CN103359955B

CN103359955B - A kind of preparation method mixing zinc anti-reflection emitting automatic cleaning coating

Info

Publication number: CN103359955B
Application number: CN201210090740.XA
Authority: CN
Inventors: 姚伯龙; 胡张顺; 褚路轩; 倪才华; 关晓
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2012-03-31
Filing date: 2012-03-31
Publication date: 2016-04-13
Anticipated expiration: 2032-03-31
Also published as: CN103359955A

Abstract

Mix a preparation for zinc anti-reflection emitting automatic cleaning coating, it adopts a kind of sol-gel (sol-gel) technology first to prepare one deck SiO at glass surface ₂film, then continues to adopt sol-gel technique at SiO ₂film surface prepares the TiO that one deck mixes zinc ₂film, prepares a kind of anti-reflection emitting automatic cleaning coating.SiO ₂film with mix zinc TiO ₂film forms double layer antireflection film, and the doping of zine ion significantly improves TiO ₂photocatalysis efficiency.This coating technology is mainly applicable to the automatically cleaning of solar energy glass plate and anti-reflection, to improve its utilization ratio to sun power.

Description

A kind of preparation method mixing zinc anti-reflection emitting automatic cleaning coating

Technical field

Mix a preparation method for zinc anti-reflection emitting automatic cleaning coating, belong to self-cleaning coating field.

Background technology

Optical thin film is as the important application research direction of contemporary optics, be widely used in the fields such as industry, agricultural, medical science, communications and transportation, military affairs, building, astronomy, infrared physics, laser technology, increasing on the impact of daily life and work.Developing rapidly of further developing of science and technology, particularly optical communication and technique of display, propose renewal, higher requirement to all types of optical thin film design and preparation technology, the Design & preparation technology of optical thin film is faced with stern challenge.Antireflection film is most important one in optical thin film, and its development is also paid close attention to widely, from silicon solar cell to be applied on all types of display device universal, the use research of antireflection film will become one and significantly work.

Energy and environment are two principal themes of 21 century scientific research, and the problem solving current day by day serious energy shortage and environmental pollution is the active demand realizing Sustainable development, improve people's living standard and safeguard national security.TiO is found from fujishima and honda in 1972 ₂since electrode photocatalytic water, conductor photocatalysis material becomes the focus of people's research owing to having potential application foreground widely in environmental purification and Solar use.

Current self-cleaning glass is all be coated with TiO on the glass surface ₂film is lower to visible light catalytic efficiency.Energy gap is 3.2eV, and the UV-light only having wavelength to be less than 387nm just can play katalysis, and sunlight medium ultraviolet light only has 3% ~ 4%, and visible ray accounts for 40% ~ 44%.Zine ion doped with the photocatalytic activity enough effectively improving coating.

Easily form washmarking at the sun power plate surface of outdoor life-time service or be infected with the greasy dirt etc. of not easy cleaning, thus affect the transmitance of sunlight, the serious function reducing solar panels.This coating technology is mainly applicable to the automatically cleaning of solar energy glass plate and anti-reflection, to improve its utilization ratio to sun power.

Summary of the invention

The object of the invention is to work in coordination with and utilize SiO ₂with mix zinc TiO ₂the antireflective of film and self-cleaning performance prepare a kind of anti-reflection emitting automatic cleaning coating, for improve solar energy glass plate to too can utilization ratio.

Resin structure design of the present invention and synthesis thinking are: (1) SiO ₂the preparation of coating: utilize sol-gel (sol-gel) technology to prepare one deck SiO at glass surface ₂coating, utilizes crystal pulling method to prepare film forming; (2) zinc TiO is mixed ₂the preparation of film: utilize sol-gel technique scribbling SiO equally ₂coated glass surface is prepared one deck and is mixed zinc TiO ₂film, utilizes crystal pulling method to prepare film forming; (3) thermal treatment: to Manufactured TiO ₂film is heat-treated and is obtained Detitanium-ore-type TiO ₂film, to improve photocatalytic activity.

Synthetic reaction process is as follows:

(1) SiO ₂the preparation of coating

Sol-gel technique is utilized to prepare one deck SiO at glass surface ₂coating, with analytically pure tetraethoxy, dehydrated alcohol and ammoniacal liquor, at room temperature with volume ratio V [Si (OC ₂h ₅) ₄]: V (H ₂o): V (NH ₃): V [C ₂h ₅oH]=1: 2: 0.6: 37 mix and blends, often liter of solution adds polyoxyethylene glycol (molecular weight 400) 1ml, and solution sealing ageing, extracts the NH in suspensoids by circumfluence method ₃catalyzer, obtains silica based coating suspensoids, prepares film with crystal pulling method.

(2) zinc TiO is mixed ₂the preparation of film:

Sol-gel technique is utilized to scribble SiO equally ₂coated glass surface is prepared one deck and is mixed zinc TiO ₂film.With butyl (tetra) titanate [Ti (OC ₄h ₉) ₄] and ZnCl ₄5H ₂o (analytical pure) is raw material, accurately measures a certain amount of butyl (tetra) titanate and a certain amount of ZnCl ₂5H ₂o is dissolved in dehydrated alcohol, slowly adds a small amount of water, makes inhibitor with diethanolamine, delays the intense hydrolysis of butyl (tetra) titanate, constantly stirs and obtains stable mixing zinc TiO ₂colloidal sol, Ti (OC ₄h ₉) ₄: C ₂h ₅oH: H ₂o: NH (C ₂h ₅oH) ₂=1: 26.5: 1: 1 (mol ratio).Mix zinc TiO ₂film adopts crystal pulling method scribbling SiO equally ₂glass surface be prepared from.

