CN105621901A - Rare earth doped and modified single crystal silver Low-E glass and preparation method thereof - Google Patents
Rare earth doped and modified single crystal silver Low-E glass and preparation method thereof Download PDFInfo
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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
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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
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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
- C03C17/3626—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
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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
- C03C17/3642—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 containing a metal layer
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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
- C03C17/3647—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 in combination with other metals, silver being more than 50%
-
- 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
- C03C2218/155—Deposition methods from the vapour phase by sputtering by reactive sputtering
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses rare earth doped and modified single crystal silver Low-E glass, and relates to the field of manufacturing of low-radiation coated glass. The rare earth doped and modified single crystal silver Low-E glass comprises a glass base layer, a first protective layer, a first medium layer, a functional layer, a second medium layer and a second protective layer which are arranged in sequence; the functional layer is formed by mixing a metal material with a rare earth material, wherein the metal material is selected from at least one of gold, silver, silver-copper alloy and copper; the rare earth material is selected from one of yttrium, lanthanum, samarium, cerium, gadolinium, neodymium, erbium and scandium; the adding proportion of the rare earth material is 0.001 to 2 percent of the weight of the mixture of the metal material and the rare earth material. According to the rare earth doped and modified single crystal silver low-E glass, a rare earth element is added into the metal material to serve as the functional layer, and the rare earth material is oxidized preferentially in the process of forming a metal material oxide film, so that the rare earth material has a remarkable influence on an ion diffusion high-temperature oxidation mechanism. Meanwhile, the rare earth element has an effect on refining grains, so that the crystallinity degree of a silver alloy functional layer can be reduced, the uniformity of the functional layer is improved, the thickness of the silver alloy layer is reduced to the maximal extent, and the visible light transmittance is improved.
Description
Technical field
The present invention relates to the manufacture field of Low-E low radiation coated glass, particularly to a kind of rare-earth-doped modification list silver Low-E glass and preparation method thereof.
Background technology
China is energy consumption big country, energy resource consumption the first in the world, wherein building energy consumption accounts for about the 30% of total energy consumption, particularly the energy consumption of glass part just account for more than the 50% of building energy consumption, this means will from the performance of change glass to reduce hot loss of energy, and most efficient method is to suppress the radiation of its inner surface. The radiance of common float glass is up to 0.84, when, after plating last layer low radiation film based on silver, its radiance can be down to less than 0.15. Therefore, with Low-E glass manufacture building window, the indoor heat caused because of radiation can be substantially reduced to outdoor transmission, reach desirable energy-saving effect.
Existing Low-E low emissivity glass has the silver layer that relatively low surface resistance is excellent mainly due to having electric conductivity, so fine silver layer is the Core Feature layer of Low-E thin film. But cause Low-E hollow to lose efficacy owing to the fine silver layer of existing Low-E thin film exists oxidized, the defect of variable color, additionally, although increasing silver thickness can reduce the surface resistance of rete thus promoting heat-proof quality, but the thickness increase of silver layer is limited, the too thick visible light transmissivity that can reduce low emissivity glass of silver layer, slackens the effect of glass transmission. Therefore, how to ensure that the energy-saving effect reached on the basis of Low-E low emissivity glass visible light transmission is that the subject matter run into applied by current Low-E low emissivity glass.
Therefore, need that a kind of light transmission is good, thickness is low badly and there is single silver Low-E glass of good energy-saving effect.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of rare-earth-doped modification list silver Low-E glass, and this glass has good light transmission and energy-saving effect.
In order to solve above-mentioned technical problem, the technical scheme is that a kind of rare-earth-doped modification list silver Low-E glass, including the glass-base set gradually, first protective layer, first medium layer, functional layer, second dielectric layer, second protective layer, wherein, functional layer is mixed by metal material and rare earth material, and metal material is selected from gold, silver, yellow gold, at least one in copper, and rare earth material is selected from yttrium, lanthanum, samarium, cerium, gadolinium, neodymium, erbium, one in scandium, the adding proportion of rare earth material is after metal material mixes with rare earth material the 0.001%��2% of weight.
Further, functional layer thickness is 7��15nm.
Further, the adding proportion of rare earth is preferably the 0.001%��1% of weight of metallic materials.
Further; it is at least one that first protective layer, the second protective layer are selected from titanium oxide, niobium oxide, zirconium oxide, silicon oxide, silicon nitride, zirconium nitride, niobium nitride; thickness is 5��50nm, and the first protective layer and the second protective layer can be symmetrical arranged and also can asymmetric arrange.
