CN113061357A - A kind of antireflection hydrophobic coating and preparation method thereof - Google Patents

A kind of antireflection hydrophobic coating and preparation method thereof Download PDF

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CN113061357A
CN113061357A CN202110322185.8A CN202110322185A CN113061357A CN 113061357 A CN113061357 A CN 113061357A CN 202110322185 A CN202110322185 A CN 202110322185A CN 113061357 A CN113061357 A CN 113061357A
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hydrophobic
silicon dioxide
hydrophobic coating
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CN113061357B (en
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谭新玉
吴瑛琳
王云宽
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China Three Gorges University CTGU
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    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract

本发明公开了一种增透疏水涂层及其制备方法,该涂层包括二氧化硅层和其上的甲基‑MQ硅树脂层,其中二氧化硅层采用溶胶‑凝胶法制得。该涂层在300‑900nm光波段范围内,其透过率高于空白玻璃。在552nm处透过率达到99.539%;水接触角可达141.49°。其具有良好的耐久性,机械性能和优异的抗紫外性能,所得样品在分别经过在UVA‑340紫外线灯管下暴露17小时,10g沙砾40cm的高度下4次冲击,实验测试后其透光率仍远高于空白玻璃的透光率。本发明提供的制备工艺简单,成本低;可用于光学器件、光伏电池板上,在材料领域、新能源领域以及环境领域都有巨大的发展潜力。

Figure 202110322185

The invention discloses an anti-reflection hydrophobic coating and a preparation method thereof. The coating comprises a silicon dioxide layer and a methyl-MQ silicone resin layer thereon, wherein the silicon dioxide layer is prepared by a sol-gel method. The transmittance of the coating is higher than that of blank glass in the range of 300-900nm. The transmittance at 552nm reaches 99.539%; the water contact angle can reach 141.49°. It has good durability, mechanical properties and excellent UV resistance. The obtained samples were exposed to UVA‑340 UV lamps for 17 hours and impacted 4 times at a height of 10g sand and gravel at a height of 40cm. After the experimental test, their light transmittance was measured. Still much higher than the transmittance of blank glass. The preparation process provided by the invention is simple and the cost is low; it can be used for optical devices and photovoltaic cell panels, and has great development potential in the field of materials, new energy and the environment.

