CN107200580B - A kind of optical nano ceramic insulation glass and preparation method thereof enhancing visible light-transmissive - Google Patents

A kind of optical nano ceramic insulation glass and preparation method thereof enhancing visible light-transmissive Download PDF

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CN107200580B
CN107200580B CN201710478161.5A CN201710478161A CN107200580B CN 107200580 B CN107200580 B CN 107200580B CN 201710478161 A CN201710478161 A CN 201710478161A CN 107200580 B CN107200580 B CN 107200580B
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nano
layer
tio
solution
glass
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CN107200580A (en
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崔明培
余力
韩金保
龙甫强
邝耀庭
梁文平
林改
苏龙庆
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FOSHAN CITY JUSHITAI POWDER METALLURGY Co Ltd
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FOSHAN CITY JUSHITAI POWDER METALLURGY Co Ltd
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Abstract

The present invention relates to functional glass technical field, specially a kind of optical nano ceramic insulation glass and preparation method thereof for enhancing visible light-transmissive.Consistency >=98% of the nano ceramics target prepared by the method for the invention, purity >=99.99%.Using the nano ceramics target of the method for the present invention preparation on heat insulating function glass, and the first TiO is sequentially formed on the glass substrate2Layer, by XmZnCs0.3WO3The nano ceramics film layer and the 2nd TiO of composition2Layer, in nano ceramics film layer, the first TiO2Layer and the 2nd TiO2Prepared nano ceramics heat-protecting glass is set to be provided simultaneously with the performance of selective absorbing and selective reflecting to solar spectrum under the collective effect of layer, it again can good absorption and reflection ultraviolet and infrared ray while guaranteeing visible light high permeability, and structure is simple, not metal-containing layer, the production cost of heat insulating function glass can be reduced, industrial production is suitble to.

Description

A kind of optical nano ceramic insulation glass and preparation method thereof enhancing visible light-transmissive
Technical field
The present invention relates to functional glass technical field more particularly to it is a kind of enhance visible light-transmissive optical nano ceramics every Hot glass and preparation method thereof.
Background technique
As developing country, the storage level that China is faced with the energy is insufficient, the not high Pressure on Energy of utilization rate.Door and window Glass energy consumption accounts for the 50% of building energy consumption, and energy-saving glass can enhance the heat-proof quality of door glass, is reduced to cold and hot in equalization chamber Environment and bring energy consumption, therefore produce the better glass of thermal insulation and reducing energy consumption, it is played more in terms of promoting building energy conservation Carry out more important role.The high heat-proof quality of energy-saving glass is mainly reflected in the infrared ray and ultraviolet in barrier solar radiation at present On linear energy.The method of magnetron sputtering is industrially mostly used to be attached to various functional materials preparation film forming on glass or directly will be each Kind functional material sputtering uses on the glass substrate.Chinese patent CN103342022A is disclosed ZnO through magnetron sputtering method Or ZnSnOx, silver sputters on glass formation MULTILAYER COMPOSITE layer, be made the glass of fire prevention and Low emissivity, the transmitting of this glass heat less and It can block sunlight to a certain extent.But glass disclosed in the research is in terms of reducing heat transmitting and stop portions sunlight It plays a role, to stopping sunlight irradiation to bring the ability of heat limited, room temperature can not be effectively reduced, it is negative to reduce air-conditioning Lotus is to reach energy-efficient effect.Chinese patent CN103587167A discloses a kind of visible light transmission increasing low emissivity glass, this glass The outer layer of glass posts TiO2And MgF2The anti-reflection film of composition, internal layer post Ag system low-radiation film, such glass to visible light have compared with High transmissivity, to infrared and far infrared reflectivity with higher.Chinese patent CN205416573U discloses one kind can heat Curved infrared block energy conservation coated glass sputters 20 layer films in glass surface by the method for vacuum magnetic-control sputtering, wherein wrapping Include the metal alloy layers such as Ag, Cu and SnO2、ZnSnOx、TiOx、ZrO2And Si3N4Equal composite layers, the glass that the method is worked it out Solar energy transmission is low, and summer use can make the substantially impervious mistake of infrared energy, and winter use can keep heating not to be lost, play Energy-efficient effect.But it is coated with the glass of metal Ag, Cu film, and it is easy to oxidize rotten after a period of use, in addition, more Layer magnetron sputtering membrane process is complicated, at high cost, is unfavorable for industrial production.
Nano ceramic material is a kind of transparent conductive oxide (TCO), mainly with the aluminium oxide of different size, zirconium oxide, Titanium oxide and silica etc. are fired through surface coating, high temperature, and chemical stability is good, have low reflective, high light transmission, it is high every The features such as hot and be widely used.Nano ceramic material is existing mostly on plastics or nanometer heat isolation paint.Chinese patent CN102643037A discloses a kind of eva film of functionalization, successively plated on film by way of coating nano yttrium oxide, Nano silica, nano aluminium oxide, nano zircite, nano calcium oxide, nano-titanium dioxide, nano zine oxide, nano oxygen Change oxides and the nano cerium doped stannum oxide antimony such as cerium and is made, the visible light transmittance height of the eva film, ultraviolet light and infrared Light shield is higher.Chinese patent CN104130725A also discloses a kind of core-shell type infrared resistant auxiliary agent and heat-insulated EVA not gummosis The preparation method of film, wherein counter infrared ray auxiliary agent is made of the stannic oxide of Doped Tungsten cerium antimony with EVA resin and organic solvent, EVA Gummosis film is not made of EVA resin, counter infrared ray auxiliary agent, coupling agent, crosslinking agent and ultraviolet absorber, and gummosis film does not significantly improve for this The rejection rate of ultraviolet and infrared ray, thickness homogeneity are high.Chinese patent CN104275889A discloses a kind of high-performance and receives Rice compound heat-insulation film, the manufacturing process of this thermal isolation film are to form sputtering layer by sputtering first on pet layer, are then coated with one layer Tungstic acid adiabatic gum, compound one layer of pet layer, is coated one layer of installation being made of polyacrylate resin and ultraviolet absorber Layer, finally for by surface-treated laminated polyester film.This film has excellent visible light transmittance and infrared and ultraviolet resistance Every rate, and there is good mechanical performance, scratch resistant performance and high and low temperature resistance.Chinese patent CN105778830A is disclosed A kind of preparation method of the heat-insulated PVB film of spectral selectivity nano, this patent by near-infrared long wave obstruct nano material dispersion liquid, Near-infrared shortwave nano dispersion fluid and near-infrared reflection nano dispersion fluid are mixed with PVB, so that film is in visible light high transmittance While high, and can good absorption and reflection near infrared ray.Near-infrared length wave resistance is every nano material dispersion liquid by dividing LaB is added in powder6、ScB6Deng be made, near-infrared long wave barrier by wetting dispersing agent and defoaming agent add ITO, ATO, The metal oxides such as AZO and Ce-ATO are made.EVA disclosed in the above research, PET, PVB are organic high molecular polymer, It is chronically exposed to easy to aging in air, and has the energy-absorbings group such as-C-O-, C=O ,-OH in polymer, easily cause a nanometer material The thermal contraction of material.