Further, it is at least one that first medium layer, second dielectric layer are selected from stannum oxide, zinc oxide, zinc-tin oxide, AZO, and thickness is 10��50nm, and first medium layer, second dielectric layer can be symmetrical arranged and also can asymmetric arrange.
Further, the thickness 2��15mm of glass-base, the one in common float glass, ultra-white float glass, coloured glass, it is preferred that the ultra-white float glass of 4��8mm, the ultra-white float glass of 5 optimum��6mm.
A kind of rare-earth-doped modification list silver Low-E glass, comprises the steps:
1) glass-base sends into vacuum film coating chamber after pure water cleaning, drying;
2) the first protective layer sputtering: medium frequency reactive sputtering sial target, setting power 70KW, argon and the sputtering of nitrogen mixture atmosphere, Ar:N2=5:1, air pressure 5 �� 10-4Mbar;
3) first medium layer sputtering: medium frequency reactive sputtering zinc oxide target, setting power 40KW, argon and the sputtering of oxygen mix atmosphere, Ar:O2=10:1, air pressure 5 �� 10-4Mbar;
4) functional layer sputtering: DC source magnetron sputtering plane silver-bearing copper ginseng yttrium target, setting power 8KW, electric current 12A, pure argon sputters, air pressure 5 �� 10-4Mbar, walking speed 3m/min;
5) second dielectric layer sputtering: medium frequency reactive sputtering zinc oxide target, setting power 40KW, argon and the sputtering of oxygen mix atmosphere, Ar:O2=5:1, air pressure 5 �� 10-4Mbar;
6) the second protective layer sputtering: medium frequency reactive sputtering sial target, setting power 80KW, argon and the sputtering of nitrogen mixture atmosphere, Ar:N2=5:1, air pressure 5 �� 10-4Mbar;
The present invention by adding metal material as functional layer using rare earth element, and rare earth material is preferential oxidation in metal material oxide film forming process, makes it that ion is spread high-temperature oxydation mechanism and plays appreciable impact, along with the elevating effect of temperature is particularly evident. Simultaneously as rare earth element has the effect of crystal grain thinning, the rare earth element of interpolation, it is possible to reduce the degree of crystallinity of silver alloy functional layer, thus improving the uniformity of functional layer, reducing the thickness of ag alloy layer to greatest extent, improving visible light transmissivity.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described. At this it should be noted that be adapted to assist in for the explanation of these embodiments and understand the present invention, but it is not intended that limitation of the invention. As long as just can be mutually combined additionally, technical characteristic involved in each embodiment of invention described below does not constitute conflict each other.
Embodiment 1
A kind of rare-earth-doped modification list silver Low-E glass, film layer structure glass-base/the first protective layer/first medium layer/functional layer/second dielectric layer/the second protective layer corresponds to common float glass/SiN/ZnO/AgCu:Y/ZnSnO/SiN, wherein AgCu (yellow gold): Y (yttrium) Core Feature layer composition part by weight is Ag:Cu:Y=90:9.9:0.1, the thickness of common float glass is 6mm, first protective layer thickness is 20nm, first medium layer thickness is 15nm, functional layer thickness is 12nm, second medium layer thickness is 25nm, second protective layer thickness is 35nm.
Preparation method:
1) first, common float glass is sent into after pure water cleaning, drying vacuum film coating chamber;
2) the first protective layer sputtering: medium frequency reactive sputtering sial target, setting power 70KW, argon and the sputtering of nitrogen mixture atmosphere, Ar:N2=5:1, air pressure 5 �� 10-4Mbar, forms the SiN protective layer that thickness is 20nm;
3) first medium layer sputtering: medium frequency reactive sputtering zinc oxide target, setting power 40KW, argon and the sputtering of oxygen mix atmosphere, Ar:O2=10:1, air pressure 5 �� 10-4Mbar, forms the ZnO dielectric layer that thickness is 15nm;
4) functional layer sputtering: DC source magnetron sputtering plane silver-bearing copper ginseng yttrium target, setting power 8KW, electric current 12A, pure argon sputters, air pressure 5 �� 10-4Mbar, walking speed 3m/min, form the yellow gold functional layer of the doped with yttrium that thickness is 12nm;
5) second dielectric layer sputtering: medium frequency reactive sputtering zinc oxide target, setting power 40KW, argon and the sputtering of oxygen mix atmosphere, Ar:O2=5:1, air pressure 5 �� 10-4Mbar, forms the ZnSnO dielectric layer that thickness is 25nm;
6) the second protective layer sputtering: medium frequency reactive sputtering sial target, setting power 80KW, argon and the sputtering of nitrogen mixture atmosphere, Ar:N2=5:1, air pressure 5 �� 10-4Mbar, forms the SiN protective layer that thickness is 35nm.
