CN116640437A - Optical broadband angle range selective atomization film - Google Patents
Optical broadband angle range selective atomization film Download PDFInfo
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- CN116640437A CN116640437A CN202310741894.9A CN202310741894A CN116640437A CN 116640437 A CN116640437 A CN 116640437A CN 202310741894 A CN202310741894 A CN 202310741894A CN 116640437 A CN116640437 A CN 116640437A
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- 238000000889 atomisation Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 229920000620 organic polymer Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920000307 polymer substrate Polymers 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
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- 238000013329 compounding Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The application discloses an optical broadband angle range selective atomization film, which is prepared by blending isotropic organic/inorganic micro-nano particles with an anisotropic organic polymer substrate, wherein the prepared material has an anisotropic optical refractive index, and the optical broadband angle range selective atomization film can be obtained based on the material. The film has excellent optical performance, is simple in preparation method, can be continuously prepared in a large scale, is suitable for industrial method application, can be designed into different composite films according to requirements, and is suitable for the fields of solar cells, display, illumination, peep prevention and the like.
Description
Technical Field
The application relates to the technical field of optical films, in particular to a selective atomization film in an optical broadband angle range, which is suitable for the fields of solar cells, display, illumination, peep prevention and the like.
Background
Planar electromagnetic waves have three basic characteristics: frequency, polarization, and propagation direction. Over the past decades, optics have made tremendous progress in achieving frequency and polarization selectivity. However, the progress of the angular selectivity is relatively slow. Some studies explore angle selectivity based on metamaterials and photonic crystals, but these methods can only achieve narrow-band angle selectivity due to their inherent resonance characteristics. Some progress has been made in achieving optical broadband angular selectivity, including those based on unconventional transmission, combinations of polarizers and birefringent films, or parabolic antennas. However, the first method is difficult to achieve in the visible spectrum, while the other two methods can only be used as angle selective absorbers.
One major application of wideband angular range selective membranes is solar energy collection, for example for solar cells. The broadband angle selective film can help to alleviate emission losses caused by radiative recombination and incomplete absorption through photon recycling and light capturing processes, and achieve better energy collection effects. The peep-proof screen is another main application, and can be widely applied to mobile phones and computer displays. Other applications include detectors to improve signal-to-noise ratio, window privacy and sunshades. Practical applications require mass production and low cost, and therefore it is important to realize a manufacturable optical film having a wide-band angular range selectivity. Shen et al, U.S. miltiorrhizae, propose that the brewster angle of two isotropic media can be utilized to achieve broadband angle selectivity; however, the film can only function when immersed in a liquid whose refractive index is matched, and this method cannot be used for mass film production and implementation. Some theoretical studies have shown that materials based on optical anisotropy can achieve optical broadband angular selectivity.
After any unpolarized light enters an anisotropic crystal, it is refracted into two orthogonal linearly polarized light beams, which undergo different refractive index transmission at different polarization states and at the same speed, and this phenomenon is called a birefringence phenomenon, where the optical anisotropy of the crystal is manifested as birefringence.
For anisotropic crystals with ordered molecular structure, birefringence is an inherent property; whereas for polymeric materials, their birefringence is mainly represented by two of the following:
aoriented birefringence. Since the material does not possess anisotropy while having no birefringence when the chains/segments within the polymer are in a completely disordered state or the monomer molecular structure of the polymer is completely symmetrical. When the molecular structure of the polymer monomer is anisotropic and the internal chains/segments form a certain alignment along a certain direction, the polymer has birefringence, and is called as an oriented polymer. In particular, the polymer becomes crystalline when the chains/segments are fully formed into a three-dimensional ordered arrangement.
And B, stress birefringence. The polymer material is generally considered isotropic in that short chain/segment oriented alignment occurs locally within the polymer, but the overall chain alignment tends to be disordered. The birefringence that an isotropic medium temporarily exhibits under stress (mechanical force, electric or magnetic field, etc.) is called stress birefringence, and when the external stress is removed, the birefringence of the medium disappears.
Because the whole chain/chain segment arrangement in the polymer material is disordered, and only weak birefringence exists locally, improving the internal chain orientation of the polymer to realize stable orientation birefringent material is the first problem in designing and preparing anisotropic polymer waveguide material.
