CN113368791B - Flexible foldable aerogel film with gradient pore structure, and preparation method and application thereof - Google Patents
Flexible foldable aerogel film with gradient pore structure, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a flexible stretchable gradient pore structure aerogel film, and a preparation method and application thereof. The flexible foldable gradient pore structure aerogel film has a communicated three-dimensional network gradient pore structure, can be stretched by more than 7 times, and can be folded and curled at any angle. The preparation method comprises the following steps: uniformly mixing the thermoplastic elastomer solution with the nanopore module suspension to obtain a mixed solution; and applying the mixed solution on a substrate, transferring the substrate to a phase separation pore-forming agent, carrying out solvent-induced phase separation to form a porous film, and drying to obtain the flexible foldable gradient pore structure aerogel film. The flexible foldable gradient pore structure aerogel film has good mechanical, flexibility, moisture permeability and hydrophobic properties, is easy to realize continuous and large-scale production, can be directly used as a heat insulation and heat preservation material, a hydrophobic moisture permeable and breathable material, a filter membrane material and the like, and can also be used as a substrate of a flexible functional composite material.
Description
Technical Field
The invention relates to a preparation method of an aerogel film, in particular to a flexible foldable gradient pore structure aerogel film and a preparation method and application thereof, and belongs to the technical field of nano materials.
Background
Aerogel is a solid form, the least dense solid in the world. The common aerogel is silicon aerogel, and for silicon dioxide aerogel, the porosity is as high as 90%, the pore diameter is distributed in the range of 1-100 nm, and the specific surface area is 200-1000 m 2 The advantages are numerous per gram, and the advantages are,however, these high properties result in poor strength and toughness, and thus it is difficult to solve the problems of brittleness and poor mechanical properties of aerogels.
Currently, CN104609430A mentions that a wet gel film is obtained by dipping a cleaned and dried glass substrate in a silica sol and then pulling up the coating film at a constant speed; then drying at normal pressure to obtain a silicon dioxide aerogel film; CN1544324A directly spin-coating by a sol-gel method to obtain a silicon dioxide film; CN111977644A utilizes a sol-gel method assisted by a wet spinning film to obtain a graphene hydrogel film, and then the graphene hydrogel film is obtained by replacement drying. Aerogel films at the present stage include silicon dioxide aerogel films, polyimide aerogel films, graphene aerogel films, chitosan aerogel films and the like, the types are still limited, and more aerogel films with excellent performance are urgently needed to be researched and developed.
Disclosure of Invention
In view of the defects and material limitations of the prior art, the main object of the present invention is to provide a flexible stretch-foldable gradient pore structure aerogel film, a preparation method and applications thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a flexible foldable gradient pore structure aerogel film, which has a communicated three-dimensional network gradient pore structure, wherein the gradient pore structure consists of mesopores with the pore diameter of 2-50 nm and macropores with the pore diameter of 50 nm-1000 mu m, the flexible foldable gradient pore structure aerogel film can be stretched by more than 7 times, the tensile strength is 0.1-10 MPa, the elongation at break is 1-700%, and the flexible foldable gradient pore structure aerogel film can be folded and curled at any angle.
In some embodiments, the flexible foldable gradient pore structure aerogel film is a flexible self-supporting film with a thickness of 10-1000 μm and a density of 0.01-0.10 g/cm 3 The hydrophobic angle is 100-170 degrees, and the thermal conductivity is 0.0328-0.1000W/m.K.
The embodiment of the invention also provides a preparation method of the flexible foldable gradient pore structure aerogel film, which comprises the following steps:
uniformly mixing a thermoplastic elastomer with a first organic solvent to form a thermoplastic elastomer solution;
uniformly dispersing the nanopore module in a second organic solvent to form a nanopore module suspension;
uniformly mixing the thermoplastic elastomer solution with the nanopore module suspension to obtain a mixed solution;
applying the mixed solution on a substrate, then transferring the substrate to a phase separation pore-forming agent, and carrying out phase separation by the induction of a solvent to form a porous film;
and drying the porous film to obtain the flexible foldable gradient pore structure aerogel film.
