CN101333075B - Method for preparing self-cleaning toughened glass - Google Patents
Method for preparing self-cleaning toughened glass Download PDFInfo
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Abstract
The invention belongs to the technical field of functional materials, particularly relating to the offline and online production technology for normal temperature and pressure nano self-cleaning glass, especially to a manufacturing method for normal temperature self-cleaning tempered glass. The invention will first enables the nano-coating with visible light activity to be pre-crystalled, and coat the pre-crystalled coating on the surface of the glass, then form crystal rapidly under the condition of 700 DEG C transient high temperature treatment required in the tempered glass preparation process, so as to achieve tempering and simultaneously realize super-hydrophilicity and photocatalytic activity on the glass surface. The nano-self-cleaning coating on the glass surface is more strengthened through transient high temperature, so as to improve the service life of the self-cleaning coating.
Description
Technical field
The invention belongs to technical field of function materials, particularly relate to off-line and online production technology, the especially preparation method of normal temperature self-cleaning toughened glass of normal temperature and pressure nano self-cleaning glass.
Background technology
In recent years, China's building glass industry fast development, but its cleaning way is but without any change.The artificial cleaning is that inconvenience is also dangerous, and in addition, the life-time service clean-out system is not only wasted resource, also will bring pollution to environment, do not meet environmental protection, saving policy that present country advocates.The appearance of self-cleaning nona glass has brought the brand-new glass of people and has cleaned and maintenance mode.
Studies show that TiO
2Film has self-cleaning function, under illumination condition, and the TiO on various matrixes (comprising glass, pottery, plastics etc.) surface
2Can decompose adsorbed organic matter, avoid adhering to of organic pollutant, thereby reach self-cleaning effect.Therefore utilize TiO
2The self-cleaning glass of preparation is the most noticeable.If building and venue all are equipped with TiO
2The glass of coating, pollutent can not improve the looks in city in surface attachment, protect beautiful color forever.
The method of production self-cleaning glass has a variety of, as: magnetron sputtering method, sol-gel method, chemical Vapor deposition process or the like.Chinese invention patent application (application number: 200610019338.7) propose to adopt magnetron sputtering technique to prepare self-cleaning glass, will be through 500 ℃ high-temperature heat treatment 30～60 minutes, though rete possesses good hydrophilicity, but cost height, be difficult to apply, the photocatalytic activity of rete was not mentioned in this invention yet.And the automatically cleaning effect of self-cleaning glass not only will possess good hydrophilicity, and will possess higher photocatalytic activity simultaneously.Chinese invention patent application (application number: 200610035099.4) once proposed a kind of permanent self-cleaning glass and preparation method with visible-light response type, earlier at clean glass surface sputter silica membrane, the modifying titanium dioxide film that sputter one deck yin, yang ion is mixed altogether on the nanometer titanium dioxide silicon film surface then, the glass that has plated bilayer film is 500～600 ℃ of annealing down, and naturally cooling promptly in the sintering oven.Wherein, this method more complicated for preparing self-cleaning glass should use also very inconvenient.Number of patent application: 03113881.0 application for a patent for invention relates to the preparation method of the nano oxidized titanium glass of a kind of mixed crystal, and its main component is rutile-phase nano titanium oxide, anatase-phase nano titanium dioxide and silicon-dioxide, adopts the crystal pulling method film forming.Wherein the rutile-phase nano titanium oxide can derive from the rutile-phase nano titania slurry, also can be obtained by anatase phase nano titanium oxide phase transformation after heat treatment.Because the difference of crystalline structure, the existence of mixed crystal can promote separating of light induced electron and hole charge effectively, thereby improves the photocatalysis characteristic of the nano-titanium dioxide film of preparation.The experiment proved that the nano titanium oxide self-cleaning glass that the method that is proposed by this invention prepares has good photocatalysis characteristic and Superhydrophilic.
