In a possible embodiment of the preparation process according to the invention, the toughening agent is added directly or in the form of a solution to the solid material dispersion. The solution is in the form of a solution obtained by dispersing the toughening agent in a solvent.
In a possible implementation manner of the preparation method, the toughening agent is added into the solid material dispersion liquid in the form of a solution, the mass concentration of the toughening agent is 1-99%, and further optionally, the mass concentration of the toughening agent is 1-50%; preferably, the mass concentration of the toughening agent is 2-20%. The mass concentration of the toughening agent refers to the mass of the toughening agent divided by the mass of the solution ("solution before the toughening agent is added to the solid material dispersion").
In a possible implementation manner of the preparation method, the addition amount of the toughening agent is 1-2000% of the mass of the solid material. When the addition amount of the toughening agent is too low, the strength of the foam wall is not enough during foaming, and the foaming is not easy to be fully performed, so that the molding is influenced; too high an amount of addition results in a final product with too high a density. Preferably, the addition amount of the toughening agent is 10-1000% of the mass of the solid material, the content just enables the solid dispersion liquid to be easily foamed, and meanwhile the integrity of the final integral structure cannot be affected, for example, the content is too high, the prepared solid material contains a large amount of toughening agent, and the integral structure of the solid material is easily collapsed due to the disintegration of the toughening agent in the later heating treatment process.
In a possible implementation manner of the preparation method, the toughening agent comprises sodium fatty alcohol-polyoxyethylene ether sulfate, alkylphenol polyoxyethylene polyoxypropylene ether, disodium fatty alcohol-polyoxyethylene sulfosuccinate monoester, triethanolamine dodecylbenzene sulfonate, alpha-olefin sulfonate, sodium abietate, sodium diisooctyl succinate sulfonate, potassium laurate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, lauryl alcohol, cetyl alcohol, polyethylene glycol, lauryl glyceryl ether, octylamine, n-decanol, n-octyl glyceryl ether, n-decyl glyceryl ether, dodecyl sulfamide, dodecyl ethanolamine, starch, arabic gum, sodium alginate, bone meal, gelatin, casein, hydroxymethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, sodium alginate, calcium carbonate, sodium alginate, Hydroxyethyl cellulose, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt, polyethylene glycol, alcohol ether glycoside, alkyl polyglycoside, isomeric polyoxyethylene polyoxypropylene ether, fatty acid polyglycol ester, isomeric polyoxyethylene undecylenate, isomeric polyoxyethylene tridecylenate, lauryl hydroxypropyl sulfobetaine, tetradecyl dihydroxyethyl amine oxide, cocoalkyl dimethyl amine oxide, lauryl dimethyl amine oxide, octadecyl dimethyl amine oxide, lauryl amidopropyl dimethyl amine oxide, cocoamidopropyl dimethyl amine oxide, lauryl amidopropyl dimethyl amine oxide, tallowamidopropyl dimethyl amine oxide, lauryl dihydroxyethyl amine oxide, stearyl amidopropyl dimethyl amine oxide, cocoyl hydroxypropyl sulfobetaine, stearyl hydroxypropyl sulfobetaine, polyglykol, polykol, alkyl polyglycoside, polykol, alkyl glyceryl, lauryl dimethyl amine oxide, stearyl alcohol, polykol, polyoxyethylene glycol, polyoxyethylene, At least one of lauramide hydroxypropyl sulfobetaine, oleamide propyl betaine, octadecylamine polyoxyethylene ether oxide, dodecylamine polyoxyethylene ether oxide, octadecyldihydroxyethyl amine oxide, octadecylamide propyl dimethyl amine oxide, dodecyl phosphate betaine or laurylamide propyl betaine.
The vacuum foaming method is characterized in that the mixed slurry is foamed in a vacuum negative pressure environment, and the initiated foam can keep the shape without cracking under the assistance of the toughening agent. In a possible implementation manner of the preparation method of the invention, the pressure of the vacuum foaming is 0.1 Pa-2000 Pa, and further the optional pressure is 1 Pa-1000 Pa, and in the pressure range, the foam expansion ratio can be ensured to be most suitable (the foam can not break), and the pressure range can be selected according to the required final foam density.