The existing methods for improving the chain orientation performance of the polymer material mainly comprise a mechanical stretching method, an electromagnetic induction orientation method and the like, the methods can only enable the polymer chain to have certain orientation under the action of external force, the orientation of the polymer chain disappears after the external force is eliminated, the polymer material with stable chain orientation cannot be formed, and the application limit is extremely large. Therefore, how to obtain a polymer material having a stable chain orientation becomes a primary problem in obtaining a stable optically anisotropic material.
Yin et al, university of boston in the united states, can achieve optical broadband angle selectivity using one-dimensional photonic crystals (1D PhC) based on anisotropic and isotropic bilayer polymer structures. But are limited by the nature of the material itself, the fine-grained requirements of the photonic crystal and the complex multilayer coextrusion processes employed thereby, all limit the further production applications of the film.
To date, the large-scale, low cost production of broadband angularly selective films has remained challenging.
Disclosure of Invention
Aiming at the problems of poor spectrum selection performance, complex preparation method, high cost and the like in the prior art, the application uses the organic polymer substrate with anisotropic optical refractive index and the organic/inorganic micro-nano particles with isotropic optical refractive index to form the optical film, can achieve excellent wide spectrum angle selection performance, and can prepare corresponding products suitable for the fields of solar cells, display, illumination, peeping prevention and the like by adopting the optical broadband angle range selective atomization film.
The application is realized by adopting the following technical scheme:
an optical broadband angle range selective atomization film is an anisotropic material, and is specifically obtained by doping isotropic organic/inorganic micro-nano particles on an organic polymer substrate with anisotropic optical refractive index;
when incident light is normally incident along the normal direction of the surface of the film, the polymer substrate and the micro-nano particles have the same optical refractive index, the optical impedance is matched, and the film is in a transparent state;
the incident angle increases as the incident light gradually deviates from the normal direction of the surface of the film, the difference of the optical refractive indexes of the polymer substrate and the micro-nano particles is gradually pulled, the micro-nano particles show the Mie scattering characteristic of broadband, and the film is in an atomized state.
In the above technical solution, preferably, the doping concentration of the organic/inorganic micro-nano particles with isotropic optical refractive index in the atomized film is 10vol.% to 70vol.%. Further preferred doping concentrations are from 30vol.% to 50vol.%.
The preparation method of the optical broadband angle range selective atomization film comprises the following steps:
1) The isotropic organic/inorganic micro-nano particles and the polymer substrate material are uniformly compounded through chemical dissolution mixing and/or physical blending steps.
2) The atomized film is prepared by at least one of a hot pressing method, a sleeve method, a film winding method, a thermosetting method, a melt extrusion method, 3D printing and mechanical polishing cutting.
Preferably, the temperature at which the film is pressed by hot pressing is set with reference to the glass transition temperatures of the substrate and the particles, and is ensured to be between the glass transition temperature of the polymer base and the melting point of the doped particles. The hot pressing time of the hot pressing method for pressing the preform is 5-500 minutes, and the preferable hot pressing time is 10-20 minutes; the pressure intensity of the hot pressing method for pressing the preform is 1MPa-50MPa, and the preferable hot pressing pressure intensity is 10-20MPa, and the more preferable hot pressing pressure intensity is 15MPa.
Preferably, the temperature at which the film is extruded by melt extrusion is set with reference to the glass transition temperature of the substrate and the particles, and is ensured to be between the glass transition temperature of the polymer substrate and the melting point of the dopant particles.
Preferably, the curing time of the film prepared by the thermosetting method is 1 to 500 minutes, and the curing time is preferably 20 to 40 minutes.
Preferably, the temperature for preparing the film by 3D printing is set with reference to the glass transition temperature of the substrate and the particles, and is ensured to be between the glass transition temperature of the polymer substrate and the melting point of the doped particles.