The common issue with that the self-cleaning glass that utilizes sol-gel method and above-mentioned prior art (magnetron sputtering method) to make exists is:
(1) have good wetting ability, but photocatalytic activity does not have the raising of essence, and the self-cleaning glass most critical is that the common raising of these two performances could realize automatically cleaning truly.
(2) thermal treatment temp to super hydrophilic film is low, and in the existing glass production line, the temperature that is suitable for modifying the processing step of super hydrophilic film on glass all is higher than 600 ℃, therefore, the preparation technology of super hydrophilic film is not suitable for existing glass production line on the self-cleaning glass of being mentioned in the invention, and resulting super hydrophilic film strength is lower, production cost height, thereby the commercial application of restriction self-cleaning glass.
(3) applicable occasion is restricted, has no idea to carry out automatically cleaning for already installed glass curtain wall and handles.
Summary of the invention
One of purpose of the present invention is, the preparation method of the photoactive self-cleaning toughened glass of a kind of efficient ultraviolet-visible is provided, make the nanometer titanium dioxide titanium compound coating at the glass surface that cleans up, improve the automatically cleaning ability of glass, a kind of brand-new glass clean and maintenance mode is provided.
A further object of the present invention is, overcome self-cleaning glass unstable properties in the prior art, induce that mode is single, thermal treatment temp is high and be not suitable for problems such as existing glass production line, photocatalytic activity be low, and provide one kind of multiple modes to induce to excite, the self-cleaning toughened glass of stable performance.
Another object of the present invention is to, can utilize in the tempering process and must handle through 700 ℃ of TRANSIENT HIGH TEMPERATURE, thus the raising of the firm more and photocatalytic activity of realization glass surface nano titanium dioxide film layer.
Toughened glass realizes that its automatically cleaning character is significant because characteristics such as its intensity height, difficult fragmentation, safety are mainly used in fields such as building and automobile.
Since the time of tempering process pyroprocessing short (550～650 seconds), nano material crystallization fully, thus can not realize photochemical catalysis and super hydrophilic function.It (promptly is at one of presoma for preparing coating that the present invention will at first have the pre-crystallization of the photoactive nano paint of ultraviolet-visible, prepare anatase titanium dioxide when being TiO 2 sol), then with pre-crystalline applying coating in glass surface, utilize in the toughened glass preparation process and must form crystallization fast, in tempering, realize the super hydrophilicity of glass surface and the raising of photocatalytic activity performance through the condition that 700 ℃ of TRANSIENT HIGH TEMPERATURE are handled.The nano self-cleaning rete has improved the work-ing life of automatic cleaning coating through will be more firm after the TRANSIENT HIGH TEMPERATURE.
Nano self-cleaning paint among the present invention is to be the anatase titanium dioxide of 10～30% organosilicon and 20～40% and 30～70% solvent composition by molar content, organosilicon caking agent and titanium dioxide form the microfacies mixture in the coating, this mixture has not only kept the photochemical catalysis and the super hydrophilicity of original titanium dioxide, and improved cementability between mixture and the glass, guaranteed the stability and the wear resistance of self-cleaning nona coating on glass.Described nano self-cleaning paint is 10～30nm at the particle diameter of the microfacies mixture of the automatically cleaning rete of glass surface formation, and described self-cleaning glass all has super hydrophilicity under ultraviolet-visible.
Described solvent is selected from one or more the mixture in water, dehydrated alcohol, 95% ethanol, Virahol, acetone, butanols, butanone, emulsifying agent, the membrane-forming agent etc.
The preparation method of normal temperature self-cleaning toughened glass of the present invention may further comprise the steps:
(1). with glass clean up, natural air drying or oven dry;
Glass all will carry out clean before carrying out the processing of nano surface coating.The cleaning of glass surface directly influences the quality of product, filming with the glass surface of pollutions such as grease, dust, not only can have influence on the firmness of film and glass, more can influence the automatically cleaning effect.For the base material of particular requirement, after can cleaning glass surface, carry out drying, with high pure nitrogen glass surface is purged.
