Glass surface functional film and preparation and application thereof

Abstract

The application discloses a glass surface functional thin film and preparation and application thereof, and belongs to the technical field of film materials. The application discloses a preparation method of a glass surface functional thin film, which comprises the following steps: S1, uniformly mixing ammonium persulfate, sodium dodecyl sulfate and deionized water, heating and stirring to obtain a dispersion liquid; mixing modified silicon dioxide nanoparticles, aluminum oxide nanoparticles and a solvent, ultrasonicating, adding chitosan and stirring to obtain a mixed liquid; mixing the dispersion liquid and the mixed liquid, continuously heating and stirring to obtain a prepolymer; uniformly stirring an initiator into the prepolymer to obtain modified silicon dioxide nanoparticle / aluminum oxide polymer; S2, in an inert gas atmosphere, forming a functional thin film on the surface of a pretreated substrate by a magnetron plating method.

Description

Technical Field

[0001] This invention belongs to the field of membrane material technology, specifically relating to a functional thin film on a glass surface and its preparation and application. Background Technology

[0002] Functional thin films on glass surfaces refer to thin film materials with special functions deposited or coated on the glass surface through physical or chemical methods, thereby endowing the glass with new properties, such as optical, electronic, protective, self-cleaning, and antibacterial functions. These films can change the optical properties of glass (such as transmittance and reflectivity), improve wear resistance and hardness, enhance antistatic properties, or achieve special functions such as antibacterial and self-cleaning.

[0003] Patent application CN106746736A discloses a superhydrophobic glass coating and its preparation method. The coating comprises a nanoporous glass membrane and a low surface energy hydrophobic membrane sequentially attached to the glass surface from the inside out. However, the hydrophobic coating material mainly uses fluorinated resin, and its preparation process is cumbersome, with harsh conditions and a curing temperature exceeding 300℃, posing risks of harm and pollution to humans and the environment. Furthermore, fluorinated compounds are expensive, resulting in high preparation costs. Alternatively, adding silica particles to the glass surface to increase the microscopic roughness of the glass substrate can also achieve hydrophobicity. For example, patent application CN105670393A discloses a method for preparing a superhydrophobic coating using a cellulose nanocrystal / silica composite template method. This application belongs to the heterogeneous addition method. Due to the high surface energy and brittleness of silica particles, the mechanical properties of the coating are somewhat reduced.

[0004] Therefore, it is essential to prepare a functional glass film that possesses both good wear resistance and hydrophobicity as well as excellent mechanical properties. Summary of the Invention

[0005] The purpose of this invention is to provide a functional thin film on a glass surface, its preparation and application, so as to improve the wear resistance of the film.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A method for preparing a functional thin film on a glass surface includes the following steps:

[0008] S1. Mix silica nanoparticles, silane coupling agent and deionized water, adjust pH, heat and stir, wash and dialyze to obtain modified silica nanoparticles.

[0009] S2. Mix ammonium persulfate, sodium dodecyl sulfate, and deionized water evenly, heat and stir to obtain a dispersion; mix modified silica nanoparticles, alumina nanoparticles, and solvent, sonicate, add chitosan and stir to obtain a mixture; mix the dispersion and mixture, heat and stir continuously to obtain a prepolymer; add initiator to the prepolymer and stir evenly, centrifuge, wash, and dry to obtain a modified silica nanoparticle / alumina polymer;

[0010] S3. In an inert gas atmosphere, modified silica nanoparticles / alumina polymer are deposited on the surface of a pretreated substrate to form a functional film.

[0011] Furthermore, the ratio of the silica nanoparticles, silane coupling agent, and deionized water is (6-10)g:(1-1.5)g:(35-40)mL.

[0012] Furthermore, the silane coupling agent is one or a combination of several of 3-(methacryloyloxy)propyltrimethoxysilane, monoethoxysilane-PEG-carboxylic acid, and 2-(carboxymethylthio)ethyltrimethylsilane.

[0013] Furthermore, the pH is adjusted to 3-4.

[0014] Furthermore, the ratio of ammonium persulfate, sodium dodecyl sulfate, and deionized water in the dispersion is (0.2-0.4)g:(15-25)g:(80-120)g.

[0015] Furthermore, the ratio of modified silica nanoparticles, alumina nanoparticles, solvent and chitosan in the mixture is (8-10)g:(12-15)g:(80-100)g:(1-2)g.

[0016] Furthermore, the solvent is a mixture of acetic acid and ethanol in a volume ratio of 1:1.

[0017] Furthermore, the heating and stirring is carried out at 60-80℃ for 2-4 hours.

[0018] Furthermore, the initiator is ammonium persulfate, and the amount of initiator added is 1% to 2% of the weight of the prepolymer.

