CN104609740A - Solar control coated glass capable of being used in one piece and preparation method of solar control coated glass - Google Patents
Solar control coated glass capable of being used in one piece and preparation method of solar control coated glass Download PDFInfo
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- CN104609740A CN104609740A CN201510058675.6A CN201510058675A CN104609740A CN 104609740 A CN104609740 A CN 104609740A CN 201510058675 A CN201510058675 A CN 201510058675A CN 104609740 A CN104609740 A CN 104609740A
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- layer
- sacrifice layer
- coated glass
- sacrifice
- monolithic
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal layers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Abstract
The invention discloses a solar control coated glass capable of being used in one piece and a preparation method of the solar control coated glass. The coated glass comprises a glass substrate and a coating layer arranged at one side surface of the glass substrate, wherein the coating layer sequentially comprises a dielectric barrier layer, a first sacrificial layer, a functional layer, a second sacrificial layer, a dielectric support layer and a top protective layer which are sequentially arranged from the glass substrate to the outer side. The solar control coated glass capable of being used in one piece according to an embodiment of the invention is good in weather resistance and excellent in decorative effect and can be used in one piece.
Description
Technical field
The present invention relates to coated glass technical field, particularly relate to one and can use sunlight controlling coated glass and preparation method thereof by monolithic.
Background technology
Modern building is usually equipped with big area window, particularly commercial building, the heavy construction such as megastore and office building often uses glass curtain wall, a large amount of sunlights is caused to enter indoor by glass curtain wall, during the broiling summer because the solar radiant energy of incidence is more than the heat lost by glass curtain wall, room temp is caused to continue to raise, increase the weight of the energy consumption of room conditioning refrigeration, now just need to use sunlight controlling coated glass, by functional layer, sunlight transmittance is reduced to the absorption of sunlight and reflection, reduce and enter indoor solar radiant heat, thus minimizing air conditioning energy consumption, reach energy-conservation effect, sunlight controlling coated glass can also regulate the reflection colour of glass simultaneously, building is played to the effect of decoration.Film system many employings glass/Si of conventional off-line sunlight controlling coated glass
3n
4/ functional layer/Si
3n
4trilamellar membrane architecture, functional layer can be the materials such as NiCr, Fe, TiN, and that the most frequently used is NiCr.Glass/Si as is known
3n
4/ NiCr/CrN/Si
3n
4the solar control film system of structure, using NiCr and CrNx as functional layer, but the two not acidproof and salt air corrosion, outermost Si
3n
4not alkali corrosion resistance; Also has glass/SnO
x/ SSTN
x/ SnO
xfilm structure, but functional layer SSTN
xnot acid corrosion-resistant, SnO
xquality is softer, can not provide enough mechanics protections for functional layer; Another known glass/Si
3n
4or TiO
2/ Cr/Si
3n
4the sunlight controlling coated glass of three-decker, functional layer Cr is acid corrosion-resistant not, top layer Si
3n
4film is alkali corrosion resistance not; And glass/TiO
2/ ZnO
x/ Cu/NiCr/Si
3n
4coated glass in film system also has same shortcoming.Because present sunlight controlling coated glass has the shortcoming of acid and alkali-resistance and the not good and sealer adhesion strength difference of salt spray corrosion resistance; so general coated glass needs to be reprocessed into double glazing; rete is in cavity side; such heat-insulating property that can improve glass, plays a protective role to rete simultaneously.But the heat-insulating property of the weather condition in south China area to glass door and window is less demanding, the more mainly shaded effects of glass, therefore wish that sunlight controlling coated glass can use by monolithic, so namely reach energy-saving benefit, can reduce building cost again.When coated glass monolithic uses, rete is directly exposed in atmospheric environment, can be subject to the corrosion of rainwater, corrosive gases, washing composition etc. and the scraping of external force in use procedure, this has good anticorrosive and scratch resistant performance with regard to the solar-control glazing requiring monolithic to use.
Summary of the invention
In view of this, the embodiment of the present invention provides one can use sunlight controlling coated glass and preparation method thereof by monolithic, and it is good that main purpose is to provide a kind of weathering resistance, can use by monolithic, and the sunlight controlling coated glass that decorative effect is all good.