Summary of the invention
The present invention needs to be further increased for existing energy-saving glass energy-saving effect, and the problems such as easy aging, provides A kind of number of plies is less, it is non-aging, have good spectral selection to sunlight while can be improved visible light transmittance The preparation method of the optical nano ceramic insulation glass and this kind of optical nano ceramic insulation glass that absorb and reflect.
To achieve the above object, the present invention uses following technical scheme.
A kind of optical nano ceramic insulation glass enhancing visible light-transmissive, including glass baseplate, in the glass baseplate On be successively arranged the first TiO2Layer, nano ceramics film layer and the 2nd TiO2Layer；The nano ceramics film layer is by XmZnCs0.33WO3Structure At；Wherein, X is Ce or Y or Er or Yb and Gd, and Z is Sn or Sb or Bi, m 0.001-0.1, n 0.001-0.1.
Preferably, the first TiO2Layer is rutile type nano TiO2Layer.It is furthermore preferred that the first TiO2The thickness of layer Degree is 15-50nm.
Preferably, the 2nd TiO2Layer is anatase type nano TiO2Layer.It is furthermore preferred that the 2nd TiO2The thickness of layer Degree is 25-65nm.
Preferably, the nano ceramics film layer with a thickness of 100-300nm.
The preparation method of the optical nano ceramic insulation glass of the above enhancing visible light-transmissive, comprising the following steps:
S1 prepares precursor powder: solution B, solution C and colloidal sol D being uniformly mixed, solution E is obtained；Then by solution E with it is transparent Sol A is uniformly mixed, and colloidal sol F is made；Then make colloidal sol F gelation, and after washed and drying process, obtain precursor powder.
Preferably, solution E is added drop-wise to dropwise in vitreosol A, and return stirring 3-5 hours at 70-80 DEG C, is formed Colloidal sol F；Colloidal sol F is placed in 70-120 DEG C of vacuum environment, its gelation is made, simultaneously centrifugal treating is washed out, gel is set It is freeze-dried 10-24h in -40-20 DEG C of vacuum environment, obtains precursor powder.
The vitreosol A is the vitreosol of tungsten compound；The solution B is the solution of cesium compound；The solution C For the solution containing Sn or Sb or the compound of Bi；The colloidal sol D is the transparent molten of the compound containing Ce or Y or Er or Yb or Gd Glue.The ratio between element X contained in the vitreosol A, solution B, solution C and colloidal sol D, amount of substance of element Z, Cs and W are 0.001-0.1:0.001-0.1:0.33:1。
Preferably, the tungsten compound is tungsten hexachloride, and the cesium compound is cesium chloride.
Preferably, the vitreosol A is dissolved in dehydrated alcohol by tungsten compound is made into clear solution, and clear solution exists It is formed within return stirring 2-4 hours at 70-80 DEG C.
Preferably, the solution B is dissolved in deionized water by cesium compound, stirs evenly to be formed.
Preferably, the solution C is dissolved in deionized water for the chloride containing Sn or Sb or Bi and being formed.
Preferably, the colloidal sol D is dissolved in dehydrated alcohol for the chloride containing Ce or Y or Er or Yb or Gd, and in 70-80 It is formed within return stirring 1 hour at DEG C.
S2 prepares nano-ceramic powder: nano-ceramic powder is made after high temperature sintering is handled in precursor powder.
Preferably, precursor powder is placed in high temperature furnace, while is passed through hydrogen and nitrogen/inert gas, nitrogen/indifferent gas Body and hydrogen flowing quantity ratio are 3-10:1, and temperature is risen to 350-650 DEG C with the heating rate of 1-3 DEG C/min, keeps the temperature 2-3h；Then Stop heating, is ground after cooling down, obtains nano-ceramic powder.
S3 prepares nano ceramics target: nano-ceramic powder being fitted into mold, nano-ceramic powder and mold are placed in very Reciprocal of duty cycle is 6.0 × 10-3In the environment of Pa, nano-ceramic powder is 10-30Mpa, the condition that temperature is 500-1000 DEG C in pressure Lower heat-insulation pressure keeping 1-3h；Obtain nano ceramics target.
Preferably, consistency >=98% of the nano ceramics target, purity >=99.99%.
Preferably, first apply the pressure of 5-15Mpa to the nano-ceramic powder in mold, then vacuumize, vacuum degree 10-2-10-3Pa, and heating while vacuumizing, heating rate are 1-20 DEG C/min, heat preservation when temperature rises to 100-300 DEG C 10-40min；Then the nano-ceramic powder in mold is pressurized and heating, pressure rises to 15-30Mpa, temperature rises to 500- 1000℃；It is cooling after heat preservation 1-3h, obtain nano ceramics target.
Preferably, heat resistant spacer layer is equipped between the nano-ceramic powder and mold.It is furthermore preferred that the separation layer is The boron nitride of polyvinyl alcohol dispersion.
S4 makes functional layer: respectively with TiO2It is magnetic control spattering target with nano ceramics target, on the glass substrate successively Plate the first TiO2Layer, nano ceramics film layer and the 2nd TiO2Optical nano ceramic insulation glass is made in layer.
Preferably, in vacuum degree < 2.0 × 10-3In the environment of Pa, it is passed through argon gas and oxygen, the stream of the argon gas and oxygen Then amount carries out magnetron sputtering plating than being 2-8:1 with the power of 50-200W.
Preferably, with rutile type nano TiO2Form the first TiO on the glass substrate for magnetic control spattering target2Layer, it is described First TiO2Layer is rutile type nano TiO2Layer.
Preferably, with anatase type nano TiO2Form the 2nd TiO on the glass substrate for magnetic control spattering target2Layer, it is described 2nd TiO2Layer is anatase type nano TiO2Layer.
