CN108911521A - A kind of wear-resisting self-cleaning glass of middle light transmission and preparation method thereof - Google Patents
A kind of wear-resisting self-cleaning glass of middle light transmission and preparation method thereof Download PDFInfo
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- CN108911521A CN108911521A CN201810900185.XA CN201810900185A CN108911521A CN 108911521 A CN108911521 A CN 108911521A CN 201810900185 A CN201810900185 A CN 201810900185A CN 108911521 A CN108911521 A CN 108911521A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Abstract
The invention discloses a kind of middle wear-resisting self-cleaning glass of light transmission and preparation method thereof.The glass includes glass matrix and the film layer that is formed on glass matrix surface by magnetron sputtering method；The film layer includes the raw material of following mass percent meter：FeOOH 15~25%, fowler alkenyl carboxylic acid derivative 5~15%, nano-titanium dioxide 65~75%, thin film layer thickness obtained are 100~300nm.The wear-resisting self-cleaning glass of middle light transmission provided by the invention has strong photocatalytic activity and hydrophily, self-cleaning ability is strong, to the degradation rate of oleic acid up to 87.4%, to the degradation rate of methyl orange up to 90.0%, to the transmitance of visible light up to 74.2%, and wearability is good, while obtaining preferably self-cleaning net effect, has high visible light permeability and useful life longevity.
Description
Technical field
The present invention relates to a kind of functional glass, and in particular to a kind of middle wear-resisting self-cleaning glass of light transmission and preparation method thereof.
Background technique
Functional glass is the new material being widely used at present.With the constantly high stratification of building and glass curtain wall, glass
The large-scale application and world wide environment pollution problem of roof, glass structure in skyscraper are increasing, glass
The cleaning problems of glass become increasingly conspicuous, and seek a kind of glass with high-efficiency self-cleaning net work energy, become the hot spot of countries in the world research
And difficult point.
Currently, self-cleaning glass on the market mainly passes through sol-gel method, chemical vapour deposition technique, magnetron sputtering
The coating techniques such as method form one layer of TiO in surface of ordinary glass2Film realizes cleaning function.Its principle is mainly：TiO2
With stronger photocatalytic activity, under the action of sunlight, TiO2The electron-hole pair with Strong oxdiative ability is generated, it can
By the almost all of organic pollutant complete oxidation of glass surface and it is degraded to CO2、HO2And inorganic matter, such glass surface
Inorganic matter is easy to be fallen by rain-out, and glass surface is made to keep clean, in addition, TiO2The photoproduction that film generates after light irradiates
Electrons react to form Lacking oxygen with the bridging oxygen of film surface, and the oxygen in such hydrone will occupy these Lacking oxygens, are formed
Chemical absorbed water, titanium deoxid film surface formed water membrane, be formed by moisture film can by the pollutant of film surface with
Film separates, and pollutant is swum on the water surface, it is easy to be fallen by rain-out, to realize the self-cleaning net effect of glass.
However, above-mentioned utilize TiO2Photocatalytic activity and film forming after hydrophily made from self-cleaning glass there are following
It is insufficient：1)TiO2Photocatalysis quantum yield is low, and overall reaction rate is slow, and photo-generated carrier is easy to again compound, directly affects light
Catalytic efficiency, organic matter discomposing effect；2) due to TiO2Band structure determine that ultraviolet part can only be absorbed and utilized in film layer,
Photocatalytic activity is just only generated under ultraviolet light irradiation, greatly limits the use scope of self-cleaning glass；3) porous
TiO2Film is easy the smiles pollutants such as accumulation dust in actual application, is easy to produce multiple light induced electron and hole is multiple
Conjunction approach, leads to TiO2Film glass rapid failure shortens life of product；4)TiO2Film mirror surface reflex is more serious, holds
Easily cause light pollution, and with TiO2The increase of content, it is seen that light transmission rate reduces, and influences indoor lighting.5) porous TiO2
Film scratch resistant performance is poor, is prone to wear under external force, or even falls off, and leads to TiO2The funeral of film glass self-cleaning performance
It loses.Therefore, the photocatalytic degradation efficiency and service life for improving film are concentrated mainly on to the research of cleaned glass at present, is passed through
In TiO2ZnO, Fe are adulterated in film2O3、SnO2、CdS、ZnFe2O4Equal substances, or the hydrophily of glass surface is improved, to make
The pollutant of glass surface is easy to be cleaned, or makes the forbidden bandwidth stenosis of semiconductor, and excitation wavelength is mobile to long wave direction, makes
Visible light can also play photocatalysis, or can effectively facilitate TiO2Point of carrier is realized in the separation of middle light induced electron and vacancy
From to realize the self-cleaning performance for improving glass.The Chinese patent application of 105948525 A of Publication No. CN discloses one
Super hydrophilic wear-resisting Zinc oxide/titanium dioxide film self-cleaning glass of kind and preparation method thereof, which is mentioned by dipping
Daraf(reciprocal of farad) forms Zinc oxide/titanium dioxide film on glass matrix can be improved the hydrophily of glass, make the pollutant of glass surface
Be easy to be cleaned, and the scratch resistant performance of glass can be improved, but the photocatalytic of film without be improved significantly.Publication number
A kind of net film of fine and close high transmission high catalytic activity super-hydrophilic self-cleaning is disclosed for the Chinese patent application of 107759099 A of CN
Glass and preparation method thereof, the thin-film material of the self-cleaning film glass is by nano-TiO2, ZnO and SnO2Compound composition, by same
When mix ZnO and SnO2Improve TiO2Photocatalytic activity, wetability and durability.