[0019] Furthermore, the surface of the pretreated substrate is clean and free of contamination.

[0020] Furthermore, the thickness of the film is 50-70 μm.

[0021] A functional thin film on a glass surface is prepared by the above-described preparation method.

[0022] Furthermore, the application of the aforementioned functional thin film on the glass surface in LOW-E glass.

[0023] The beneficial effects of this invention are:

[0024] (1) The present invention provides a functional thin film for glass surface, which improves the modified silica nanoparticle / alumina polymer formulation; modifies the silica nanoparticles, optimizes the compatibility between silica nanoparticles and alumina nanoparticles; improves the dispersibility of silica nanoparticles in the film, and enhances the wear resistance of the functional thin film.

[0025] (2) The modified nano silica used in this invention benefits from its own properties, which can give the film the properties of reducing ultraviolet light transmission and high transparency; while the alumina used has high hardness and wear resistance, which not only further improves the wear resistance of the film, but also improves the dispersibility of nano silica and reduces the migration of silica through electrostatic adsorption with the modified silica nanoparticles. Detailed Implementation

[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1

[0028] This embodiment provides a functional thin film on a glass surface, which is prepared through the following steps:

[0029] S1. Mix 8g of silica nanoparticles, 1.5g of 3-(methacryloyloxy)propyltrimethoxysilane and 40mL of deionized water, adjust the pH to 4, stir in a 60℃ water bath for 4h, wash 3 times with a 1:1 mixture of diethyl ether and acetone, centrifuge at 10000r / min, dialyze with a dialysis bag with a molecular weight cutoff of 10000 for 5d, changing the deionized water daily to obtain modified silica nanoparticles.

[0030] S2. Mix 0.3g ammonium persulfate, 20g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 9g modified silica nanoparticles, 15g alumina nanoparticles, and 100g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 1.5g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, and continue heating and stirring to obtain a prepolymer. Add ammonium persulfate to the prepolymer and stir evenly. The amount of initiator added is 1.5% of the weight of the prepolymer. Centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0031] S3. In an inert gas atmosphere, modified silica nanoparticles / alumina polymer are deposited on the surface of a pretreated substrate to form a functional film with a thickness of 60 μm.

[0032] The functional thin film prepared above is applied to LOW-E glass.

[0033] Example 2

[0034] The difference between this embodiment and Example 1 is that the ratio of raw materials in the S2 dispersion is changed. The specific implementation steps are as follows:

[0035] S2. Mix 0.2g ammonium persulfate, 21g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 9g modified silica nanoparticles, 15g alumina nanoparticles, and 100g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 1.5g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, and continue heating and stirring to obtain a prepolymer. Add ammonium persulfate to the prepolymer and stir evenly. The amount of initiator added is 1.5% of the weight of the prepolymer. Centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0036] The remaining raw materials and preparation process are the same as in Example 1.

[0037] Example 3

[0038] The difference between this embodiment and Embodiment 1 is that the proportion of raw materials in the S2 mixture is changed. The specific implementation steps are as follows:

[0039] S2. Mix 0.3g ammonium persulfate, 20g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 10g modified silica nanoparticles, 12g alumina nanoparticles, and 100g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 1g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, and continue heating and stirring to obtain a prepolymer. Add ammonium persulfate to the prepolymer and stir evenly. The amount of initiator added is 1.5% of the weight of the prepolymer. Centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0040] The remaining raw materials and preparation process are the same as in Example 1.

[0041] Example 4

[0042] The difference between this embodiment and Embodiment 1 is that the ratio of raw materials in both the S2 dispersion and the mixture is changed. The specific implementation steps are as follows:

[0043] S2. Mix 0.4g ammonium persulfate, 19g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 8g modified silica nanoparticles, 15g alumina nanoparticles, and 100g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 2g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, and continue heating and stirring to obtain a prepolymer. Add ammonium persulfate to the prepolymer and stir evenly. The amount of initiator added is 1.5% of the weight of the prepolymer. Centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0044] The remaining raw materials and preparation process are the same as in Example 1.

[0045] Example 5

[0046] Compared with Example 1, the difference in this embodiment is that "8g of silica nanoparticles and 1.5g of 3-(methacryloyloxy)propyltrimethoxysilane" in S1 is changed to "10g of silica nanoparticles and 1g of 3-(methacryloyloxy)propyltrimethoxysilane". The specific implementation steps are as follows:

[0047] S1. Mix 10g of silica nanoparticles, 1g of 3-(methacryloyloxy)propyltrimethoxysilane and 40mL of deionized water, adjust the pH to 4, stir in a 60℃ water bath for 4h, wash 3 times with a 1:1 mixture of diethyl ether and acetone, centrifuge at 10000r / min, dialyze with a dialysis bag with a molecular weight cutoff of 10000 for 5d, changing the deionized water daily to obtain modified silica nanoparticles.