Compared with prior art, the beneficial effects of the present invention are: the present invention passes through suitable vitreosol A, solution B, molten Liquid C and colloidal sol D, which prepares the nano ceramics target to be formed, has the characteristics that stability is good, not oxidizable and aging, is applied to heat-insulated It can solve the problems, such as that there are easy to aging for existing heat insulating function glass on functional glass.Pass through each technique ginseng in control preparation process Number, the material that can effectively reduce nano ceramics target in preparation process are reduced the problem of precipitating metal simple substance, and avoid institute There is stomata and causes consistency not high enough in nano ceramics target processed.The cause of the nano ceramics target prepared by the method for the invention Density >=98%, purity >=99.99%.Using the nano ceramics target of the method for the present invention preparation on heat insulating function glass, and The first TiO is sequentially formed on the glass substrate2Layer, by XmZnCs0.3WO3The nano ceramics film layer and the 2nd TiO of composition2Layer, is receiving Rice ceramic film, the first TiO2Layer and the 2nd TiO2Make prepared nano ceramics heat-protecting glass to the sun under the collective effect of layer Spectrum is provided simultaneously with the performance of selective absorbing and selective reflecting, again can good absorption while guaranteeing visible light high permeability With reflection ultraviolet and infrared ray, and structure is simple, and metal-containing layer, can not reduce the production cost of heat insulating function glass, is suitble to Industrial production.
Detailed description of the invention
Fig. 1 is the nano ceramics film layer SEM cross-sectional view of embodiment 3；
Fig. 2 is UV-VL-NIR (300-2500nm) transmitted spectrum of optical nano ceramic insulation glass prepared by embodiment 3 Figure and reflectance spectrum figure；
Fig. 3 is the XRD diagram of the nano-ceramic powder in embodiment 4；
Fig. 4 is the XRD diagram of the optical nano ceramic insulation glass BL18 in embodiment 18.
Specific embodiment
In order to more fully understand technology contents of the invention, combined with specific embodiments below to technical solution of the present invention It is described further and illustrates.
Embodiment 1
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 2 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 1.14g antimony trichloride, which is dissolved in deionized water, forms solution C, 1.23g Cerous chloride is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D stirring are mixed Uniform solution E is closed, solution E is slowly dropped in Sol A, 76 DEG C form homogeneous and transparent colloidal sol in return stirring 4 hours.It will Colloidal sol is placed in 90 DEG C of vacuum environments, and after gelation, by washing, alcohol is washed three times, then is placed in -40 DEG C of vacuum environments and is freezed Drying for 24 hours, obtains Ce0.01Sb0.01Cs0.33WO3Precursor powder.
Again by Ce0.01Sb0.01Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 500 DEG C, and heating rate is 1 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2.5h in the range of 3-10:1 after heating, wait drop Dispersion is ground up to Ce after temperature is cooling0.01Sb0.01Cs0.33WO3Nano-ceramic powder.
By Ce obtained0.01Sb0.01Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 5MPa to powder to nano-ceramic powder Precompressed is carried out, then is vacuumized, vacuum degree is 3.0 × 10-3Pa is started to warm up while vacuumizing, and heating rate is 6 DEG C/min, 20min is kept the temperature when being warming up to 300 DEG C, continues to heat up after heat preservation and pressurize, and heating rate is 6 DEG C/min, and pressure is upgraded to 20MPa stops heating up when temperature is 550 DEG C and carries out heat-insulation pressure keeping, 2.5h maintained under this process conditions, then annealing obtains height The Ce of consistency0.01Sb0.01Cs0.33WO3Nano ceramics target is denoted as BC1, consistency 98.5%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1.5 × 10-3Pa, then is passed through argon gas and oxygen, argon gas Flow-rate ratio with oxygen is 2:1, then opens magnetron sputtering power supply, regulation power 80W successively plates 15nm rutile type nano two Titanium oxide layer, 150nm ternary doping nano ceramics film layer and 25nm anatase-type nanometer titanium dioxide layer.
Embodiment 2
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 2 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 5.7g antimony trichloride, which is dissolved in deionized water, forms solution C, 6.15g tri- Cerium chloride is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred It is uniform to obtain solution E, solution E is slowly dropped in Sol A, 76 DEG C form homogeneous and transparent colloidal sol in return stirring 4 hours.It will be molten Glue is placed in 90 DEG C of vacuum environments, and after gelation, by washing, alcohol is washed three times, then is placed in freeze in -20 DEG C of vacuum environments and be done It is dry for 24 hours, obtain Ce0.05Sb0.05Cs0.33WO3Precursor powder.
Again by Ce0.05Sb0.05Cs0.33WO3Be placed in high temperature furnace, sintering temperature be 450 DEG C, heating rate be 1.5 DEG C/ Min, while it being passed through hydrogen and nitrogen, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, to Dispersion is ground up to Ce after cooling down0.05Sb0.05Cs0.33WO3Nano-ceramic powder.
By Ce obtained0.05Sb0.05Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 10MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, and vacuum degree is 8.0 × 10-3Pa is started to warm up while vacuumizing, heating rate be 10 DEG C/ Min keeps the temperature 30min, continues to heat up after heat preservation and pressurize when being warming up to 250 DEG C, heating rate is 10 DEG C/min, pressure It is upgraded to 20MPa, stop heating up when temperature is 750 DEG C and carries out heat-insulation pressure keeping, 1h is maintained under this process conditions, then annealing obtains The Ce of high-compactness0.05Sb0.05Cs0.33WO3Nano ceramics target, is denoted as BC2, consistency 99.5%, and purity is 99.995%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then be passed through argon gas and oxygen, argon gas and The flow-rate ratio of oxygen is 6:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 35nm rutile type nano two Titanium oxide layer, 250nm ternary doping nano ceramics film layer and 50nm anatase-type nanometer titanium dioxide layer.
Embodiment 3
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 2 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 6.3g bismuth trichloride, which is dissolved in deionized water, forms solution C, 2.73g chlorine Change erbium to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred It is even to obtain solution E, solution E is slowly dropped in Sol A, 76 DEG C form homogeneous and transparent colloidal sol in return stirring 4 hours.By colloidal sol It is placed in 80 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in freeze in -30 DEG C of vacuum environments and be done Dry 20h, obtains Er0.02Bi0.04Cs0.33WO3Precursor powder.
Again by Er0.02Bi0.04Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 550 DEG C, and heating rate is 3 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Er after cooling0.02Bi0.04Cs0.33WO3Nano-ceramic powder.
By Er obtained0.02Bi0.04Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 15MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-2Pa is started to warm up while vacuumizing, and heating rate is 15 DEG C/min, is risen 30min is kept the temperature when temperature is to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 25MPa stops heating up when temperature is 800 DEG C and carries out heat-insulation pressure keeping, 1.5h maintained under this process conditions, then annealing obtains height The Er of consistency0.02Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC3, consistency 99.8%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then be passed through argon gas and oxygen, argon gas and The flow-rate ratio of oxygen is 8:1, then opens magnetron sputtering power supply, regulation power 50W successively plates 30nm rutile type nano dioxy Change titanium layer, 200nm ternary doping nano ceramics film layer and 40nm anatase-type nanometer titanium dioxide layer.Nano ceramics film layer SEM Cross section is as shown in Figure 1；UV-VL-NIR (300-2500nm) transmitted light spectrogram and reflected light of optical nano ceramic insulation glass Spectrogram is as shown in Figure 2.