In some embodiments, the thermoplastic elastomer includes thermoplastic polyurethane masterbatches, polystyrene based elastomers, and the like.
In some embodiments, the nanopore module comprises any one or a combination of two or more of a superhydrophobic silica aerogel, a hydrophilic silica aerogel, an alumina aerogel, a polymer-based aerogel, a cellulose aerogel, and the like.
The embodiment of the invention also provides the flexible foldable gradient pore structure aerogel film prepared by the method.
The embodiment of the invention also provides application of the flexible foldable gradient pore structure aerogel film in preparation of products such as heat insulation materials, hydrophobic moisture-permeable air-permeable materials, filter membrane materials or flexible functional composite material substrates.
Compared with the prior art, the invention has the advantages that:
1) the flexible foldable gradient pore structure aerogel film provided by the invention has excellent mechanics, flexibility, hydrophobic property and excellent moisture permeability and air permeability; meanwhile, the flexible foldable gradient pore structure aerogel film can be cut, folded, curled and twisted;
2) the flexible foldable gradient pore structure aerogel film provided by the invention is simple in preparation method, wide in raw material source, low in price and easy for continuous and large-scale production;
3) the flexible foldable gradient pore structure aerogel film provided by the invention has a good application prospect, and can be used as a heat insulation material, a hydrophobic moisture permeable and breathable material, a filter membrane material, a flexible functional composite material substrate and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a preparation process of a flexible foldable gradient pore structure aerogel thin film in examples 1 to 7 of the present invention;
FIG. 2 is a scanning electron microscope image of a flexible foldable gradient pore structure aerogel thin film obtained in example 1 of the present invention;
FIG. 3 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in example 1 of the present invention;
FIG. 4 is an infrared spectrum of a flexible, collapsible, gradient pore structure aerogel film obtained in example 1 of the present invention;
FIG. 5 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in example 1 of the present invention in a stretching mode;
FIG. 6 is a scanning electron microscope image of a flexible foldable gradient pore structure aerogel thin film obtained in example 2 of the present invention;
FIG. 7 is a photograph of the hydrophobic angle of the flexible stretch-foldable gradient pore structure aerogel film obtained in example 2 of the present invention;
FIG. 8 is an infrared spectrum of a flexible, collapsible, gradient pore structure aerogel film obtained in example 2 of the present invention;
FIG. 9 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in example 2 of the present invention in a stretching mode;
FIG. 10 is a scanning electron microscope image of a flexible foldable gradient pore structure aerogel thin film obtained in example 3 of the present invention;
FIG. 11 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in example 3 of the present invention;
FIG. 12 is an infrared spectrum of a flexible, collapsible, gradient pore structure aerogel film obtained in example 3 of the present invention;
FIG. 13 is a stress-strain curve of a flexible, collapsible, gradient pore structure aerogel thin film obtained in example 3 of the present invention in a stretching mode;
FIG. 14 is a scanning electron microscope image of a flexible foldable gradient pore structure aerogel thin film obtained in example 4 of the present invention;
FIG. 15 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in example 4 of the present invention;
FIG. 16 is an infrared spectrum of a flexible, collapsible, gradient pore structure aerogel film obtained in example 4 of the present invention;
FIG. 17 is a stress-strain curve of a flexible, collapsible, gradient pore structure aerogel thin film obtained in example 4 of the present invention in a stretching mode;
FIG. 18 is a scanning electron microscope image of a flexible foldable gradient pore structure aerogel thin film obtained in example 5 of the present invention;
FIG. 19 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in example 5 of the present invention;
FIG. 20 is an infrared spectrum of a flexible, collapsible, gradient pore structure aerogel film obtained in example 5 of the present invention;
FIG. 21 is a stress-strain curve of a flexible, collapsible, gradient pore structure aerogel thin film obtained in example 5 of the present invention in a stretching mode;
FIG. 22 is a scanning electron microscope image of a flexible foldable gradient pore structure aerogel thin film obtained in example 6 of the present invention;
FIG. 23 is a photograph of the hydrophobic corners of the flexible, collapsible, gradient pore structure aerogel film obtained according to example 6 of the present invention;
FIG. 24 is an infrared spectrum of a flexible, collapsible, gradient pore structure aerogel film obtained in example 6 of the present invention;
FIG. 25 is a stress-strain curve of a flexible, collapsible, gradient pore structure aerogel film obtained in example 6 of the present invention in a stretched mode;
FIG. 26 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in example 7 of the present invention;
FIG. 27 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in example 8 of the present invention;
FIG. 28 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in example 9 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventors of the present invention have made long-term research and extensive practice to provide a technical scheme of the present invention, and mainly provide a flexible stretchable gradient pore structure aerogel thin film and a preparation method thereof. The technical solution, its implementation and principles, etc. will be further explained as follows.