In a possible implementation manner of the preparation method, the low temperature of the freezing and shaping is-200 ℃ to 0 ℃, and preferably, the low temperature of the freezing and shaping is-100 ℃ to-20 ℃.
In one possible implementation manner of the preparation method, the freezing and shaping are carried out by a refrigerator, an ice chest, frozen ice blocks, a low-temperature heat sink, a freeze dryer cold trap or liquid nitrogen.
In one possible implementation manner of the preparation method of the present invention, the drying manner includes at least one of freeze drying, natural drying or supercritical drying, and preferably freeze drying. Freeze-drying may be preferred as it allows the porous structure of the solid material to be kept from significant structural changes, which is advantageous in maintaining the porous, low density characteristics of the product.
In one possible implementation manner of the preparation method, the method further comprises a step of further post-treating the dried product, wherein the post-treatment comprises heat treatment, chemical treatment or excitation treatment. The post-treatment serves to remove excess additives and to improve the microstructure and properties of the solid material.
Embodiments of the present invention also provide a use of the ultra-low density solid material as described above, based on its ultra-low density, porous structure, low thermal conductivity, excellent elasticity, etc., the ultra-low density solid material may be used as a thermal insulation material, a deformation sensor, a micro-pressure sensor, an ultra-high temperature electrothermal material, an electrode material, etc.
Advantageous effects
The invention foams the mixed slurry by a vacuum foaming method and freezes and shapes in situ, the volume of the foamed mixed slurry can be foamed and expanded by about 5 to 100 times under the condition of vacuum air extraction, and finally, the ultralow-density solid material is obtained by freeze drying, and the density is 0.001mg/cm3～0.1mg/cm3The time can be regulated and controlled. The density breaks through the density record of the lightest solid material in the world at present, and develops a new boundary for exploring low-density solids by human beings.
The preparation method of the ultralow-density solid material provided by the embodiment of the invention can control the density and the internal pore size of a final product by controlling the foam volume expansion multiple and the concentration of the solid dispersion liquid. Under the same solid dispersion concentration, the foam volume expansion ratio is further controlled by controlling the vacuum foaming pressure, and the lower the pressure is in the vacuum foaming pressure range, the larger the foam volume expansion ratio is, and the lower the density of the obtained final product is.
The preparation method is simple, environment-friendly and easy to operate, is suitable for preparing the ultralow-density solid material with various building units as elements, can break through the existing low-density world record in density, and has important significance for the development of the ultralow-density solid material and the expansion of the application of the ultralow-density solid material.
The ultralow-density solid material has extremely low density and excellent mechanical and thermal insulation properties.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Fig. 1 is a photograph of an ultra-low density solid material of graphene oxide prepared in example 1 of the present invention.
Fig. 2 is a photograph of the graphene ultra-low density solid material prepared in example 1 of the present invention.
Fig. 3 is a photograph of a graphene ultra-low density solid material prepared in example 1 of the present invention supported by three thin hair strands.
FIG. 4 is an infrared spectrum test curve of the graphene ultra-low density solid material prepared in example 1 of the present invention.
Fig. 5 is a compression test stress-strain curve of the graphene ultra-low density solid material prepared in example 1 of the present invention.
Fig. 6 is a picture of the graphene ultra-low density solid material prepared in example 2 of the present invention.
FIG. 7 is a photograph of the graphene oxide/montmorillonite ultra-light solid material prepared in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
The starting materials used in the following examples are all commercially available products.
Example 1
Fully stirring and mixing graphene oxide water dispersion with the mass concentration of 0.1% and alkylphenol polyoxyethylene polyoxypropylene ether at the stirring speed of 1600r/min by mechanical stirring to form uniform slurry with a plurality of small bubbles (the mass ratio of the graphene oxide to the alkylphenol polyoxyethylene polyoxypropylene ether is 1:1), placing the mixed slurry into a plastic cup, then placing the plastic cup into a cold trap of a freeze dryer at the temperature of minus 60 ℃, vacuumizing the interior by a vacuum pump to enable the interior to present a negative pressure environment (300 Pa-500 Pa), integrally foaming the slurry, controlling the foaming expansion ratio to be about 30 times, stopping vacuumizing and keeping the internal pressure of the cold trap unchanged, performing freeze forming for about 40min in the cold trap at the temperature of minus 60 ℃, performing freeze drying for 6h at the temperature of minus 60 ℃ to obtain a graphene oxide ultralow-density solid material (figure 1), and performing heat treatment for 2h at the temperature of 800 ℃, finally obtaining the graphene ultra-low density solid material (figure 2), wherein the main pore diameter of the porous structure is 0.5mm-8mm, and the density is about 0.02mg/cm3Density world record (0.12 mg/cm) of the lowest density solid reported in the open at present3) 16.7% of the total weight of the hair can be supported and suspended by 3 vertical hair strands (figure 3).
