CN101215190A - Ceramic products with transparent heat reflection coat on surface and preparation method thereof - Google Patents
Ceramic products with transparent heat reflection coat on surface and preparation method thereof Download PDFInfo
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- CN101215190A CN101215190A CNA200710033036XA CN200710033036A CN101215190A CN 101215190 A CN101215190 A CN 101215190A CN A200710033036X A CNA200710033036X A CN A200710033036XA CN 200710033036 A CN200710033036 A CN 200710033036A CN 101215190 A CN101215190 A CN 101215190A
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Abstract
The invention discloses a ceramic product which is provided with a transparent heat-reflective coating on surface. The invention uses ceramic as a substrate to coat sequentially a layer of ionic barrier layer thin film and a layer of transparent conductive oxidation thin film on the surface of the ceramics, or uses the ceramic as the substrate to coats sequentially a layer of ionic barrier layer thin film, a layer of metallic film and a layer of transparent conductive oxidation film on the surface of the ceramics. The invention further discloses a method for preparing the ceramic product. The transparent heat-reflective coating on the surface of the ceramic product provided by the invention does not contain macromolecular film-forming agent and has perfect conductivity property. And surface resistance of the coating can be below 100 omega/cm, resistivity is less than 1*10 -3omega,cm, and infrared reflectivity of the thin film can reach above 70 percent.
Description
Technical field
The present invention relates to a kind of surface and have ceramic of transparent heat reflection coat and preparation method thereof.
Background technology
China's building energy consumption at present accounts for 1/3 of social primary energy source wastage in bulk or weight, and raising along with The development in society and economy, living standards of the people, the building energy consumption ratio will continue to improve, and it is also very low from rate of energy, China's building heating energy consumption is about 3 times of developed country, wherein exterior wall is 4～5 times, and the roof is 2.5～5.5 times, and exterior window is 1.5～2.2 times.This shows that China has many work to do aspect building energy conservation.
Skin mainly is concrete, brick wall structure, and these materials are wide to the absorption region of light, and heat storage capacity is big, and heat radiation is slow, causes the buildings quick heating, and high-temperature duration is long.Particularly in summer, the free air temperature height, intensity of solar radiation is big, and the radiant heat that absorbs from the roof and the body of wall of buildings causes room temp to rise, and the load of air-conditioning increases, and consumes more primary energy source.Infrared light accounts for more than 45% of solar energy, and reflective infrared plays an important role to energy-conservation.For this reason, the development of infra-red heat reflecting material and coating and exploitation become focus.
The ceramic surface heat-reflective coating is made up of macromolecule film former and the color stuffing with heat reflection function mostly at present, because the existence of macromolecule film former has significantly reduced the reflectivity of coating to ir radiation, heat insulation and preservation effect is limited; In addition, adhesive force of coatings is undesirable, comes off or runs off under rain drop erosion easily.The preparation method that the surface has transparent conductive oxide film in the ceramic of transparent heat reflection coat mainly comprises magnetron sputtering method, chemical Vapor deposition process, sol-gel method and spray pyrolysis.Wherein spray pyrolysis has the advantages that preparation cost is cheap relatively, be convenient to scale operation, is subjected to people's favor.Ultrasonic spray pyrolysis mode particularly, carrier gas flux is little, and the ullrasonic spraying air-flow is little to the influence of underlayer temperature, makes the control of depositing operation relatively easy.But traditional ultrasonic spray pyrolysis film-forming method all is after ultrasonic hazing, and carries fog to nozzle by carrier gas, and aerosol deposition film forming then, this mode exist ultrasonic frequency height, mechanism's complexity, aerosol instability, become problems such as film uniformity is relatively poor.
Summary of the invention
One of purpose of the present invention provides the ceramic that a kind of surface has transparent heat reflection coat.
The technical scheme that realizes above-mentioned purpose is as follows:
A kind of surface has the ceramic of transparent heat reflection coat, it is substrate with the pottery, applying one deck ion barrier layer film and layer of transparent conductive oxide film successively on the surface of pottery. but this ceramic reflection wavelength is greater than the infrared emanation of 2.5 μ m, be applicable to cold district, can effectively reduce the external thermal radiation of exterior wall pottery, reach the heat-insulation and heat-preservation effect.