The flexible foldable gradient pore structure aerogel film provided by one aspect of the embodiment of the invention has a communicated three-dimensional network gradient pore structure, the gradient pore structure is composed of mesopores with the pore diameter of 2-50 nm and macropores with the pore diameter of 50 nm-1000 μm, the mesopores are provided for a nanopore module, the macropores are caused by a phase separation pore-forming agent, and the flexible foldable gradient pore structure aerogel film can be stretched by more than 7 times, has the tensile strength of 0.1 MPa-10 MPa and the elongation at break of 1% -700%, and can be folded and curled at any angle.
In some preferred embodiments, the flexible foldable gradient pore structure aerogel film is a flexible self-supporting film, the thickness of the flexible self-supporting film is 10 to 1000 μm, and the density of the flexible self-supporting film is 0.01 to 0.10g/cm 3 The hydrophobic angle is 100-170 degrees, and the thermal conductivity is 0.0328-0.1000W/m.K.
Another aspect of the embodiments of the present invention provides a method for preparing a flexible foldable gradient pore structure aerogel thin film, including:
uniformly mixing a thermoplastic elastomer with a first organic solvent to form a thermoplastic elastomer solution;
uniformly dispersing the nanopore module in a second organic solvent to form a nanopore module suspension;
uniformly mixing the thermoplastic elastomer solution with the nanopore module suspension to obtain a mixed solution;
applying the mixed solution on a substrate, then transferring the substrate to a phase separation pore-forming agent, and carrying out phase separation by the induction of a solvent to form a porous film;
and drying the porous film to obtain the flexible foldable gradient pore structure aerogel film.
In some preferred embodiments, the preparation method specifically comprises:
(1) dissolving a thermoplastic elastomer in a first organic solvent at a certain temperature, and uniformly stirring to obtain a thermoplastic elastomer solution (also called as 'solution 1');
(2) dispersing the nanopore module in a second organic solvent to obtain a stable nanopore module suspension (also called as "suspension 2");
(3) uniformly mixing the solution 1 and the suspension 2 at a certain temperature, and removing bubbles by ultrasonic waves to obtain a mixed solution (also called as a solution 3);
(4) applying the solution 3 on a substrate, then transferring the substrate to a phase separation pore-forming agent, and demoulding, drying and forming after solvent-induced phase separation to form a porous film;
(5) and drying the porous film to obtain the flexible foldable gradient pore structure aerogel film.
In a more preferred embodiment, the thermoplastic elastomer includes, but is not limited to, thermoplastic polyurethane masterbatch, polystyrene based elastomer, and the like.
Further, the density of the thermoplastic elastomer (also called elastomer masterbatch) is 1-1.5 g/cm 3 。
In a more preferred embodiment, step (1) may specifically comprise: dissolving a thermoplastic elastomer in a first organic solvent to form the thermoplastic elastomer solution.