For achieving the above object, the present invention mainly provides following technical scheme:
On the one hand; embodiments provide one and can use sunlight controlling coated glass by monolithic; comprise glass substrate and be located at the rete of described glass substrate one side, described rete is outwards followed successively by dielectric barrier, the first sacrifice layer, functional layer, the second sacrifice layer, dielectric support layer and protective top layer from glass substrate.
As preferably, the thickness of described glass substrate is 3mm, 5mm, 6mm, 8mm or 12mm.
As preferably, functional layer is corroded to stop alkalimetal ion diffusion in glass substrate in the surface that described dielectric barrier is attached directly to glass substrate; The material of described dielectric barrier is Si
3n
4, SiO
2, TiO
2, ZrO
2or Al
2o
3in one or more; The thickness of described dielectric barrier is 20-200nm.
As preferably, described dielectric barrier is Si
3n
4film.
As preferably, described first sacrifice layer and the second sacrifice layer are located at the both sides of functional layer respectively with defencive function layer, and described first sacrifice layer and the second sacrifice layer are not suffered erosion by stronger anti-oxidant and corrosion resistance defencive function layer; The material of described first sacrifice layer and the second sacrifice layer is Nb, Nb base alloy, the nitride of Nb base alloy or Ta; The material of described first sacrifice layer and the second sacrifice layer is NbZr, NbZrN
x, NbCr or NbN
xin one or more; The thickness of described first sacrifice layer and the second sacrifice layer is 1-10nm.
As preferably, the material of described first sacrifice layer and the second sacrifice layer is NbZr, and wherein Zr atomic percentage conc is 7%-15%; The material of described first sacrifice layer and the second sacrifice layer is NbCr, and wherein the atomic percentage conc of Cr is 5%-20%.
As preferably, described functional layer absorbs and the near-infrared radiation energy of 780nm-2500nm wavelength region in reflected sunlight; The material of described functional layer is NiCr, Cr, NiCrN
xor CrN
xin one or more.
As preferably, the thickness of described functional layer is 1-18nm.
As preferably, described dielectric support layer stops that extraneous oxygen is through diffusing into rete inside, defencive function layer and sacrifice layer not oxidized.The material of described dielectric support layer is Si
3n
4, SiO
2, TiO
2, ZrO
2or Al
2o
3in one or more; The thickness of described dielectric support layer is 20-200nm.Preferred Si
3n
4.
As preferably, described protective top layer improves whole rete weather resistance, has good hardness, wear resistance and acid-alkali-corrosive-resisting performance.The material of described protective top layer is ZrO
2, ZrYO
xor ZrSiO
xin one or more, the thickness range of described protective top layer is 2-20nm.The preferred ZrYO of material of described protective top layer
xand ZrO
2.The material of described protective top layer is ZrYO
xtime, the atomic percentage conc of Y is 6%-9%.
On the other hand, embodiments provide and a kind ofly above-mentionedly can use the preparation method of sunlight controlling coated glass by monolithic, comprise the steps:
A) cleaning glass substrate is clean and dry rear for subsequent use;
B) intermediate frequency power supply and rotating cathode depositing medium barrier layer on the glass substrate cleaned up is adopted;
C) adopt pulse dc power or intermediate frequency power supply and rotating cathode or planar cathode on dielectric barrier, deposit the first sacrifice layer;
D) pulse dc power or intermediate frequency power supply and rotating cathode or planar cathode deposit functional layers on the first sacrifice layer is adopted;
E) pulse dc power or intermediate frequency power supply and rotating cathode or planar cathode depositing second sacrificial layer is on a functional adopted;
F) intermediate frequency power supply and rotating cathode deposition medium supporting layer on the second sacrifice layer is adopted;
G) intermediate frequency power supply and rotating cathode deposited top layer protective layer on dielectric support layer is adopted.