Embodiment 2
A kind of rare-earth-doped modification list silver Low-E glass, film layer structure glass-base/the first protective layer/first medium layer/functional layer/second dielectric layer/the second protective layer corresponds to ultra-white float glass/SiN/ZnO/AgCu:La/SnO2/ SiN; wherein AgCu:La (lanthanum) Core Feature layer composition part by weight is Ag:Cu:La=92.5:7.3:0.2; the thickness of ultra-white float glass is 6mm; first protective layer thickness is 5nm; first medium layer thickness is 15nm; functional layer thickness is 15nm, and second medium layer thickness is 25nm, and the second protective layer thickness is 35nm.
Preparation method is identical with embodiment 1.
Embodiment 3
A kind of rare-earth-doped modification list silver Low-E glass; film layer structure glass-base/the first protective layer/first medium layer/functional layer/second dielectric layer/the second protective layer corresponds to ultra-white float glass/SiN/ZnO/AgCu:Ce/ZnO/SiN; wherein AgCu:Ce Core Feature layer composition part by weight is AgCu:Ce=92.5:7.48:0.02; the thickness of ultra-white float glass is 15mm; first protective layer thickness is 20nm; first medium layer thickness is 15nm; functional layer thickness is 7nm; second medium layer thickness is 10nm, and the second protective layer thickness is 50nm.
Preparation method is identical with embodiment 1.
Embodiment 4
A kind of rare-earth-doped modification list silver Low-E glass; film layer structure glass-base/the first protective layer/first medium layer/functional layer/second dielectric layer/the second protective layer; correspond to blue-colored glass/SiN/ZnO/Ag:Gd/ZnSnO/SiN; wherein Ag:Gd Core Feature layer composition mass ratio is Ag:Gd=99.8:0.2; the thickness of blue-colored glass is 5mm; first protective layer thickness is 20nm; first medium layer thickness is 15nm; functional layer thickness is 12nm; second medium layer thickness is 10nm, and the second protective layer thickness is 35nm.
Preparation method is identical with embodiment 1.
Embodiment 5
A kind of rare-earth-doped modification list silver Low-E glass, film layer structure glass-base/the first protective layer/first medium layer/functional layer/second dielectric layer/the second protective layer, correspond to dark brown coloured glass/NbN/AZO/Ag:Nd/ZnSnO/TiO2, wherein Ag:Nd Core Feature layer composition mass ratio is Ag:Nd=99.999:0.001, and the thickness of dark brown coloured glass is 4mm; first protective layer thickness is 20nm, and first medium layer thickness is 10nm, and functional layer thickness is 10nm; second medium layer thickness is 50nm, and the second protective layer thickness is 5nm.
Preparation method is identical with embodiment 1.
Embodiment 6
A kind of rare-earth-doped modification list silver Low-E glass, film layer structure glass-base/the first protective layer/first medium layer/functional layer/second dielectric layer/the second protective layer, correspond to ultra-white float glass/Nb2O5/ ZnO/Au:Gd/AZO/NbN; wherein Ag:Gd Core Feature layer composition mass ratio is Ag:Gd=98:2; the thickness of ultra-white float glass is 2mm; first protective layer thickness is 20nm; first medium layer thickness is 50nm; functional layer thickness is 12nm, and second medium layer thickness is 25nm, and the second protective layer thickness is 35nm.
Preparation method is identical with embodiment 1.
Embodiment 7
A kind of rare-earth-doped modification list silver Low-E glass, film layer structure glass-base/the first protective layer/first medium layer/functional layer/second dielectric layer/the second protective layer corresponds to ultra-white float glass/SiO2/ ZnSnO/AgCu:Er/AZO/ZrN; wherein AgCu:Er Core Feature layer composition mass ratio is AgCu:Er=94:5:1; the thickness of ultra-white float glass is 8mm; first protective layer thickness is 20nm; first medium layer thickness is 35nm; functional layer thickness is 12nm, and second medium layer thickness is 25nm, and the second protective layer thickness is 35nm.