Preferably, described transparent conductive oxide film is a kind of semiconductor material with wide forbidden band of metal ion mixing, antimony doped tin oxide (ATO) preferably, tin-doped indium oxide (ITO), Al-Doped ZnO (ZAO) or mix a kind of in the niobium titanium dioxide (TNO).Wherein the infra-red heat reflectivity of tin-doped indium oxide film is the highest; Mix niobium titanium deoxid film transmission of visible light height, up to more than 80%, and have good infra-red heat reflecting properties, infrared reflectance reaches 40%-70%, and has the photocatalysis antibacterial self-cleaning function.
Preferably, described ion barrier layer can prevent that foreign ion forms uncontrollable ion doping to the diffusion of transparency conducting layer in the ceramic substrate under hot conditions (350 ℃-600 ℃), cause the deterioration of conductivity.The ion barrier layer material is a kind of in silicon-dioxide, tindioxide, zinc oxide or the titanium dioxide, usually silicon-dioxide can be used with any transparency conducting layer material-mix, other oxide ion barrier material then should be identical with the material component of transparency conducting layer, can prevent that foreign ion from spreading to transparency conducting layer on the one hand, in trilamellar membrane structural membrane system, can cooperate the antireflecting effect of playing on the one hand with transparency conducting layer.
Another object of the present invention provides a kind of method that above-mentioned surface has the ceramic of transparent heat reflection coat for preparing.
A kind of surface has the ceramic products preparation method of transparent heat reflection coat, can take the method for the following stated:
A) preparation ion barrier layer colloidal sol.
B) preparation transparent conductive oxide colloidal sol: respectively with antimonic salt, pink salt, indium salt, zinc salt, aluminium salt, niobate or titanium salt are raw material, with ethanol, methyl alcohol or ethylene glycol monomethyl ether are solvent, with methyl ethyl diketone, monoethanolamine or diethanolamine are stablizer, the hydrolysis that adds hydrochloric acid or acetic acid inhibition metal-salt, prepare above-mentioned metal salt solution respectively, strength of solution is 0.1-1mol/l, the mol ratio of stablizer and metal ion is 1-4: 1, wherein two kinds of solution mix at last, preparation obtains antimony doped tin oxide, tin-doped indium oxide, Al-Doped ZnO or mix the niobium TiO 2 sol makes doped metal ion and base metal ionic mol ratio reach 5-12: 100.
C) film forming and thermal treatment: ion barrier layer colloidal sol is coated in the ceramic substrate surface, and underlayer temperature is 350 ℃-600 ℃, is that room temperature condition at first forms gel-film at underlayer temperature perhaps, then through after the super-dry under 350 ℃ of-600 ℃ of conditions thermal treatment 0.5-2h; Then apply transparent conductive oxide colloidal sol on the ion barrier layer, underlayer temperature is 350 ℃-600 ℃, is that room temperature condition at first forms gel-film at underlayer temperature perhaps, then through after the super-dry under 350 ℃ of-600 ℃ of conditions thermal treatment 0.5-2h.
Preferably, the compound method of ion barrier layer silicon dioxide gel can be: be raw material with the tetraethoxy, ethanol is solvent, and compound concentration is the silicon dioxide gel of 0.1-1mol/l;
The compound method of other oxide ion blocking layer (tindioxide, zinc oxide or titanium dioxide) colloidal sol can be:
Be raw material with pink salt, zinc salt, titanium salt or alkyl titanate respectively, with ethanol, methyl alcohol or ethylene glycol monomethyl ether is solvent, with methyl ethyl diketone, monoethanolamine or diethanolamine is stablizer, add the hydrolysis of hydrochloric acid or acetic acid inhibition metal-salt, can obtain tindioxide, zinc oxide or TiO 2 sol respectively.
The compound method of described antimony doped tin oxide colloidal sol can be: get 13g SnCl
22H
2O is dissolved in 50ml dehydrated alcohol and the 50ml acetate, and adding the 5ml methyl ethyl diketone is stablizer, stirring reaction 2h under 70 ℃ of conditions; Then take by weighing SbCl
3Be dissolved in 25ml dehydrated alcohol and the 25ml acetate, make the Sb ion and Sn ion mol ratio reach 8%, stirring reaction 2h under 70 ℃ of conditions; Then with SbCl
3Solution and SnCl
2Solution mixes, and stirs 2h, and last ageing 24h forms antimony doped tin oxide colloidal sol.