Figure 202110322185

Description

Anti-reflection hydrophobic coating and preparation method thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an anti-reflection hydrophobic coating and a preparation method thereof.
Background
With the deep research make internal disorder or usurp on the super-hydrophobic structure of the bionic lotus leaf, people gradually recognize the important significance and application of the super-hydrophobic characteristic in the daily life of people. Therefore, how to construct a lotus leaf-like super-hydrophobic film through material modification and surface microstructure design has become one of the research hotspots in the field of functional materials. Many teams at home and abroad research and develop bionic lotus leaf structure hydrophobic materials, and the bionic lotus leaf structure hydrophobic materials are used on the surfaces of glass, building materials and the like, so that the super-hydrophobic materials which can achieve the hydrophobic self-cleaning effect have more and more delicate division of labor. Many groups at home and abroad do a lot of researches around the point, but most of prepared films only have the characteristic of hydrophobicity and are not generally enhanced in permeability, and most of film preparation methods are complicated and medicines are expensive to prepare.
Based on this, the team has conducted a series of studies aiming to find a more effective solution to these problems.
Disclosure of Invention
The invention provides an anti-reflection hydrophobic coating and a preparation method thereof. The anti-reflection hydrophobic coating is a silicon dioxide hydrophobic coating, and the transmittance of the anti-reflection film is higher than that of the blank glass within the light wave band range of 300-900 nm. The maximum transmittance can reach 99.539%; the water contact angle can reach more than 141 degrees.
The invention adopts the technical scheme that the anti-reflection hydrophobic coating comprises a silicon dioxide layer and a methyl-MQ silicon resin layer arranged on the silicon dioxide layer, wherein the silicon dioxide layer is prepared by adopting a sol-gel method.
Further, when the silicon dioxide layer is prepared, the raw materials are tetraethyl orthosilicate, deionized water, ethanol and ammonia water, and the volume ratio of the tetraethyl orthosilicate to the deionized water to the ethanol to the ammonia water is 4-6: 0.6-1.3: 45-51: 0.5-1.1.
Further, prior to preparation of the methyl-MQ silicone resin layer, it was mixed with tetrahydrofuran in a ratio of 0.5-1.5: 2, mixing uniformly and then using.
The invention also relates to a method for preparing the anti-reflection hydrophobic coating, which comprises the following steps:
s1, mixing tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and ammonia water, magnetically stirring for 20-30 hours to obtain light blue sol, and aging for 5-15 days at room temperature to obtain silicon dioxide sol for later use;
s2, mixing the methyl-MQ silicon resin and tetrahydrofuran, and magnetically stirring for 0.5-1h at 25-30 ℃ to obtain a hydrophobic solution for later use;
s3, pulling the cleaned base material on a dip coating machine to form silica sol coated with the film S1, so that silica is attached to the base material to form a silica antireflection film, and drying;
s4, coating the hydrophobic solution in the S2 on the silicon dioxide antireflection film in the S3 in a scraping mode, and drying and annealing the treated base material to obtain the high-hydrophobicity coating.
Further, the substrate is glass, a resin material, or a metal material. Glass materials are preferred. It can also be used for aluminium sheet, fan blade, etc.
Further, before the substrate is subjected to dip coating in S3, the substrate is sequentially cleaned by detergent, ultrasonic cleaning, common water cleaning, ultrasonic cleaning, ethanol cleaning and deionized water cleaning, then dried, and finally subjected to surface treatment by a plasma machine. In the plasma treatment, the plasma power was 600w and the treatment time was 60 s.
Further, when dipping and pulling treatment are carried out in S3, the base material is dipped in the silica sol for 6-10min and then is pulled at a constant speed of 500-1500 μm/S; the thickness of the hydrophobic solution in S4 is 45-55 μm when the solution is coated by a blade.
Furthermore, the drying temperature in S3 is 100-150 ℃, and the drying time is 0.1-0.5 h.
Further, the drying temperature in S4 is 100-150 ℃, and the time is 0.2-0.6 h; and during annealing, annealing for 5-20 min at 320-450 ℃ in a muffle furnace.
The invention also relates to an application of the anti-reflection hydrophobic coating in a photovoltaic cell panel.
The methyl-MQ silicon resin is a novel organic silicon high polymer material with a three-dimensional (nonlinear) structure formed by taking Si-O bonds as a framework in molecules, and has good mechanical properties and excellent properties of high and low temperature resistance, electrical insulation, moisture resistance, water resistance and the like due to the long-chain spherical molecular structure. The structural formula is shown as follows.
Figure BDA0002993231220000021
The invention has the following beneficial effects:
the anti-reflection hydrophobic coating provided by the invention has a special nano-scale upper and lower layer coarse structure, has good hydrophobic and self-cleaning capabilities, and has a contact angle of 141.49 degrees; the anti-reflection effect is very good, the transmittance is higher than that of the blank glass within the light wave band range of 300-900nm, and the transmittance at 552nm reaches 99.539%.
The anti-reflection hydrophobic coating also has good durability and mechanical property and excellent uvioresistant property. The resulting samples were exposed to UVA-340 UV light for 17 hours, 4 impacts at a height of 40cm of 10g grit, and the light transmittance was still much higher than that of the clear glass after experimental testing.
The preparation method provided by the invention has the advantages of simple process and low cost, and the anti-reflection hydrophobic coating can be used on an optical device and can improve the antifouling and decontamination capabilities; the solar cell panel can be used for a photovoltaic cell panel, the visible light absorption rate of the photovoltaic panel is obviously improved, the photoelectric conversion efficiency of the photovoltaic panel is improved, and meanwhile, the solar cell panel can be effectively antifouling, dustproof and the photoelectric conversion efficiency of the solar cell is improved. The excellent uvioresistant performance of the material has great development potential in the material field, the new energy field and the environment field.
The invention adopts a two-step method, firstly uses tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water to prepare light blue sol, and then uses methyl-MQ silicon resin to carry out blade coating modification. The obtained silicon dioxide antireflection film has an antireflection value of 8.437%, and the multifunctional antireflection film with self-cleaning and high hydrophobicity is simple in preparation method and high in cost performance.
Drawings
FIG. 1 is a transmission spectrum test chart of the obtained product.
FIG. 2 shows the transmittance of the resulting product; the left side of the figure is coated and the right side is uncoated.
FIG. 3 shows the variation of water contact angle of the surface of the film with the number of sand impacts on the resulting product.
FIG. 4 shows the change in contact angle of the glass before and after the coating, wherein the left graph shows the glass before coating and the right graph shows the glass after coating.
FIG. 5 is a graph of durability of a hydrophobic antireflective film under UVA-340 ultraviolet light.
FIG. 6 is a plan SEM view of a hydrophobic antireflective film.
FIG. 7 is a graph showing a transmission spectrum test of the surface of a film in a comparative test of a silica antireflection film.
FIG. 8 is a comparison of self-cleaning of the resulting product, wherein the top is a photograph after dust flooding, the bottom is a photograph after self-cleaning, the upper product is a coated product and the lower product is an uncoated product.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
Coating the small-area glass: the glass size in this example is 25 ﹡ 75 mm. The glass model is as follows: shitai pathological microscope slide.
The substrate can be written as other resin materials or metal materials, but the glass material has the best effect, and the adhesion effect between the anti-reflection hydrophobic coating and the glass is good.
Preparation of silica sol (antireflective solution): tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water are mixed in a 100ml beaker according to the volume ratio of 4.6:1.2:45:0.8, and are magnetically stirred for 25 hours at the temperature of 30 ℃ to obtain light blue sol, and the light blue sol is aged for 10 days at room temperature.
Preparation of a hydrophobic modified solvent: mixing methyl-MQ silicon resin and tetrahydrofuran according to a volume ratio of 1:2, placing the mixture in a 100ml beaker, and magnetically stirring the mixture for 0.5h at the temperature of 30 ℃ for later use;
cleaning glass: washing glass with washing powder, ultrasonic cleaning for 10min, cleaning with common water, ultrasonic cleaning with deionized water for 5min, cleaning with ethanol for 5min, and cleaning with deionized water. After drying in an oven at 60 ℃ the mixture was treated with a maximum power of 600W for 60 s.
Plasma machine 100% power treatment for 60s
Preparing a silicon dioxide antireflection film: and (3) soaking the cleaned glass for later use in silica sol (anti-reflection solution) for 10min, and then uniformly pulling the glass by using a dipping pulling film coating machine at a speed of 1200 um/s. After the silicon dioxide antireflection film is obtained, processing the silicon dioxide antireflection film in a drying oven at 110 ℃ for 0.5 h;
hydrophobic treatment of the silica sol film: and (3) coating a layer of hydrophobic modified solvent on the glass coated with the silica sol in a scraping way, placing the sample subjected to hydrophobic modification in an oven at 110 ℃ for processing for 0.5h, and annealing in a muffle furnace at 450 ℃ for 10 min. And taking out the glass after the temperature is reduced to the room temperature to obtain the high-hydrophobicity glass with the anti-reflection effect.
