CN106007392B - The preparation method of ZnO nano coated glass with hydrophobic performance - Google Patents

Abstract

The invention discloses a kind of preparation methods of the ZnO nano coated glass with hydrophobic performance.First ZnO aggregate species sublayer colloidal sols are prepared with sol-gal process；Then ZnO compound seed layer films are plated on ito glass using dip-coating method, is heat-treated with certain temperature in Muffle furnace；Then the above-mentioned ZnO compound seed layer film substrates prepared are put into hydro-thermal reaction in ZnO growth solutions to handle, prepare ZnO nano coating, obtains the ZnO nano coated glass materials with hydrophobic performance.The ZnO nano coated glass with hydrophobic performance that is obtained of the present invention transmitance to visible light and can reach 65% or more after ultra-violet and visible spectrophotometer is tested to UV Absorption, shield effectiveness；After contact angle tester (DSA series) test, 131 ° or more are reached to the contact angle of water.Method provided by the invention does not have secondary harm generation, is conducive to environmental protection.

Description

Preparation method of ZnO nano-coated glass with hydrophobic properties

technical field

The invention belongs to the field of preparation of hydrophobic coating materials, in particular to a preparation method of ZnO nano-coated glass with hydrophobic properties.

Background technique

The contact angle refers to the angle formed between a tangent line drawn by the edge of the solid surface in contact with the liquid surface and the solid plane. We can judge whether the wettability of solid surface is good or not by using the value of contact angle. In daily life, the hydrophobic surface we refer to refers to the surface when the contact angle of the substrate to water is greater than 90°. In recent years, research on hydrophobic glass surfaces has developed rapidly. When the contact angle of water between a water droplet and the glass surface is greater than 90°, we call this glass surface a hydrophobic glass surface. When a droplet is placed on a substrate surface, the droplet will appear in different shapes due to the different wettability of the solid surface. The surface wettability of the material depends on the surface chemical composition and surface topography of the material. Therefore, controlling the surface chemical composition and surface topography of the material can effectively control the wettability of the material surface. When the surface of the material has a very low surface free energy, the material can exhibit hydrophobicity.

As a novel method of building wall decoration, glass curtain wall has become a prominent feature of the era of modern high-rise and super high-rise buildings. However, ordinary glass is not resistant to pollution. With the increasing environmental pollution, people's awareness of the harm caused by environmental deterioration and the requirements for environmental protection are gradually increasing; people use it with environmental protection and use natural conditions to achieve automatic cleaning. , and the requirement for green building materials that can beautify the environment is becoming more and more urgent. The emergence of glass with hydrophobic properties satisfies people's good wishes and makes people get closer and closer to the realization of their goals. After ordinary glass is treated by special physical or chemical methods, hydrophobic glass with unique physical properties on the surface can be obtained, so that water droplets have a certain degree of hydrophobicity on its surface. After further treatment, it can be prepared without the need for traditional Artificial scrubbing is a coated glass that can be cleaned under the action of natural rainwater. Therefore, research on the preparation of hydrophobic glass has very good development prospects.

As a third-generation semiconductor material, ZnO has received extensive attention. There are many preparation methods of ZnO, which has the characteristics of wide band gap, small dielectric constant and fast electron transport ability. Nano-ZnO is a new type of inorganic product facing the 21st century. It has many special properties, such as large specific surface area, fast electron transport capability, large band gap, and good UV shielding performance, with a UV shielding rate as high as 98%. ZnO The nano-rough structure of the nano-rod makes its surface have a hydrophobic mechanism.

Contents of the invention

In the present invention, ZnO is used as a coating material to coat the ITO glass. Compared with ordinary glass, the ZnO-based nano coating glass has better hydrophobic performance.

The purpose of the present invention is to propose a method for preparing ZnO nano-coated glass with hydrophobic properties.

The preparation method of a kind of ZnO nano-coated glass with hydrophobic property provided by the invention is as follows: first prepare ZnO compound seed layer sol with sol-gel method; Adopt ZnO composite seed layer film on ITO glass then by immersion pulling method, Heat treatment at a certain temperature in a muffle furnace; then put the prepared ZnO composite seed layer film substrate into the ZnO growth solution for hydrothermal reaction treatment to prepare a ZnO nano-coating, and obtain a ZnO nano-coating with hydrophobic properties glass material.