[0048] The remaining raw materials and preparation process are the same as in Example 1.

[0049] Example 6

[0050] The difference between this embodiment and Example 1 is that "3-(methacryloyloxy)propyltrimethoxysilane" is replaced with "2-(carboxymethylthio)ethyltrimethylsilane". The specific implementation steps are as follows:

[0051] S1. Mix 8g of silica nanoparticles, 1.5g of 2-(carboxymethylthio)ethyltrimethylsilane and 40mL of deionized water, adjust the pH to 4, stir in a 60℃ water bath for 4h, wash 3 times with a 1:1 mixture of diethyl ether and acetone, centrifuge at 10000r / min, dialyze with a dialysis bag with a molecular weight cutoff of 10000 for 5d, and change the deionized water every day to obtain modified silica nanoparticles.

[0052] The remaining raw materials and preparation process are the same as in Example 1.

[0053] Example 7

[0054] The difference between this embodiment and Example 1 is that "3-(methacryloyloxy)propyltrimethoxysilane" is replaced with "monoethoxysilane-PEG-carboxylic acid". The specific implementation steps are as follows:

[0055] S1. Mix 8g of silica nanoparticles, 1.5g of monoethoxysilane-PEG-carboxylic acid and 40mL of deionized water, adjust the pH to 4, stir in a 60℃ water bath for 4h, wash 3 times with a 1:1 mixture of diethyl ether and acetone, centrifuge at 10000r / min, dialyze with a dialysis bag with a molecular weight cutoff of 10000 for 5d, and change the deionized water every day to obtain modified silica nanoparticles.

[0056] The remaining raw materials and preparation process are the same as in Example 1.

[0057] Comparative Example 1

[0058] The difference between this comparative example and Example 1 is that no silane coupling agent is added. The specific implementation steps are as follows:

[0059] S1. Mix 0.3g ammonium persulfate, 20g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 9g silica nanoparticles, 15g alumina nanoparticles, and 100g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 1.5g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, and continue heating and stirring to obtain a prepolymer. Add ammonium persulfate to the prepolymer and stir evenly. The amount of initiator added is 1.5% of the weight of the prepolymer. Centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0060] S3. In an inert gas atmosphere, modified silica nanoparticles / alumina polymer are deposited on the surface of a pretreated substrate to form a functional film with a thickness of 60 μm.

[0061] The remaining raw materials and preparation process are the same as in Example 1.

[0062] Comparative Example 2

[0063] The difference between this comparative example and Example 1 is that no modified silica nanoparticles were added. The specific implementation steps are as follows:

[0064] S1. Mix 0.3g ammonium persulfate, 20g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 24g alumina nanoparticles and 100g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 1.5g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, and continue heating and stirring to obtain a prepolymer. Add ammonium persulfate to the prepolymer and stir evenly. The amount of initiator added is 1.5% of the weight of the prepolymer. Centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0065] S2. In an inert gas atmosphere, modified silica nanoparticles / alumina polymer are deposited on the surface of a pretreated substrate to form a functional film with a thickness of 60 μm.

[0066] The remaining raw materials and preparation process are the same as in Example 1.

[0067] Comparative Example 3

[0068] The difference between this comparative example and Example 1 is that no initiator was added. The specific implementation steps are as follows:

[0069] S2. Mix 0.3g ammonium persulfate, 20g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 9g modified silica nanoparticles, 15g alumina nanoparticles, and 100g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 1.5g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, continue heating and stirring, centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0070] The remaining raw materials and preparation process are the same as in Example 1.

[0071] Comparative Example 4

[0072] The difference between this comparative example and Example 1 is that modified silica and alumina nanoparticles are not added. The specific implementation steps are as follows:

[0073] S1. Mix 0.3g ammonium persulfate, 20g sodium dodecyl sulfate, and 100g deionized water evenly and stir at 80℃ for 2h to obtain a dispersion. Mix 124g acetic acid and ethanol in a volume ratio of 1:1, sonicate, add 1.5g chitosan and stir to obtain a mixture. Mix the dispersion and the mixture, and continue heating and stirring to obtain a prepolymer. Add ammonium persulfate to the prepolymer and stir evenly. The amount of initiator added is 1.5% of the weight of the prepolymer. Centrifuge, wash, and dry to obtain the modified silica nanoparticle / alumina polymer.

[0074] S2. In an inert gas atmosphere, modified silica nanoparticles / alumina polymer are deposited on the surface of a pretreated substrate to form a functional film with a thickness of 60 μm.