The compound method of described tin-doped indium oxide colloidal sol can be: get 2-10g InCl
34H
2O is dissolved in the 100ml dehydrated alcohol, and adding methyl ethyl diketone, monoethanolamine or diethanolamine is stablizer, and stablizer and In ionic mol ratio are 1-6: 1 under 60-80 ℃ of condition stirring reaction 2h, obtain solution A; Then take by weighing SnCl
4Be dissolved in the 25ml dehydrated alcohol, obtain solution B, make in the B solution that In ionic mol ratio reaches 5-12 in the Sn ion and A solution: 100, stirring reaction 2h under 60-80 ℃ of condition; Then A solution is mixed with B solution, and stir 2h, last ageing 24h forms tin-doped indium oxide colloidal sol.Wherein the kind of stablizer is very big to the homogeneity influence of film, if do not add stablizer, be stablizer perhaps with methyl ethyl diketone or monoethanolamine, when collosol concentration big (as 0.3mol/l), colloidal sol is assembled under surface tension effects easily, cause the film forming inequality, film electricity and optical performance degradation.For this reason, preferred stablizer is a diethanolamine.
The preparation method of described Al-Doped ZnO colloidal sol can be: get 7.68g Zn (OAC)
2H
2O is dissolved in the 70ml ethylene glycol monomethyl ether, and the monoethanolamine that adds 2.1ml is a stablizer, at 80 ℃ of stirred in water bath reaction 2h; Then take by weighing Al (NO
3)
39H
2O is dissolved in the 8ml dehydrated alcohol, make the Al ion and Zn ion mol ratio reach 2wt%, be added drop-wise to then in the ZnO solution, and stir 2h, last ageing 24h forms Al-Doped ZnO colloidal sol.
Described compound method of mixing the niobium TiO 2 sol can be: get tetrabutyl titanate 5-15ml and be dissolved in the 90ml butanols, the concentrated hydrochloric acid of adding 37% reaches about 3 pH value of solution, and drips monoethanolamine 1-5ml, and at room temperature ultrasonic agitation 2h obtains solution A; Oxo niobic acid ammonium is added in the 15ml butanols, add 37% hydrochloric acid pH value of solution is reached about 3, at room temperature ultrasonic agitation 2h obtains B solution; The B drips of solution is added in the A solution, and making the Nb/Ti atomic ratio is 3-10%, mixes and stirs 2h, and last ageing 24h obtains mixing the niobium TiO 2 sol.
The film forming method of described coating can comprise pulling film forming method, spin-coating method, spray pyrolysis and ultrasonic spray pyrolysis etc.Wherein pulling film forming method colloidal sol consumption is big, is not suitable at the ceramic surface deposit film.
Wherein, described employing spin-coating method, it is even to have film forming, the advantage of film electricity, good in optical property, concrete grammar is that ceramic substrate is fixed on the universal stage, get colloidal sol and drip on ceramic substrate, with the speed of rotation of 2000-4000RPM colloidal sol is launched at substrate surface, along with the volatilization of solvent, the further polymerization of colloidal particle forms gel-film, after the gel-film drying, repeat above operation, at last gel-film is heat-treated under 350 ℃ of-600 ℃ of conditions until reaching the thickness that needs.Normally, the conductivity and the properties of infrared reflection of transparent conductive film strengthen along with the increase of thickness, and general film thickness monitoring is between 200-500nm.
Spray pyrolysis has the characteristics that preparation cost is cheap relatively, be convenient to scale operation, particularly ultrasonic spray pyrolysis mode, and carrier gas flux is little, and the ullrasonic spraying air-flow is little to the influence of underlayer temperature, makes the control of depositing operation relatively easy.But traditional ultrasonic spray pyrolysis film-forming method all is after ultrasonic hazing, and carries fog to nozzle by carrier gas, and fog deposition film forming then, this mode exist ultrasonic frequency height, mechanism's complexity, aerosol instability, become problems such as film uniformity is relatively poor.The present invention proposes to adopt the integrative ultrasonic nozzle to spray, disc shaped piezoelectric type ceramic transducer converts high-frequency electrical energy to the mechanical vibrational energy of same frequency, and be delivered near the atomizing face by horn, make behind the effusive colloidal sol ultrasonic atomizatio of horn and deposit film forming, ultrasonic frequency range is 30-120kHz, and injection rate is 1-20ml/min, and the height of nozzle distance substrate is 30-250mm, spray time is 2-20 minute, and underlayer temperature is 350-600 ℃.The present invention has following advantage compared with the prior art:
1) pbz polymer membrane-forming agent not in the transparent heat reflection coat on the ceramic surface that proposes of the present invention, conductive coating performance is good, and the surface resistivity of coating can be at 100 Ω/below the, and resistivity is less than 1 * 10
-3Ω cm, the film infrared reflectivity can reach more than 70%.