Although having obtained many progress to the research of self-cleaning glass at present, there can be strong photocatalysis living simultaneously
Property and hydrophilic wettability self-cleaning glass it is relatively fewer, and most of self-cleaning glass is adopted more in order to obtain high translucency
With porous membrane, durability is poor, cannot be simultaneously by meeting the requirement of high light transmittance and strong durability.Therefore, it is still necessary to develop
A kind of novel wear-resisting self-cleaning glass with high visible light permeability and makes while obtaining preferably self-cleaning net effect
Use durability.
Summary of the invention
The object of the present invention is to provide a kind of middle wear-resisting self-cleaning glass of light transmission, and the glass is by magnetron sputtering method common
One layer of film being made of FeOOH, fowler alkenyl carboxylic acid derivative and nano-titanium dioxide is formed on glass matrix surface
Layer, photocatalytic activity with super strength and hydrophily, sterilizing ability is strong, and wear-resisting self-cleaning effect is good, and film surface layer arranges
Closely, it is not easy to accumulate dust, wearability is high, makes glass long service life.
Another object of the present invention is to provide a kind of preparation method of wear-resisting self-cleaning glass of middle light transmission, and this method is logical
It crosses magnetron sputtering method and carries out plated film on simple glass body surface, not only can get the thin of large area uniform deposition high quality
Film, and it is easy popularization and industrialization large-scale production.
The present invention is achieved by the following technical programs：
A kind of wear-resisting self-cleaning glass of middle light transmission, including glass matrix and by magnetron sputtering method on glass matrix surface
The film layer of formation；The film layer includes the raw material of following mass percent meter：FeOOH 15~25%, fullerene
Carboxylic acid derivates 5~15%, nano-titanium dioxide 65~75%.
Preferably, the film layer includes the raw material of following mass percent meter：FeOOH 20%, fullerene carboxylic
Acid derivative 10%, nano-titanium dioxide 70%.
Specifically, the film layer with a thickness of 100~300nm.
The glass matrix is borate glass, silicate glass or phosphate glass.
The FeOOH can be commercial product, can also be prepared by the following method, specifically, hydroxyl
The preparation method of iron oxide includes the following steps：Iron chloride, urea and PEG-2000 are placed in reaction kettle, water is added, 105
~125 DEG C of 24~36h of reaction, are cooled to room temperature, and filtering obtains Tan solid, solid is used to dehydrated alcohol, deionization respectively
Water cleaning, is dried in vacuo to get FeOOH；Wherein, the molar ratio of the iron chloride and urea is 1:0.2~0.3；It is described
The additional amount of PEG-2000 is 0.3~0.4 times of chlorination weight of iron.
The fowler alkenyl carboxylic acid derivative is prepared by the following method to obtain：Under nitrogen protection, by fullerene C60, to carboxylic
Benzaldehyde and sarcosine are scattered in toluene, in 100~115 DEG C of reactions 8~10h, the fullerene C60：To carboxyl benzene first
Aldehyde：Sarcosine：The molar ratio of toluene is：1:(10~12):(8~10):Gained is washed with water after reaction in (35~40)
Solid, drying, obtains fowler alkenyl carboxylic acid derivative.