Through infrared spectrum testing (figure 4), the graphene oxide is converted into graphene after heat treatment at 800 ℃ for 2h, so that the graphene oxide ultra-low density solid material is converted into the graphene ultra-low density solid material.
The graphene ultra-low density solid material was subjected to a compression test using a compression tester (fig. 5), and it was found that the maximum strain of the prepared graphene ultra-low density solid material was as high as 99%, which corresponds to a stress of about 500 Pa.
The thermal conductivity of the graphene oxide ultra-low density solid and the thermal conductivity of the graphene ultra-low density solid are both less than 0.015W/mK through a thermal conductivity meter.
Example 2
Fully stirring and mixing 0.4 mass percent graphene oxide aqueous dispersion and isomeric tridecanol polyoxyethylene ether aqueous solution (the concentration is 5%) at a stirring speed of 1600r/min by mechanical stirring to obtain uniform slurry with a plurality of small bubbles (the mass ratio of the graphene oxide to the isomeric tridecanol polyoxyethylene ether is 1:1), placing the mixed slurry into a plastic cup, then placing the plastic cup into a cold trap of a vacuum freeze dryer at-60 ℃, vacuumizing by a vacuum pump to ensure that the interior of the plastic cup presents a negative pressure environment (200 Pa-400 Pa), integrally foaming the slurry, controlling the foaming expansion ratio to be about 40 times, stopping vacuumizing and keeping the internal pressure of the cold trap unchanged, freezing and shaping for about 60min in the cold trap at (-50 ℃), and freeze-drying for 8h at-50 ℃ by a freeze-drying mode to obtain the graphene oxide solid material with ultralow density, then carrying out thermal reduction treatment at 1000 ℃ for 2h to prepare the graphene ultralow-density solid material (figure 6), wherein the main pore diameter of the porous structure of the graphene ultralow-density solid material is 0.2-4 mm, and the density of the graphene ultralow-density solid material is about 0.06mg/cm3. The thermal conductivity coefficient of the graphene ultralow-density solid is tested by a thermal conductivity coefficient instrument and is less than 0.020W/mK.
Example 3
Fully stirring and mixing a graphene oxide and montmorillonite mixed dispersion liquid (the mass ratio of graphene oxide to montmorillonite is 1:1) with the mass concentration of 0.5% and a sodium dodecyl benzene sulfonate aqueous solution (the concentration is 5%) at a stirring speed of 2000r/min by mechanical stirring to form uniform slurry with a plurality of small bubbles (the mass ratio of the sum of the mass of graphene oxide and montmorillonite to the mass of sodium dodecyl benzene sulfonate is 1:2), placing the mixed slurry into a plastic cup, then placing the plastic cup into a cold trap of a vacuum freeze dryer which is started to be frozen in advance, and vacuumizing by a vacuum pump to enable the interior to present negative pressure (100 Pa-300P)a) Foaming the slurry integrally, controlling the foaming expansion ratio to be about 50 times, stopping vacuumizing and keeping the pressure inside the cold trap unchanged, freezing and shaping the foam by liquid nitrogen for about 2min, freeze-drying the foam at-80 ℃ for 6h in a freeze-drying mode to obtain the graphene oxide/montmorillonite ultralow-density solid material (figure 7), and carrying out thermal reduction treatment at 600 ℃ for 2h to obtain the graphene/montmorillonite ultralow-density solid material, wherein the main pore diameter of the porous structure of the graphene/montmorillonite ultralow-density solid material is 0.3-8 mm, and the density of the graphene/montmorillonite ultralow-density solid material is about 0.08mg/cm3. The thermal conductivity coefficient of the graphene/montmorillonite ultra-low density solid is tested by a thermal conductivity coefficient instrument and is less than 0.020W/mK.