2) the present invention proposes based on the transparent heat reflection coat of mixing niobium titanium dioxide transparent conductive film, and its transmission of visible light is up to more than 80%, and infrared reflectance can reach 40%-70%, and has the photocatalysis antibacterial self-cleaning function.
3) compound method of the tin-doped indium oxide colloidal sol of the present invention's proposition, the employing diethanolamine is a stablizer, guarantees that forming thin film is even, and film surface resistance reaches 20-50 Ω/, and the infra-red heat reflectivity reaches about 80%.
4) the present invention proposes to adopt the ultrasonic spray pyrolysis film forming, adopts the integrative ultrasonic nozzle with colloidal sol atomizing back deposition film forming, has that ultrasonic frequency and ultrasonic power are low, nebulizer gas pressure is little, the characteristics of film forming good uniformity.
Description of drawings
Fig. 1 is the coating structure synoptic diagram of ceramic;
Fig. 2 is an integrative ultrasonic nozzle arrangements synoptic diagram.
Embodiment:
(ATO/SiO
2The ceramic of)-spin-coating
Film layer structure is ATO/SiO
2/ ceramic substrate, the preparation method is as follows:
1. silicon dioxide gel preparation: get the 50ml tetraethoxy and join in the 200ml ethanol, and with 17% HCl regulator solution pH value to 2-3, stirring at room is reacted 2h, obtaining concentration is the 1.2mol/l silicon dioxide gel.
2. ATO colloidal sol preparation: get 13.54g SnCl
22H
2O is dissolved in 50ml dehydrated alcohol and the 50ml acetate, and adding the 5ml methyl ethyl diketone is stablizer, stirring reaction 2h under 70 ℃ of conditions; Then take by weighing SbCl
3Be dissolved in 25ml dehydrated alcohol and the 25ml acetate, make the Sb ion and Sn ion mol ratio reach 10%, stirring reaction 2h under 70 ℃ of conditions; Then with SnCl
2Solution mixes, and stirs 2h, and last ageing 24h forms antimony doped tin oxide colloidal sol.
3. spin-coating and thermal treatment: ceramic substrate 1 is fixed on the universal stage, at underlayer temperature is under the room temperature, getting the 5ml silicon dioxide gel drips on ceramic substrate, speed spin coating with 3500RPM becomes ion barrier layer film 2, temperature rise rate with 5 ℃/min, dry 10min under 120 ℃, 250 ℃ conditions successively was 450 ℃ of following thermal treatments 1 hour; Get 5mlATO colloidal sol at last and drip on ceramic substrate, become transparent oxide layer film 3 with the speed spin coating of 3500RPM, with the temperature rise rate of 5 ℃/min, dry 10min under 120 ℃ of conditions repeats above operation 9 times; Thermal treatment 2h obtains ceramic under 550 ℃ of conditions at last.
Embodiment 2 (ITO/SiO2)-spin-coating
Film layer structure is ITO/SiO
2/ ceramic substrate, the preparation method is as follows for ITO colloidal sol, and all the other are with embodiment 1.
ITO colloidal sol preparation method: get 2g InCl
34H
2O is dissolved in the 100ml dehydrated alcohol, and adding the 1m methyl ethyl diketone is stablizer, stirring reaction 2h under 60 ℃ of conditions; Then take by weighing SnCl
4Be dissolved in the 25ml dehydrated alcohol, make the Sn ion and In ion mol ratio reach 5: 100, stirring reaction 2h under 60 ℃ of conditions; Then with SnCl
4Solution mixes, and stirs 2h, and last ageing 24h forms tin-doped indium oxide colloidal sol.
Embodiment 3 (ITO/SiO2)-spin-coating
Film layer structure is ITO/SiO
2/ ceramic substrate, ITO colloidal sol preparation method is as follows respectively, and all the other are with embodiment 1.
Get 10g InCl
34H
2O is dissolved in the 100ml dehydrated alcohol, and the diethanolamine that adds 5ml is a stablizer, stirring reaction 2h under 70 ℃ of conditions; Then take by weighing SnCl
4Be dissolved in the 25ml dehydrated alcohol, make the Sn ion and In ion mol ratio reach 12: 100, stirring reaction 2h under 70 ℃ of conditions; Then with SnCl
4Solution mixes, and stirs 2h, and last ageing 24h forms tin-doped indium oxide colloidal sol.