Embodiment 4
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 0.23g antimony trichloride, which is dissolved in deionized water, forms solution C, 0.70g Ytterbium chloride is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred It is uniform to obtain solution E, solution E is slowly dropped in Sol A, 76 DEG C form homogeneous and transparent colloidal sol in return stirring 3 hours.It will be molten Glue is placed in 90 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -40 DEG C of vacuum environments and is freezed Dry 15h, obtains Yb0.005Sb0.002Cs0.33WO3Precursor powder.
Again by Yb0.005Sb0.002Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 450 DEG C, and heating rate is 3 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Yb after cooling0.005Sb0.002Cs0.33WO3Nano-ceramic powder, the XRD diagram of nano-ceramic powder such as Fig. 3 institute Show.
By Yb obtained0.005Sb0.002Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 15MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 10 DEG C/min, is risen 30min is kept the temperature when temperature is to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 25MPa stops heating up when temperature is 1000 DEG C and carries out heat-insulation pressure keeping, 1h maintained under this process conditions, then annealing obtains height The Yb of consistency0.005Sb0.002Cs0.33WO3Nano ceramics target is denoted as BC4, consistency 99.9%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then be passed through argon gas and oxygen, argon gas and The flow-rate ratio of oxygen is 6:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 50nm rutile type nano two Titanium oxide layer, 300nm ternary doping nano ceramics film layer and 65nm anatase-type nanometer titanium dioxide layer.
Embodiment 5
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 5.70g anhydrous stannous chloride, which is dissolved in deionized water, forms solution C, 3.95g gadolinium chloride is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred Mix uniformly mixed solution E, solution E be slowly dropped in Sol A, 76 DEG C formed within return stirring 5 hours it is homogeneous and transparent molten Glue.Colloidal sol is placed in 80 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -40 DEG C of vacuum environments Middle freeze-drying 15h, obtains Gd0.03Sn0.06Cs0.33WO3Precursor powder.
Again by Gd0.03Sn0.06Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 500 DEG C, and heating rate is 3 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Gd after cooling0.03Sn0.06Cs0.33WO3Nano-ceramic powder.
By Gd obtained0.03Sn0.06Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 15MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 10 DEG C/min, is risen 30min is kept the temperature when temperature is to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 25MPa stops heating up when temperature is 800 DEG C and carries out heat-insulation pressure keeping, 1h maintained under this process conditions, then annealing obtains high cause The Gd of density0.03Sn0.06Cs0.33WO3Nano ceramics target is denoted as BC5, consistency 99.9%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then be passed through argon gas and oxygen, argon gas and The flow-rate ratio of oxygen is 4:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 35nm rutile type nano two Titanium oxide layer, 250nm ternary doping nano ceramics film layer and 45nm anatase-type nanometer titanium dioxide layer.
Embodiment 6
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and the anhydrous bismuth chloride of 15.76g, which is dissolved in deionized water, forms solution C, 0.10g yttrium chloride is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred Mix uniformly mixed solution E, solution E be slowly dropped in Sol A, 76 DEG C formed within return stirring 4 hours it is homogeneous and transparent molten Glue.Colloidal sol is placed in 90 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -30 DEG C of vacuum environments Middle freeze-drying for 24 hours, obtains Y0.001Bi0.1Cs0.33WO3Precursor powder.
Again by Y0.001Bi0.1Cs0.33WO3It is placed in high temperature furnace, sintering temperature is 500 DEG C, and heating rate is 3 DEG C/min, together When be passed through hydrogen and nitrogen, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, cold wait cool down But dispersion is ground up to Y afterwards0.001Bi0.1Cs0.33WO3Nano-ceramic powder.
By Y obtained0.001Bi0.1Cs0.33WO3Nano-ceramic powder is added in graphite jig, and graphite jig connects with powder Contacting surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 10MPa to powder to nano-ceramic powder Precompressed is carried out, then is vacuumized, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 10 DEG C/min, heating 30min is kept the temperature when to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 20MPa stops heating up when temperature is 700 DEG C and carries out heat-insulation pressure keeping, 1h maintained under this process conditions, then annealing obtains high cause The Gd of density0.03Sn0.06Cs0.33WO3Nano ceramics target is denoted as BC6, consistency 99.93%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then be passed through argon gas and oxygen, argon gas and The flow-rate ratio of oxygen is 6:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 50nm rutile type nano two Titanium oxide layer, 300nm ternary doping nano ceramics film layer and 50nm anatase-type nanometer titanium dioxide layer.
Embodiment 7
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and the anhydrous bismuth chloride of 6.30g, which is dissolved in deionized water, forms solution C, 1.23g anhydrous cerium chloride is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D is uniformly mixed to obtain solution E, and solution E is slowly dropped in Sol A, and 76 DEG C of formation in return stirring 4 hours are homogeneous and transparent Colloidal sol.Colloidal sol is placed in 90 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -30 DEG C of vacuum rings It is freeze-dried in border for 24 hours, obtains Ce0.01Bi0.04Cs0.33WO3Precursor powder.
Again by Ce0.01Bi0.04Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 400 DEG C, and heating rate is 2 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Ce after cooling0.01Bi0.04Cs0.33WO3Nano-ceramic powder.
By Ce obtained0.01Bi0.04Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 10MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 8 DEG C/min, heating 40min is kept the temperature when to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 20MPa stops heating up when temperature is 600 DEG C and carries out heat-insulation pressure keeping, 1h maintained under this process conditions, then annealing obtains high cause The Ce of density0.01Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC7, consistency 99.9%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then be passed through argon gas and oxygen, argon gas and The flow-rate ratio of oxygen is 6:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 40nm rutile type nano two Titanium oxide layer, 200nm ternary doping nano ceramics film layer and 60nm anatase-type nanometer titanium dioxide layer.
Embodiment 8
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and the anhydrous antimony chloride of 3.42g, which is dissolved in deionized water, forms solution C, The anhydrous yttrium chloride of 1.95g is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D is uniformly mixed to obtain solution E, and solution E is slowly dropped in Sol A, and 76 DEG C of formation in return stirring 4 hours are homogeneous and transparent Colloidal sol.Colloidal sol is placed in 85 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -40 DEG C of vacuum rings It is freeze-dried in border for 24 hours, obtains Y0.02Sb0.03Cs0.33WO3Precursor powder.
Again by Y0.02Sb0.03Cs0.33WO3It is placed in high temperature furnace, sintering temperature is 450 DEG C, and heating rate is 3 DEG C/min, together When be passed through hydrogen and nitrogen, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, cold wait cool down But dispersion is ground up to Y afterwards0.02Sb0.03Cs0.33WO3Nano-ceramic powder.