Example 4
Fully mixing layered titanium phosphate and starch mixed dispersion liquid (the mass ratio of the layered titanium phosphate to the starch is 1:2) with polyvinyl alcohol aqueous solution (the concentration is 10%) by mechanical stirring (300r/min) and ultrasonic water bath to form uniform slurry (the mass ratio of the total mass of the layered titanium phosphate and the starch to the polyvinyl alcohol is 1:2), placing the mixed slurry in a glass beaker, then placing the glass beaker into a cold trap of a vacuum freeze dryer which is started to freeze in advance, placing a copper block (copper block heat sink) which is subjected to liquid nitrogen full cooling treatment on the beaker, vacuumizing by a vacuum pump to enable the interior of the freeze dryer to present negative pressure (200 Pa-400 Pa), integrally foaming the slurry, controlling the foaming expansion ratio to be about 100 times, stopping vacuumizing and keeping the pressure intensity in the cold trap unchanged, fully freezing and molding the foam by the copper block heat sink after about 20min, and finally, drying for 3 hours by a supercritical drying method to obtain a primary product. Processing the primary product at 800 ℃ for 2h to obtain the layered titanium phosphate ultralow-density solid material, wherein the main pore diameter of the porous structure of the layered titanium phosphate ultralow-density solid material is 0.1-10 mm, and the density of the layered titanium phosphate ultralow-density solid material is about 0.09mg/cm3. The heat conductivity coefficient of the layered titanium phosphate ultralow-density solid material is tested by using a heat conductivity coefficient instrument and is less than 0.020W/mK.
Example 5
Fully and uniformly mixing magnesium-aluminum layered double hydroxide with the total mass concentration of 1% and lauryl sodium sulfate dispersion liquid (the mass ratio of the magnesium-aluminum layered double hydroxide to the lauryl sodium sulfate is 1:9) through mechanical stirring (800r/min) and ultrasonic water bath to form uniform slurry, placing the slurry in a glass beaker, and then adding the slurry into the glass beakerThen placing the slurry into a cold trap of a vacuum freeze dryer which is started to freeze in advance, vacuumizing by using a vacuum pump to enable the interior of the freeze dryer to present negative pressure (500-800 Pa), integrally foaming the slurry, controlling the foaming expansion ratio to be about 30 times, stopping vacuumizing and keeping the pressure in the cold trap unchanged, standing for about 30min, fully freezing and molding the foam, and drying for 2h by using a supercritical drying method to obtain an initial product. Processing the primary product at 800 deg.C for 2h to obtain magnesium-aluminum layered double hydroxide ultralow density solid material with main pore diameter of 0.1-6 mm and density of about 0.04mg/cm3. The thermal conductivity coefficient of the magnalium layered double hydroxide ultralow density solid material is tested by a thermal conductivity coefficient instrument and is less than 0.020W/mK.
Example 6
Adding dodecyl dihydroxyethyl amine oxide (the mass ratio of the carbon nano tube to the graphene oxide is 4:1) into a water dispersion of the carbon nano tube and the graphene oxide (the mass ratio of the carbon nano tube to the graphene oxide is 4:1) with the mass total concentration of 0.05 percent, fully and uniformly mixing the mixture through mechanical stirring (500r/min) and ultrasonic water bath to form uniform slurry, placing the slurry into a paper cup, placing the paper cup into a cold trap of a vacuum freeze dryer which is started to freeze in advance, enabling the interior of the freeze dryer to present negative pressure (500 Pa-800 Pa) through vacuum pump vacuum pumping to enable the slurry to foam integrally, controlling the foaming expansion ratio to be about 30 times, stopping the vacuum pumping and keeping the internal pressure of the cold trap unchanged, placing the paper cup for about 30min, fully freezing and molding the foam, and drying the paper cup for 2h through a supercritical drying method to obtain an initial product. Processing the primary product at 800 ℃ for 2h to obtain the graphene/carbon nano tube ultralow-density solid material, wherein the main pore diameter of the porous structure of the solid material is 0.2-8 mm, and the density of the solid material is about 0.03mg/cm3. The thermal conductivity coefficient of the graphene/carbon nano tube ultralow-density solid material is tested by a thermal conductivity coefficient instrument and is less than 0.020W/mK.