Embodiment 4 (ZAO/SiO2)-spin-coating
Film layer structure is ZAO/SiO
2/ ceramic substrate, the preparation method is as follows for ZAO colloidal sol, and all the other are with embodiment 1.
Get 7.68g Zn (OAC)
2H
2O is dissolved in the 70ml ethylene glycol monomethyl ether, and the monoethanolamine that adds 2.1ml is a stablizer, at 80 ℃ of stirred in water bath reaction 2h; Then take by weighing Al (NO
3)
39H
2O is dissolved in the 8ml dehydrated alcohol, make the Al ion and Zn ion mol ratio reach 2wt%, be added drop-wise to then in the ZnO solution, and stir 2h, last ageing 24h forms Al-Doped ZnO colloidal sol.
Embodiment 5 (ATO/SnO2)-spin-coating
Film layer structure is ATO/SnO
2/ ceramic substrate.
ATO colloidal sol compound method is with embodiment 1, SnO
2The colloidal sol compound method is as follows, and all the other are with embodiment 1.
Get 13g SnCl
22H
2O is dissolved in 50ml dehydrated alcohol and the 50ml acetate, and adding the 5ml methyl ethyl diketone is stablizer, and stirring reaction 2h under 70 ℃ of conditions removes throw out through after the centrifugal settling, obtain SnO
2Colloidal sol.
Embodiment 6 (ZAO/ZnO)-spin-coating
Film layer structure is the ZAO/ZnO/ ceramic substrate.
ZAO colloidal sol compound method is with embodiment 5, and ZnO colloidal sol compound method is as follows, and all the other are with embodiment 1.
Get 7.68g Zn (OAC)
2H
2O is dissolved in the 70ml ethylene glycol monomethyl ether, and the monoethanolamine that adds 2.1ml is a stablizer, at 80 ℃ of stirred in water bath reaction 2h, obtains ZnO colloidal sol.
Embodiment 7 (ITO/SiO2)-super spray pyrolysis system film
Film layer structure is ITO/SiO
2/ ceramic substrate, the colloidal sol preparation method is with embodiment 3.The integrative ultrasonic nozzle is mainly by piezoelectric type transducing sheet 5 as shown in Figure 2, nozzle rear casing 6, and fluid inlet 7, horn 8, atomizing face 9 is formed.Adopt following method film forming:
At first adopt the integrative ultrasonic nozzle on ceramic substrate, to spray SiO
2Colloidal sol, ultrasonic frequency range are 45kHz, and the height of nozzle distance substrate is 100mm, and nozzle moves back and forth in the 0-50mm distance range with the horizontal velocity of 50mm/min, and injection rate is 2ml/min, and spray time is 4 minutes, and underlayer temperature is 450 ℃; Spray ATO colloidal sol at last, injection rate is 2ml/min, and spray time is 10 minutes, and underlayer temperature is 550 ℃.
Embodiment 8 (ITO/SiO2)-ultrasonic spray pyrolysis system film
Film layer structure is ITO/SiO
2/ ceramic substrate, the colloidal sol preparation method is with embodiment 3.Adopt following method film forming:
At first adopt the integrative ultrasonic nozzle on ceramic substrate, to spray SiO
2Colloidal sol, ultrasonic frequency range are 120kHz, and the height of nozzle distance substrate is 200mm, and nozzle moves back and forth in the 0-50mm distance range with the horizontal velocity of 50mm/min, and injection rate is 2ml/min, and spray time is 4 minutes, and underlayer temperature is 450 ℃; Spray ATO colloidal sol at last, injection rate is 2ml/min, and spray time is 10 minutes, and underlayer temperature is 400 ℃.
Embodiment 9 (ITO/SiO2)-ultrasonic spray pyrolysis system film
Film layer structure is ITO/SiO
2/ ceramic substrate, the colloidal sol preparation method is with embodiment 3.Adopt following method film forming:
At first adopt the integrative ultrasonic nozzle on ceramic substrate, to spray SiO
2Colloidal sol, ultrasonic frequency range are 120kHz, and the height of nozzle distance substrate is 100mm, and nozzle moves back and forth in the 0-50mm distance range with the horizontal velocity of 50mm/min, and injection rate is 2ml/min, and spray time is 4 minutes, and underlayer temperature is 450 ℃; Spray ATO colloidal sol at last, injection rate is 2ml/min, and spray time is 10 minutes, and underlayer temperature is 500 ℃.