By Y obtained0.02Sb0.03Cs0.33WO3Nano-ceramic powder is added in graphite jig, and graphite jig connects with powder Contacting surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 12MPa to powder to nano-ceramic powder Precompressed is carried out, then is vacuumized, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 8 DEG C/min, is warming up to 30min is kept the temperature at 300 DEG C, is continued to heat up after heat preservation and be pressurizeed, heating rate is 10 DEG C/min, and pressure is upgraded to 20MPa, Stop heating up when temperature is 600 DEG C and carry out heat-insulation pressure keeping, 1h is maintained under this process conditions, then annealing obtains high-compactness Y0.02Sb0.03Cs0.33WO3Nano ceramics target is denoted as BC8, consistency 99.9%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL1 is denoted as.Specific as follows: the glass baseplate that will be cleaned up is dry to be dried with nitrogen, It is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then be passed through argon gas and oxygen, argon gas and The flow-rate ratio of oxygen is 6:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 50nm rutile type nano two Titanium oxide layer, 250nm ternary doping nano ceramics film layer and 50nm anatase-type nanometer titanium dioxide layer.
Embodiment 9
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that erbium chloride is different with the dosage of bismuth trichloride in the preparation step of precursor powder, tool Body is as follows: 0.136g erbium chloride and 0.315g bismuth trichloride, and precursor powder obtained is Er0.001Bi0.002Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Er0.001Bi0.002Cs0.33WO3, it is denoted as BC9, consistency 98.2%, purity 99.99%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL9。
Embodiment 10
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that erbium chloride is different with the dosage of bismuth trichloride in the preparation step of precursor powder, tool Body is as follows: 0.136g erbium chloride and 0.158g bismuth trichloride, and precursor powder obtained is Er0.001Bi0.001Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Er0.001Bi0.001Cs0.33WO3, it is denoted as BC10, consistency 98.8%, purity 99.99%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL10。
Embodiment 11
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that erbium chloride is different with the dosage of bismuth trichloride in the preparation step of precursor powder, tool Body is as follows: 13.65g erbium chloride and 14.18g bismuth trichloride, and precursor powder obtained is Er0.1Bi0.09Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder
Er0.1Bi0.09Cs0.33WO3, it is denoted as BC11, consistency 98.6%, purity 99.99%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL11。
Embodiment 12
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that erbium chloride is different with the dosage of bismuth trichloride in the preparation step of precursor powder, tool Body is as follows: 13.65g erbium chloride and 15.75g bismuth trichloride, and precursor powder obtained is Er0.1Bi0.1Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Er0.1Bi0.1Cs0.33WO3, it is denoted as BC12, consistency 98.1%, purity 99.99%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL12。
Embodiment 13
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 70 DEG C of return stirrings, 2 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 6.3g bismuth trichloride, which is dissolved in deionized water, forms solution C, 2.73g chlorine Change erbium to be dissolved in dehydrated alcohol, 70 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred It is even to obtain solution E, solution E is slowly dropped in Sol A, 70 DEG C form homogeneous and transparent colloidal sol in return stirring 4 hours.By colloidal sol It is placed in 70 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -30 DEG C of vacuum environments and is freeze-dried 10h obtains Er0.02Bi0.04Cs0.33WO3Precursor powder.
Again by Er0.02Bi0.04Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 350 DEG C, and heating rate is 3 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 3h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Er after cooling0.02Bi0.04Cs0.33WO3Nano-ceramic powder.
By Er obtained0.02Bi0.04Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 15MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-2Pa is started to warm up while vacuumizing, and heating rate is 20 DEG C/min, is risen 40min is kept the temperature when temperature is to 100 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 30MPa stops heating up when temperature is 500 DEG C and carries out heat-insulation pressure keeping, 3h maintained under this process conditions, then annealing obtains high cause The Er of density0.02Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC13, consistency 99.8%, purity 99.99%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL13。
Embodiment 14
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 80 DEG C of return stirrings, 2 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 6.3g bismuth trichloride, which is dissolved in deionized water, forms solution C, 2.73g chlorine Change erbium to be dissolved in dehydrated alcohol, 80 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred It is even to obtain solution E, solution E is slowly dropped in Sol A, 80 DEG C form homogeneous and transparent colloidal sol in return stirring 4 hours.By colloidal sol It is placed in 120 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in freeze in -30 DEG C of vacuum environments and be done Dry 20h, obtains Er0.02Bi0.04Cs0.33WO3Precursor powder.
Again by Er0.02Bi0.04Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 650 DEG C, and heating rate is 3 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Er after cooling0.02Bi0.04Cs0.33WO3Nano-ceramic powder.
By Er obtained0.02Bi0.04Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 15MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-2Pa is started to warm up while vacuumizing, and heating rate is 1 DEG C/min, heating 10min is kept the temperature when to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 15MPa stops heating up when temperature is 1000 DEG C and carries out heat-insulation pressure keeping, 1.5h maintained under this process conditions, then annealing obtains The Er of high-compactness0.02Bi0.04Cs0.33WO3Nano ceramics target, is denoted as BC14, consistency 98.3%, and purity is 99.99%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL14。
Embodiment 15
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 2 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 1.14g antimony trichloride, which is dissolved in deionized water, forms solution C, solution B, Solution C is uniformly mixed to obtain solution D, solution D is slowly dropped in Sol A, and 76 DEG C of formation in return stirring 4 hours are uniform Transparent colloidal sol.Colloidal sol is placed in 90 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -40 DEG C It is freeze-dried in vacuum environment for 24 hours, obtains Sb0.01Cs0.33WO3Precursor powder.
Again by Sb0.01Cs0.33WO3It is placed in high temperature furnace, sintering temperature is 500 DEG C, and heating rate is 1 DEG C/min, is led to simultaneously Enter hydrogen and nitrogen, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2.5h in the range of 3-10:1 after heating, to cooling down Dispersion is ground up to Sb afterwards0.01Cs0.33WO3Nano-ceramic powder.
By Sb obtained0.01Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder contact surface It is isolated with the boron nitride using polyvinyl alcohol dispersion, the pressure for first applying 5MPa to nano-ceramic powder carries out in advance powder Pressure, then vacuumize, vacuum degree is 3.0 × 10-3Pa is started to warm up while vacuumizing, and heating rate is 6 DEG C/min, is warming up to 20min is kept the temperature at 300 DEG C, is continued to heat up after heat preservation and be pressurizeed, heating rate is 6 DEG C/min, and pressure is upgraded to 20MPa, Stop heating up when temperature is 550 DEG C and carry out heat-insulation pressure keeping, 2.5h is maintained under this process conditions, then annealing obtains Sb0.01Cs0.33WO3Nano ceramics target is denoted as BC15, consistency 98.5%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL15 is denoted as.Specific as follows: the nitrogen for the glass baseplate drying that will be cleaned up is blown It is dry, it is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1.5 × 10-3Pa, then it is passed through argon gas and oxygen, argon The flow-rate ratio of gas and oxygen is 2:1, then opens magnetron sputtering power supply, regulation power 80W successively plates 15nm rutile type nano Titanium dioxide layer, 150nm ternary doping nano ceramics film layer and 25nm anatase-type nanometer titanium dioxide layer.