In addition, the present invention also provides the preparation method of the wear-resisting self-cleaning glass of middle light transmission described in one kind, this method includes
Following steps：
(1) pretreatment of glass matrix：The spot on glass matrix surface is cleaned with soda ash first, it is then super with dehydrated alcohol
Sound cleans 5~15min, then elutes 30~60min with deionized water, dries the glass matrix to get cleanliness without any pollution；
(2) preparation of film feed liquid：Feed liquid A containing nano-titanium dioxide and hydroxyl iron oxide and fullerene are prepared respectively
The feed liquid B of carboxylic acid derivates；
(3) magnetron sputtering is handled：The glass matrix for the cleanliness without any pollution that step (1) obtains is fixed on sample stage,
It is then placed in transition vacuum chamber and vacuumizes 5~10min, be passed to by magnetic force transmission lever to sputtering vacuum chamber, open silicon
Glass matrix is heated to 400~450 DEG C and kept constant by system；The feed liquid A that step (2) obtains is placed in titanium dioxide pottery
Feed liquid B is placed in metallic cobalt target by porcelain target, and by feed liquid A and feed liquid B, sputtering is resistance to get middle light transmission simultaneously by the way of cosputtering
Grind self-cleaning glass.
Specifically, the feed liquid A containing nano-titanium dioxide is prepared as in above-mentioned steps (2)：Nano-titanium dioxide is added
In n-butanol, the agate bead for the use of diameter being 2~3cm disperses 25~30min with the revolving speed ball milling of 200~250r/min, obtains
The molar ratio of feed liquid A, the nano-titanium dioxide and n-butanol is 1:6~8；
The feed liquid B's of hydroxyl iron oxide and fowler alkenyl carboxylic acid derivative is prepared as：By FeOOH, fowler olefinic carboxylic acid
Derivative is added in methanol aqueous solution, and in 60~70 DEG C, 1~2h is stirred to react under the conditions of 50~60r/min, obtains feed liquid B, institute
The volume ratio of first alcohol and water is 0.7~1 in the methanol aqueous solution stated:2, the additional amount of the methanol aqueous solution is hydroxyl oxidation
4~5 times of iron and fowler alkenyl carboxylic acid derivative total weight；
In above-mentioned steps (3), the radio-frequency power of the titanium dioxide ceramic target is 120~150W, the metallic cobalt target
Radio-frequency power is 10~50W, and sputter gas is argon gas, and flow velocity is 25~35sccm.
Titanium dioxide can generate light induced electron and hole after ultraviolet light irradiates, and the bridging oxygen of light induced electron and film surface is anti-
Lacking oxygen should be formed, the oxygen in hydrone is made to can take up these Lacking oxygens, chemical absorbed water is formed, shows to form one in film
Layer moisture film, so that pollutant and film be separated, and is conducive to pollutant and is washed away by rainwater etc.；In addition, photohole and film
On water or hydroxyl react to form hydroxyl radical free radical OH, hydroxyl radical free radical have Strong oxdiative activity, it is almost degradable all
Organic matter, to realize the self-cleaning function of film.
However, containing only the porous membrane of titanium dioxide, it is easy to produce the compound phenomenon of multiple light induced electron and hole, is made
Photocatalytic activity obviously weakens, and the present invention creatively joined FeOOH and fowler alkenyl carboxylic acid derivative, can overcome on
The defect stated promotes the separation of light induced electron and hole, improves the photocatalysis performance and wetability of film.Wherein, the hydroxyl
Base iron oxide is a kind of common conductor oxidate, has cheap and easy to get, environmentally protective, the characteristics of absorbing visible light, not only
Film layer can be improved to the utilization rate of sunlight, and there is unique 2 × 2 tunnel structure in its crystal, have a large amount of empty
Gap is conducive to the transmitting of light induced electron, makes light induced electron and hole quick separating；Fowler in the fowler alkenyl carboxylic acid derivative
Alkene C60Cage structure with 32 faces, not only have high hardness and toughness, can enhanced film wearability, and when its with
FeOOH, nano-titanium dioxide blending, also show superpower photoconductivity energy, accelerate photogenerated charge migration rate,
Improve the photocatalytic activity of film.
In addition, the present invention in advance carries out FeOOH and fowler alkenyl carboxylic acid derivative before plated film at a certain temperature
Hybrid reaction, then obtained product is respectively placed in target different in magnetic control sputtering system from nano-titanium dioxide, using altogether
The mode of sputtering carries out plated film, not only remarkably promotes film and substrate of glass is firmly combined, also the tightness of raising film arrangement,
It reduces film layer hole to be formed, improves the wearability and weatherability of glass.Further, since coating process is once to complete, it is ensured that
The uniformity of film layer not only can get the film of large area uniform deposition high quality, and be easy to promote and industrialize extensive
Production.
Compared with prior art, the invention has the advantages that：
The wear-resisting self-cleaning glass of middle light transmission provided by the invention has strong photocatalytic activity and hydrophily, self-cleaning ability
By force, to the degradation rate of oleic acid up to 87.4%, to the degradation rate of methyl orange up to 90.0%, to the transmitance of visible light up to 74.2%,
And wearability is good, while obtaining preferably self-cleaning net effect, has high visible light permeability and useful life longevity.