Compared with prior art, beneficial effect of the present invention is:
The coated glass that the embodiment of the present invention provides adds antiacid alkali and the excellent sacrifice layer of salt spray corrosion resistance in the both sides of functional layer, solve the not corrosion resistant problem of functional layer in prior art, improve weathering resistance and the useful life longevity of whole film system.The coated glass of the embodiment of the present invention has wider color adaptation scope.Adopt ZrO
2or ZrYO
xor ZrSiO
xas top layer protective membrane, mechanics and corrosion resistance nature are better than conventional Si
3n
4, TiO
2deng rete, and water contact angle reaches 90 °, has characteristic easy to clean.The below of top layer protective membrane adds supporting layer; avoid direct contact of the softer functional layer of hard coating and quality; such functional layer, supporting medium layer and protective top layer can form the gradient layer that hardness strengthens gradually, and this structure makes the rub resistance of whole film system and anti-extrusion performance enhancement.The coated glass of the embodiment of the present invention has the adhesion strength of acid and alkali-resistance, resisting salt fog corrosion and oxidation-resistance property and excellence, by the reflection colour and the sunlight transmitance that regulate thicknesses of layers can change glass surface.The film coating method of the embodiment of the present invention belongs to off-line coated, provides a kind of weathering resistance good, can use by monolithic, and the sunlight controlling coated glass that decorative effect is all good.
Accompanying drawing explanation
Fig. 1 is the Rotating fields schematic diagram of the coated glass of the embodiment of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, but not as a limitation of the invention.In the following description, the not necessarily same embodiment that different " embodiment " or " embodiment " refers to.In addition, special characteristic, structure or feature in one or more embodiment can be combined by any suitable form.
Embodiment 1
Fig. 1 is the Rotating fields schematic diagram of the coated glass of the embodiment of the present invention.With reference to Fig. 1; the present embodiment can sunlight controlling coated glass be used to comprise from glass substrate 1 and the solar control film layer that is coated with successively on glass substrate 1 one side by monolithic; rete in the present embodiment totally 6 layers, is outwards followed successively by dielectric barrier 2, first sacrifice layer 3, functional layer 4, second sacrifice layer 5, dielectric support layer 6 and protective top layer 7 from glass substrate 1.In the present embodiment, glass substrate 1 is the thick common float glass of 6mm; Dielectric barrier 2 is Si
3n
4rete, thickness is 42nm; First sacrifice layer 3 is NbZr rete, and thickness is 2nm; Functional layer 4 is NiCr rete, and thickness is 6nm; Second sacrifice layer 5 is NbZr rete, and thickness is 2nm; Dielectric support layer 6 is Si
3n
4rete, thickness is 170nm; Protective top layer 7 is ZrYO
xrete, thickness is 10nm.
Before being prepared complete sunlight controlling coated glass, first to understand the optical constant of layer 1-7 material, adopt the automatic angle spectroscopic ellipsometer that J.A.Woollam company of the U.S. produces, through measuring and the optical constant of the Fitting Calculation acquisition layers of material, test wavelength scope is 300 ~ 2500nm, step-length is 5nm, and incident angle is 55 ° and 65 °.
First adopt the processing parameter provided in pulsed dc magnetron sputtering method and the present invention to prepare the unitary film of 2-7 layer in the present embodiment, obtain the optical constant of each unitary film.Wherein glass substrate is within the scope of wavelength 300-2500nm, specific refractory power is between 1.56-1.49, within the scope of wavelength 300-455nm, optical extinction coefficient is between 7.77E-5-1.92E-7, and within the scope of wavelength 455-2500nm, optical extinction coefficient is in 1.92E-7-5.66E-6; Si
3n
4within the scope of wavelength 300-2500nm, specific refractory power is between 2.18-1.96, and within the scope of wavelength 300-2500nm, optical extinction coefficient is 0; NbZr is within the scope of wavelength 300-2500nm, and specific refractory power is between 1.78-5.70, and optical extinction coefficient is between 2.73-7.75; NiCr is within the scope of wavelength 300-2500nm, and specific refractory power is between 1.50-7.21, and optical extinction coefficient is between 2.23-8.78; ZrYO
2within the scope of wavelength 300-2500nm, specific refractory power is between 2.11-1.94, and optical extinction coefficient is 0.