Embodiment 16
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and the anhydrous antimony chloride of 3.42g, which is dissolved in deionized water, forms solution C, The anhydrous yttrium chloride of 1.95g is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D is uniformly mixed to obtain solution E, and solution E is slowly dropped in Sol A, and 76 DEG C of formation in return stirring 4 hours are homogeneous and transparent Colloidal sol.Colloidal sol is placed in 85 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in -40 DEG C of vacuum rings It is freeze-dried in border for 24 hours, obtains Y0.02Sb0.03Cs0.33WO3Precursor powder.
Again by Y0.02Sb0.03Cs0.33WO3It is placed in high temperature furnace, sintering temperature is 450 DEG C, and heating rate is 3 DEG C/min, together When be passed through hydrogen and nitrogen, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, cold wait cool down But dispersion is ground up to Y afterwards0.02Sb0.03Cs0.33WO3Nano-ceramic powder.
By Y obtained0.02Sb0.03Cs0.33WO3Nano-ceramic powder is added in graphite jig, and graphite jig connects with powder Contacting surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 12MPa to powder to nano-ceramic powder Precompressed is carried out, then is vacuumized, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 8 DEG C/min, is warming up to 30min is kept the temperature at 300 DEG C, is continued to heat up after heat preservation and be pressurizeed, heating rate is 10 DEG C/min, and pressure is upgraded to 20MPa, Stop heating up when temperature is 600 DEG C and carry out heat-insulation pressure keeping, 1h is maintained under this process conditions, then annealing obtains Y0.02Sb0.03Cs0.33WO3Nano ceramics target is denoted as BC16, consistency 99.9%, purity 99.99%.
Using nano ceramics target as magnetic control spattering target, plating nano ceramics film layer on the glass substrate, (ternary doping is received Rice ceramic film), optical nano ceramic insulation glass is made, is denoted as BL16.It is specific as follows: the glass baseplate cleaned up is used Dry is dried with nitrogen, and is then placed in coating chamber, shuts coating chamber and starts to vacuumize, and vacuum degree is 1 × 10-3Pa, then it is passed through argon The flow-rate ratio of gas and oxygen, argon gas and oxygen is 6:1, then opens magnetron sputtering power supply, regulation power 100W plates 250nm tri- First dopen Nano ceramic film.
Embodiment 17
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 3.95g gadolinium chloride is dissolved in dehydrated alcohol, 76 DEG C return stirring 1 hour Form vitreosol C.Solution B, colloidal sol C are uniformly mixed to obtain solution D, solution D are slowly dropped in Sol A, and 76 DEG C are returned Stream stirring forms homogeneous and transparent colloidal sol in 5 hours.Colloidal sol is placed in 80 DEG C of vacuum environments, after gelation, by washing, Alcohol is washed three times, then is placed in -40 DEG C of vacuum environments and is freeze-dried 15h, and Gd is obtained0.03Cs0.33WO3Precursor powder.
Again by Gd0.03Cs0.33WO3It is placed in high temperature furnace, sintering temperature is 500 DEG C, and heating rate is 3 DEG C/min, is led to simultaneously Enter hydrogen and nitrogen, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, after cooling down Dispersion is ground up to Gd0.03Cs0.33WO3Nano-ceramic powder.
By Gd obtained0.03Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder contact surface It is isolated with the boron nitride using polyvinyl alcohol dispersion, the pressure for first applying 15MPa to nano-ceramic powder carries out powder Precompressed, then vacuumize, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 10 DEG C/min, is warming up to 300 DEG C when keep the temperature 30min, continue to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 25MPa, temperature Stop heating up when degree is 800 DEG C and carry out heat-insulation pressure keeping, 1h is maintained under this process conditions, then annealing obtains Gd0.03Cs0.33WO3 Nano ceramics target is denoted as BC17, consistency 99.9%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL17 is denoted as.Specific as follows: the nitrogen for the glass baseplate drying that will be cleaned up is blown It is dry, it is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then it is passed through argon gas and oxygen, argon gas Flow-rate ratio with oxygen is 4:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 35nm rutile type nano Titanium dioxide layer, 250nm ternary doping nano ceramics film layer and 45nm anatase-type nanometer titanium dioxide layer.
Embodiment 18
It is specific as follows the present embodiment provides a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive:
It weighs 200g tungsten hexachloride to be dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 3 hours formation vitreosol A, then weighs 28 grams of cesium chlorides are dissolved in deionized water and form solution B, and 13.68g antimony trichloride, which is dissolved in deionized water, forms solution C, 20.95g ytterbium chloride is dissolved in dehydrated alcohol, 76 DEG C of return stirrings, 1 hour formation vitreosol D.Solution B, solution C, colloidal sol D are stirred Uniformly mixed solution E is mixed, solution E is slowly dropped in Sol A, 76 DEG C form non-uniform colloidal sols in return stirring 3 hours.It will Colloidal sol is placed in 90 DEG C of vacuum environments, after gelation, by washing, alcohol is washed three times, then is placed in cold in -40 DEG C of vacuum environments Dry 15h is lyophilized, obtains Yb0.15Sb0.12Cs0.33WO3Precursor powder.Again by Yb0.15Sb0.12Cs0.33WO3It is placed in high temperature furnace, is sintered Temperature is 450 DEG C, and heating rate is 3 DEG C/min, while being passed through hydrogen and nitrogen, and the flow-ratio control of nitrogen and hydrogen is in 3- In the range of 10:1,2h is kept the temperature after heating, dispersion is ground up to Yb after cooling down0.15Sb0.12Cs0.33WO3Nano-ceramic powder Body.
By Yb obtained0.15Sb0.12Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 15MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-3Pa is started to warm up while vacuumizing, and heating rate is 10 DEG C/min, is risen 30min is kept the temperature when temperature is to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 25MPa stops heating up when temperature is 1000 DEG C and carries out heat-insulation pressure keeping, 1h maintained under this process conditions, then annealing obtains Yb0.15Sb0.12Cs0.33WO3Nano ceramics target is denoted as BC18, consistency 99.9%, purity 99.99%.