Further, the dissolving temperature of the master batch is 20-80 ℃.
Further, the first organic solvent includes, but is not limited to, any one or a combination of two or more of nitrogen dimethyl acetamide, tetrahydrofuran, acetone, dimethyl sulfoxide, etc., and is magnetically stirred at a certain temperature (20-80 ℃) until a stable and uniform thermoplastic elastomer solution is formed, and according to different requirements, thermoplastic elastomer solutions (preferably polyurethane solutions) with the concentration of 5-30 wt% are respectively prepared.
In a more preferred embodiment, the nanopore module comprises any one or a combination of two or more of a super-hydrophobic silica aerogel, a hydrophilic silica aerogel, an alumina aerogel, a polymer-based aerogel, a cellulose aerogel, and the like, but is not limited thereto.
Further, the nano-pore module has a three-dimensional network porous structure, the particle size is 1-1000 mu m, and the porosity is 80-98.45%.
Further, the second organic solvent includes any one or a combination of two or more of acetone, ethanol, n-hexane, nitrogen-dimethyl acetamide, and the like, but is not limited thereto.
Further, the concentration of the nanopore module suspension is 0.6-25 wt%.
Further, the method for dispersing the nanopore module in the second organic solvent comprises any one of mechanical stirring and ultrasonic dispersion.
In a more preferred embodiment, step (2) may specifically comprise: uniformly dispersing a nano-pore module (such as preferably aerogel micro-powder) in a second organic solvent, wherein the solvent comprises but is not limited to ethanol, magnetically stirring and ultrasonically dispersing at a certain temperature (20-80 ℃), and respectively preparing 0.6-25 wt% of aerogel dispersion liquid (namely nano-pore module suspension liquid) according to different requirements.
In a more preferred embodiment, the mass ratio of the nanopore module to the thermoplastic elastomer is 1: 99-44: 56.
in a more preferred embodiment, in the step (4), the mixed solution (also referred to as a thermoplastic elastomer/aerogel dispersion) is coated on the substrate by a doctor blade coating method, a spin coating method, a roll-to-roll coating method, etc., and the thickness of the porous film is adjusted by controlling the distance (10-1000 μm) between the doctor blade and the substrate, the rotation speed (200-5000 rpm) of a spin coater, or the distance (10-1000 μm) between the reels; other methods of coating may also be used.
Further, the distance between the scraper and the substrate in the scraper coating method is 10-1000 μm.
Further, the rotating speed adopted by the spin coating method is 200-5000 rpm.
Further, the distance between the reels adopted by the roll-to-roll coating method is 10-1000 μm.
Further, the substrate includes, but is not limited to, tempered glass, organic glass, aluminum foil, and the like.
In a more preferred embodiment, in step (4), the coated sample is transferred to a phase separation pore former, wherein the phase separation pore former comprises any one or a combination of two or more of water (preferably deionized water), ethanol water, acetone water, tetrahydrofuran water and the like, and the mixture is allowed to stand to form the aerogel porous film.
In a more preferred embodiment, in the step (5), the preparation method comprises subjecting the aerogel porous film to a drying treatment, wherein the drying treatment comprises an atmospheric drying method, a reduced pressure drying method, a vacuum drying method, a supercritical drying method (preferably supercritical carbon dioxide drying) and the like, and is not limited thereto, preferably an atmospheric drying method.
In conclusion, the flexible foldable gradient pore structure aerogel film provided by the invention has excellent mechanics, flexibility, hydrophobic property and excellent moisture permeability and air permeability; simultaneously, the gradient pore structure aerogel film can be tailor to flexible stretch-fold, and is collapsible, can curl, can distort.
The flexible foldable gradient pore structure aerogel film provided by the invention is simple in preparation method, wide in raw material source, low in price and easy for large-scale production.
The flexible foldable gradient pore structure aerogel film provided by the invention has a good application prospect, and can be used as a heat insulation material, a hydrophobic moisture permeable and breathable material, a filter membrane material, a flexible functional composite material substrate and the like.