The present embodiment adopts the method for pulsed dc magnetron sputtering, prepares sunlight controlling coated glass step as follows:
Using high purity water tentatively to clean glass substrate 1, then carrying out radio-frequency plasma cleaning by sending into after glass substrate 1 drying of wash clean into sheet room, removing surface contamination layer and zone of oxidation, promote substrate surface active.Radio-frequency plasma cleaning is specific as follows: working gas Ar (99.99%) flow is 30sccm, radio-frequency power supply power 200W, and resistance vacuum rule display operating air pressure is 3.4 × 10-2Torr, scavenging period 600S.
Glass substrate is entered the transmission of sheet room via filming equipment and enters sputtering chamber, wherein the base vacuum of sputtering chamber is better than 2 × 10-6Torr.
Glass substrate 1 is prepared dielectric barrier 2: adopt pulsed dc magnetron reactive sputtering to deposit Si on the glass substrate
3n
4film forms dielectric barrier 2, and the target of use is silumin target (containing Al 10%wt), and working gas is Ar and N
2, design parameter arranges as follows: pulse dc power sputtering power is 1500W, and operating air pressure is 3mTorr, Ar flow 30sccm, N
2flow 30sccm, does not heat in coating process.
The preparation of the first sacrifice layer 3: the surface deposition NbZr film of the dielectric barrier 2 of the product adopting pulse dc power magnetically controlled sputter method to obtain in upper step forms the first sacrifice layer 3, the target used is niobium zirconium alloy target (wherein containing Zr10%wt), design parameter arranges as follows: pulse dc power sputtering power is 1500W, operating air pressure is 3mTorr, working gas Ar (purity 99.99%) flow is 30sccm, do not heat in coating process, the thickness of the niobium zirconium alloy layer obtained is 2nm, the atomic percentage conc recording niobium in niobium zirconium alloy layer is 90%.
The preparation of functional layer 4: the first sacrifice layer 3 of the product adopting pulse dc power magnetically controlled sputter method to obtain in upper step deposits NiCr film and forms functional layer 4, the target used is nichrome target (containing Cr 20%wt), design parameter arranges as follows: pulse dc power sputtering power is 1500W, operating air pressure is 3mTorr, working gas Ar (purity 99.99%) flow is 30sccm, does not heat in coating process.
The preparation of the second sacrifice layer 5: the functional layer 4 of the product adopting pulse dc power magnetically controlled sputter method to obtain in upper step deposits NbZr film and forms the second sacrifice layer 5, the target used is niobium zirconium alloy target (containing Zr 10%wt), its design parameter arranges as follows: pulse dc power sputtering power is 1500W, operating air pressure is 3mTorr, working gas Ar (purity 99.99%) flow is 30sccm, does not heat in coating process.
The preparation of dielectric support layer 6: the second sacrifice layer 5 of the product adopting pulsed dc magnetron reactive sputtering to obtain in step 6 deposits Si
3n
4film forms dielectric support layer 6, and the target of use is silumin target (containing Al 10%wt), and working gas is Ar and N
2, design parameter arranges as follows: pulse dc power sputtering power is 1500W, and operating air pressure is 3mTorr, Ar flow 30sccm, N
2flow 30sccm, does not heat in coating process.
The preparation of protective top layer 7: the dielectric support layer 6 of the product adopting pulsed dc magnetron reactive sputtering to obtain in upper step deposits ZrYO
xfilm forms protective top layer 7, and the target of use is zirconium yttrium alloy target (containing Y 8%wt), and working gas is Ar and N
2, design parameter arranges as follows: pulse dc power sputtering power is 1500W, and operating air pressure is 3mTorr, Ar flow 30sccm, N
2flow 30sccm, does not heat in coating process.
Embodiment 2
The coated glass of glass surface reflection colour different from embodiment 1 has been prepared according to the optical constant of unitary film, film interference principle the present embodiment.The present embodiment is different from embodiment 1 to be only, dielectric barrier 2 is Si
3n
4rete, thickness is 30nm; First sacrifice layer 3 is NbZr rete, and thickness is 2nm; Functional layer 4 is NiCr rete, and thickness is 4nm; Second sacrifice layer 5 is NbZr rete, and thickness is 2nm; Dielectric support layer 6 is Si
3n
4rete, thickness is 28nm; Protective top layer 7 is ZrYO
xrete, thickness is 13nm.