Respectively with rutile type nano TiO2, nano ceramics target and anatase type nano TiO2For magnetic control spattering target, The first TiO is successively plated on glass baseplate2Layer, nano ceramics film layer (ternary doping nano ceramics film layer) and the 2nd TiO2Layer, system Optical nano ceramic insulation glass is obtained, BL18 is denoted as.Specific as follows: the nitrogen for the glass baseplate drying that will be cleaned up is blown It is dry, it is then placed in coating chamber, coating chamber is shut and starts to vacuumize, vacuum degree is 1 × 10-3Pa, then it is passed through argon gas and oxygen, argon gas Flow-rate ratio with oxygen is 6:1, then opens magnetron sputtering power supply, regulation power 100W successively plates 50nm rutile type nano Titanium dioxide layer, 300nm ternary doping nano ceramics film layer and 65nm anatase-type nanometer titanium dioxide layer.Optical nano ceramics The XRD diagram of heat-protecting glass BL18 is as shown in Figure 4.
Embodiment 19
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that erbium chloride is different with the dosage of bismuth trichloride in the preparation step of precursor powder, tool Body is as follows: 14.96g erbium chloride and 17.32g bismuth trichloride, and precursor powder obtained is Er0.11Bi0.11Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Er0.11Bi0.11Cs0.33WO3, it is denoted as BC19, consistency 98.9%, purity 99.99%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL19。
Embodiment 20
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that erbium chloride is different with the dosage of bismuth trichloride in the preparation step of precursor powder, tool Body is as follows: 14.96g erbium chloride and 18.9g bismuth trichloride, and precursor powder obtained is Er0.11Bi0.12Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Er0.11Bi0.12Cs0.33WO3, it is denoted as BC20, consistency 98.0%, purity 99.72%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL20。
Embodiment 21
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that substituting chlorination with the equal scandium chloride of the amount of substance in the preparation step of precursor powder Erbium, precursor powder obtained are Sc0.001Bi0.002Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Sc0.001Bi0.002Cs0.33WO3, it is denoted as BC21, consistency 97.9%, purity 96.21%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL21。
Embodiment 22
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that substituting chlorine with the mutually same lanthanum chloride of the amount of substance in the preparation step of precursor powder Change erbium, precursor powder obtained is La0.001Bi0.002Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder La0.001Bi0.002Cs0.33WO3, it is denoted as BC22, consistency 97.9%, purity 96.21%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL22。
Embodiment 23
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that substituting chlorination with the identical terbium chloride of the amount of substance in the preparation step of precursor powder Erbium, precursor powder obtained are Tb0.001Bi0.002Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Tb0.001Bi0.002Cs0.33WO3, it is denoted as BC23, consistency 97.2%, purity 95.95%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL23。
Embodiment 24
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that substituting chlorination with the identical samarium trichloride of the amount of substance in the preparation step of precursor powder Erbium, precursor powder obtained are Sm0.001Bi0.002Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Sm0.001Bi0.002Cs0.33WO3, it is denoted as BC24, consistency 98.0%, purity 97.94%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL24。
Embodiment 25
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that substituting trichlorine with the identical gallium chloride of the amount of substance in the preparation step of precursor powder Change bismuth, precursor powder obtained is Ga0.001Bi0.002Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Ga0.001Bi0.002Cs0.33WO3, it is denoted as BC25, consistency 98.0%, purity 99.87%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL25。
Embodiment 26
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that substituting trichlorine with the identical germanium chloride of the amount of substance in the preparation step of precursor powder Change bismuth, precursor powder obtained is Ge0.001Bi0.002Cs0.33WO3。
Nano ceramics target is made after preparation step as described in Example 3 in precursor powder Ge0.001Bi0.002Cs0.33WO3, it is denoted as BC26, consistency 97.2%, purity 99.71%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL26。
Embodiment 27
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that the step of nano-ceramic powder is made in precursor powder, specific as follows:
Again by Er0.02Bi0.04Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 700 DEG C, and heating rate is 5 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 3h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Er after cooling0.02Bi0.04Cs0.33WO3Nano-ceramic powder.
Last Er obtained0.02Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC27, consistency 96.1%, purity It is 99.65%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL27。
Embodiment 28
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that the step of nano-ceramic powder is made in precursor powder, specific as follows:
Again by Er0.02Bi0.04Cs0.33WO3It being placed in high temperature furnace, sintering temperature is 300 DEG C, and heating rate is 1 DEG C/min, It is passed through hydrogen and nitrogen simultaneously, the flow-ratio control of nitrogen and hydrogen keeps the temperature 3h in the range of 3-10:1 after heating, wait cool down Dispersion is ground up to Er after cooling0.02Bi0.04Cs0.33WO3Nano-ceramic powder.
Last Er obtained0.02Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC28, consistency 96.5%, purity It is 99.71%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL28。
Embodiment 29
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that the step of nano-ceramic powder is made in precursor powder, specific as follows:
Again by Er0.02Bi0.04Cs0.33WO3Be placed in high temperature furnace, sintering temperature be 550 DEG C, heating rate be 0.5 DEG C/ Min, while it being passed through hydrogen and nitrogen, the flow-ratio control of nitrogen and hydrogen keeps the temperature 2h in the range of 3-10:1 after heating, to Dispersion is ground up to Er after cooling down0.02Bi0.04Cs0.33WO3Nano-ceramic powder.
Last Er obtained0.02Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC29, consistency 96.8%, purity It is 99.74%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL29。
Embodiment 30
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that the step of nano ceramics target is made in nano-ceramic powder, specific as follows:
By Er obtained0.02Bi0.04Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 20MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-2Pa is started to warm up while vacuumizing, and heating rate is 25 DEG C/min, is risen 60min is kept the temperature when temperature is to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 10 DEG C/min, and pressure is upgraded to 25MPa stops heating up when temperature is 1000 DEG C and carries out heat-insulation pressure keeping, 3h maintained under this process conditions, then annealing obtains Er0.02Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC30, consistency 95.8%, purity 99.61%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL30。
Embodiment 31
The optical nano ceramic insulation glass of enhancing visible light-transmissive provided in this embodiment and preparation described in embodiment 3 Method is not substantially identical, the difference is that the step of nano ceramics target is made in nano-ceramic powder, specific as follows:
By Er obtained0.02Bi0.04Cs0.33WO3Nano-ceramic powder is added in graphite jig, graphite jig and powder Contact surface is isolated with the boron nitride using polyvinyl alcohol dispersion, first applies the pressure of 15MPa to powder to nano-ceramic powder Body carries out precompressed, then vacuumizes, vacuum degree 10-2Pa is started to warm up while vacuumizing, and heating rate is 25 DEG C/min, is risen 30min is kept the temperature when temperature is to 300 DEG C, continues to heat up after heat preservation and pressurize, heating rate is 25 DEG C/min, and pressure is upgraded to 25MPa stops heating up when temperature is 1100 DEG C and carries out heat-insulation pressure keeping, 3h maintained under this process conditions, then annealing obtains Er0.02Bi0.04Cs0.33WO3Nano ceramics target is denoted as BC31, consistency 96.3%, purity 99.76%.