The invention also provides application of the flexible foldable gradient pore structure aerogel thin film in preparation of products such as heat insulation materials, hydrophobic moisture-permeable and breathable materials, filter membrane materials and flexible functional composite material substrates.
In conclusion, the flexible foldable gradient pore structure aerogel film provided by the invention is composed of a thermoplastic elastomer (preferably polyurethane) and a nano-pore module (preferably aerogel micropowder), has adjustable density, porosity, mechanical properties and the like, and has a very wide application prospect.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
Example 1
Adding thermoplastic polyurethane master batch into nitrogen dimethyl acetamide, stirring at 50 ℃ to prepare polyurethane dispersion liquid with the mass fraction of 10 wt%, adding super-hydrophobic silica aerogel micropowder into ethanol solution, stirring at 20 ℃ and ultrasonically dispersing to prepare aerogel dispersion liquid with the mass fraction of 3.3 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 5: and 95, uniformly mixing the polyurethane dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then carrying out spin coating, carrying out solvent induced phase separation by adopting a rotating speed of 5000rpm, then transferring to a 10 wt% ethanol aqueous solution to form a film, and drying at normal pressure to obtain the flexible stretchable gradient pore structure aerogel film with the thickness of 200 mu m and the thermal conductivity of 0.0680W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. Fig. 2 is a scanning electron microscope image of the flexible foldable gradient pore structure aerogel thin film obtained in this example. FIG. 3 is a photograph of the hydrophobic angle of the flexible, collapsible gradient pore structure aerogel film obtained in this example. Fig. 4 is an infrared spectrum of the flexible foldable gradient pore structure aerogel thin film obtained in this example. Fig. 5 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in this embodiment of the present invention in a stretching mode.
Example 2
Adding a thermoplastic polyurethane master batch into nitrogen-nitrogen dimethylacetamide, stirring at 80 ℃ to prepare a polyurethane dispersion liquid with the mass fraction of 10 wt%, adding hydrophilic silica aerogel micro powder into an ethanol solution, stirring at 20 ℃ and ultrasonically dispersing to prepare an aerogel dispersion liquid with the mass fraction of 7 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 10: and 90, uniformly mixing the polyurethane dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then carrying out spin coating, carrying out solvent induced phase separation by adopting a rotation speed of 200rpm, then transferring to a 10 wt% tetrahydrofuran aqueous solution to form a film, and then drying at normal pressure to obtain the flexible drawable gradient pore structure aerogel film with the thickness of 200 mu m and the thermal conductivity of 0.0625W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. Fig. 6 is a scanning electron microscope image of the flexible foldable gradient pore structure aerogel thin film obtained in this example. FIG. 7 is a photograph of the hydrophobic angle of the flexible, collapsible gradient pore structure aerogel film obtained in this example. Fig. 8 is an infrared spectrum of the flexible foldable gradient pore structure aerogel thin film obtained in this example. Fig. 9 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in this embodiment of the present invention in a stretching mode.
Example 3
Adding thermoplastic polyurethane master batch into acetone/nitrogen dimethyl acetamide and stirring at 60 ℃ to prepare 15 wt% of polyurethane dispersion liquid, adding alumina aerogel micro powder into ethanol solution and stirring at 60 ℃ and ultrasonically dispersing to prepare 11.1 wt% of aerogel dispersion liquid, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 15: and 85, uniformly mixing the polyurethane dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then carrying out spin coating, carrying out solvent induced phase separation by adopting a rotating speed of 500rpm, then transferring to a 10 wt% acetone aqueous solution to form a film, and drying at normal pressure to obtain the flexible stretchable gradient pore structure aerogel film with the thickness of 200 mu m and the thermal conductivity of 0.0713W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. Fig. 10 is a scanning electron microscope image of the flexible foldable gradient pore structure aerogel thin film obtained in this example. FIG. 11 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in this example. FIG. 12 is an infrared spectrum of a flexible foldable gradient pore structure aerogel film obtained in this example. Fig. 13 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in this embodiment of the present invention in a stretching mode.