Preferably, in the method for hot drawing the film, the hot drawing temperature of the film needs to be selected according to the glass transition temperature of the selected polymer material and the micro-nano particle material, and the temperature is specifically ensured to be between the glass transition temperature of the polymer substrate and the melting point of the doped particles. A drawing tension in the range of 0 to 500g, preferably a drawing tension in the range of 10 to 50g; the feed speed ranges from 0.01 mm/min to 10mm/min, and the feed speed ranges from 0.3 mm/min to 3mm/min; traction speed ranges from 0.1 to 5000m/min, with a preferred traction speed range of 0.1 to 20m/min.
Preferably, the optically refractive index isotropic organic/inorganic micro-nano particles include, but are not limited to: silicon dioxide (SiO) 2 ) Alumina (Al) 2 O 3 ) Magnesium oxide (MgO), calcium fluoride (CaF) 2 ) Magnesium fluoride (MgF) 2 ) Lithium fluoride (LiF), polyethylene (PE), polypropylene (PP), polyester (PET), polyamide (PA), polymethyl methacrylate (PMMA), fluorinated polymethacrylate (F-PMMA), polystyrene (PS), polyvinylidene fluoride (PVDF), polyurethane (PU) and polyethylene terephthalate (PETG)One or more than one kind of mixture.
Preferably, the particle size of the organic/inorganic micro-nano particles with isotropic optical refractive index is in the range of 0.01-100um. The particle size range is more preferably 0.1 to 10. Mu.m.
Preferably, the organic polymer substrate material having optical refractive index anisotropy is a thermoplastic material, comprising: at least one of Polyethylene (PE), polypropylene (PP), polyester (PET), polyamide (PA), polymethyl methacrylate (PMMA), fluorinated polymethacrylate (F-PMMA), polystyrene (PS), polyvinylidene fluoride (PVDF), polyurethane (PU) and polyethylene terephthalate (PETG) or a mixture of more than one of the above.
An optical broadband angle range selective atomization film is obtained by superposing a plurality of layers of the optical broadband angle range selective atomization films.
By means of the technical scheme, the technical scheme provided by the application has at least the following advantages:
the application realizes the spectral angle selection characteristic of broadband by the comprehensive application of material design and structural design and by utilizing the Mie scattering characteristic of the anisotropic crystal of optical refractive index and micro-nano particles.
The preparation process is simple, can realize large-area production, and has great significance in the fields of solar cells, display, illumination, peep prevention and the like.
Drawings
FIG. 1 is a diagram showing the effect of the selective atomization film for an angle range of an optical broadband according to embodiment 1 of the present application; a. a schematic diagram of a demonstration device is provided, a rainbow fringe pattern is placed behind a selectively atomized film sample in an optical broadband angle range, and observation is carried out under each angle; b.0 degrees incidence and high transmission; c, incidence at an angle of 30 degrees, increased haze and semitransparent samples; and d, incidence is carried out at an angle of 60 degrees, the haze is greatly increased, and the glass is almost opaque.
FIG. 2 is a graph showing the regular transmission spectrum of the optical broadband angle range selective atomization film according to the embodiment 1 of the present application in the visible light band.
Detailed Description
Exemplary embodiments of the present application will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present application are shown in the drawings, it should be understood that the present application may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.
Example 1:
in the embodiment, the provided optical broadband angle range selective atomization film has excellent optical broadband angle range selective performance, and is suitable for the fields of solar cells, display, illumination, peep prevention and the like.
Wherein the organic polymer substrate material with anisotropic optical refractive index is Polyamide (PA); the doped optical refractive index isotropic micro-nano particles are polyethylene terephthalate glycol (PETG) particles, the average particle diameter is about 600nm, and the doped optical refractive index isotropic micro-nano particles account for 40% of the total volume of the optical refractive index anisotropic composite material;
the two materials are compounded by using a physical melting method, wherein the melting temperature is between the glass-state melting point of the polymer substrate and the melting point of the micro-nano particles, and specifically 200 ℃.
The temperature at which the above material is extruded into a film by melt extrusion should be set with reference to the glass transition temperature of the substrate and the melting point of the particles, and the extrusion temperature is 200 ℃.
In the next drawing induction process of the film obtained after extrusion, the hot drawing temperature is required to be selected according to the compound concentration of the selected polymer material and the micro-nano particle material, and the fiber drawing temperature is 180 ℃; specifically, the drawing tension ranges from 0 to 500g, and the preferred drawing tension ranges from 10 to 50g; traction speed ranges from 0.1 to 5000m/min, with a preferred traction speed range of 0.1 to 20m/min.