Embodiment 10 (ITO/SiO
2)-ultrasonic spray pyrolysis system film
Film layer structure is ITO/SiO
2/ ceramic substrate, the colloidal sol preparation method is with embodiment 3.Adopt following method film forming:
At first adopt the integrative ultrasonic nozzle on ceramic substrate, to spray SiO
2Colloidal sol, ultrasonic frequency range are 45kHz, and the height of nozzle distance substrate is 200mm, and nozzle moves back and forth in the 0-50mm distance range with the horizontal velocity of 50mm/min, and injection rate is 4ml/min, and spray time is 4 minutes, and underlayer temperature is 450 ℃; Spray ATO colloidal sol at last, injection rate is 6ml/min, and spray time is 8 minutes, and underlayer temperature is 500 ℃.
Embodiment 11 (TNO/SiO2)-spin-coating
Film layer structure is TNO/SiO
2/ ceramic substrate, the preparation method is as follows for TNO colloidal sol, and all the other are with embodiment 1.
Get tetrabutyl titanate 10ml and be dissolved in the 90ml butanols, the concentrated hydrochloric acid of adding 37% reaches about 3 pH value of solution, and drips monoethanolamine 3ml, and at room temperature ultrasonic agitation 2h obtains solution A; Oxo niobic acid ammonium is added in the 15ml butanols, add 37% hydrochloric acid pH value of solution is reached about 3, at room temperature ultrasonic agitation 2h obtains B solution; The B drips of solution is added in the A solution, and making the Nb/Ti atomic ratio is 10%, mixes and stirs 2h, and last ageing 24h obtains mixing the niobium TiO 2 sol.
Embodiment 12 (TNO/SiO2)-spin-coating
Film layer structure is TNO/SiO
2/ ceramic substrate, the preparation method is as follows for TNO colloidal sol, and all the other are with embodiment 1.
Get tetrabutyl titanate 5ml and be dissolved in the 90ml butanols, the concentrated hydrochloric acid of adding 37% reaches about 3 pH value of solution, and drips monoethanolamine 2ml, and at room temperature ultrasonic agitation 2h obtains solution A; Oxo niobic acid ammonium is added in the 15ml butanols, add 37% hydrochloric acid pH value of solution is reached about 3, at room temperature ultrasonic agitation 2h obtains B solution; The B drips of solution is added in the A solution, and making the Nb/Ti atomic ratio is 6%, mixes and stirs 2h, and last ageing 24h obtains mixing the niobium TiO 2 sol.
Embodiment 13 (TNO/SiO2)-spin-coating
Film layer structure is TNO/SiO
2/ ceramic substrate, the preparation method is as follows for TNO colloidal sol, and all the other are with embodiment 1.
Get tetrabutyl titanate 15ml and be dissolved in the 90ml butanols, the concentrated hydrochloric acid of adding 37% reaches about 3 pH value of solution, and drips monoethanolamine 2ml, and at room temperature ultrasonic agitation 2h obtains solution A; Oxo niobic acid ammonium is added in the 15ml butanols, add 37% hydrochloric acid pH value of solution is reached about 3, at room temperature ultrasonic agitation 2h obtains B solution; The B drips of solution is added in the A solution, and making the Nb/Ti atomic ratio is 3%, mixes and stirs 2h, and last ageing 24h obtains mixing the niobium TiO 2 sol.
Embodiment 14 (TNO/TiO
2)-spin-coating
TNO colloidal sol compound method is with embodiment 11, TiO
2The colloidal sol compound method is as follows, and all the other are with embodiment 1.
Get tetrabutyl titanate 10ml and be dissolved in the 90ml butanols, the concentrated hydrochloric acid of adding 37% reaches about 3 pH value of solution, and drips monoethanolamine 3ml, and at room temperature ultrasonic agitation 2h obtains TiO
2Colloidal sol.