(2). nano self-cleaning paint evenly is sprayed on the clean glass surface that step (1) obtains, regulates spraying rate and flow to obtain the self-cleaning nona coating of different thickness according to different needs;
(3). the self-cleaning glass that step (2) is obtained dries under field conditions (factors) or uses electrically heated rod with the self-cleaning glass skin drying, thereby quickens the curing of automatically cleaning rete; Then nano self-cleaning glass is immersed in and carries out acid treatment in the acid solution, (that is: in the acid solution of finite concentration, volume, soaked 1～2 hour, after rinse well with tap water the taking-up back, use deionized water rinsing again, dry under the natural condition and get final product) displace the sodium ion and the calcium ion of glass surface, the photocatalytic activity of the self-cleaning toughened glass that is coated with titanium deoxid film can be improved more than 1 times.After surface acid was handled, the carbon content of film surface descended and surface hydrophilic group hydroxy radical content increases, for next step glass surface treatment is provided convenience;
(4). utilize the condition in the toughened glass preparation process to form crystallization fast, in tempering, realize the Superhydrophilic and the photocatalytic activity of glass surface.With the self-cleaning glass that step (3) prepares, to handle 550～650 seconds at 700 ℃ of following tempering, the nano self-cleaning rete has improved the work-ing life of automatic cleaning coating through will be more firm after the TRANSIENT HIGH TEMPERATURE, realizes tempering and self-cleaning once shaped.This method is not only simple, has made full use of the energy when tempering is handled simultaneously, save energy.
The concentration of described nano self-cleaning paint is 1～30g/l.
Described spraying rate be greater than 0.5 meter per second to less than 2.5 meter per seconds, preferred spraying rate is 0.6～2.0 meter per second.
Described nano self-cleaning paint in the automatically cleaning rete that glass surface forms nano titanium oxide and the particle diameter of nano silicon be 10～30nm.
The concentration of the described acid of step (3) is 0.001～4M, and described acid is organic acid or mineral acid.
Described organic acid is formic acid or acetate etc.; Mineral acid is one or more the mixing acid in hydrochloric acid, sulfuric acid, the nitric acid.
The self-cleaning toughened glass that the inventive method obtains has good photocatalytic and photic wetting ability under visible light, stable performance, almost effectively permanent, and glass transmittance height, water white transparency, the glass curtain wall that can be widely used in skyscraper, vehicle glass, the street lamp lampshade, kitchen glass, and antifog glass, can exempt the artificial cleaning of skyscraper indoor and outdoor glass, use manpower and material resources sparingly, and reduce the artificial corrosion and the destruction to glass and building structure of using sanitising agent to bring of cleaning, embody the environmental protection notion.
Adopt method of the present invention at formation automatically cleaning rete on glass, nano titanium oxide and silicon-dioxide microfacies mixture uniform particle diameter in this rete, size is all about 10～30nm, the nano titanium dioxide film of this self-cleaning toughened glass has Superhydrophilic, all has the automatically cleaning effect under the ultraviolet-visible light action, is being subjected to rain (water) when washing away, form hydrophilic film at the glassy membrane laminar surface, do not stay washmarking, inorganic pollutants such as dust are easy to be flushed away, thereby reach the effect of cleaning surfaces.
Description of drawings
Fig. 1. the XRD figure in the embodiment of the invention 1.
Fig. 2. the photochemical catalysis effect contrast figure in the embodiment of the invention 8;
On behalf of spraying rate, " ● " point be the film forming photocatalytic activity of 2.0 meter per seconds, and on behalf of spraying rate, " ◆ " point be the film forming photocatalytic activity of 1.0 meter per seconds.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described:
The nano self-cleaning paint of following examples is to be the anatase titanium dioxide of 10～30% organosilicon and 20～40% and 30～70% solvent composition by molar content.