Specific embodiment
The following examples are further illustrations of the invention, rather than limiting the invention.
The preparation of 1 FeOOH of embodiment
Weigh 270.3g FeCl3·6H2O, 12.01g urea, 81.09g PEG-2000, are placed in reaction kettle, by feed liquid
Than for 1g:The ratio of 100mL is added water and is cooled to room temperature in 105 DEG C of reaction 36h, filters, Tan solid is obtained, by solid
It is cleaned, is dried in vacuo to get FeOOH with dehydrated alcohol, deionized water respectively.
The preparation of 2 FeOOH of embodiment
Weigh 270.3g FeCl3·6H2O, 18.01g urea, 108.12g PEG-2000, are placed in reaction kettle, by feed liquid
Than for 1g:Water is added in the ratio of 100mL, reacts for 24 hours, is cooled to room temperature at 125 DEG C, filters, Tan solid is obtained, by solid
It is cleaned, is dried in vacuo to get FeOOH with dehydrated alcohol, deionized water respectively.
The preparation of 3 fowler alkenyl carboxylic acid derivative of embodiment
Under nitrogen protection, by 72g fullerene C60, 150.1g p -carboxybenzaldehyde, 71.3g sarcosine be scattered in 322.5g
In toluene, obtained solid is washed with water after reaction in 100 DEG C of reaction 10h, dries, obtains fowler alkenyl carboxylic acid derivative.
The preparation of 4 fowler alkenyl carboxylic acid derivative of embodiment
Under nitrogen protection, by 72g fullerene C60, 180.2g p -carboxybenzaldehyde, 89.1g sarcosine be scattered in 368.6g
In toluene, obtained solid is washed with water after reaction in 115 DEG C of reaction 8h, dries, obtains fowler alkenyl carboxylic acid derivative.
Below using fowler alkenyl carboxylic acid derivative made from FeOOH made from embodiment 1 and embodiment 3 as raw material into
The preparation of row self-cleaning glass.
The preparation of 5 self-cleaning glass of embodiment
Using common soda lime glass as matrix, self-cleaning glass preparation is carried out, wherein preparation system is magnetic control sputtering system, should
System includes a transition chamber and a main sputtering chamber (diameter 45cm).Main sputtering chamber is connect with a molecule diffusion pump, the limit
Vacuum degree is 2.0 × 10-6Pa.There are three the different targets that target position is 2 inches for three diameters of installation for sputtering chamber.Each target position
It is tilted upwards with 30 ° of angles, the upward cosputtering of the type of focusing can be total to or the independent mode of three targets sputters upwards.Sample stage can
It is warming up to 600 DEG C or more and continuous rotation can be kept in sputtering process, specifically include following steps：
(1) pretreatment of glass matrix：The spot on glass matrix surface is cleaned with soda ash first, it is then super with dehydrated alcohol
Sound cleans 10min, then elutes 40min with deionized water, dries the glass matrix to get cleanliness without any pollution.
(2) preparation of film feed liquid：
1. the preparation of the feed liquid A containing nano-titanium dioxide：700g nano-titanium dioxide is added in 3900g n-butanol, is made
The agate bead for being 3cm with diameter disperses 30min with the revolving speed ball milling of 200r/min, obtains feed liquid A.
2. the preparation of the feed liquid B of hydroxyl iron oxide and fowler alkenyl carboxylic acid derivative：200g FeOOH, 100g is rich
It strangles alkenyl carboxylic acid derivative and 1200g methanol aqueous solution (methanol is added：Water=0.7:In 2v/v), in 60 DEG C, stirred under the conditions of 60r/min
Reaction 2h is mixed, feed liquid B is obtained.
(3) magnetron sputtering is handled：The glass matrix for the cleanliness without any pollution that step (1) obtains is fixed on sample stage,
It is then placed in transition vacuum chamber and vacuumizes 5min, be passed to by magnetic force transmission lever to sputtering vacuum chamber, open substrate heating system,
Glass matrix is heated to 400 DEG C and is kept constant；The feed liquid A that step (2) obtains is placed in titanium dioxide ceramic target, setting is penetrated
Frequency power is 120W, and feed liquid B is placed in metallic cobalt target, and setting radio-frequency power is 20W, by the way of cosputtering by feed liquid A with
Feed liquid B is sputtered simultaneously, and sputter gas is argon gas, and flow velocity is 25sccm to get the wear-resisting self-cleaning glass of middle light transmission.
The preparation of 6 self-cleaning glass of embodiment
Using common soda lime glass as matrix, self-cleaning glass preparation is carried out, wherein preparation system is specific to wrap with embodiment 5
Include following steps：
(1) pretreatment of glass matrix：The spot on glass matrix surface is cleaned with soda ash first, it is then super with dehydrated alcohol
Sound cleans 15min, then elutes 60min with deionized water, dries the glass matrix to get cleanliness without any pollution.