Example 7
Graphene oxide (average sheet diameter) with a mass concentration of 0.02%>60 microns) water dispersion and dodecyl ethanolamine are fully stirred and mixed into uniform slurry with more small bubbles by mechanical stirring at the stirring speed of 300r/min (the mass ratio of the graphene oxide to the dodecyl ethanolamine is 1:5), and the slurry is mixedPlacing the slurry in a plastic cup, then placing the plastic cup into a cold trap of a freeze dryer at the temperature of-60 ℃, vacuumizing the plastic cup by a vacuum pump to ensure that the interior of the plastic cup presents a negative pressure environment (200 Pa-300 Pa), integrally foaming the slurry, controlling the foaming expansion ratio to be about 30 times, stopping vacuumizing the plastic cup and keeping the pressure inside the cold trap unchanged, performing freeze forming for about 30min at the temperature of-60 ℃ in the cold trap, performing freeze drying for 5h at the temperature of-60 ℃ to obtain a graphene oxide ultralow density solid material, and performing heat treatment for 2h at the temperature of 900 ℃ to finally obtain the graphene ultralow density solid material, wherein the main pore diameter of the porous structure of the graphene ultralow density solid material is 1mm-9mm, and the density of the graphene ultralow density solid material is about 0.004mg/cm3. The thermal conductivity coefficient of the graphene ultralow-density solid material is tested by a thermal conductivity coefficient instrument and is less than 0.012W/mK.
Example 8
Black phosphorus nanosheet (average plate diameter) with mass concentration of 0.08 percent>10 microns) water dispersion and polyethylene glycol are fully stirred and mixed into uniform slurry with more small bubbles (the mass ratio of the black phosphorus nanosheet to the dodecylethanolamine is 1:3) at the stirring speed of 600r/min by mechanical stirring, the slurry is placed in a plastic cup, then the plastic cup is placed in a cold trap of a freeze dryer at the temperature of-60 ℃, the interior of the plastic cup is vacuumized by a vacuum pump to form a negative pressure environment (200 Pa-500 Pa), the slurry is integrally foamed, the foaming expansion ratio is controlled to be about 25 times, the vacuumizing is stopped, the pressure inside the cold trap is kept unchanged, the black phosphorus ultralow-density solid material is obtained by freeze-drying for 8 hours at the temperature of-60 ℃ in a freeze setting at the temperature of-60 ℃ and is subjected to heat treatment for 2 hours at the temperature of 800 ℃ to finally obtain the black phosphorus ultralow-density solid material, the main aperture of the porous structure of the black phosphorus ultralow-density solid material is 1mm-5mm, the density is about 0.1mg/cm3. The thermal conductivity coefficient of the black phosphorus ultralow-density solid material is tested by a thermal conductivity coefficient instrument and is less than 0.02W/mK.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The ultralow-density solid material is characterized by having a porous structure with the pore diameter of 10 mu m-10mm, wherein the porous structure is built up by solid material building units, and the density of the ultralow-density solid material is 0.001mg/cm3～0.1mg/cm3。
2. The ultra low density solid material of claim 1, wherein the ultra low density solid material has a density of 0.001mg/cm3～0.1mg/cm3(ii) a Preferably, the density is 0.005mg/cm3～0.05mg/cm3；
Preferably, the pore size of the porous structure is 100 μm to 5 mm.
3. The ultra-low density solid material of claim 1 or 2, wherein the solid material building elements comprise at least one of graphene oxide, graphene, graphite nanoplatelets, layered phosphates, layered hydroxides, layered double hydroxides, layered silicates, layered clays, layered chalcogenides, layered oxides, layered nitrides, layered carbides, layered silicides, layered borides, layered black phosphorus, layered elemental metals, layered covalent organic framework materials, layered metal organic framework materials, carbon nanotubes, carbon nanofibers, silicon carbide whiskers, copper nanowires, silver nanowires, titanium dioxide nanowires, fullerenes, quantum dots, nanoclusters, natural fibers, proteins, natural rubbers, dextrans, synthetic resins, synthetic fibers, or starches;
preferably, the solid material building elements comprise at least one of graphene oxide, layered phosphate, layered hydroxide, layered double hydroxide, layered silicate, layered oxide, carbon nanotubes, carbon nanofibers, copper nanowires or silver nanowires.