The present invention further provides concrete process parameters on the basis of the above-mentioned method:

1. Process parameters for preparing ZnO composite seed layer sol: use sol-gel method, use zinc acetate as precursor, monoethanolamine as complexing agent, ethylene glycol methyl ether as solvent, anionic surfactant dodecylbenzene Sodium sulfonate, prepare 0.1mol/L～0.3mol/L ZnO composite seed layer sol.

2. Process parameters for preparing the ZnO composite seed layer: vertically immerse the ITO glass substrate in the prepared ZnO composite sol for 20s, so that the sol is fully in contact with the surface of the ITO glass substrate, and then pull the ITO vertically at a speed of 6cm/min For glass substrates, put the wet film in a constant temperature box and dry it at 100°C for 15-20 minutes, repeat the above operation, put the film in a muffle furnace for heat treatment at 400°C for 3-4 hours, and obtain a ZnO composite seed layer film.

3. Process parameters for preparing ZnO nano-coating: 200mL of growth solution of 0.02mol/L～0.05mol/L was prepared with zinc nitrate and hexamethylenetetramine at a ratio of 1:1, and 0.2g of anionic surfactant was added. Sodium alkylbenzene sulfonate, stir well until completely dissolved. Put the prepared ITO glass substrate with the ZnO composite seed layer film, with the conductive side down, into the ZnO growth solution, and react in a water bath at 90°C for 3 to 4 hours to prepare a ZnO nano-coating, and obtain a ZnO nano-coating with hydrophobic properties. Coated glass material.

The present invention also provides preferred scheme, specifically as follows:

First, prepare 100mL of 0.1mol/L-0.3mol/L ZnO seed layer sol by sol-gel method, and add 0.2g of anionic surfactant sodium dodecylbenzenesulfonate to obtain a composite seed layer sol; then use Immerse the pulled Faraday membrane, prepare the ZnO composite seed layer film on the ITO glass, and heat-treat it in a muffle furnace at 400°C for 3 to 4 hours; 0.05mol/L of ZnO growth solution doped with 0.2g of anionic surfactant sodium dodecylbenzenesulfonate was reacted in a water bath at 90°C for 3 to 4 hours to prepare ZnO nano-coating and obtain ZnO with hydrophobic properties. Nano-coated glass material.

The mechanism of action of the present invention is: the specific surface area of ZnO nanorod is bigger, the performance that shields ultraviolet ray is good; Further changing the nano-rough structure of ZnO can also change the surface chemical composition of ZnO, that is, the surface free energy, so that the surface of the ZnO nano-coating has a hydrophobic mechanism.

The ZnO nano-coating material has two advantages: one is that it has good photochemical effect and shielding ultraviolet rays; the other is that the ZnO nano-coating has a nano-rough structure and low surface free energy, which makes ZnO an ideal ultraviolet absorber. With shielding material and hydrophobic inorganic film material.

The ZnO nano-coated glass material with hydrophobic properties obtained by the present invention, due to the addition of sodium dodecylbenzenesulfonate, after the UV-visible spectrophotometer test, the transmittance of visible light and the absorption and shielding of ultraviolet light The efficiency can reach more than 65%; after being tested by a contact angle tester (DSA series), the contact angle to water can reach more than 131°.

Beneficial effects of the present invention:

1. The method of the present invention is easy to operate, has good repeatability of results and stable properties, and can meet the market development prospect of hydrophobic glass.

2. The raw materials are easy to purchase and the cost is low, and it has good performance while realizing stable functions.

3. The product of the method of the present invention does not produce secondary hazards, which is beneficial to environmental protection.

Description of drawings

Fig. 1 is the image observed by the scanning electron microscope of the ZnO nano-coated glass material with hydrophobic properties obtained in the embodiment.

Fig. 2 is the result of measuring the absorptivity of the ZnO nano-coated glass material with hydrophobic properties obtained in the embodiment by an ultraviolet-visible spectrophotometer.