(2) preparation of film feed liquid：
1. the preparation of the feed liquid A containing nano-titanium dioxide：750g nano-titanium dioxide is added in 5571g n-butanol, is made
The agate bead for being 2cm with diameter disperses 25min with the revolving speed ball milling of 250r/min, obtains feed liquid A.
2. the preparation of the feed liquid B of hydroxyl iron oxide and fowler alkenyl carboxylic acid derivative：150g FeOOH, 100g is rich
It strangles alkenyl carboxylic acid derivative and 1250g methanol aqueous solution (methanol is added：Water=1:In 2v/v), in 70 DEG C, stirred under the conditions of 50r/min
1h is reacted, feed liquid B is obtained.
(3) magnetron sputtering is handled：The glass matrix for the cleanliness without any pollution that step (1) obtains is fixed on sample stage,
It is then placed in transition vacuum chamber and vacuumizes 10min, be passed to by magnetic force transmission lever to sputtering vacuum chamber, open silicon system
System, is heated to 450 DEG C for glass matrix and keeps constant；The feed liquid A that step (2) obtains is placed in titanium dioxide ceramic target, if
Setting radio-frequency power is 150W, feed liquid B is placed in metallic cobalt target, setting radio-frequency power is 50W, by feed liquid by the way of cosputtering
A and feed liquid B are sputtered simultaneously, and sputter gas is argon gas, and flow velocity is 35sccm to get the wear-resisting self-cleaning glass of middle light transmission.
The preparation of 7 self-cleaning glass of embodiment
Using common soda lime glass as matrix, self-cleaning glass preparation is carried out, wherein preparation system is specific to wrap with embodiment 5
Include following steps：
(1) pretreatment of glass matrix：The spot on glass matrix surface is cleaned with soda ash first, it is then super with dehydrated alcohol
Sound cleans 10min, then elutes 30min with deionized water, dries the glass matrix to get cleanliness without any pollution.
(2) preparation of film feed liquid：
1. the preparation of the feed liquid A containing nano-titanium dioxide：650g nano-titanium dioxide is added in 4225g n-butanol, is made
The agate bead for being 3cm with diameter disperses 25min with the revolving speed ball milling of 250r/min, obtains feed liquid A.
2. the preparation of the feed liquid B of hydroxyl iron oxide and fowler alkenyl carboxylic acid derivative：250g FeOOH, 100g is rich
It strangles alkenyl carboxylic acid derivative and 1575g methanol aqueous solution (methanol is added：Water=0.8:In 2v/v), in 65 DEG C, stirred under the conditions of 55r/min
Reaction 1.5h is mixed, feed liquid B is obtained.
(3) magnetron sputtering is handled：The glass matrix for the cleanliness without any pollution that step (1) obtains is fixed on sample stage,
It is then placed in transition vacuum chamber and vacuumizes 8min, be passed to by magnetic force transmission lever to sputtering vacuum chamber, open substrate heating system,
Glass matrix is heated to 420 DEG C and is kept constant；The feed liquid A that step (2) obtains is placed in titanium dioxide ceramic target, setting is penetrated
Frequency power is 135W, and feed liquid B is placed in metallic cobalt target, and setting radio-frequency power is 35W, by the way of cosputtering by feed liquid A with
Feed liquid B is sputtered simultaneously, and sputter gas is argon gas, and flow velocity is 30sccm to get the wear-resisting self-cleaning glass of middle light transmission.
The preparation of 1 self-cleaning glass of comparative example
The composition of 1 self-cleaning glass of comparative example is substantially the same manner as Example 5, and difference is, the hydroxyl in the film layer
Base iron oxide replaces with Fe2O3, remaining composition and preparation method are the same as embodiment 5.
The preparation of 2 self-cleaning glass of comparative example
The composition of 2 self-cleaning glass of comparative example is substantially the same manner as Example 5, and difference is, the richness in the film layer
It strangles alkenyl carboxylic acid derivative and replaces with fullerene C60, remaining composition and preparation method are the same as embodiment 5.
The preparation of 3 self-cleaning glass of comparative example
The composition of 3 self-cleaning glass of comparative example is substantially the same manner as Example 5, and difference is, the film layer is free of hydroxyl
Base iron oxide, and it is increase accordingly the content of nano-titanium dioxide and fowler alkenyl carboxylic acid derivative, specifically, the film layer packet
Include the raw material of following weight percent meter：Fowler alkenyl carboxylic acid derivative 15% and nano-titanium dioxide 85%.