4. A method of preparing the ultra low density solid material according to any one of claims 1 to 3, comprising the steps of:
providing a solid material dispersion liquid, and adding a toughening agent into the solid material dispersion liquid to obtain a mixed dispersion liquid;
foaming the mixed dispersion liquid through vacuum foaming, and then freezing and shaping at low temperature; and
and drying to obtain the ultra-low density solid material.
5. The method of claim 4, wherein the solid material is dispersed in a solvent to form a solid material dispersion;
preferably, the solvent is any one of the following solvents:
(a) water; (b) a mixed solvent of water and an organic solvent;
preferably, the mass fraction of the solid material in the solid material dispersion is 0.001% to 10%, and preferably, the mass fraction of the solid material in the solid material dispersion is 0.005% to 5%.
6. A method according to claim 4 or 5, wherein the toughening agent is added directly or in solution to the solid material dispersion;
preferably, the toughening agent is added into the solid material dispersion liquid in the form of a solution, and the mass concentration of the toughening agent is 1-99%, preferably 1-50%, and further preferably 2-20%;
preferably, the addition amount of the toughening agent is 1-2000% of the mass of the solid material, and preferably, the addition amount of the toughening agent is 10-1000% of the mass of the solid material;
preferably, the flexibilizer comprises sodium fatty alcohol-polyoxyethylene ether sulfate, disodium fatty alcohol-polyoxyethylene ether sulfosuccinate, alkylphenol polyoxyethylene polyoxypropylene ether, triethanolamine dodecylbenzene sulfonate, alpha-olefin sulfonate, sodium abietate, sodium diisooctyl succinate sulfonate, potassium laurate, sodium dodecylbenzene sulfonate, sodium dodecylsulfate, lauryl alcohol, cetyl alcohol, polyethylene glycol, lauryl glyceryl ether, caprylic amine, n-decyl alcohol, n-octyl glyceryl ether, n-decyl glyceryl ether, lauryl sulfamide, lauryl ethanolamine, starch, gum arabic, sodium alginate, bone meal, gelatin, casein, hydroxymethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyacrylic acid, sodium lauryl sulfate, cetyl alcohol, polyethylene glycol, lauryl glyceryl ether, caprylic acid amine, n-decyl alcohol, n-octyl glyceryl ether, n-decyl glyceryl ether, lauryl sulfamide, lauryl ethanolamine, starch, gum arabic, sodium alginate, bone meal, gelatin, casein, hydroxymethyl cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, polyacrylamide, polyacrylic acid, sodium alginate, sodium salt, sodium, Polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt, polyethylene glycol, alcohol ether glycoside, alkyl polyglycoside, isomeric alcohol polyoxyethylene polyoxypropylene ether, fatty acid polyethylene glycol ester, isomeric undecyl polyoxyethylene ether, isomeric tridecyl alcohol polyoxyethylene ether, lauryl hydroxypropyl sulfobetaine, tetradecyl dihydroxyethyl amine oxide, cocoyl dimethyl amine oxide, lauryl dimethyl amine oxide, octadecyl dimethyl amine oxide, lauryl amidopropyl dimethyl amine oxide, cocoamidopropyl dimethyl amine oxide, lauryl amidopropyl dimethyl amine oxide, tallowamidopropyl dimethyl amine oxide, lauryl dihydroxyethyl amine oxide, stearyl amidopropyl dimethyl amine oxide, cocoyl hydroxypropyl sulfobetaine, stearyl hydroxypropyl sulfobetaine, lauryl amidohydroxypropyl sulfobetaine, polyquaternary ammonium salt, polyethylene glycol, alcohol ether glycoside, alkyl polyglycoside, isomeric alcohol polyoxyethylene polyoxypropylene ether, fatty acid polyethylene glycol ester, lauryl alcohol polyoxyethylene ether, stearyl alcohol, lauryl alcohol, amidopropyl dimethyl amine oxide, lauryl alcohol propyl dimethyl amine, lauryl alcohol, hydroxypropyl sulfobetaine, lauryl alcohol, hydroxypropyl sulfobetaine, lauryl ether, At least one of oleamidopropyl betaine, octadecyl amine polyoxyethylene ether oxide, dodecyl amine polyoxyethylene ether oxide, octadecyl dihydroxyethyl amine oxide, octadecyl amidopropyl dimethyl amine oxide, dodecyl phosphate betaine or lauryl amidopropyl betaine.