(3) thermal treatment

Along with the rising of thermal treatment temp, TiO ₂crystal formation changed to Detitanium-ore-type by amorphous, when thermal treatment temp is elevated to certain threshold values, part Detitanium-ore-type will be had to be converted into rutile TiO ₂, wherein maturing temperature and soaking time control crystalline phase component, grain size and specific surface area etc.; When temperature is lower than 300 DEG C, titanium dioxide is non-crystal structure, and when being warmed up to 400 DEG C, existing part anatase titanium dioxide generates, persistently overheating to 550 DEG C, and existing a small amount of rutile crystal type exists; Along with the rising of thermal treatment temp and the prolongation of heat treatment time, crystal grain is grown up gradually, and the specific surface area of film reduces, and catalytic activity is reduced.Due to anatase crystal than rutile-type and brookite type catalytic performance more excellent, consider the softening temperature of thin-film carrier glass, so thermal treatment temp should be selected below softening temperature, to obtain the TiO of excellent performance simultaneously ₂film.

Embodiment

Embodiment 1:

Get Si (OC ₂h ₅) ₄10ml, H ₂o20ml, NH ₃6ml, C ₂h ₅oH370ml adds in beaker and mixes, in beaker, then add polyoxyethylene glycol 1ml (molecular weight 400), sealing ageing 20 days, by the gel after ageing at normal temperatures circumfluence method 2h remove NH ₃catalyzer, obtains silica based coating suspensoids.SiO ₂film is impregnated in gel with clean slide glass to adopt dip-coating method to prepare, and pull rate is 2mms ^-1, at 150 DEG C, process 24h, namely obtain SiO ₂film.

Measure Ti (OC ₄h ₉) ₄17.02ml, C ₂h ₅oH77.3ml, H ₂o0.9ml, NH (C ₂h ₅oH) ₂24.8ml, and take ZnCl ₂5H ₂o0.1g, by Ti (OC ₄h ₉) ₄and ZnCl ₂5H ₂o dissolves in dehydrated alcohol, then adds 24.8mlNH (C ₂h ₅oH) ₂inhibitor, delays Ti (OC ₄h ₉) ₄intense hydrolysis, mixes solution; Then slowly add 0.9ml water, stir 2h and obtain stable mixing zinc TiO ₂colloidal sol; TiO ₂meeting film adopts dip-coating method to prepare equally, will scribble SiO ₂slide glass be impregnated into TiO ₂in colloidal sol, with 2mms ^-1speed lifts, and wet film after dry 5min, puts into the muffle furnace of 500 DEG C at 100 DEG C, and insulation 1h, takes out and naturally cool to room temperature, namely obtain mixing zinc TiO ₂laminated film.

Claims

1. mix a preparation method for zinc anti-reflection emitting automatic cleaning coating, it is characterized in that, comprise the steps:

(1) SiO ₂the preparation of coating

Sol-gel (sol-gel) technology is utilized to prepare one deck SiO at glass surface ₂film, adopts analytically pure tetraethoxy, dehydrated alcohol and ammoniacal liquor, at room temperature with volume ratio V [Si (OC ₂h ₅) ₄]: V (H ₂o): V (NH ₃): V (C ₂h ₅oH)=1: 2: 0.6: 37 mix and blends, often liter of solution adds the polyoxyethylene glycol 1mL that molecular weight is 400, and solution sealing ageing, extracts the NH in suspensoids by circumfluence method ₃catalyzer, obtains silica based coating suspensoids; Film is prepared with crystal pulling method;

(2) zinc TiO is mixed ₂the preparation of film

Sol-gel technique is utilized to scribble SiO equally ₂coated glass surface is prepared one deck and is mixed zinc TiO ₂film; With butyl (tetra) titanate [Ti (OC ₄h ₉) ₄] and ZnCl ₂5H ₂o is raw material, accurately measures a certain amount of butyl (tetra) titanate and a certain amount of ZnCl ₂5H ₂o is dissolved in dehydrated alcohol, slowly adds a small amount of water, makes inhibitor with diethanolamine, delays the intense hydrolysis of butyl (tetra) titanate, constantly stirs and obtains stable mixing zinc TiO ₂colloidal sol, wherein Ti (OC ₄h ₉) ₄, C ₂h ₅oH, H ₂o and NH (C ₂h ₅oH) ₂mol ratio be 1: 26.5: 1: 1; Mix zinc TiO ₂film adopts crystal pulling method scribbling SiO equally ₂glass surface be prepared from;

(3) thermal treatment process

Along with the rising of thermal treatment temp, TiO ₂crystal formation changed to Detitanium-ore-type by amorphous, when thermal treatment temp is elevated to certain threshold value, part Detitanium-ore-type will be had to be converted into rutile TiO ₂, wherein maturing temperature and soaking time control crystalline phase component, grain size and specific surface area; When temperature is lower than 300 DEG C, titanium dioxide is non-crystal structure, and when being warmed up to 400 DEG C, existing part anatase titanium dioxide generates, persistently overheating to 550 DEG C, and existing a small amount of rutile crystal type exists; Along with the rising of thermal treatment temp and the prolongation of heat treatment time, crystal grain is grown up gradually, and the specific surface area of film reduces, and catalytic activity is reduced; Due to anatase crystal than rutile-type and brookite type catalytic performance more excellent, consider the softening temperature of thin-film carrier glass, so thermal treatment temp should be selected below softening temperature, to obtain the TiO of excellent performance simultaneously ₂film.