Remove all labels and the dirt of glass surface, guarantee the glass surface cleaning, water washes out the dust of glass surface again.(polishing powder and deionized water blending ratio 1:10) polishes glass surface with rotating disk with the glass polishing powder about 400 orders, water is rinsed the dirt and the polishing powder of glass surface well again, blower fan with the band filtering net dries up glass surface moisture, the assurance glass surface is clean, do not have any dust, with high pure nitrogen glass surface is purged again.Is that the nano self-cleaning paint of 10g/l evenly is sprayed on glass surface (speed 1 meter per second) with spray gun with concentration, and normal temperature and pressure solidifies just can obtain super hydrophilic self-cleaning glass.
Acid treatment is carried out on self-cleaning glass surface after will solidifying again, and used acid is the HCl aqueous solution of 0.5M, and soak time is 1 hour, after rinse well with tap water the taking-up back, uses deionized water rinsing again, dries under the natural condition to get final product.
Handled 120 seconds at 700 ℃ of tempering through normal temperature and pressure solidified self-cleaning glass above-mentioned, adjust according to the required flow process of tempering program, self-cleaning glass after the processing has kept good super water-wet behavior and photocatalysis performance, and the titanium dioxide crystal form of glass surface is a Detitanium-ore-type.See Fig. 1.
The outdoor placement of self-cleaning glass after 20 days, is carried out the test of contact angle again, and contact angle is 2 degree, has kept the good hydrophilicity energy.
Embodiment 2.
Original sheet glass is cleaned up, the surface is dried up with blower, is that the self-cleaning nona coating of 25g/l evenly is sprayed on glass surface (speed 2.5 meter per seconds) with spray gun with concentration, the result is because spraying rate is fast, the automatic cleaning coating of glass surface very little, film forming is bad, causes its photocatalytic activity obviously to reduce.
Embodiment 3.
With 400 purpose glass polishing powder glass surface is polished with rotating disk, water is rinsed the dirt and the polishing powder of glass surface well again, naturally dry in clean place, is that the self-cleaning nona coating of 20g/l evenly is sprayed on glass surface (speed 0.9 meter per second) with spray gun with concentration, and normal temperature and pressure solidifies just can obtain super hydrophilic self-cleaning glass.Acid treatment is carried out on self-cleaning glass surface after will solidifying again, and used acid is the acetic acid aqueous solution of 3M, and soak time is 2 hours, after rinse well with tap water the taking-up back, uses deionized water rinsing again, dries under the natural condition to get final product.Again prepared self-cleaning glass was handled 550 seconds at 700 ℃ of tempering, self-cleaning glass after the processing has kept good super water-wet behavior and photocatalysis performance, but because spraying rate is slow excessively, the transmittance of glass surface obviously reduces, but do not influence super hydrophilicity, photocatalytic activity has improved 1.1 times simultaneously, and this is because because spraying rate is slow excessively, coat-thickness increases to some extent, and content of titanium dioxide obviously increases in the coating.
Embodiment 4.
Is that the self-cleaning nona coating of 1g/l evenly is sprayed on the glass surface (speed 0.5 meter per second) that cleans up with spray gun with concentration, glass be fresh baked have a surplus the temperature glass, about 90 ℃ of temperature, the rete of finding glass surface behind overcuring is very inhomogeneous, density is poor, rainbow phenomena is arranged, had a strong impact on result of use.Because spraying rate is too slow, nano paint presents water sample on glass, does not have thermograde during curing, in addition some solvent evaporates in the self-cleaning coating too fast and cause this phenomenon.
Embodiment 5.
With the glass polishing powder glass surface is polished with rotating disk, water is rinsed the dirt and the polishing powder of glass surface well again, naturally dry in clean place, is that the self-cleaning nona coating of 30g/l evenly is sprayed on glass surface (speed 2.0 meter per seconds) with spray gun with concentration, and normal temperature and pressure solidifies just can obtain super hydrophilic self-cleaning glass.Acid treatment is carried out on self-cleaning glass surface after will solidifying again, and used acid is the formic acid of 4M and the mixed aqueous solution of acetate, and soak time is 1.5 hours, after rinse well with tap water the taking-up back, uses deionized water rinsing again, dries under the natural condition to get final product.
