阅读说明：本技术 一种玻璃表面复合疏水薄膜的制备方法 (Preparation method of glass surface composite hydrophobic film ) 是由 李尊 汪之国 赵洪常 罗晖 于 2020-11-20 设计创作，主要内容包括：本发明专利公开了一种玻璃表面复合疏水薄膜的制备方法,具体涉及材料应用的技术领域。一种玻璃表面复合疏水薄膜的制备方法,包括如下步骤：将玻璃片依次放入去离子水、乙醇、去离子水中冲洗,并在上述各溶剂中超声清洗；将玻璃片放入表面活化溶液中；将玻璃片放入乙醇和乙醚混合溶剂中进行物理脱水,玻璃片采用冷风快速吹干备用；将玻璃片放入4.0mL/L的OTS溶液中浸泡30min；将浸泡后的玻璃片用二氯甲烷冲洗三次,再转入烘箱中烘烤；将玻璃片放入镀晶溶液中浸泡2min,浸泡后取出放在室温下晾置1h；将玻璃片用正己烷润洗3次,最后放置在室温下晾置7天。采用本发明技术方案解决了现有的OTS膜层长期条件下易水解的问题,可用于OTS膜的保护。(The invention discloses a preparation method of a glass surface composite hydrophobic film, and particularly relates to the technical field of material application. A preparation method of a glass surface composite hydrophobic film comprises the following steps: sequentially putting the glass sheet into deionized water, ethanol and deionized water for washing, and ultrasonically cleaning in the solvents; putting the glass sheet into a surface activation solution; putting the glass sheet into a mixed solvent of ethanol and ether for physical dehydration, and quickly drying the glass sheet for later use by cold air; soaking the glass sheet in 4.0mL/L OTS solution for 30 min; washing the soaked glass sheet with dichloromethane for three times, and then transferring the glass sheet into an oven for baking; soaking the glass sheet in the crystal plating solution for 2min, taking out after soaking, and airing at room temperature for 1 h; the glass pieces were rinsed 3 times with n-hexane and finally left to air at room temperature for 7 days. The technical scheme of the invention solves the problem that the existing OTS film layer is easy to hydrolyze for a long time, and can be used for protecting the OTS film.)

1. A preparation method of a glass surface composite hydrophobic film is characterized by comprising the following steps: the method comprises the following steps:

s102, sequentially putting the glass sheet into deionized water, ethanol and deionized water for washing, and ultrasonically cleaning in the solvents;

s104, putting the glass sheet cleaned in the S102 into a prepared surface activation solution, soaking for 1h, taking out the glass sheet, and washing with deionized water;

s106, sequentially putting the glass sheet washed in the S104 into three parts of the same ethanol and ether mixed solvent (the volume ratio of the ethanol to the ether is 1:1) for physical dehydration, and quickly drying the dehydrated glass sheet by adopting nitrogen flow for later use;

s108, soaking the glass sheet dried in the S106 in 4.0mL/L OTS solution for 30 min;

s110, washing the glass sheet soaked in the S108 with dichloromethane for three times, and then baking the glass sheet in an oven for 10 hours at the baking temperature of 145 ℃;

s112, soaking the glass sheet baked in the step S110 in the crystal plating solution for 2min, taking out after soaking, and airing at room temperature for 1 h;

and S114, rinsing the glass sheet dried in the S112 with n-hexane for 3 times, and finally, standing at room temperature for 7 days to obtain the hydrophobic film on the glass sheet.

2. The method for preparing the glass surface composite hydrophobic film according to claim 1, wherein the method comprises the following steps: in S102, the cleaning time of the glass sheet in various cleaning solutions is 2 min.

3. The method for preparing the glass surface composite hydrophobic film according to claim 1, wherein the method comprises the following steps: the preparation method of the surface activation solution comprises the following steps: 75mL of 98% concentrated sulfuric acid was slowly added in portions to a beaker containing 25mL of 30% aqueous hydrogen peroxide with stirring under ice-bath conditions.

4. The method for preparing the glass surface composite hydrophobic film according to claim 3, wherein the method comprises the following steps: in S108, the solvent of the OTS solution is dichloromethane and n-hexane with the volume ratio of 1:4, and the solute of the OTS solution is OTS (namely octadecyltrichlorosilane).

5. The method for preparing the glass surface composite hydrophobic film according to any one of claims 1 to 4, wherein the method comprises the following steps: in S112, the solute of the plating solution is 2g of siloxane and 3g of polysilazane, and the solvent of the plating solution is 10mL of alkane.

Technical Field

The invention relates to the technical field of material application, in particular to a preparation method of a glass surface composite hydrophobic film.