By the reflection spectrum of UV, visible light near infrared spectrometer with the Fourier infrared spectrograph specimen of band reflection annex, adopt the surface resistivity of four point probe tester working sample, test result is as shown in table 1:
| Embodiment | Film layer structure/pottery | Surface resistivity (Ω/) | Near infrared reflectivity (1.5 μ m＜λ＜2.5 μ m) | Far infrared reflectivity (λ＞2.5 μ m) |
| 1 | ATO/SiO 2 | 50 | 25％ | 80％ |
| 2 | ITO/SiO 2 | 1000 | 10％ | 10％ |
| 3 | ITO/SiO 2 | 30 | 30％ | 80％ |
| 4 | ZAO/SiO 2 | 120 | 15％ | 45％ |
| 5 | ATO/SnO 2 | 50 | 30％ | 80％ |
| 6 | ZAO/ZnO | 120 | 15％ | 45％ |
| 7 | ITO/SiO 2 | 20 | 35％ | 80％ |
| 8 | ITO/SiO 2 | 100 | 15％ | 45％ |
| 9 | ITO/SiO 2 | 20 | 35％ | 80％ |
| 10 | ITO/SiO 2 | 20 | 35％ | 80％ |
| 11 | TNO/SiO 2 | 120 | 15％ | 45％ |
| 12 | TNO/SiO 2 | 600 | 10％ | 20％ |
| 13 | TNO/SiO 2 | 700 | 15％ | 20％ |
| 14 | TNO/TiO 2 | 130 | 20％ | 45％ |
Claims (8)
1. a surface has the ceramic of transparent heat reflection coat, it is characterized in that: be substrate with the pottery, be coated with one deck ion barrier layer film and layer of transparent conductive oxide film successively on the surface of pottery.
2. have the ceramic of transparent heat reflection coat according to the described surface of claim 1, it is characterized in that: the transparent conductive oxide film material is an antimony doped tin oxide, tin-doped indium oxide, Al-Doped ZnO or mix a kind of in the niobium titanium dioxide.
3. have the ceramic of transparent heat reflection coat according to the described surface of claim 1, it is characterized in that: ion barrier layer film material is a kind of in silicon-dioxide, tindioxide, zinc oxide or the titanium dioxide.
4. one kind prepares according to claim 1 the surface and has the method for the ceramic of transparent heat reflection coat, it is characterized in that comprising the steps:
A) preparation ion barrier layer colloidal sol;
B) preparation transparent conductive oxide colloidal sol: respectively with antimonic salt, pink salt, indium salt, zinc salt, aluminium salt, niobate or titanium salt are raw material, with ethanol, methyl alcohol or ethylene glycol monomethyl ether are solvent, with methyl ethyl diketone, monoethanolamine or diethanolamine are stablizer, the hydrolysis that adds hydrochloric acid or acetic acid inhibition metal-salt, prepare above-mentioned metal salt solution respectively, strength of solution is 0.1-1mol/l, the mol ratio of stablizer and metal ion is 1-4: 1, wherein two kinds of solution mix at last, preparation obtains antimony doped tin oxide, tin-doped indium oxide, Al-Doped ZnO or mix the niobium TiO 2 sol makes doped metal ion and base metal ionic mol ratio reach 5-12: 100;
C) film forming and thermal treatment: ion barrier layer colloidal sol is coated in the ceramic substrate surface, and underlayer temperature is 350 ℃-600 ℃, is that room temperature condition at first forms gel-film at underlayer temperature perhaps, then through after the super-dry under 350 ℃ of-600 ℃ of conditions thermal treatment 0.5-2h; Then on the ion barrier layer film, apply transparent conductive oxide colloidal sol, underlayer temperature is 350 ℃-600 ℃, be that room temperature condition at first forms gel-film perhaps at underlayer temperature, then through after the super-dry under 350 ℃ of-600 ℃ of conditions thermal treatment 0.5-2h obtain ceramic.
5. surface according to claim 4 has the ceramic products preparation method of transparent heat reflection coat, it is characterized in that, the compound method of tin-doped indium oxide colloidal sol is: get 2-10g InCl
34H
2O is dissolved in the 100ml dehydrated alcohol, and adding methyl ethyl diketone, monoethanolamine or diethanolamine is stablizer, and stirring reaction 2h under 60-80 ℃ of condition obtains solution A; Then take by weighing SnCl
4Be dissolved in the 25ml dehydrated alcohol, obtain solution B, make in the B solution that In ionic mol ratio reaches 5-12 in the Sn ion and A solution: 100, stirring reaction 2h under 60-80 ℃ of condition; Then A solution is mixed with B solution, and stir 2h, last ageing 24h forms tin-doped indium oxide colloidal sol.