Prepared self-cleaning glass was handled 600 seconds at 700 ℃ of tempering, and the self-cleaning glass after the processing has kept good super hydrophilic and photocatalysis performance, and the sticking power and the hardness of rete all increase.
Embodiment 6.
The glass surface that is cleaning up, is that the self-cleaning nona coating of 5g/l evenly is sprayed on glass surface (speed 1.5 meter per seconds) with spray gun with concentration, normal temperature and pressure solidifies just can obtain super hydrophilic nano self-cleaning glass, do not need high temperature sintering, the ageing-resistant performance of rete, acidproof and alkaline resistance properties, sticking power all reach national coating standard.See Table 1.
Above self-cleaning glass was handled 560 seconds at 700 ℃ of tempering, and the self-cleaning glass after the processing has not only kept original good super hydrophilic and photocatalysis performance, and the sticking power and the ageing-resistant performance of rete all increase simultaneously.See Table 1.Table 1 is the ageing-resistant performance, transmissivity, contamination resistance of rete, acidproof and alkaline resistance properties, sticking power, hardness parameters.
Table 1
| Test event | The result | Estimate | |
| Artificial ageing resistance performance (2000 hours) | 0 grade of efflorescence | The outward appearance no change | |
| Transmissivity | 87 | Improve | 1～2% than the former substrate of glass |
| Polluting proofing |
0 grade | By force | |
| Acid resistance | 5wt% sulfuric acid soaked 48 hours | Outward appearance does not have efflorescence | |
| Alkali resistance | Saturated calcium hydroxide soaked 48 hours | Outward appearance does not have | |
| Sticking power | |||
| 0 grade of cross-hatching | Strong adhesion | ||
| Hardness | 0.89 | Near original sheet glass |
Embodiment 7.
The glass surface that is cleaning up, is that the self-cleaning nona coating of 3g/l evenly is sprayed on glass surface (speed 1.2 meter per seconds) with spray gun with concentration, normal temperature and pressure solidifies just can obtain super hydrophilic nano self-cleaning glass, do not need high temperature sintering, the ageing-resistant performance of rete, acidproof and alkaline resistance properties, sticking power all reach national coating standard.Acid treatment is carried out on self-cleaning glass surface after will solidifying again, and used acid is the aqueous sulfuric acid of 0.001M, and soak time is 1.1 hours, after rinse well with tap water the taking-up back, uses deionized water rinsing again, dries under the natural condition to get final product.
Above self-cleaning glass was handled 560 seconds at 700 ℃ of tempering, and the self-cleaning glass after the processing has not only kept original good super hydrophilic and photocatalysis performance, and the sticking power and the ageing-resistant performance of rete all increase simultaneously.Table 2 is the influence result of tempering to the self-cleaning glass surface property.
Table 2
| The film outward appearance | Sticking power | Wetting ability | Digestion time | Visible light transmittance rate | ||
| | Homogeneous | 0 grade of |
0 | 1000 hours no changes | 87％ | |
| Toughened | Homogeneous | 0 grade of |
0 | 2000 hours no changes | 89％ |
Get 5 blocks of glass and carry out control experiment, respectively the glass surface water is cleaned, after with high pure nitrogen glass surface being purged, carry out drying; Is that the self-cleaning nona coating of 15g/l is sprayed on clean glass surface with the speed of 0.5 meter per second, 1.0 meter per seconds, 1.5 meter per seconds, 2.0 meter per seconds, 2.5 meter per seconds respectively with spray gun with concentration, after the ambient cure, coated glass is carried out acid treatment, displace sodium ion, the calcium ion of glass surface, the photocatalytic activity of titanium deoxid film self-cleaning toughened glass can be improved more than 1 times.Used acid is the aqueous nitric acid of 0.05M, and soak time is 1.0 hours, after rinse well with tap water the taking-up back, uses deionized water rinsing again, dries under the natural condition to get final product.After surface acid was handled, the carbon content of film surface descended and surface hydrophilic group hydroxy radical content increases, for next step glass surface treatment is provided convenience.Handled 650 seconds at 700 ℃ of tempering through normal temperature and pressure solidified self-cleaning glass above-mentioned, obtain super hydrophilic nano self-cleaning glass, spraying rate to the self-cleaning glass surface property to influence the result as shown in table 3 below.