Background

A protective layer is formed on the surface of an organic layer by a crystal plating technology to improve the protection of the organic layer, and the protective layer is widely applied to the maintenance of various organic layers, particularly automobile paint surfaces, and has good hydrophobicity, sun protection performance and corrosion resistance. On the other hand, modifying the surface of various materials by the OTS self-assembly film-forming technology is an important research direction in the chemical and material fields. Although the glass coated with the OTS film shows good hydrophobic performance, the OTS film layer is easy to hydrolyze under long-term conditions, and how to overcome the problem is a great problem at present.

Disclosure of Invention

The invention aims to provide a preparation method of a glass surface composite hydrophobic film, which solves the problem that the existing OTS film layer is easy to hydrolyze for a long time.

In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of a glass surface composite hydrophobic film comprises the following steps:

s102, sequentially putting the glass sheet into deionized water, ethanol and deionized water for washing, and ultrasonically cleaning in the solvents;

s104, putting the glass sheet cleaned in the S102 into a prepared surface activation solution, soaking for 1h, taking out the glass sheet, and washing with deionized water;

s106, sequentially putting the glass sheet washed in the S104 into three parts of the same ethanol and ether mixed solvent (the volume ratio of the ethanol to the ether is 1:1) for physical dehydration, and quickly drying the dehydrated glass sheet by adopting nitrogen flow for later use;

s108, soaking the glass sheet dried in the S106 in 4.0mL/L OTS solution for 30 min;

s110, washing the glass sheet soaked in the S108 with dichloromethane for three times, and then baking the glass sheet in an oven for 10 hours at the baking temperature of 145 ℃;

s112, soaking the glass sheet baked in the step S110 in the crystal plating solution for 2min, taking out after soaking, and airing at room temperature for 1 h;

and S114, rinsing the glass sheet dried in the S112 with n-hexane for 3 times, and finally, standing at room temperature for 7 days to obtain the hydrophobic film on the glass sheet.

Further, the cleaning time of the glass sheet in each cleaning solution in S102 was 2 min.

Further, the preparation method of the surface activation solution comprises the following steps: 75mL of 98% concentrated sulfuric acid was slowly added in portions to a beaker containing 25mL of 30% aqueous hydrogen peroxide with stirring under ice-bath conditions.

Through the arrangement, the function of cleaning and activating the surface can be achieved.

Further, in S108, the solvent of the OTS solution is dichloromethane and n-hexane with a volume ratio of 1:4, and the solute of the OTS solution is OTS (i.e., octadecyltrichlorosilane).

Further, solute of the plating solution in S112 is 2g of chloromethyltrimethoxysilane and 3g of polysilazane, and solvent of the plating solution is 10mL of alkane.

With the above arrangement, the hydrophobicity of the glass sheet can be maintained by using siloxane and polysilazane.

Compared with the prior art, the beneficial effect of this scheme:

according to the scheme, when the hydrophobicity of the glass sheet is maintained, the protective film is added on the OTS film layer by means of a polysilazane and siloxane reaction curing method, so that the hydrolysis time is delayed, and the service life of the OTS film layer is prolonged.

Detailed Description

The present invention will be described in further detail below by way of specific embodiments:

example 1

A preparation method of a glass surface composite hydrophobic film comprises the following steps:

s102, washing the square flat glass sheet in deionized water, ethanol and deionized water in sequence for 2min, and ultrasonically cleaning the square flat glass sheet in the solvents for 2 min.

S104, placing the plate glass sheet cleaned in the S102 in a prepared surface activation solution, soaking for 1h, taking out the plate glass sheet by using tweezers, and washing for 2min by using deionized water; the preparation method of the surface activation solution comprises the following steps: under the condition of ice bath, concentrated sulfuric acid and hydrogen peroxide solution are prepared according to the volume ratio of 3:1, 75mL of concentrated sulfuric acid with the concentration of 98% is slowly added in batches into a beaker filled with 25mL of 30% hydrogen peroxide solution in the embodiment, and the concentrated sulfuric acid is continuously stirred in the adding process, and the adding and preparing sequence can enhance the safety of the experiment because the density of the concentrated sulfuric acid is higher than that of the hydrogen peroxide solution.

S106, sequentially putting the washed flat glass sheet in the step S104 into three parts of completely same mixed solvent of ethanol and ether (the volume ratio of the ethanol to the ether in the mixed solvent is 1:1) by using tweezers, wherein the putting time is 30S each time, and stirring the solvent by using a glass rod in the process to realize physical dehydration of the flat glass sheet; after dehydration, the flat glass sheet is taken out by tweezers, is quickly dried by nitrogen flow, and is then placed in a clean environment for later use.

S108, putting the dried glass sheet in the S106 into a prepared OTS solution with the concentration of 4.0mL/L, and soaking for 30 min; the preparation method of the OTS solution comprises the following steps: in a chemical fume hood, 10mL of dichloromethane and 40mL of n-hexane are respectively taken by a pipette and added into a 100mL beaker, then 0.2mL of OTS (namely, octadecyltrichlorosilane) is taken by the pipette and added into a solvent, and a glass rod is used for stirring uniformly to prepare a 4.0mL/L OTS solution.