In the embodiment of the present invention, the thickness of glass substrate 1 can be any thickness, specification 3mm as common in existing glass, 5mm, 6mm, 8mm, 12mm etc.; The effect being attached directly to the dielectric barrier 2 on glass substrate 1 is that functional layer 4 is corroded in the alkalimetal ion diffusion stopped in glass substrate 1, special in the process of hot tempering, tempering temperature is up to about 630 DEG C, ion in glass at high temperature can accelerate to spread the erosion caused functional layer 4, now dielectric barrier 2 is particularly important, the preferred Si of material of dielectric barrier 2
3n
4, thickness range is at 20nm-200nm.
The effect of the first sacrifice layer 3 and the second sacrifice layer 5 is defencive function layers 4; the coated glass of the embodiment of the present invention is in high temperature or acidity, alkalescence and salt fog etc. when having in corrosive environment; first sacrifice layer 3 has precedence over functional layer 4 with the second sacrifice layer 5 and contacts objectionable impurities, and the first sacrifice layer 3 and the second sacrifice layer 5 are not suffered erosion by self stronger anti-oxidant and corrosion resistance defencive function layer 4.Experiment proves: (1) deposits the thick NbZr unitary film of 20nm and NiCr unitary film respectively according to the method for embodiment 1 and to be put in the hydrochloric acid soln of 1mol/L after 48 hours on glass substrate 1, NbZr film stands intact, NiCr film is eroded completely, and this proves that NbZr film has very strong acid corrosion-resistant performance; (2) NbZr unitary film thick for 20nm and Si
3n
4the sodium hydroxide solution that unitary film puts into 0.1mol/L simultaneously boils 2 hours, and NbZr film is still intact, and Si
3n
4tie and eroded completely, proved that NbZr rete has and compare Si
3n
4better alkali corrosion resistance performance.(3) NbZr and NiCr unitary film thick for 20nm is put into salt-spray cabinet simultaneously carry out salt mist experiment, after 24 hours, NbZr film surface is intact, and the surperficial spot having occurred coming off after rete is corroded of NiCr, this proves that NbZr film has good salt spray corrosion resistance, and the salt spray resistance of NiCr film is not good.Sacrifice layer can provide available protecting to functional layer.The acid-alkali-corrosive-resisting experiment of the pure Zr metallic diaphragm of individual layer proves, Zr has good acid-alkali-corrosive-resisting performance, but high temperature oxidation resistance is poor, and optical extinction coefficient comparatively Nb is low, and pure Nb metallic membrane has good acid corrosion-resistant performance and high temperature oxidation resistance, but alkali corrosion resistance poor performance; Therefore appropriate Zr is preferably doped in Nb to improve the alkali corrosion resistance performance of Nb by the embodiment of the present invention, for optical extinction coefficient and the high temperature oxidation resistance of avoiding the Zr content mixed can reduce again NbZr too much, therefore in control NbZr alloy firm, Zr atomic percentage conc is 7%-15%.The atomic percentage conc of NbZr material can approximate mass percentage in the present embodiment.The resistance to high temperature oxidation of the first sacrifice layer and the second sacrifice layer and corrosion resistance are higher than functional layer, and defencive function layer does not suffer erosion.The existence of the first sacrifice layer 3 and the second sacrifice layer 5 can avoid the corrosion of acid-base material and salt fog, the weather resistance that the sunlight controlling coated glass substantially increasing the embodiment of the present invention uses by defencive function layer 4.
The effect of functional layer 4 can be reduced by the near-infrared radiation of 780nm-2500nm wavelength region in absorption and reflected sunlight to enter indoor heat, has certain perviousness simultaneously, do not affect indoor daylighting to the visible ray of 380nm-780nm.The preferred NiCr of material of functional layer 4.