Table 3
| Spraying rate (m/s) | The film outward appearance | Sticking power | Aging resistance | Wetting ability | |
| 0.5 | Film is opaque, is | Efflorescence | 1000 |
0 | |
| 1.0 | Homogeneous, transparent | 0 grade of cross-hatching | 2000 |
0 | |
| 1.5 | Homogeneous, transparent | 0 grade of cross-hatching | 2000 |
0 | |
| 2.0 | Homogeneous, transparent | 0 grade of cross-hatching | 2000 |
0 | |
| 2.5 | Film-forming properties is bad | 0 grade of cross-hatching | 2000 |
0 |
Claims (8)
1. the preparation method of a self-cleaning toughened glass is characterized in that, this method may further comprise the steps:
(1). with glass clean up, natural air drying or oven dry;
(2). nano self-cleaning paint evenly is sprayed on the clean glass surface that step (1) obtains;
(3). the self-cleaning glass that step (2) is obtained dries under field conditions (factors) or uses electrically heated rod with the self-cleaning glass skin drying; To be coated with super hydrophilic nano self-cleaning film glass then and be immersed in and carry out acid treatment in the acid solution, displace the sodium ion and the calcium ion of glass surface;
(4). with the self-cleaning glass that step (3) prepares, handled 550～650 seconds at 700 ℃ of following tempering;
Described nano self-cleaning paint is to be the anatase titanium dioxide of 10～30% organosilicon and 20～40% and 30～70% solvent composition by molar content.
2. method according to claim 1 is characterized in that: the concentration of described nano self-cleaning paint is 1～30g/L.
3. method according to claim 1 and 2 is characterized in that: described spraying rate is extremely less than 2.5 meter per seconds greater than 0.5 meter per second.
4. method according to claim 3 is characterized in that: described spraying rate is 0.6～2.0 meter per second.
5. method according to claim 1 is characterized in that: described nano self-cleaning paint in the automatically cleaning rete that glass surface forms nano titanium oxide and the particle diameter of nano silicon be 10～30nm.
6. method according to claim 1 is characterized in that: described solvent is selected from more than one in water, dehydrated alcohol, 95wt% ethanol, Virahol, acetone, butanols, the butanone.
7. method according to claim 1 is characterized in that: the concentration of the described acid of step (3) is 0.001～4M, and described acid is organic acid or mineral acid.
8. method according to claim 7 is characterized in that: described organic acid is formic acid or acetate; Mineral acid is more than one in hydrochloric acid, sulfuric acid, the nitric acid.
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| CN104876452A (en) * | 2015-02-06 | 2015-09-02 | 北京中科赛纳玻璃技术有限公司 | Novel preparation method of nanometer self-cleaning glass |
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| CN1400185A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1400185A (en) * | 2001-07-31 | 2003-03-05 | 武汉理工大学 | Method for preparing high-activity titanium dioxide film self-cleaning glass material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876452A (en) * | 2015-02-06 | 2015-09-02 | 北京中科赛纳玻璃技术有限公司 | Novel preparation method of nanometer self-cleaning glass |
| CN104876452B (en) * | 2015-02-06 | 2018-01-05 | 北京中科赛纳玻璃技术有限公司 | A kind of preparation method of new nano self-cleaning glass |
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