Preparation method：
Using common soda lime glass as matrix, self-cleaning glass preparation is carried out, wherein preparation system is specific to wrap with embodiment 5
Include following steps：
(1) pretreatment of glass matrix：The spot on glass matrix surface is cleaned with soda ash first, it is then super with dehydrated alcohol
Sound cleans 10min, then elutes 40min with deionized water, dries the glass matrix to get cleanliness without any pollution.
(2) preparation of film feed liquid：
1. the preparation of the feed liquid A containing nano-titanium dioxide：850g nano-titanium dioxide is added in 4735g n-butanol, is made
The agate bead for being 3cm with diameter disperses 30min with the revolving speed ball milling of 200r/min, obtains feed liquid A.
2. the preparation of the feed liquid B of the alkenyl carboxylic acid derivative containing fowler：750g methanol is added in 150g fowler alkenyl carboxylic acid derivative
Aqueous solution (methanol：Water=0.7:In 2v/v), in 60 DEG C, it is stirred to react 2h under the conditions of 60r/min, obtains feed liquid B.
(3) magnetron sputtering is handled：The glass matrix for the cleanliness without any pollution that step (1) obtains is fixed on sample stage,
It is then placed in transition vacuum chamber and vacuumizes 5min, be passed to by magnetic force transmission lever to sputtering vacuum chamber, open substrate heating system,
Glass matrix is heated to 400 DEG C and is kept constant；The feed liquid A that step (2) obtains is placed in titanium dioxide ceramic target, setting is penetrated
Frequency power is 120W, and feed liquid B is placed in metallic cobalt target, and setting radio-frequency power is 20W, by the way of cosputtering by feed liquid A with
Feed liquid B is sputtered simultaneously, and sputter gas is argon gas, and flow velocity is 25sccm to get the wear-resisting self-cleaning glass of middle light transmission.
The preparation of 4 self-cleaning glass of comparative example
The composition of 4 self-cleaning glass of comparative example is substantially the same manner as Example 5, and difference is, the film layer is without richness
Alkenyl carboxylic acid derivative is strangled, and increase accordingly the content of nano-titanium dioxide and FeOOH, specifically, the film layer packet
Include the raw material of following weight percent meter：FeOOH 15% and nano-titanium dioxide 85%.Preparation method refers to comparative example
3。
Test example one, self-cleaning glass are to the degradation effect of oleic acid
Self-cleaning glass made from 5-7 of the embodiment of the present invention and comparative example 1-4 is detected respectively to the degradation rate of oleic acid, specifically
Ground, compound concentration are 1 × 10-2The oleic acid methanol solution of mol/L is drawn the solution drop of 0.03mL on self-cleaning glass surface, is used
Rotary process film coats one layer of fatty sorrel on glass with clean surface through the 2min time with 1000r/min speed, finally in air
It is middle that fatty sorrel is made with vapor heating removing methanol, it is 1.5W/cm in ultraviolet irradiation intensity2Under conditions of handle 60min,
Fatty acid degradation rate is detected, since fatty acid infrared absorption peak is 2700~3000nm, with Fourier transform ir spectrophotometry
The variation for counting (FTIR-1725) measurement infrared absorption peak, can obtain photocatalytic activity, the results are shown in Table 1.
Degradation rate of 1 self-cleaning glass of table to oleic acid
| Group | The degradation rate (%) of oleic acid |
| Embodiment 5 | 87.4 |
| Embodiment 6 | 83.8 |
| Embodiment 7 | 85.7 |
| Comparative example 1 | 66.9 |
| Comparative example 2 | 80.1 |
| Comparative example 3 | 55.2 |
| Comparative example 4 | 60.4 |
The results show that self-cleaning glass made from 5-7 of the embodiment of the present invention has preferable degradation effect, degradation rate to oleic acid
Up to 87.4%, hence it is evident that due to comparative example 1 and comparative example 3-4.By comparative example 1 it is found that FeOOH is replaced with Fe2O3,
Since the composition and structure of the two are different, Photocatalytic activity differs greatly；By comparative example 2 it is found that by fowler olefinic carboxylic acid
Derivative replaces with fullerene C60, Photocatalytic activity is influenced little；By comparative example 3 and 4 it is found that lacking hydroxyl oxygen respectively
Change iron, fowler alkenyl carboxylic acid derivative, weakens self-cleaning glass obviously to the degradation effect of oleic acid.