7. Method according to claim 4 or 5, wherein the pressure of the vacuum foaming is between 0.1Pa and 2000Pa, preferably between 1Pa and 1000 Pa.
8. The method according to claim 4 or 5, wherein the temperature of the low-temperature freezing and shaping is-200 to 0 ℃, preferably-100 to-20 ℃;
preferably, the freezing and shaping are carried out by a refrigerator, an ice chest, frozen ice blocks, a low-temperature heat sink, a freeze dryer cold trap or liquid nitrogen;
preferably, the drying comprises at least one of freeze drying, natural drying or supercritical drying, preferably freeze drying.
9. The method according to claim 4 or 5, further comprising the step of post-treating the dried product further, wherein the post-treatment comprises a heat treatment, a chemical treatment or an excitation treatment.
10. Use of the ultra-low density solid material according to any one of claims 1 to 3 as a thermal insulation material, a deformation sensor, a micro-pressure sensor, an ultra-high temperature electrothermal material or an electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210144808.1A CN114455573B (en) | 2022-02-17 | 2022-02-17 | Ultra-low density solid material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210144808.1A CN114455573B (en) | 2022-02-17 | 2022-02-17 | Ultra-low density solid material, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114455573A true CN114455573A (en) | 2022-05-10 |
| CN114455573B CN114455573B (en) | 2023-07-07 |
Family
ID=81414092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210144808.1A Active CN114455573B (en) | 2022-02-17 | 2022-02-17 | Ultra-low density solid material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114455573B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115624922A (en) * | 2022-10-17 | 2023-01-20 | 烟台大学 | Amidoxime functionalized covalent organic framework and graphene oxide hybrid aerogel, and preparation method and application thereof |
| CN116120092A (en) * | 2022-12-30 | 2023-05-16 | 爱迪特（秦皇岛）科技股份有限公司 | High-strength resin-infiltrated ceramic composite material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104943050A (en) * | 2015-05-01 | 2015-09-30 | 长春富维—江森自控汽车饰件系统有限公司 | High-resilience polyurethane foam vacuum foaming method |
| CN106698415A (en) * | 2016-12-29 | 2017-05-24 | 陈大明 | High-strength carbon foam (CF) material and preparation method thereof |
| CN108329051A (en) * | 2017-07-04 | 2018-07-27 | 中国科学院金属研究所 | A kind of superelevation porosity and low green body shrinking percentage Y2SiO5The preparation method of porous ceramics |
| CN109485047A (en) * | 2018-12-14 | 2019-03-19 | 中国科学院深圳先进技术研究院 | Three-dimensional structure silicon carbide and its preparation method and application |
| CN113045332A (en) * | 2021-02-08 | 2021-06-29 | 中国科学院金属研究所 | Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof |
| CN113145031A (en) * | 2021-04-27 | 2021-07-23 | 中国人民解放军国防科技大学 | Cellulose/graphene oxide composite aerogel and preparation method thereof |
| CN113527753A (en) * | 2020-04-15 | 2021-10-22 | 吴娜 | Bio-based foam material prepared under normal pressure and preparation method and application thereof |
-
2022
- 2022-02-17 CN CN202210144808.1A patent/CN114455573B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104943050A (en) * | 2015-05-01 | 2015-09-30 | 长春富维—江森自控汽车饰件系统有限公司 | High-resilience polyurethane foam vacuum foaming method |
| CN106698415A (en) * | 2016-12-29 | 2017-05-24 | 陈大明 | High-strength carbon foam (CF) material and preparation method thereof |
| CN108329051A (en) * | 2017-07-04 | 2018-07-27 | 中国科学院金属研究所 | A kind of superelevation porosity and low green body shrinking percentage Y2SiO5The preparation method of porous ceramics |
| CN109485047A (en) * | 2018-12-14 | 2019-03-19 | 中国科学院深圳先进技术研究院 | Three-dimensional structure silicon carbide and its preparation method and application |
| CN113527753A (en) * | 2020-04-15 | 2021-10-22 | 吴娜 | Bio-based foam material prepared under normal pressure and preparation method and application thereof |