The resulting optical broadband angular range selective atomized film (fig. 1), polymer substrate refractive index (nx, ny, nz) = (1.57,1.53,1.51), micro-nano particle refractive index n=1.57, demonstrated effect as shown in fig. 1. The regular transmittance spectrum of the visible light wave band at each angle is shown in figure 2, the film is high in transmittance within the range of 0-30 degrees, the transmittance is reduced and increased in amplitude after the transmittance is more than 30 degrees, and the film is gradually in an atomized state. The film is provided with selective atomization over an optically broad angular range. Comparative example 1:
in this comparative example, a polymethyl methacrylate (PMMA) substrate (n=1.49) with isotropic optical refractive index was used as the polymer substrate, and the composition of the doped inorganic particulate material and the processing parameters were the same as in example 1.
The films of example 1 and comparative example 1 were compared, and since the substrate and the doped particles were isotropic materials and had different refractive indices (substrate n=1.49, particle n=1.57), the optical impedance was not matched at each angle, so that comparative example 2 was fully atomized at each angle, with no angular selectivity.
Comparative example 2:
in this comparative example, an optically refractive index isotropic polyethylene terephthalate (PETG) substrate was also used as the polymer substrate, and the doped inorganic particulate material composition and processing parameters were the same as in example 1.
The films of example 1 and comparative example 2 were compared, and since the substrate and the doped particles were isotropic materials and had the same refractive index and the optical impedance was matched at each angle, the films of comparative example 1 were all transparent at each angle and were not angle selective.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the application and is not intended to limit the application, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the application are intended to be included within the scope of the application.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article or apparatus that comprises an element.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are to be included in the scope of the claims of the present application.
Claims (7)
1. The selective atomization film for the optical broadband angle range is characterized in that the material of the atomization film is obtained by doping isotropic organic/inorganic micro-nano particles on an organic polymer substrate with anisotropic optical refractive index; the doping concentration of the organic/inorganic micro-nano particles is 10-70 vol%.
2. The optical broadband angular range selective atomization film of claim 1 wherein the optically refractive index isotropic organic/inorganic micro-nano particles are: silica, alumina, magnesia, calcium fluoride, magnesium fluoride, lithium fluoride, polyethylene, polypropylene, polyester, polyamide, polymethyl methacrylate, fluorinated polymethacrylate, polystyrene, polyvinylidene fluoride, polyurethane and polyethylene terephthalate.
3. The optical broadband angular range selective atomization film of claim 1 wherein the optically refractive index isotropic organic/inorganic micro-nano particles have a particle size in the range of 0.01 to 100um.
4. The optical broadband angular range selective atomization film of claim 1 wherein the optically refractive index anisotropic organic polymer substrate material is a thermoplastic material selected from the group consisting of: at least one of polyethylene, polypropylene, polyester, polyamide, polymethyl methacrylate, fluorinated polymethacrylate, polystyrene, polyvinylidene fluoride, polyurethane and polyethylene terephthalate or a mixture of more than one of them.
5. A method for preparing an optically broadband angular range selective atomized film as claimed in any one of claims 1 to 4, comprising the steps of:
1) Uniformly compounding isotropic organic/inorganic micro-nano particles and anisotropic polymer base materials through chemical dissolution mixing and/or physical blending steps;
2) Based on the uniformly compounded material obtained in the step 1), an atomized film is prepared.
6. The method for preparing an optically wide-band angular range selective atomized film as claimed in claim 5, wherein in the step 2), the atomized film is prepared at a temperature between the glass transition temperature of the polymer substrate and the melting point of the dopant particles.
7. An optical broadband angular range selective atomization film, wherein the film is laminated with a plurality of layers of the optical broadband angular range selective atomization film according to any one of claims 1-4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310741894.9A CN116640437A (en) | 2023-06-21 | 2023-06-21 | Optical broadband angle range selective atomization film |
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|---|---|---|---|
| CN202310741894.9A CN116640437A (en) | 2023-06-21 | 2023-06-21 | Optical broadband angle range selective atomization film |
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