Example 4
Adding a polystyrene-based elastomer into tetrahydrofuran, stirring at 50 ℃ to prepare a polystyrene-based elastomer dispersion liquid with the mass fraction of 10 wt%, adding cellulose aerogel micro powder into an ethanol solution, stirring at 25 ℃, performing ultrasonic dispersion to prepare an aerogel dispersion liquid with the mass fraction of 15.8 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 20: and 80, uniformly mixing the polystyrene-based elastomer dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then coating by using a scraper, wherein the distance between the scraper and the substrate is 1000 micrometers, then transferring to deionized water, carrying out solvent induced phase separation to form a film, and then drying at normal pressure to obtain the stretchable gradient pore structure aerogel film with the thickness of 1000 micrometers and the thermal conductivity of 0.0775W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. Fig. 14 is a scanning electron microscope image of the flexible foldable gradient pore structure aerogel thin film obtained in this example. FIG. 15 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in this example. FIG. 16 is an infrared spectrum of a flexible foldable gradient pore structure aerogel film obtained in this example. Fig. 17 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in this embodiment of the present invention in a stretching mode.
Example 5
Adding a polystyrene-based elastomer into nitrogen dimethyl acetamide, stirring at 80 ℃ to prepare polystyrene-based elastomer dispersion liquid with the mass fraction of 12.5 wt%, adding hydrophilic silica aerogel micro powder into an ethanol solution, stirring at 25 ℃, performing ultrasonic dispersion to prepare aerogel dispersion liquid with the mass fraction of 25 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 24: and 76, uniformly mixing the polystyrene-based elastomer dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then coating by using a scraper, wherein the distance between the scraper and the substrate is 250 micrometers, then transferring to deionized water, carrying out solvent induced phase separation to form a film, and then drying at normal pressure to obtain the stretchable gradient pore structure aerogel film with the thickness of 250 micrometers and the thermal conductivity of 0.0710W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. Fig. 18 is a scanning electron microscope image of the flexible foldable gradient pore structure aerogel thin film obtained in this example. FIG. 19 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in this example. Fig. 20 is an infrared spectrum of the flexible foldable gradient pore structure aerogel thin film obtained in this example. Fig. 21 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in this embodiment of the present invention in a stretching mode.
Example 6
Adding a polystyrene-based elastomer into nitrogen dimethyl acetamide, stirring at 75 ℃ to prepare a polystyrene-based elastomer dispersion liquid with the mass fraction of 9 wt%, adding high-molecular-base aerogel micro powder into an ethanol solution, stirring at 25 ℃ and ultrasonically dispersing to prepare an aerogel dispersion liquid with the mass fraction of 15 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 20: and 80, uniformly mixing the polystyrene-based elastomer dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then carrying out roll-to-roll coating, wherein the distance between a reel and the reel is 500 mu m, then transferring to deionized water, carrying out solvent induced phase separation to form a film, and then drying at normal pressure to obtain the stretchable gradient pore structure aerogel film with the thickness of 500 mu m and the thermal conductivity of 0.0787W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. FIG. 22 is a scanning electron microscope photograph of the aerogel thin film with a flexible, collapsible, gradient pore structure obtained in this example. FIG. 23 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in this example. FIG. 24 is an infrared spectrum of a flexible foldable gradient pore structure aerogel film obtained in this example. Fig. 25 is a stress-strain curve diagram of the flexible foldable gradient pore structure aerogel thin film obtained in this example in a stretching mode.
Example 7
Adding a thermoplastic polyurethane master batch into nitrogen dimethyl acetamide, stirring at 20 ℃ to prepare a polyurethane dispersion liquid with the mass fraction of 10 wt%, adding hydrophilic silica aerogel micropowder into a nitrogen dimethyl acetamide solution, stirring at 20 ℃ and ultrasonically dispersing to prepare an aerogel dispersion liquid with the mass fraction of 0.6 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 1: and 99, uniformly mixing the polyurethane dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then carrying out roll-to-roll coating, wherein the distance between a reel and a reel is 1000 microns, then transferring to deionized water, carrying out solvent induced phase separation to form a film, and drying at normal pressure to obtain the stretchable gradient pore structure aerogel film with the thickness of 1000 microns and the thermal conductivity of 0.0687W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. FIG. 26 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in this example.
Example 8
Adding a thermoplastic polyurethane master batch into dimethyl sulfoxide, stirring at 80 ℃ to prepare a thermoplastic polyurethane dispersion liquid with the mass fraction of 5 wt%, adding super-hydrophobic silica aerogel micro powder into an acetone solution, stirring at 25 ℃ and ultrasonically dispersing to prepare an aerogel dispersion liquid with the mass fraction of 25 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 44: and 56, uniformly mixing the polyurethane dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then coating by using a scraper, wherein the distance between the scraper and the substrate is 10 mu m, then transferring to deionized water to perform solvent-induced phase separation to form a film, and performing supercritical drying to obtain the stretchable gradient pore structure aerogel film with the thickness of 10 mu m and the thermal conductivity of 0.0697W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. FIG. 27 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in this example.
Example 9
Adding a polystyrene-based elastomer into dimethyl sulfoxide, stirring at 50 ℃ to prepare polystyrene-based elastomer dispersion liquid with the mass fraction of 30 wt%, adding high-molecular-base aerogel micro powder into n-hexane solution, stirring at 25 ℃ and ultrasonically dispersing to prepare aerogel dispersion liquid with the mass fraction of 5 wt%, wherein the mass ratio of the nanopore module to the thermoplastic elastomer is 6: and 94, uniformly mixing the polystyrene-based elastomer dispersion liquid and the aerogel dispersion liquid, ultrasonically defoaming, then carrying out roll-to-roll coating, wherein the distance between a reel and a scroll is 10 mu m, then transferring to deionized water, carrying out solvent induced phase separation to form a film, and then carrying out freeze drying to obtain the stretchable gradient pore structure aerogel film with the thickness of 10 mu m and the thermal conductivity of 0.0812W/m.K. Fig. 1 is a schematic diagram of a preparation route of the flexible foldable gradient pore structure aerogel thin film according to this embodiment. FIG. 28 is a photograph of the hydrophobic angle of the flexible, collapsible, gradient pore structure aerogel film obtained in this example.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the above describes only some embodiments of the present invention and that various other changes and modifications may be affected therein by one of ordinary skill in the related art without departing from the scope or spirit of the invention.
Claims (10)
1. The flexible foldable gradient pore structure aerogel thin film is characterized by having a communicated three-dimensional network gradient pore structure, wherein the gradient pore structure consists of mesopores with the pore diameter of 2-50 nm and macropores with the pore diameter of 50 nm-1000 microns, the flexible foldable gradient pore structure aerogel thin film can be stretched by more than 7 times, the tensile strength is 0.1 MPa-10 MPa, the elongation at break is 1% -700%, and the flexible foldable gradient pore structure aerogel thin film can be folded and curled at any angle; the preparation method of the flexible foldable gradient pore structure aerogel film comprises the following steps:
uniformly mixing a thermoplastic elastomer with a first organic solvent to form a thermoplastic elastomer solution, wherein the thermoplastic elastomer comprises a thermoplastic polyurethane master batch and/or a polystyrene-based elastomer;
uniformly dispersing a nano-pore module in a second organic solvent to form a nano-pore module suspension, wherein the nano-pore module comprises any one or the combination of more than two of super-hydrophobic silica aerogel, hydrophilic silica aerogel, alumina aerogel and cellulose aerogel;
uniformly mixing the thermoplastic elastomer solution with the nanopore module suspension to obtain a mixed solution;
applying the mixed solution on a substrate, transferring the substrate to a phase separation pore-forming agent, and performing solvent-induced phase separation to form a porous film;
and drying the porous film to obtain the flexible foldable gradient pore structure aerogel film.
2. The flexible, collapsible gradient pore structure aerogel film of claim 1, wherein: the flexible foldable gradient pore structure aerogel film is a flexible self-supporting film, the thickness of the flexible self-supporting film is 10-1000 mu m, and the density of the flexible self-supporting film is 0.01-0.10 g/cm 3 The hydrophobic angle is 100-170 degrees, and the thermal conductivity is 0.0328-0.1000W/m.K.
3. A method of making a flexible, collapsible, gradient pore structure aerogel film according to any of claims 1-2, comprising:
uniformly mixing a thermoplastic elastomer with a first organic solvent to form a thermoplastic elastomer solution, wherein the thermoplastic elastomer comprises a thermoplastic polyurethane master batch and/or a polystyrene-based elastomer;
uniformly dispersing a nano-pore module in a second organic solvent to form a nano-pore module suspension, wherein the nano-pore module comprises any one or the combination of more than two of super-hydrophobic silica aerogel, hydrophilic silica aerogel, alumina aerogel and cellulose aerogel;
uniformly mixing the thermoplastic elastomer solution with the nanopore module suspension to obtain a mixed solution;
applying the mixed solution on a substrate, transferring the substrate to a phase separation pore-forming agent, and performing solvent-induced phase separation to form a porous film;
and drying the porous film to obtain the flexible foldable gradient pore structure aerogel film.
4. The production method according to claim 3, characterized in that: the density of the thermoplastic elastomer is 1-1.5 g/cm 3 ；
And/or, the preparation method comprises: dissolving a thermoplastic elastomer in a first organic solvent to form a thermoplastic elastomer solution; the concentration of the thermoplastic elastomer solution is 5-30 wt%, and the dissolving temperature is 20-80 ℃;
and/or the first organic solvent comprises any one or the combination of more than two of nitrogen dimethyl acetamide, tetrahydrofuran, acetone and dimethyl sulfoxide.
5. The production method according to claim 3, characterized in that: the nano-pore module has a three-dimensional network porous structure, the particle size is 1-1000 mu m, and the porosity is 80-98.45%;
and/or the second organic solvent comprises any one or the combination of more than two of acetone, ethanol, n-hexane and nitrogen dimethyl acetamide;
and/or the concentration of the nanopore module suspension is 0.6-25 wt%;
and/or the method for dispersing the nanopore module in the second organic solvent comprises any one of mechanical stirring and ultrasonic dispersion;
and/or the mass ratio of the nanopore module to the thermoplastic elastomer is 1: 99-44: 56.
6. the method according to claim 3, characterized by comprising: coating the mixed solution on a substrate by adopting at least any one of a doctor blade coating method, a rotary coating method and a roll-to-roll coating method; wherein the distance between the scraper and the substrate in the scraper coating method is 10-1000 μm; the rotating speed adopted by the rotary coating method is 200-5000 rpm; the distance between the reels adopted by the reel-to-reel coating method is 10-1000 mu m;
and/or the substrate comprises any one of tempered glass, organic glass and aluminum foil.
7. The production method according to claim 3, characterized in that: the phase separation pore-forming agent comprises one or the combination of more than two of water, ethanol water solution, acetone water solution and tetrahydrofuran water solution.
8. The production method according to claim 3, characterized in that: the drying treatment comprises any one or combination of more than two of an atmospheric drying method, a vacuum drying method under reduced pressure, a freeze drying method and a supercritical drying method.
9. The method of claim 8, wherein: the drying treatment is a normal pressure drying method.
10. Use of the flexible, collapsible, gradient pore structure aerogel thin film of any of claims 1-2 in the preparation of thermal insulation materials, hydrophobic moisture permeable air permeable materials, filter membrane materials, or flexible functional composite substrates.
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