A UV2500 type ultraviolet-visible-near infrared spectrophotometer is used for testing the transmissivity of the silicon dioxide antireflection film, and the transmissivity of the antireflection film in the range of 300-804 nm is more than 95% in the range of 300-900nm optical band. And the maximum transmittance at 553.5nm is 99.539%, which is much higher than that of the blank glass (see figure 1), the maximum transmittance of the blank glass is 91.102%, and the anti-reflection value of the silicon dioxide anti-reflection film is 8.437%. The water contact angle of the anti-reflection film subjected to hydrophobic modification measured by a contact angle measuring instrument is 141.49 degrees, and the specific figure is shown in figure 2.
Example 2:
the glass of the anti-reflection high-hydrophobicity film prepared in the example 1 is subjected to a durability test under a UVA-340 ultraviolet lamp tube:
the prepared product is placed in a UVA-340 ultraviolet lamp tube for testing specific values of water contact angles and transmittance on the surface of the film under different irradiation times.
1. Placing the prepared product at 50cm of UVA-340 ultraviolet lamp tube in parallel;
2. the water contact angle and transmittance of the film surface at different times were measured in units of one hour.
The water contact angle and transmittance of the film surface tended to decrease with time, and the water contact angle of the film surface was 134.49 ° at 17h of irradiation. The transmittance at this time was still greater than 95%, which was much higher than 91.1% of the blank glass. Tests show that the film has excellent durability. See in particular fig. 5, where T and WCA are hydrophobic angles and transmittance as a function of exposure time.
Example 3:
application of the coating on aluminum sheets:
preparation of silica sol (antireflective solution): tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water are mixed in a 100ml beaker according to the volume ratio of 5.5:1.2:50:1, and are magnetically stirred for 25 hours at the temperature of 30 ℃ to obtain light blue sol, and the light blue sol is aged for 10 days at room temperature.
Preparation of a hydrophobic modified solvent: mixing methyl-MQ silicon resin and tetrahydrofuran according to a volume ratio of 1:2, placing the mixture in a 100ml beaker, and magnetically stirring the mixture for 0.5h at the temperature of 30 ℃ for later use;
cleaning glass: washing glass with washing powder, ultrasonic cleaning for 10min, cleaning with common water, ultrasonic cleaning with deionized water for 5min, cleaning with ethanol for 5min, and cleaning with deionized water. Drying in an oven at 60 deg.C, and treating with 600w power of a plasma machine for 60s
Preparing a silicon dioxide antireflection film: and (3) soaking the cleaned glass for later use in silica sol (anti-reflection solution) for 10min, and then uniformly pulling the glass by using a dipping pulling film coating machine at a speed of 1200 um/s. After the silicon dioxide antireflection film is obtained, processing the silicon dioxide antireflection film in a drying oven at 110 ℃ for 0.5 h;
hydrophobic treatment of the silica sol film: and (3) coating a layer of hydrophobic modified solvent on the glass coated with the silica sol in a scraping way, placing the sample subjected to hydrophobic modification in an oven at 110 ℃ for processing for 0.5h, and annealing in a muffle furnace at 450 ℃ for 10 min. And taking out the glass after the temperature is reduced to the room temperature to obtain the high-hydrophobicity glass with the anti-reflection effect. And (5) carrying out structural and morphological analysis on the product by using the SEM. See fig. 6, which shows the obvious nanometer upper and lower layer rough structure. The low surface energy of the Me-MQ silicone resin and the coarse structure formed by aggregation of the silica nanoparticles, and the air layer between the particles are the reasons for the hydrophobicity of the film.
Comparative testing of silica antireflection films:
preparation of silica sol (antireflective solution): tetraethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water are mixed in a 100ml beaker according to the volume ratio of 3:0.4:40:1.2, and are magnetically stirred for 25 hours at the temperature of 30 ℃ to obtain light blue sol, and the light blue sol is aged for 10 days at room temperature.
Cleaning glass: washing glass with washing powder, ultrasonic cleaning for 10min, cleaning with common water, ultrasonic cleaning with deionized water for 5min, cleaning with ethanol for 5min, and cleaning with deionized water. After drying in an oven at 60 ℃, the mixture was treated with a plasma machine at 100% power for 60 seconds.
Preparing a silicon dioxide antireflection film: and (3) soaking the cleaned glass for later use in silica sol (anti-reflection solution) for 10min, and then uniformly pulling the glass by using a dipping pulling film coating machine at a speed of 1200 um/s. After the silicon dioxide antireflection film is obtained, the silicon dioxide antireflection film is treated in an oven at 110 ℃ for 0.5 h. The transmittance of the silica antireflection film was measured using a UV2500 UV-VIS-NIR spectrophotometer, and the transmittance of the control group was 87.459% maximum, as shown in FIG. 8.