| CN113045332A (en) * | 2021-02-08 | 2021-06-29 | 中国科学院金属研究所 | Ultrahigh-porosity high-entropy carbide ultrahigh-temperature ceramic and preparation method thereof |
| CN113145031A (en) * | 2021-04-27 | 2021-07-23 | 中国人民解放军国防科技大学 | Cellulose/graphene oxide composite aerogel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈士朝等: "《橡胶技术与制造概论》", 30 September 2002, 中国石化出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115624922A (en) * | 2022-10-17 | 2023-01-20 | 烟台大学 | Amidoxime functionalized covalent organic framework and graphene oxide hybrid aerogel, and preparation method and application thereof |
| CN116120092A (en) * | 2022-12-30 | 2023-05-16 | 爱迪特（秦皇岛）科技股份有限公司 | High-strength resin-infiltrated ceramic composite material and preparation method thereof |
| CN116120092B (en) * | 2022-12-30 | 2024-03-19 | 爱迪特（秦皇岛）科技股份有限公司 | High-strength resin-infiltrated ceramic composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114455573B (en) | 2023-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114455573A (en) | Ultralow-density solid material, preparation method and application thereof | |
| EP3878809B1 (en) | Flexible boron nitride nano-belt aerogel and preparation method therefor | |
| Li et al. | Preparation and optimization of ultra-light and thermal insulative aerogel foam concrete | |
| CN107128895A (en) | A kind of preparation method of high intensity network structure nanometer carrier material | |
| CN107417961A (en) | A kind of anisotropy polyimide aerogels material and preparation method thereof | |
| CN109573965A (en) | A kind of preparation method of hydroxyl modification boron nitride nanosheet dispersion liquid | |
| Shao et al. | A simple facile preparation of methyltriethoxysilane based flexible silica aerogel monoliths | |
| CN108192129A (en) | A kind of ultra-hydrophobic polyvinylidene fluoride aerogel material and preparation method thereof | |
| CN103204666A (en) | Method for preparing aerogel or aerogel-fiber composite material in aqueous condition with low cost | |
| CN110172185A (en) | A kind of anisotropy nano-cellulose aerogel and preparation method thereof and device | |
| CN106747572A (en) | A kind of preparation method of carbon nanotube aerogel | |
| CN110117000A (en) | A kind of bulk carbon nano-fiber aeroge and preparation method thereof | |
| Tian et al. | Mechanical and thermal-insulating performance of silica aerogel enhanced jointly with glass fiber and fumed silica by a facile compressing technique | |
| Farhan et al. | A novel combination of simple foaming and freeze-drying processes for making carbon foam containing multiwalled carbon nanotubes | |
| Zhang et al. | A versatile, superelastic polystyrene/graphene capsule-like framework | |
| CN108439380B (en) | Preparation method of super-elastic and super-hydrophobic pure graphene aerogel | |
| CN109824339A (en) | A kind of rock wool/aerogel composite and its preparation process with heat-proof quality | |
| JP2022539369A (en) | Continuous production method for graphene airgel microspheres | |
| CN105540618B (en) | A kind of sodium bicarbonate and preparation method thereof and application of the sodium bicarbonate in expanded material | |
| CN109912836A (en) | Amination hydroxyapatite/chitosan composite aerogel and the preparation method and application thereof | |
| Yang et al. | Preparation and characterization of clay aerogel composites reinforced by calcium sulfate whisker | |
| CN110452480B (en) | Preparation method of ultra-light heat-insulating flexible aerogel | |
| CN109851998A (en) | A kind of epoxy resin/graphite alkene/boron nitride composite aerogel and preparation method thereof | |
| CN106865509A (en) | A kind of preparation method of ultralight hexagonal boron nitride aeroge | |
| CN110467207B (en) | Preparation method of boehmite nanorod aerogel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |