CN110437469B - High polymer material with micro-bending layered structure and preparation method and application thereof - Google Patents
High polymer material with micro-bending layered structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of material processing, and particularly relates to a high polymer material with a micro-bending layered structure, and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: a) placing a bottomless freezing mould on a fan-shaped annular freezing surface of an orientation freezing device, and pouring a polymer aqueous solution into the freezing mould; b) cooling one end of the fan-shaped annular freezing surface, forming a temperature gradient on the fan-shaped annular freezing surface along with the reduction of the temperature, and gradually solidifying the polymer aqueous solution in the freezing mould along the temperature gradient until the polymer aqueous solution is completely solidified to obtain an ice block; c) freeze-drying and dehydrating the ice blocks to obtain the high polymer material with the micro-bent layered structure. The preparation method provided by the invention is an improved orientation freezing technology, and the freezing surface of the orientation freezing device is designed into a fan ring shape, so that the front edge of ice crystals can grow orderly at a certain radian in the orientation freezing process, and the high polymer material with a microcosmic curved lamellar structure is obtained.
Description
Technical Field
The invention belongs to the field of material processing, and particularly relates to a high polymer material with a micro-bending layered structure, and a preparation method and application thereof.
Background
At present, the macroscopic three-dimensional nano-assembly material shows extremely promising application value in various fields, great progress is made in the aspects of construction and application of macroscopic scale nano-assemblies at home and abroad, and researchers make a series of new methods and make certain progress. However, the controllable design of the three-dimensional structure of the macrostructure assembly of nanostructure units is still in the research stage, and many key scientific problems and technical problems are needed to be overcome for realizing the industrialization and the commercial popularization and application of the macrostructure assembly. The development of an efficient, controllable and convenient macroscopic three-dimensional assembly method is one of important strategies for meeting the requirements of the high-precision field on novel nano-assembly-level block materials.
The technology of oriented freezing has incomparable technical advantages in the aspect of accurately regulating and controlling the hierarchical structure. In journal of science 2008, 1516, the three-hundred twenty-two volume reports that a three-dimensional macroscopic bracket is constructed by using alumina and polymethyl methacrylate as raw materials and adopting an ice template method as a main method, and a three-dimensional blocky shell-like structure high-strength composite material is prepared. In journal 2014, page 508 of thirteen volume of natural materials reports that a three-dimensional blocky shell-like structure high-strength composite material is finally prepared by a series of steps of orientation freezing and the like by using silicon dioxide particles, alumina micron sheets and the like as raw materials. The first volume and eleventh phase of the journal 2015 of scientific progress reports that the bidirectional freezing technology assembles ceramic particles into a large-scale arranged, multi-layer and porous pearl layered structure and a centimeter-level long-range ordered scaffold, and the nucleation and growth of ice crystals are controlled by regulating the temperature gradient by using polydimethylsiloxane wedges, so that higher-level control on a microscopic layered structure is realized.
With the intensive research on the oriented freezing technology, how to further explore and mine the oriented freezing technology and research the preparation of novel micro-morphology materials is a research hotspot in the field.
Disclosure of Invention
In view of the above, the present invention provides a polymer material with a micro-curved layered structure, and a preparation method and an application thereof, and the method provided by the present invention can be used to prepare a novel polymer material with a micro-curved layered structure, and has a potential application prospect in many fields.
The invention provides a preparation method of a high polymer material with a micro-bending layered structure, which comprises the following steps:
a) placing a bottomless freezing mould on a fan-shaped annular freezing surface of an orientation freezing device, and pouring a polymer aqueous solution into the freezing mould;
b) cooling one end of the fan-shaped annular freezing surface, forming a temperature gradient on the fan-shaped annular freezing surface along with the reduction of the temperature, and gradually solidifying the polymer aqueous solution in the freezing mould along the temperature gradient until the polymer aqueous solution is completely solidified to obtain an ice block;
c) and freeze-drying and dehydrating the ice blocks to obtain the high polymer material with the micro-bent layered structure.
Preferably, the inner diameter of the fan-shaped annular freezing surface is 10-20 mm, the outer diameter is 40-60 mm, and the thickness is 2-5 mm.
Preferably, the central angle of the fan-shaped freezing surface is 90-270 degrees.
Preferably, the thermal conductivity of the fan-shaped annular freezing surface is 10-50 Wm-1K-1。
Preferably, the material of the fan-shaped freezing surface is mirror steel.
Preferably, the orientation freezing device further comprises two conducting columns, and each conducting column is connected with one end of the fan-shaped annular freezing surface;
and in the step b), the temperature of one end of the fan-shaped annular freezing surface is reduced by pouring liquid nitrogen into the conduction column at one end.
Preferably, the polymer contained in the polymer aqueous solution comprises one or more of sodium alginate, chitosan, polydopamine, starch, gelatin, collagen, fibroin, polyvinyl alcohol, sodium polyacrylate, polylactic acid and polycaprolactone.
Preferably, the concentration of the polymer in the polymer aqueous solution is 5-40 mg/mL.
Preferably, the polymer aqueous solution further contains a carbon nanomaterial.
The invention provides a high polymer material which has a micro-curved layered structure.
The invention provides application of the polymer material in the technical scheme as a heat insulating material or an impact resistant material.
Compared with the prior art, the invention provides a high polymer material with a micro-bending layered structure, and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: a) placing a bottomless freezing mould on a fan-shaped annular freezing surface of an orientation freezing device, and pouring a polymer aqueous solution into the freezing mould; b) cooling one end of the fan-shaped annular freezing surface, forming a temperature gradient on the fan-shaped annular freezing surface along with the reduction of the temperature, and gradually solidifying the polymer aqueous solution in the freezing mould along the temperature gradient until the polymer aqueous solution is completely solidified to obtain an ice block; c) and freeze-drying and dehydrating the ice blocks to obtain the high polymer material with the micro-bent layered structure. The preparation method provided by the invention is an improved orientation freezing technology, and the preparation method can enable the front edge of ice crystals to grow orderly in a certain radian in the orientation freezing process by designing the freezing surface of an orientation freezing device into a fan ring shape, so that the high polymer material with a microcosmic curved lamellar structure is obtained. The polymer material prepared by the invention has a micro-bending layered structure, and has potential application prospects in the fields of heat insulation materials, impact-resistant materials 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 embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a 3D block diagram of an orientation freezer provided in accordance with an embodiment of the invention;
FIG. 2 is a 2D engineering drawing of an oriented freezing apparatus provided by an embodiment;
FIG. 3 is a graph comparing temperature gradient fields of freezing surfaces with different curvatures of a finite element simulation provided in example 1 of the present invention;
FIG. 4 is a schematic structural diagram of a test bed provided in embodiment 1 of the present invention;
FIG. 5 is a sectional scanning electron microscope image of the material provided in example 1 of the present invention;
FIG. 6 is a macro topography of the material provided in example 1 of the present invention;
FIG. 7 is a temperature-time curve of a different material freezer as provided in example 2 of the present invention under liquid nitrogen quenching;
FIG. 8 is a sectional scanning electron microscope image of a material provided in example 2 of the present invention;
FIG. 9 is a temperature-time plot of a freezer of varying thickness as provided in example 2 of the present invention, quenched with liquid nitrogen.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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.
The invention provides a preparation method of a high polymer material with a micro-bending layered structure, which comprises the following steps:
a) placing a bottomless freezing mould on a fan-shaped annular freezing surface of an orientation freezing device, and pouring a polymer aqueous solution into the freezing mould;
b) cooling one end of the fan-shaped annular freezing surface, forming a temperature gradient on the fan-shaped annular freezing surface along with the reduction of the temperature, and gradually solidifying the polymer aqueous solution in the freezing mould along the temperature gradient until the polymer aqueous solution is completely solidified to obtain an ice block;
c) and freeze-drying and dehydrating the ice blocks to obtain the high polymer material with the micro-bent layered structure.
In the preparation method provided by the invention, a bottomless freezing mould is firstly placed on a fan-shaped annular freezing surface of an orientation freezing device. The material of the freezing mould preferably keeps good elasticity at low temperature, can maintain an ideal shape when the polymer aqueous solution is transformed from a liquid state to a solid state and expands, has extremely low thermal conductivity, can isolate the heat exchange of the material and the external environment, and particularly can select polydimethylsiloxane or silica gel. In one embodiment provided by the present invention, the freezing mold is preferably a hollow cuboid, and the outer diameter of the hollow cuboid may be 10mm × 10mm × 2mm, and the inner diameter may be 6mm × 4mm × 2 mm.
In the preparation method provided by the invention, the inner diameter of the fan-shaped annular freezing surface is preferably 10-20 mm, specifically 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 16mm, 17mm, 18mm, 19mm or 20mm, and most preferably 15 mm; the outer diameter of the fan-shaped annular freezing surface is preferably 40-60 mm, and specifically can be 40mm, 41mm, 42mm, 43mm, 44mm, 45mm, 46mm, 47mm, 48mm, 49mm, 50mm, 51mm, 52mm, 53mm, 54mm, 55mm, 56mm, 57mm, 58mm59mm or 60mm, most preferably 50 mm; the thickness of the fan-shaped annular freezing surface is preferably 2-5 mm, specifically 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm or 5mm, and most preferably 3 mm; the central angle of the fan-shaped annular freezing surface is preferably 90-270 degrees, specifically 90 degrees, 120 degrees, 150 degrees, 180 degrees, 210 degrees, 240 degrees or 270 degrees, and most preferably 180 degrees; the thermal conductivity of the fan-shaped annular freezing surface is preferably 10-50 Wm-1K-1Specifically, it may be 10Wm-1K-1、15Wm-1K-1、20Wm-1K-1、25Wm-1K-1、30Wm-1K-1、35Wm-1K-1、40Wm-1K-1、45Wm-1K-1Or 50Wm-1K-1Most preferably 15Wm-1K-1(ii) a The fan-shaped freezing surface is made of mirror steel.
In the preparation method provided by the invention, the orientation freezing device further comprises two conducting columns, and each conducting column is respectively connected with one end of the fan-shaped annular freezing surface; the material and thickness of the guide post are preferably consistent with those of the fan-shaped annular freezing surface, and the included angle between the guide post and the fan-shaped annular freezing surface is preferably a right angle. In an embodiment of the present invention, the structure of the orientation refrigeration apparatus is shown in fig. 1 to 2, fig. 1 is a 3D structure diagram of the orientation refrigeration apparatus provided in the embodiment of the present invention, fig. 2 is a 2D engineering drawing of the orientation refrigeration apparatus provided in the embodiment, in fig. 1, 1 represents a refrigeration surface, and 2 represents a conduction post; in fig. 2, the upper left view is a front view, the upper right view is a side view, and the lower view is a plan view.
In the preparation method provided by the invention, a bottomless freezing mould is placed on a freezing surface, and then the polymer aqueous solution is poured into the freezing mould. Wherein the polymer contained in the polymer aqueous solution comprises one or more of sodium alginate, chitosan, polydopamine, starch, gelatin, collagen, fibroin, polyvinyl alcohol, sodium polyacrylate, polylactic acid and polycaprolactone; the concentration of the polymer in the polymer aqueous solution is preferably 5-40 mg/mL, and specifically can be 5mg/mL, 10mg/mL, 15mg/mL, 20mg/mL, 25mg/mL, 30mg/mL, 35mg/mL or 40 mg/mL. In the present invention, the aqueous polymer solution preferably further contains a carbon nanomaterial; the carbon nanomaterials include, but are not limited to, graphene oxide sheets and/or carbon nanotubes; the concentration of the carbon nano material in the polymer water solution is preferably 1-10 mg/mL, and specifically can be 1mg/mL, 3mg/mL, 5mg/mL, 7mg/mL or 9 mg/mL. In the present invention, it is preferable to add a certain amount of acetic acid in the process of preparing the aqueous polymer solution for promoting the dissolution of the polymer in the aqueous solution.
In the preparation method provided by the invention, after the polymer aqueous solution is poured into the freezing mould, one end of the sector annular freezing surface of the orientation freezing device is cooled. In the present invention, it is preferable that the temperature of one end of the fan-shaped freezing surface is lowered by pouring liquid nitrogen into a conduction column at one end of the orientation freezing device. In the invention, a temperature gradient is formed on the fan-shaped annular freezing surface along with the reduction of the temperature, the polymer aqueous solution in the freezing mould is gradually solidified along the temperature gradient to form ice crystals, and the horizontal growth speed of the front edge of the ice crystals is preferably controlled to be 0.2-0.4 mm/min, more preferably about 0.3 mm/min; the vertical growth speed of the ice crystal front is preferably controlled to be 0.05-0.15 mm/min, and more preferably controlled to be about 0.1 mm/min; after the aqueous polymer solution was completely solidified, ice was obtained.
In the preparation method provided by the invention, after the ice cubes are obtained, the ice cubes are subjected to freeze-drying and dehydration. The time for freeze-drying and dehydration is preferably 24-72 h, and specifically can be 24h, 36h, 48h, 60h or 72 h. After the freeze-drying dehydration is finished, the high polymer material with the microcosmic bent layered structure is obtained.
The preparation method provided by the invention is an improved orientation freezing technology, and the preparation method can enable the front edge of ice crystals to grow orderly in a certain radian in the orientation freezing process by designing the freezing surface of an orientation freezing device into a fan ring shape, so that the high polymer material with a microcosmic curved lamellar structure is obtained. The polymer material prepared by the invention has a micro-bending layered structure, and has potential application prospects in the fields of heat insulation materials, impact-resistant materials and the like.
The invention also provides a high polymer material with a micro-bending layered structure, which can be prepared according to the preparation method of the technical scheme. In the present invention, the components of the polymer material include, but are not limited to, one or more of sodium alginate, chitosan, polydopamine, starch, gelatin, collagen, fibroin, polyvinyl alcohol, sodium polyacrylate, polylactic acid, and polycaprolactone; the components of the high polymer material preferably further comprise carbon nano-materials; the carbon nanomaterials include, but are not limited to, graphene oxide sheets and/or carbon nanotubes.
The polymer material provided by the invention has a microcosmic bent layered structure, and has potential application prospects in the fields of heat insulation materials, impact-resistant materials and the like.
For the sake of clarity, the following examples are given in detail.
Example 1
1) Preparing a chitosan aqueous solution:
weighing 0.5g of chitosan powder (with the viscosity of 200-400 mPa.s at 20 ℃) in a 100mL beaker, weighing 50mL of deionized water in the beaker, slowly dropwise adding 0.5mL of acetic acid in a mixed system by using mechanical stirring at 300rpm, stirring for 6h to finally obtain a uniform chitosan aqueous solution with the concentration of 10mg/mL, and placing the chitosan aqueous solution in a refrigerating chamber of a refrigerator for later use.
2) Design of the orientation freezing device:
according to a heat conduction formula and related experience, an oriented refrigerating device with a refrigerating surface with a bending angle is preliminarily designed, and geometric modeling is carried out on a model through three-dimensional design software and the constitutive relation of the model is determined. And performing correlation analysis on heat exchange between the liquid nitrogen and the orientation freezing device through an empirical formula to establish parameters, and considering the convective heat exchange between the orientation freezing device and the air and the heat exchange between the orientation freezing device and the chitosan aqueous solution to further determine each parameter. And importing the geometric model designed by the three-dimensional modeling design software and the determined parameters into finite element analysis software for transient thermal analysis, and submitting a task to perform visual processing on the result. By analyzing the temperature field and the heat flux change along with time in the whole orientation refrigeration device, the design of the orientation refrigeration device is optimized by feedback and compared with some key parameters, as shown in figure 3, and figure 3 is a temperature gradient field comparison graph of finite element simulation different curvature refrigeration surfaces provided by the embodiment 1 of the invention. Thereby re-optimizing the topology of the oriented freezer. And finally obtaining the design structure of the desired orientation refrigerating device through design-feedback repeated and continuous loop optimization, and drawing a three-dimensional design structure and a two-dimensional design structure.
The structure of the orientation freezing device finally determined in the embodiment is shown in fig. 1-2, and the dimensional parameters and materials are selected as follows: the freezing surface 1 is in a fan-shaped ring shape, the inner diameter is 15mm, the outer diameter is 50mm, and the thickness is 3 mm; the guide pillars 2 are connected with the freezing surface 1 by adopting a right-angle welding mode, and the size of each guide pillar 2 is 80mm multiplied by 17.5mm multiplied by 3 mm; the material is mirror steel with the thermal conductivity of 15Wm- 1K-1。
3) Design of a freezing mold:
considering that the freezer is a narrow curved shape, the freezer mould is adapted accordingly for efficient placement on the freezer. The geometric dimension of the freezing mould is a hollow cuboid with the outer diameter of 10mm multiplied by 2mm and the inner diameter of 6mm multiplied by 4mm multiplied by 2mm, and the material is PDMS or silica gel.
4) Preparing a chitosan component micro-bending laminated structure material:
placing the components according to the mode shown in FIG. 4, wherein FIG. 4 is a schematic structural diagram of the test bed provided in the embodiment 1 of the invention, and in FIG. 4, a rectangular box at the lower part is a place for pouring liquid nitrogen, and a conducting column at one end of a refrigerating device is inserted into the rectangular box; the top rectangular volume represents the freezing mold, which is placed on the fan-ring freezing surface of the freezer. Pouring the prepared chitosan aqueous solution into a freezing mould, pouring a small amount of liquid nitrogen to one end of a freezing device to convey a guide pillar, and cooling the guide pillar at a very low speed so as to control the freezing device to uniformly reduce the temperature to be below 0 ℃. And (3) forming a temperature gradient on the fan-shaped annular freezing surface along with the reduction of the temperature, gradually solidifying the polymer aqueous solution in the freezing mould along the temperature gradient to form ice crystals, wherein the horizontal growth speed of the front edge of the ice crystals is about 0.3mm/min, the vertical growth speed is about 0.1mm/min, and after the polymer aqueous solution is completely solidified, obtaining ice blocks. And (3) placing the ice blocks in a vacuum freeze dryer for drying treatment for 24-48 h to obtain the material with the microcosmic bent layered structure.
Scanning electron microscope observation is carried out on the cross section of the prepared material, and the result is shown in fig. 5, and fig. 5 is a scanning electron microscope image of the cross section of the material provided by the embodiment 1 of the invention. As can be seen from fig. 5, the material has a microscopically curved layered structure.
The digital photograph of the prepared material is taken, and the result is shown in fig. 6, and fig. 6 is a macro topography map of the material provided in example 1 of the present invention.
Example 2
1) Investigating the cooling stability of different material freezing devices under the condition of liquid nitrogen quenching
Mirror steel (thermal conductivity 15 Wm) is respectively adopted-1K-1) 45 steel (Heat conductivity 45 Wm)-1K-1) Q235 (thermal conductivity 31 Wm)-1K-1) And red copper (thermal conductivity 200 Wm)-1K-1) The other condition parameters of the material of the freezing device are consistent with those of the embodiment 1, after liquid nitrogen is poured, the temperature of the sector ring-shaped freezing surface of the freezing device at the position with the radius of 16mm and the angle of 90 degrees is monitored in real time, and the result is shown in figure 7, and figure 7 is a temperature-time curve graph of the freezing device with different materials under the liquid nitrogen quenching condition, which is provided by the embodiment 2 of the invention. As can be seen from FIG. 7, the mirror-surface steel has the best cooling stability under liquid nitrogen quenching.
2) Investigating the influence of different material freezing devices on the appearance of the prepared material
Mirror steel (thermal conductivity 15 Wm) is respectively adopted-1K-1) Q235 (thermal conductivity 31 Wm)-1K-1) And 45 steel (thermal conductivity 45 Wm)-1K-1) Scanning electron microscope observation of the cross section of the prepared material as the material of the refrigerating device was carried out while keeping the other condition parameters consistent with those of example 1, and the result is shown in fig. 8, wherein fig. 8 is the scanning electron microscope image of the cross section of the material provided in example 2 of the present invention, and the refrigerating device is composed of the material of mirror surface steel, Q235 and 45, and the chitosan solution with the concentration of 10mg/mL is sequentially arranged from left to right. As can be seen from FIG. 8, the section texture of the material prepared by the mirror steel freezing deviceThe clearest and tidiest shape and the best microscopic appearance.
3) Investigating the temperature reduction situation of different thickness freezing devices under the liquid nitrogen quenching
Mirror steel (thermal conductivity 15 Wm) with a thickness of 3mm and 4mm was used, respectively-1K-1) The other condition parameters of the material of the freezing device are consistent with those of the embodiment 1, after the liquid nitrogen is poured, the temperature of the sector ring-shaped freezing surface of the freezing device at the position with the radius of 16mm and the angle of 90 degrees is monitored in real time, and the result is shown in figure 9, and figure 9 is a temperature-time curve graph of the freezing device with different thicknesses in the liquid nitrogen quenching process provided by the embodiment 2 of the invention.
Example 3
Preparing a chitosan-graphene oxide component micro-bending layered structure material:
the aqueous chitosan solution was prepared as in example 1.
Preparing a graphene oxide aqueous solution: weighing 0.5g of commercial graphene oxide powder in a 100mL beaker, weighing 50mL of deionized water in the beaker, stirring the deionized water by using a magneton at the temperature of 60 ℃ for 6 hours to finally obtain a uniform graphene oxide aqueous solution with the concentration of 10mg/mL, and placing the graphene oxide aqueous solution in a refrigerating chamber of a refrigerator for later use.
Preparing a chitosan-graphene oxide aqueous solution: measuring 10mL of the prepared chitosan aqueous solution into a 50mL beaker, measuring 6mL of the graphene oxide aqueous solution, adding deionized water into the beaker until the total volume is 20mL, vibrating for 10 minutes by using an ultrasonic crusher, and cooling to room temperature.
The design process of the orientation freezing device is the same as that of the embodiment 1, and the chitosan-graphene oxide component micro-bending layered structure material is prepared by taking the chitosan-graphene oxide aqueous solution as the raw material according to the steps of the embodiment 1 after the structural parameters and the materials of the orientation freezing device are determined by only changing the heat exchange parameters of the chitosan aqueous solution and the orientation freezing device into the heat exchange parameters of the chitosan-graphene oxide aqueous solution and the orientation freezing device.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (3)
1. A preparation method of a high polymer material with a micro-bending laminated structure comprises the following steps:
a) placing a bottomless freezing mould on a fan-shaped annular freezing surface of an orientation freezing device, and pouring a polymer aqueous solution into the freezing mould;
the orientation freezing device also comprises two conducting columns, and each conducting column is respectively connected with one end of the fan-shaped annular freezing surface;
the polymer contained in the polymer water solution comprises one or more of sodium alginate, chitosan, polydopamine, starch, gelatin, collagen, fibroin, polyvinyl alcohol, sodium polyacrylate, polylactic acid and polycaprolactone; the concentration of the polymer in the polymer water solution is 5-40 mg/mL;
b) the method comprises the following steps of pouring liquid nitrogen into a conducting column at one end to cool one end of a fan-shaped annular freezing surface, forming a temperature gradient on the fan-shaped annular freezing surface along with the temperature reduction, and gradually solidifying a polymer aqueous solution in a freezing mould along the temperature gradient until the polymer aqueous solution is completely solidified to obtain an ice block;
the fan-shaped freezing surface is made of mirror steel, and the heat conductivity is 10-50 Wm-1K-1；
The inner diameter of the fan-shaped annular freezing surface is 10-20 mm, the outer diameter of the fan-shaped annular freezing surface is 40-60 mm, the central angle of the fan-shaped annular freezing surface is 90-270 degrees, and the thickness of the fan-shaped annular freezing surface is 2-5 mm;
c) and freeze-drying and dehydrating the ice blocks to obtain the high polymer material with the micro-bent layered structure.
2. The method according to claim 1, wherein the aqueous polymer solution further contains a carbon nanomaterial.
3. A polymer material having a microscopically curved layered structure, which is produced by the production method according to any one of claims 1 to 2.
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