Optical nano ceramic insulation glass is made after making functional layer as described in Example 3 on the glass substrate, is denoted as BL31。
Test respectively the visible transmission ratio of above-mentioned obtained heat insulating function glass BL1-BL31, ultraviolet (uv) transmission ratio, Total solar energy transmittance, shading coefficient, heat transfer coefficient, the reflectivity in 1000-2500nm wave-length coverage, to 950nm wavelength Shielding rate and shielding rate to 1400nm wavelength, test result is as follows shown in table 1.
The optical nano ceramic insulation glass of the nano ceramics target BC1-31 production of 1 Application Example 1-31 of table production The physical property of BL1-31
As seen from the data in Table 1, nano ceramics target generates the physical property of optical nano ceramic insulation glass significant It influences.When preparing nano ceramics target, the control of temperature is equal in the materials and dosage or even preparation process of nano ceramics target Meeting generates apparent influence to the property of nano ceramics target, to influence every the physical of optical nano ceramic insulation glass Energy.
It is described above that technology contents of the invention are only further illustrated with embodiment, in order to which reader is easier to understand, But embodiments of the present invention are not represented and are only limitted to this, any technology done according to the present invention extends or recreation, is sent out by this Bright protection.

Claims (10)

1. a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive, including glass baseplate, which is characterized in that described The first TiO is successively arranged on glass baseplate2Layer, nano ceramics film layer and the 2nd TiO2Layer；The nano ceramics film layer by XmZnCs0.33WO3It constitutes；
Wherein, X is Ce or Y or Er or Yb and Gd, and Z is Sn or Sb or Bi, m 0.001-0.1, n 0.001-0.1.
2. a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 1, which is characterized in that institute State the first TiO2Layer is rutile type nano TiO2Layer.
3. a kind of optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 1, which is characterized in that institute State the 2nd TiO2Layer is anatase type nano TiO2Layer.
4. a kind of preparation method of the optical nano ceramic insulation glass of the visible light-transmissive of enhancing as described in claim 1, special Sign is, comprising the following steps:
S1 prepares precursor powder: the solution B of cesium compound, solution C and colloidal sol D being uniformly mixed, solution E is obtained；Then by solution E It is uniformly mixed with vitreosol A, colloidal sol F is made；Then make colloidal sol F gelation, and after washed and drying process, obtain forerunner Powder；
The vitreosol A is the vitreosol of tungsten compound；The solution B is the solution of cesium compound；The solution C be containing The solution of the compound of Sn or Sb or Bi；The colloidal sol D is the vitreosol of the compound containing Ce or Y or Er or Yb or Gd；
The ratio between element X contained in the vitreosol A, solution B, solution C and colloidal sol D, amount of substance of element Z, Cs and W are 0.001-0.1:0.001-0.1:0.33:1；
S2 prepares nano-ceramic powder: nano-ceramic powder is made after high temperature sintering is handled in precursor powder；
S3 prepares nano ceramics target: nano-ceramic powder being fitted into mold, nano-ceramic powder and mold are placed in vacuum degree It is 6.0 × 10-3In the environment of Pa, nano-ceramic powder is 10-30MPa in pressure, and temperature is protected under conditions of being 500-1000 DEG C Warm pressure maintaining 1-3h；Obtain nano ceramics target；
S4 makes functional layer: respectively with TiO2It is magnetic control spattering target with nano ceramics target, successively plates the on the glass substrate One TiO2Layer, nano ceramics film layer and the 2nd TiO2Optical nano ceramic insulation glass is made in layer.
5. a kind of preparation method for the optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 4, It is characterized in that, in step S2, precursor powder is placed in high temperature furnace, while being passed through hydrogen and inert gas, inert gas and hydrogen Throughput ratio is 3-10:1, and temperature is risen to 350-650 DEG C with the heating rate of 1-3 DEG C/min, keeps the temperature 2-3h；Then stop adding Heat is ground after cooling down, obtains nano-ceramic powder.
6. a kind of preparation method for the optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 4, It is characterized in that, in step S1, solution E is added drop-wise to dropwise in vitreosol A, and return stirring 3-5 hours at 70-80 DEG C, Form colloidal sol F；Colloidal sol F is placed in 70-120 DEG C of vacuum environment, its gelation is made, simultaneously centrifugal treating is washed out, will coagulate Glue is placed in -40 to -20 DEG C of vacuum environment and is freeze-dried 10-24h, obtains precursor powder.
7. a kind of preparation method for the optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 4, It is characterized in that, in step S3, first applies the pressure of 5-15MPa to the nano-ceramic powder in mold, then vacuumize, vacuum degree It is 10-2-10-3Pa, and heating while vacuumizing, heating rate is 1-20 DEG C/min, when temperature rises to 100-300 DEG C Keep the temperature 10-40min；Then the nano-ceramic powder in mold is pressurized and heating, pressure rises to 15-30MPa, temperature rises to 500-1000℃；It is cooling after heat preservation 1-3h, obtain nano ceramics target.
8. a kind of preparation method for the optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 4, It is characterized in that, in step S1, the vitreosol A is dissolved in dehydrated alcohol by tungsten compound is made into clear solution, clear solution It is formed within return stirring 2-4 hours at 70-80 DEG C.
9. a kind of preparation method for the optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 4, It being characterized in that, in step S1, the colloidal sol D is dissolved in dehydrated alcohol for the chloride containing Ce or Y or Er or Yb or Gd, and It is formed within return stirring 1 hour at 70-80 DEG C.
10. a kind of preparation method for the optical nano ceramic insulation glass for enhancing visible light-transmissive according to claim 4, It is characterized in that, in step S4, in vacuum degree < 2.0 × 10-3In the environment of Pa, it is passed through argon gas and oxygen, the argon gas and oxygen Flow-rate ratio is 2-8:1, then carries out magnetron sputtering plating with the power of 50-200W.
CN201710478161.5A 2017-06-21 2017-06-21 A kind of optical nano ceramic insulation glass and preparation method thereof enhancing visible light-transmissive Active CN107200580B (en)

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CN110255918A (en) * 2019-06-05 2019-09-20 新沂市铭达玻璃有限公司 A kind of Low emissivity energy-saving automobile glass
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CN113667468B (en) * 2021-08-13 2022-07-01 广州中达新材料科技有限公司 Thermochromic material, light adjusting film and preparation method and application thereof
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