Claims (10)

1.一种增透疏水涂层,其特征在于,包括二氧化硅层和其上的甲基-MQ硅树脂层,其中二氧化硅层采用溶胶-凝胶法制得。1. An anti-reflection hydrophobic coating, characterized in that it comprises a silicon dioxide layer and a methyl-MQ silicone resin layer thereon, wherein the silicon dioxide layer is obtained by a sol-gel method. 2.根据权利要求1所述的增透疏水涂层,其特征在于:所述二氧化硅层制备时,原料为正硅酸四乙酯,去离子水,乙醇和氨水,体积比为4~6:0.6-1.3:45~51:0.5~1.1。2. The anti-reflection hydrophobic coating according to claim 1 is characterized in that: when the silicon dioxide layer is prepared, the raw materials are tetraethyl orthosilicate, deionized water, ethanol and ammonia water, and the volume ratio is 4~ 6:0.6-1.3:45~51:0.5~1.1. 3.根据权利要求1所述的增透疏水涂层,其特征在于:所述甲基-MQ硅树脂层制备前,将其与四氢呋喃按0.5-1.5:2混合均匀后使用。3. The anti-reflection hydrophobic coating according to claim 1, characterized in that: before the methyl-MQ silicone resin layer is prepared, it is evenly mixed with tetrahydrofuran at a ratio of 0.5-1.5:2 before use. 4.制备权利要求1~3任意一项所述增透疏水涂层的方法,其特征在于,包括以下步骤:4. the method for preparing the anti-reflection hydrophobic coating described in any one of claim 1~3, is characterized in that, comprises the following steps: S1、将正硅酸四乙酯,无水乙醇,去离子水和氨水进行混合,磁力搅拌20~30h,得到淡蓝色溶胶,在室温下陈化5~15天,得二氧化硅溶胶,备用;S1. Mix tetraethyl orthosilicate, absolute ethanol, deionized water and ammonia water, stir magnetically for 20 to 30 hours to obtain a light blue sol, and age at room temperature for 5 to 15 days to obtain a silica sol, spare; S2、将甲基-MQ硅树脂和四氢呋喃混合,在25~30℃磁力搅拌0.5-1h,得疏水溶液,备用;S2. Mix methyl-MQ silicone resin and tetrahydrofuran, and stir magnetically at 25-30° C. for 0.5-1 h to obtain a hydrophobic solution, which is for later use; S3、将清洗干净的基材在浸渍提拉镀膜机上提拉镀膜S1中得到的二氧化硅溶胶,使其二氧化硅附着在基材上形成二氧化硅增透膜,干燥;S3, pulling the cleaned substrate on the dipping and pulling coating machine to pull the silica sol obtained in the coating S1, so that the silica is attached to the substrate to form a silica antireflection film, and drying; S4、将S2中的疏水溶液刮涂在S3中二氧化硅增透膜上,处理后的基材进行烘干和退火,得到高疏水涂层。S4, scraping the hydrophobic solution in S2 on the silica antireflection film in S3, and drying and annealing the treated substrate to obtain a highly hydrophobic coating. 5.根据权利要求4所述的方法,其特征在于:所述基材为玻璃、树脂材料或者金属材料。5. The method according to claim 4, wherein the substrate is glass, resin material or metal material. 6.根据权利要求4所述的方法,其特征在于:S3中基材在提拉镀膜之前,依次采用洗涤剂清洗、超声清洗、普通水清洗、超声清洗、乙醇清洗、去离子水清洗后烘干,最后用等离子体机进行表面处理。6. method according to claim 4, is characterized in that: in S3, before the substrate is pulled and coated, successively adopts detergent cleaning, ultrasonic cleaning, ordinary water cleaning, ultrasonic cleaning, ethanol cleaning, deionized water cleaning and drying after cleaning. dry, and finally surface-treated with a plasma machine. 7.根据权利要求4所述的方法,其特征在于:S3中浸渍提拉处理时,先将基材浸渍在二氧化硅溶胶中6-10min,然后用500~1500μm/s的速度匀速提拉;S4中疏水溶液刮涂时厚度在45~55μm。7. The method according to claim 4, characterized in that: during the dipping and pulling treatment in S3, the substrate is first dipped in the silica sol for 6-10 min, and then pulled at a uniform speed at a speed of 500-1500 μm/s ; The thickness of the hydrophobic solution in S4 is 45~55μm when it is scraped. 8.根据权利要求4所述的方法,其特征在于:S3中干燥温度为100~150℃,时间为0.1~0.5h。8 . The method according to claim 4 , wherein the drying temperature in S3 is 100-150° C., and the time is 0.1-0.5 h. 9 . 9.根据权利要求4所述的方法,其特征在于:S4中烘干温度为100~150℃,时间为0.2~0.6h;退火时,在马弗炉中320~450℃下退火5~20min。9. The method according to claim 4, characterized in that: the drying temperature in S4 is 100-150°C, and the time is 0.2-0.6h; during annealing, annealing is performed at 320-450°C for 5-20min in a muffle furnace . 10.权利要求1-3任意一项所述增透疏水涂层在光伏电池板中的应用。10. The application of the antireflection hydrophobic coating according to any one of claims 1-3 in a photovoltaic cell panel.
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