The effect of dielectric support layer 6 has two: (1) stops that extraneous O is through diffusing into rete inside, defencive function layer 4 and the first sacrifice layer 3 and the second sacrifice layer 5 not oxidized.(2) first sacrifice layers 3, second sacrifice layer 5 and functional layer 4 are all the softer metal levels of quality, if Direct precipitation ganoine thin film on these metallic membranes, as Ti, Al, Si, the oxide compound of the metals such as Zr is as top layer protective film, then because thermal expansivity between soft or hard film and not mating of lattice easily demoulding occur, and easily there is " caving in " when the hard films not having hardness moderate supports by external force collision or extruding in protective top layer, rete is more vulnerable to destruction, so in order to make protective top layer 7 better play a role, dielectric support layer 6 is added necessary between protective top layer 7 and the second sacrifice layer 5.The preferred Si of material of supporting medium layer 6
3n
4.
Protective top layer 7 is the key components improving whole rete weather resistance, as the first line of defence protective top layer 7 except having good hardness and wear resistance, also will have excellent acid-alkali-corrosive-resisting performance.We prove ZrO through experiment
2film has good wear resisting property and acid-alkali-corrosive-resisting performance, and outmost surface is coated with Si respectively
3n
4and ZrO
2solar control film to be placed on concentration be in the hydrochloric acid soln of 1mol/L, invade bubble after 24 hours, observing rete outward appearance does not all have considerable change; The NaOH solution above sample being put into 0.1mol/L boils one hour, then can observe Si
3n
4rete is eroded completely, and ZrO
2rete is intact.In addition ZrO
2the water contact angle of film is at about 90 °, and the smooth roughness of film surface is little, has self-cleaning function, is not easily infected with spot, and the dust on surface and mud water rinse can be removed.Visible ZrO
2there is more excellent mechanics, corrosion-resistant and self-cleaning performance, so the preferred ZrYO of the material of protective top layer 7
xand ZrO
2.
Each layer of the coated glass of the embodiment of the present invention can be monofilm Rotating fields also can be multiple film layer structure, for the first sacrifice layer 3, can be single NbZr film, also can be NbZr film+NbCr film, or other array configurations.Dielectric support layer can be single Si
3n
4membrane structure or Si
3n
4film+TiO
2film two mode field, or other forms such as combination or 3 films.By that analogy, do not repeating at this.
Use the glass surface reflection of the sunlight controlling coated glass of spectrophotometer U4100 test preparation, face reflection and transmission spectrum curve, calculate Lab chrominance space color value according to GB GB/T3977-2008.The color value of embodiment 1 and spectral value are in table 1, and the glass surface reflection colour of embodiment 1 is blue-greenish colour, and glass surface reflectivity is 15.8%.Table 2 is color value and the spectral value of embodiment 2, is grey by the glass surface reflection colour of embodiment 2, and glass surface reflectivity is 18.28%, and lower glass surface reflectivity effectively can reduce outdoor optical and pollute.
Table 1
Table 2
By the sample in the embodiment of the present invention 1 and common glass/Si
3n
4/ NiCr/Si
3n
4the sunlight controlling coated glass of structure carries out contrast frictional wear experiment, and abrading-ball is the silicon nitride bead of diameter 4mm, and load is 20g, and friction frequency is 100r/min.The rete 1600s of the embodiment of the present invention 1 is not damaged, and common Si
3n
4/ NiCr/Si
3n
4the solar-control glazing of structure only can maintain 600s.
By the coated glass of the embodiment of the present invention 1 and with Si
3n
4for the coated glass of protective top layer is vertically placed, the mud prepared with sandy soil is splashed to sample surfaces, the quantity of sand and mud of the coated glass remained on surface of the embodiment of the present invention 1 is significantly smaller than with Si
3n
4for the coated glass of protective top layer, this demonstrate that the sunlight controlling coated glass of the embodiment of the present invention has good self-cleaning function.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of described claim.
Claims (10)
1. can use sunlight controlling coated glass by monolithic; it is characterized in that; comprise glass substrate and be located at the rete of described glass substrate one side, described rete is outwards followed successively by dielectric barrier, the first sacrifice layer, functional layer, the second sacrifice layer, dielectric support layer and protective top layer from glass substrate.
2. according to claim 1 can monolithic use sunlight controlling coated glass, it is characterized in that, the thickness of described glass substrate is 3mm, 5mm, 6mm, 8mm or 12mm.