Test example two, self-cleaning glass are to the degradation effect of methyl orange
Self-cleaning glass made from 5-7 of the embodiment of the present invention and comparative example 1-4 is detected respectively to the degradation rate of methyl orange, tool
Body, self-cleaning glass (20mm × 65mm) is inserted perpendicularly into and is tried equipped with the quartz that 40mL concentration is 10mg/L methyl orange aqueous solution
Quartz test tube is placed on away from ultraviolet source 6cm, is 1.5W/cm in ultraviolet irradiation intensity by Guan Zhong2Under conditions of handle 60min,
The absorbance of methyl orange solution after being handled by ultraviolet specrophotometer survey, since the methyl orange concentration dissolved in solution is proportional to
Absorbance can calculate the degradation rate of methyl orange according to the variation of absorbance, the results are shown in Table 2.
Degradation rate of 2 self-cleaning glass of table to methyl orange
| Group | The degradation rate (%) of methyl orange |
| Embodiment 5 | 90.0 |
| Embodiment 6 | 87.6 |
| Embodiment 7 | 88.2 |
| Comparative example 1 | 74.8 |
| Comparative example 2 | 85.0 |
| Comparative example 3 | 63.4 |
| Comparative example 4 | 69.7 |
The results show that self-cleaning glass made from 5-7 of the embodiment of the present invention to methyl orange have preferable degradation effect, and with
The effect of embodiment 5 is best, is up to 90.0% to the degradation rate of methyl orange, hence it is evident that due to comparative example 1 and comparative example 3-4.
The visible light transmittance detection of test example three, self-cleaning glass
With reference to ISO 9050：Measured in 2003 the correlation technique of visible light transmittance respectively to 5-7 of the embodiment of the present invention and
Self-cleaning glass made from comparative example 1-4 carries out visible light transmittance measurement, the results are shown in Table 3.
The visible light transmittance testing result of 3 self-cleaning glass of table
| Group | Visible light transmittance (%) |
| Embodiment 5 | 72.0 |
| Embodiment 6 | 73.6 |
| Embodiment 7 | 74.2 |
| Comparative example 1 | 71.5 |
| Comparative example 2 | 68.7 |
| Comparative example 3 | 62.4 |
| Comparative example 4 | 79.2 |
The results show that the visible light transmittance of self-cleaning glass made from 5-7 of the embodiment of the present invention is 70% or so.By right
Ratio 1 is it is found that replace with Fe for FeOOH2O3, the visible light transmittance of glass is influenced little；By comparative example 2 it is found that
Fowler alkenyl carboxylic acid derivative is replaced with into fullerene C60, it is decreased slightly as the visible light transmittance of low glass；By comparative example 3 it is found that lacking
FeOOH increases the content of fowler alkenyl carboxylic acid derivative, can reduce the visible light transmittance of glass；By comparative example 4 it is found that
Lack fowler alkenyl carboxylic acid derivative, increases the content of FeOOH, the visible light transmittance of glass can be improved, it follows that
The addition of fowler alkenyl carboxylic acid derivative will affect the visible light transmittance of glass to a certain extent, and with the increasing of its content
Add, the visible light transmittance of glass can reduce.
Test example four, the detection of the wearability of self-cleaning glass
Using Tabor abrasion instrument method of testing respectively to self-cleaning glass made from 5-7 of the embodiment of the present invention and comparative example 1-4
Carry out wearability measurement, wherein loading 1000g, 300 circle of grinding test the visible light transmittance of front and back glass by detection
Value added △ T=T2-T1Carry out the wearability (T of quantitative comparison glass film layers1、T2Respectively visible transmission before and after glass grinding
Rate), the smaller wearability for indicating glass of △ T is better, the results are shown in Table 4.
The wearability testing result of 4 self-cleaning glass of table
| Group | △ T (%) |
| Embodiment 5 | 5.6 |
| Embodiment 6 | 6.0 |
| Embodiment 7 | 5.3 |
| Comparative example 1 | 6.9 |
| Comparative example 2 | 7.0 |
| Comparative example 3 | 5.2 |
| Comparative example 4 | 8.0 |
The results show that △ T≤6.0% of self-cleaning glass made from 5-7 of the embodiment of the present invention, has preferably wear-resisting
Property.By comparative example 1 and 2 it is found that replacing with Fe with FeOOH2O3Or fullerene is replaced with fowler alkenyl carboxylic acid derivative
C60, the △ T of self-cleaning glass obtained is increased slightly, this is because the mixing of FeOOH and fowler alkenyl carboxylic acid derivative is anti-
The wearability for answering product that can make glass thin-film layers enhances；By comparative example 3 it is found that the increase of fowler alkenyl carboxylic acid derivative content, is omited
Improve the wearability of glass thin-film layers；By comparative example 4 it is found that being free of fowler alkenyl carboxylic acid derivative, glass thin-film layers can be reduced
Wearability.
The above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
Limitation of the invention, protection scope of the present invention should be defined by the scope defined by the claims..For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
It also should be regarded as protection scope of the present invention into retouching.