Fig. 3 is the I test result of the transmittance of the ZnO nano-coating glass material with hydrophobic properties obtained in the embodiment through a UV-visible spectrophotometer.

Fig. 4 is the test result of the ZnO nano-coated glass material with hydrophobic properties obtained in the embodiment by a contact angle tester (DSA series).

Detailed ways

The following examples can enable those skilled in the art to understand the present invention more comprehensively, but do not limit the present invention in any way.

Example

First, prepare 100 mL of 0.3 mol/L ZnO seed layer sol by sol-gel method, add 0.2 g of anionic surfactant sodium dodecylbenzene sulfonate, and stir at 50 °C for 2 hours to obtain a composite seed layer sol ; Then, the ZnO composite seed layer film was prepared on the ITO glass by dipping the pulling film, and heat treatment was carried out at 400°C in a muffle furnace for 4h; then the above-mentioned prepared ZnO composite seed layer film was prepared in a well-configured 0.05mol/L The ZnO growth solution doped with 0.2g of anionic surfactant sodium dodecylbenzenesulfonate was reacted in a water bath at a constant temperature of 90°C for 4 hours to prepare a ZnO nano-coating and obtain a ZnO nano-coated glass material with hydrophobic properties , Fig. 1 is the image observed by the scanning electron microscope of the ZnO nano-coated glass material with hydrophobic properties.

The ZnO nano-coated glass with hydrophobic properties obtained by the present invention, after being tested by an ultraviolet-visible light spectrophotometer, can reach more than 65% to the transmittance of visible light and to ultraviolet light absorption and shielding efficiency, and the test results are shown in Figure 2 , as shown in Figure 3; after the contact angle tester (DSA series) test, the contact angle to water reaches more than 131 °, and the test results are shown in Figure 4.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of changes or modifications within the technical scope disclosed in the present invention. Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (2)

1. the preparation method of the ZnO nano coated glass with hydrophobic performance, which is characterized in that steps are as follows for this method：

(1) sol-gal process is used to prepare ZnO aggregate species sublayer colloidal sols, using zinc acetate as presoma, monoethanolamine is complexing agent, Ethylene glycol monomethyl ether is solvent, and anionic surfactant neopelex prepares 0.1mol/L~0.3mol/L's ZnO aggregate species sublayer colloidal sols；

(2) ZnO compound seed layer films are plated on ito glass using dip-coating method, is carried out with certain temperature in Muffle furnace Heat treatment, obtains ZnO compound seed layer films；

(3) the ZnO compound seed layer film substrates that above-mentioned steps (2) prepare are put into ZnO growth solutions at hydro-thermal reaction Reason, prepares ZnO nano coating, obtains the ZnO nano coated glass materials with hydrophobic performance；The step of hydro-thermal reaction, is specific To press 1 with zinc nitrate and hexamethylenetetramine：The growth solution 200mL of 1 configuration 0.02mol/L~0.05mol/L, is added 0.2g Anionic surfactant neopelex, is evenly stirred until and is completely dissolved；There are ZnO compound seeds by what is prepared The ito glass substrate of layer film, it is conductive to be put into ZnO growth solutions, 3~4h of water-bath at 90 DEG C downwards, it prepares ZnO nano coating obtains the ZnO nano coated glass materials with hydrophobic performance；It is characterized in that, using anionic table Change the nanometer of ZnO nano coating in face activating agent neopelex incorporation ZnO seed layers colloidal sol and ZnO growth solutions Coarse structure and surface free energy.

2. the preparation method of the ZnO nano coated glass according to claim 1 with hydrophobic performance, which is characterized in that ZnO compound seed layer films are plated on ito glass using dip-coating method in the step (2), with certain in Muffle furnace It is that ito glass substrate is dipped vertically into 20s in the ZnO complex sols prepared that temperature, which carries out heat treatment, makes colloidal sol and ito glass base Piece surface comes into full contact with, and then vertically lifts ito glass substrate with the speed of 6cm/min, by wet film be put into insulating box into 100 DEG C of 15~20min of drying and processing of row repeat aforesaid operations, and film is put into Muffle furnace 3~4h of heat treatment at 400 DEG C, Obtain ZnO compound seed layer films.