[0075] The remaining raw materials and preparation process are the same as in Example 1.

[0076] Performance tests were conducted on Examples 1-7 and Comparative Examples 1-4.

[0077] According to HG / T 4303-2012, the wear resistance of the functional films obtained in the various embodiments and comparative examples of this application was tested (5000 cycles of friction under a 500g load).

[0078] According to GB / T 2410-2008, the light transmittance of the functional films obtained in the various embodiments and comparative examples of this application was tested.

[0079] According to GB / T 2680-2021, the ultraviolet blocking rate of the functional films obtained in the various embodiments and comparative examples of this application was tested.

[0080] The results are shown in Table 1:

[0081] Table 1

[0082]

[0083]

[0084] Based on the established examples, comparative examples, and the data in Table 1, it can be seen that the difference between Examples 2-7 and Example 1 lies in the raw material ratio and variations within a reasonable range. The test data shows that the prepared films exhibit good wear resistance, high light transmittance, and strong UV shielding. Furthermore, we found that using a silane coupling agent containing carboxyl groups significantly improves the film performance. This is because carboxyl groups can combine with alumina, enhancing the chemical bond between nano-silica and alumina, thereby improving the film's performance.

[0085] Compared to Example 1, Comparative Example 1, without the addition of a silane coupling agent, showed a decrease in the dispersibility of nano-silica and its bonding effect with alumina nanoparticles, resulting in a reduction in the overall performance of the film. Comparative Example 2, compared to Example 1, did not add silica nanoparticles, leading to a significant reduction in the film's wear resistance and UV protection performance. Comparative Example 3, compared to Example 1, differed in its optimized process; the addition of an initiator after mixing the dispersion and mixture helped the modified silica nanoparticles / alumina polymer to better bond and form a film, improving film performance. Comparative Example 4, combining Comparative Examples 1-2 with Example 1, showed that due to the high hardness and wear resistance of alumina, it not only further improved the film's wear resistance but also improved the dispersibility of nano-silica through electrostatic adsorption with the modified silica nanoparticles, playing a synergistic role.

[0086] In summary, the present invention provides a functional thin film for glass surface, its preparation and application. The prepared thin film has good wear resistance, light transmittance and ultraviolet blocking rate, and its application in LOW-E glass has good application prospects.

[0087] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0088] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a functional thin film on a glass surface, characterized in that, Includes the following steps: S1. Mix ammonium persulfate, sodium dodecyl sulfate, and deionized water evenly, heat and stir to obtain a dispersion; mix modified silica nanoparticles, alumina nanoparticles, and solvent, sonicate, add chitosan and stir to obtain a mixture; mix the dispersion and mixture, heat and stir continuously to obtain a prepolymer; add initiator to the prepolymer and stir evenly, centrifuge, wash, and dry to obtain a modified silica nanoparticle / alumina polymer; S2. In an inert gas atmosphere, modified silica nanoparticles / alumina polymer are deposited on the surface of a pretreated substrate to form a functional film. The modified silica nanoparticles are prepared by the following steps: Silica nanoparticles, silane coupling agent and deionized water were mixed, pH was adjusted, heated and stirred, washed and dialyzed to obtain modified silica nanoparticles. The ratio of silica nanoparticles, silane coupling agent, and deionized water is (6-10) g: (1-1.5) g: (35-40) mL; the pH is adjusted to 3-4. The silane coupling agent is one or a combination of several of 3-(methacryloyloxy)propyltrimethoxysilane, monoethoxysilane-PEG-carboxylic acid, and 2-(carboxymethylthio)ethyltrimethylsilane; The ratio of modified silica nanoparticles, alumina nanoparticles, solvent and chitosan in the mixture is (8-10)g:(12-15)g:(80-100)g:(1-2)g.

2. The method for preparing a functional thin film on a glass surface according to claim 1, characterized in that, The ratio of ammonium persulfate, sodium dodecyl sulfate, and deionized water in the dispersion is (0.2-0.4)g:(15-25)g:(80-120)g.

3. The method for preparing a functional thin film on a glass surface according to claim 1, characterized in that, The solvent is a mixture of acetic acid and ethanol in a volume ratio of 1:1; the heating and stirring is carried out at 60-80℃ for 2-4 hours; the initiator is ammonium persulfate, and the amount of initiator added is 1% to 2% of the weight of the prepolymer.

4. The method for preparing a functional thin film on a glass surface according to claim 1, characterized in that, The pretreated substrate surface is clean and free of contaminants; the thickness of the film is 50-70 μm.

5. A functional thin film for a glass surface, characterized in that, It is prepared by the method for preparing a functional thin film on a glass surface according to any one of claims 1-4.

6. The application of a glass surface functional film as described in claim 5 in LOW-E glass.

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