3. according to claim 1ly can use sunlight controlling coated glass by monolithic, it is characterized in that, the surface that described dielectric barrier is attached directly to glass substrate is spread with the alkalimetal ion stopping in glass substrate and corrodes functional layer; The material of described dielectric barrier is Si
3n
4, SiO
2, TiO
2, ZrO
2or Al
2o
3; The thickness of described dielectric barrier is 20-200nm.
4. according to claim 1 can monolithic use sunlight controlling coated glass, it is characterized in that, described first sacrifice layer and the second sacrifice layer are located at the both sides of functional layer respectively with defencive function layer, and described first sacrifice layer and the second sacrifice layer are not suffered erosion by stronger anti-oxidant and corrosion resistance defencive function layer; The material of described first sacrifice layer and the second sacrifice layer is Nb, Nb base alloy, the nitride of Nb base alloy or Ta; The material of described first sacrifice layer and the second sacrifice layer is NbZr, NbZrN
x, NbCr or NbN
x; The thickness of described first sacrifice layer and the second sacrifice layer is 1-10nm.
5. according to claim 4 can monolithic use sunlight controlling coated glass, it is characterized in that, the material of described first sacrifice layer and the second sacrifice layer is NbZr, and wherein Zr atomic percentage conc is 7%-15%; The material of described first sacrifice layer and the second sacrifice layer is NbCr, and wherein the atomic percentage conc of Cr is 5%-20%.
6. according to claim 1ly can use sunlight controlling coated glass by monolithic, it is characterized in that, described functional layer absorbs and the near-infrared radiation energy of 780nm-2500nm wavelength region in reflected sunlight; The material of described functional layer is NiCr, Cr, NiCrN
xor CrN
x.
7. according to claim 1 can monolithic use sunlight controlling coated glass, it is characterized in that, the thickness of described functional layer is 1-18nm.
8. according to claim 1ly can use sunlight controlling coated glass by monolithic, it is characterized in that, described dielectric support layer stops that extraneous oxygen is through diffusing into rete inside, defencive function layer and sacrifice layer not oxidized; The material of described dielectric support layer is Si
3n
4, SiO
2, TiO
2, ZrO
2or Al
2o
3; The thickness of described dielectric support layer is 20-200nm.
9. according to claim 1 can monolithic use sunlight controlling coated glass, it is characterized in that, described protective top layer improves whole rete weather resistance, has good hardness, wear resistance and acid-alkali-corrosive-resisting performance; The material of described protective top layer is ZrO
2, ZrYO
xor ZrSiO
x; The thickness of described protective top layer is 2-20nm; The material of described protective top layer is ZrYO
xtime, the atomic percentage conc of Y is 6%-9%.
10. can use the preparation method of sunlight controlling coated glass by monolithic described in any one of claim 1-9, comprise the steps:
A) cleaning glass substrate is clean and dry rear for subsequent use;
B) intermediate frequency power supply and rotating cathode depositing medium barrier layer on the glass substrate cleaned up is adopted;
C) adopt pulse dc power or intermediate frequency power supply and rotating cathode or planar cathode on dielectric barrier, deposit the first sacrifice layer;
D) pulse dc power or intermediate frequency power supply and rotating cathode or planar cathode deposit functional layers on the first sacrifice layer is adopted;
E) pulse dc power or intermediate frequency power supply and rotating cathode or planar cathode depositing second sacrificial layer is on a functional adopted;
F) intermediate frequency power supply and rotating cathode deposition medium supporting layer on the second sacrifice layer is adopted;
G) intermediate frequency power supply and rotating cathode deposited top layer protective layer on dielectric support layer is adopted.
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| TWI632060B (en) * | 2017-10-26 | 2018-08-11 | 行政院原子能委員會核能硏究所 | Solar control film and manufacturing method thereof |
| CN109564312A (en) * | 2016-03-15 | 2019-04-02 | 佳殿玻璃有限公司 | Grey with low sun factor values can be heat-treated coating product |
| CN110937821A (en) * | 2019-12-30 | 2020-03-31 | 青岛锦绣前程节能玻璃有限公司 | Temperable sunlight-controlled coated glass and preparation method thereof |
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| CN104609740B (en) | 2018-04-10 |
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