6. surface according to claim 5 has the ceramic products preparation method of transparent heat reflection coat, it is characterized in that, described stablizer is a diethanolamine.
7. have the ceramic products preparation method of transparent heat reflection coat according to each described surface of claim 4-6, it is characterized in that, described film forming coating method is a kind of in spin-coating method or the ultrasonic spray pyrolysis.
8. has the ceramic products preparation method of transparent heat reflection coat according to the described surface of claim 7, it is characterized in that, described ultrasonic spray pyrolysis is, adopt the integrative ultrasonic nozzle to spray, ultrasonic frequency range is 30-120kHz, ultrasonic power is 1-15W, and nebulizer gas pressure is 0.2-0.3MPa.
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Cited By (12)
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| CN101337832B (en) * | 2008-08-14 | 2011-06-22 | 郑州鸿宾木艺有限公司 | Golden and silvery coated technological process on outer surface of ceramic body |
| CN104602375A (en) * | 2014-12-17 | 2015-05-06 | 内蒙古坤瑞玻璃工贸有限公司 | Thermal sensitive ceramic electrically heated glass and preparation method thereof |
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| CN1137503A (en) * | 1995-06-07 | 1996-12-11 | 中国科学院金属腐蚀与防护研究所 | High-toughness long-life oxide ceramic heat insulating coating |
| DE10303897A1 (en) * | 2003-01-30 | 2004-08-12 | Itn-Nanovation Gmbh | Multi-layer ceramic composite |
| CN1179922C (en) * | 2003-06-04 | 2004-12-15 | 佛山市兴龙陶瓷有限公司 | Method for producing golden ceramic products |
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| CN101337832B (en) * | 2008-08-14 | 2011-06-22 | 郑州鸿宾木艺有限公司 | Golden and silvery coated technological process on outer surface of ceramic body |
| CN107615888B (en) * | 2014-12-05 | 2022-01-04 | 北美Agc平板玻璃公司 | Plasma source utilizing macro-particle reduction coating and method of using plasma source for deposition of thin film coatings and surface modification |
| CN107615888A (en) * | 2014-12-05 | 2018-01-19 | 北美Agc平板玻璃公司 | The method for reducing the plasma source of coating using grand particle and plasma source being used for depositing thin film coatings and surface modification |
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| CN104602375A (en) * | 2014-12-17 | 2015-05-06 | 内蒙古坤瑞玻璃工贸有限公司 | Thermal sensitive ceramic electrically heated glass and preparation method thereof |
| CN104895461A (en) * | 2015-05-06 | 2015-09-09 | 内蒙古坤瑞玻璃工贸有限公司 | Efficient energy-saving intelligent electric heating hollow glass and preparation method thereof |
| CN105175010B (en) * | 2015-09-14 | 2017-10-17 | 电子科技大学 | A kind of method that sol-gal process prepares rutile titanium dioxide nano thin-film |
| CN106191775A (en) * | 2015-09-18 | 2016-12-07 | 北京大学深圳研究生院 | A kind of transparent conductive film and its preparation method and application |
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| CN105839081B (en) * | 2016-04-07 | 2019-06-04 | 广东工业大学 | A kind of preparation method of heat loss through radiation film |
| CN106245007A (en) * | 2016-08-31 | 2016-12-21 | 西安理工大学 | A kind of preparation method being orientated ito thin film |
| CN106245007B (en) * | 2016-08-31 | 2019-01-11 | 西安理工大学 | A kind of preparation method being orientated ito thin film |
| CN109163334A (en) * | 2018-08-22 | 2019-01-08 | 西安空天能源动力智能制造研究院有限公司 | A kind of refractory brick and preparation method thereof with anti-corrosion heat-reflective coating |
| CN109524497B (en) * | 2018-11-07 | 2020-10-27 | 西安交通大学 | Transparent ultrafast response self-powered ultraviolet detector and preparation method thereof |
| CN109524497A (en) * | 2018-11-07 | 2019-03-26 | 西安交通大学 | A kind of transparent super fast response self energizing ultraviolet detector and preparation method thereof |
| CN113716976A (en) * | 2020-05-25 | 2021-11-30 | 重庆鑫景特种玻璃有限公司 | Antibacterial ceramic and preparation method thereof |
| CN114272936A (en) * | 2021-12-28 | 2022-04-05 | 中国科学院宁波材料技术与工程研究所 | Multi-element metal oxide film and preparation method and application thereof |
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