And S110, taking out the plate glass soaked in the S108 by using forceps, placing the plate glass in a clean 100mL beaker, placing for 15min, sucking dichloromethane by using a dropper to wash the plate glass in the beaker for three times, and washing for 2min in the beaker. After the cleaning, the flat glass sheet is transferred into an oven for baking by using tweezers, wherein the baking temperature is 145 ℃, and the baking time is 10 hours.

S112, soaking the plate glass sheet baked in the S110 in a crystal plating solution for 2min, wherein the preparation method of the crystal plating solution comprises the following steps: in a chemical fume hood, transferring 10mL of n-heptane by a pipette into a 50mL beaker, transferring 2g of chloromethyltrimethoxysilane and 3g of polysilazane by a pipette into the n-heptane solvent respectively, and stirring uniformly by a glass rod. After soaking, the flat glass sheet attached with the plating crystal liquid is placed at room temperature and aired for 1 h.

And S114, taking out the flat glass sheet dried in the S112 by using a forceps clip, rinsing the flat glass sheet for 3 times by using 30mL of n-hexane, and finally standing the flat glass sheet at room temperature for 7 days to obtain a hydrophobic film on the glass sheet.

Example 2

This example differs from example 1 only in that: in the preparation method of the crystal plating solution of step S112, different substances are used, and in this example, 2g of methyltrimethoxysilane and 3g of polysilazane are respectively transferred by a pipette and added to an n-heptane solvent.

Comparative example 1

A preparation method of a glass surface composite hydrophobic film comprises the following steps:

s102, washing the square flat glass sheet in deionized water, ethanol and deionized water in sequence for 2min, and ultrasonically cleaning the square flat glass sheet in the solvents for 2 min.

S104, placing the plate glass sheet cleaned in the S102 in a prepared surface activation solution, soaking for 1h, taking out the plate glass sheet by using tweezers, and washing for 2min by using deionized water; the preparation method of the surface activation solution comprises the following steps: under the condition of ice bath, concentrated sulfuric acid and hydrogen peroxide solution are prepared according to the volume ratio of 3:1, in the comparative example, 75mL of concentrated sulfuric acid with the concentration of 98% is added into a beaker filled with 25mL of 30% hydrogen peroxide solution in batches and is stirred continuously during the adding process.

S106, sequentially putting the washed flat glass sheet in the step S104 into three parts of completely same mixed solvent of ethanol and ether (the volume ratio of the ethanol to the ether in the mixed solvent is 1:1) by using tweezers, wherein the putting time is 30S each time, and stirring the solvent by using a glass rod in the process to realize physical dehydration of the flat glass sheet; after dehydration, the flat glass sheet is taken out by tweezers, is quickly dried by nitrogen flow, and is then placed in a clean environment for later use.

S108, putting the glass sheet dried in the S106 into a prepared 4.0mL/L OTS solution, and soaking for 30 min; the preparation method of the OTS solution comprises the following steps: in a chemical fume hood, 10mL of dichloromethane and 40mL of n-hexane are respectively taken by a pipette and added into a 100mL beaker, then the OTS is taken by the pipette and added into the solvent, and the mixture is stirred uniformly by a glass rod, thus obtaining 4.0mL/L OTS solution.

And S110, taking out the plate glass soaked in the S108 by using forceps, placing the plate glass in a clean 100mL beaker, placing for 15min, sucking dichloromethane by using a dropper to wash the plate glass in the beaker for three times, and washing for 2min in the beaker. After the cleaning, the flat glass sheet is transferred into an oven for baking by using tweezers, wherein the baking temperature is 145 ℃, and the baking time is 10 hours.

The electroless plated glasses prepared in examples 1 and 2 and the OTS plated glass prepared in comparative example 1 described above were subjected to a water resistance test. The test method comprises the following steps: the contact angles of 2 samples of example 1, 2 samples of example 2, and 2 samples of comparative example 1, respectively, with deionized water were tested at room temperature. And (3) immediately drying after the test is finished (the drying temperature is 50 ℃ and the drying time is 5h), then respectively soaking the 6 samples in deionized water for 5 days, then taking out, respectively cleaning the soaked samples with ethanol, drying in vacuum at 100 ℃ for 5h after the cleaning is finished, and then respectively testing the contact angle of each sample and the deionized water. The experimental data as given in table 1 below were thus obtained:

TABLE 1

As shown in table 1, the coated glass prepared in the embodiments 1 and 2 can maintain good hydrophobicity after being soaked in deionized water for a long time, which indicates that the coated glass effectively alleviates the problem that the OTS film is easy to hydrolyze for a long time, and prolongs the service life of the OTS film.

The foregoing are merely examples of the present invention and common general knowledge of known specific structures and/or features of the schemes has not been described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.