Claims (10)
1. a kind of wear-resisting self-cleaning glass of middle light transmission, which is characterized in that the wear-resisting self-cleaning glass of middle light transmission includes glass
Matrix and the film layer formed on glass matrix surface by magnetron sputtering method；The film layer includes following quality percentage
Than the raw material of meter：FeOOH 15~25%, fowler alkenyl carboxylic acid derivative 5~15%, nano-titanium dioxide 65~75%.
2. the wear-resisting self-cleaning glass of middle light transmission according to claim 1, which is characterized in that the film layer with a thickness of
100~300nm.
3. the wear-resisting self-cleaning glass of middle light transmission according to claim 1, which is characterized in that the preparation of the FeOOH
Include the following steps：Iron chloride, urea and PEG-2000 are placed in reaction kettle, be added water, 105~125 DEG C react 24~
36h is cooled to room temperature, and filtering obtains Tan solid, solid is cleaned with dehydrated alcohol, deionized water respectively, and vacuum is dry
It is dry to get FeOOH.
4. the wear-resisting self-cleaning glass of middle light transmission according to claim 3, which is characterized in that the iron chloride and urea rub
You are than being 1:0.2~0.3；The additional amount of the PEG-2000 is 0.3~0.4 times of chlorination weight of iron.
5. the wear-resisting self-cleaning glass of middle light transmission according to claim 1, which is characterized in that the fowler alkenyl carboxylic acid derivative
Preparation include the following steps：Under nitrogen protection, by fullerene C60, p -carboxybenzaldehyde and sarcosine be scattered in toluene,
In 100~115 DEG C of reactions 8~10h, the fullerene C60：P -carboxybenzaldehyde：Sarcosine：The molar ratio of toluene is：1:(10
~12):(8~10):Obtained solid is washed with water after reaction in (35~40), and drying obtains fowler alkenyl carboxylic acid derivative.
6. the wear-resisting self-cleaning glass of middle light transmission according to claim 1, which is characterized in that the glass matrix is boric acid
Salt glass, silicate glass or phosphate glass.
7. a kind of method for preparing the wear-resisting self-cleaning glass of middle light transmission as described in claim 1-6 is any, which is characterized in that packet
Include following steps：
(1) pretreatment of glass matrix：The spot on glass matrix surface is cleaned with soda ash first, it is then clear with dehydrated alcohol ultrasound
5~15min is washed, then elutes 30~60min with deionized water, dries the glass matrix to get cleanliness without any pollution；
(2) preparation of film feed liquid：Feed liquid A containing nano-titanium dioxide and hydroxyl iron oxide and fowler olefinic carboxylic acid are prepared respectively
The feed liquid B of derivative；
(3) magnetron sputtering is handled：The glass matrix for the cleanliness without any pollution that step (1) obtains is fixed on sample stage, then
It is put into transition vacuum chamber and vacuumizes 5~10min, be passed to by magnetic force transmission lever to sputtering vacuum chamber, open substrate heating system,
Glass matrix is heated to 400~450 DEG C and is kept constant；The feed liquid A that step (2) obtains is placed in titanium dioxide ceramic target,
Feed liquid B is placed in metallic cobalt target, sputtering is wear-resisting self-cleaning to get middle light transmission simultaneously by feed liquid A and feed liquid B by the way of cosputtering
Net glass.
8. the preparation method of the wear-resisting self-cleaning glass of middle light transmission according to claim 7, which is characterized in that the feed liquid A
Be prepared as：Nano-titanium dioxide is added in n-butanol, the agate bead for the use of diameter being 2~3cm, with 200~250r/min
Revolving speed ball milling disperse 25~30min, obtain feed liquid A, the molar ratio of the nano-titanium dioxide and n-butanol is 1:6~8.
9. the preparation method of the wear-resisting self-cleaning glass of middle light transmission according to claim 7, which is characterized in that the feed liquid B
Be prepared as：FeOOH, fowler alkenyl carboxylic acid derivative are added in methanol aqueous solution, in 60~70 DEG C, 50~60r/min
Under the conditions of be stirred to react 1~2h, obtain feed liquid B, in the methanol aqueous solution volume ratio of first alcohol and water be 0.7~1:2, institute
The additional amount for the methanol aqueous solution stated is 4~5 times of FeOOH and fowler alkenyl carboxylic acid derivative total weight.
10. the preparation method of the wear-resisting self-cleaning glass of middle light transmission according to claim 7, which is characterized in that the dioxy
The radio-frequency power for changing titanium ceramic target is 120~150W, and the radio-frequency power of the metallic cobalt target is 10~50W, and sputter gas is argon
Gas, flow velocity are 25~35sccm.
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