Preparation method is identical with embodiment 1.
The test result of above-described embodiment is as follows:
Above embodiments of the present invention are explained in detail, but the invention is not restricted to described embodiment. For a person skilled in the art, when without departing from the principle of the invention and spirit, these embodiments are carried out multiple change, amendment, replacement and modification, still falls within protection scope of the present invention.
Claims (9)
1. a rare-earth-doped modification list silver Low-E glass; including the glass-base set gradually, the first protective layer, first medium layer, functional layer, second dielectric layer, the second protective layer; it is characterized in that: described functional layer is mixed by metal material and rare earth material; described metal material one in gold, silver, yellow gold, copper; described rare earth material one in yttrium, lanthanum, samarium, cerium, gadolinium, neodymium, erbium, the scandium, the adding proportion of rare earth material is after metal material mixes with rare earth material the 0.001%��2% of weight.
2. rare-earth-doped modification list silver Low-E glass according to claim 2, it is characterised in that: described functional layer thickness is 7��15nm.
3. rare-earth-doped modification list silver Low-E glass according to claim 1 and 2, it is characterised in that: the adding proportion of described rare earth material is 0.001%��1%.
4. rare-earth-doped modification list silver Low-E glass according to claim 1 and 2; it is characterized in that: it is at least one that described first protective layer, described second protective layer are selected from titanium oxide, niobium oxide, zirconium oxide, silicon oxide, silicon nitride, zirconium nitride, niobium nitride, and described first protective layer, described second protective layer thickness are 5��50nm.
5. rare-earth-doped modification list silver Low-E glass according to claim 3; it is characterized in that: it is at least one that described first protective layer, described second protective layer are selected from titanium oxide, niobium oxide, zirconium oxide, silicon oxide, silicon nitride, zirconium nitride, niobium nitride, and described first protective layer, described second protective layer thickness are 5��50nm.
6. rare-earth-doped modification list silver Low-E glass according to claim 4, it is characterized in that: it is at least one that described first medium layer, described second dielectric layer are selected from stannum oxide, zinc oxide, zinc-tin oxide, AZO, and described first medium layer, described second medium layer thickness are 10��50nm.
7. rare-earth-doped modification list silver Low-E glass according to claim 6, it is characterised in that: described glass-base one in common float glass, ultra-white float glass, coloured glass, the thickness 2��15mm of described glass-base.
8. rare-earth-doped modification list silver Low-E glass according to claim 7, it is characterised in that: described glass-base is the ultra-white float glass of thickness 4��8mm.
9. a manufacture method for the rare-earth-doped modification list silver Low-E glass described in claim 1, comprises the steps:
1) glass-base sends into vacuum film coating chamber after pure water cleaning, drying;
2) the first protective layer sputtering: medium frequency reactive sputtering protection material target, setting power 70KW, argon and the sputtering of nitrogen mixture atmosphere, Ar:N2=5:1, air pressure 5 �� 10-4mbar;
3) first medium layer sputtering: medium frequency reactive sputtering dielectric material target, setting power 40KW, argon and the sputtering of oxygen mix atmosphere, Ar:O2=10:1, air pressure 5 �� 10-4mbar;
4) functional layer sputtering: DC source magnetron sputtering functional material target, setting power 8KW, electric current 12A, pure argon sputters, air pressure 5 �� 10-4Mbar, walking speed 3m/min;
5) second dielectric layer sputtering: medium frequency reactive sputtering dielectric material target, setting power 40KW, argon and the sputtering of oxygen mix atmosphere, Ar:O2=5:1, air pressure 5 �� 10-4Mbar;
6) the second protective layer sputtering: medium frequency reactive sputtering protection material target, setting power 80KW, argon and the sputtering of nitrogen mixture atmosphere, Ar:N2=5:1, air pressure 5 �� 10-4mbar��
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Cited By (5)
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| CN108218253A (en) * | 2018-01-11 | 2018-06-29 | 中建材光电装备（太仓）有限公司 | A kind of high-permeability, tempered three silver medal Low-E glass and preparation method thereof |
| CN109987857A (en) * | 2019-04-29 | 2019-07-09 | 布勒莱宝光学设备（北京）有限公司 | Novel Low emissivity energy conservation membrane system and its preparation method and application |
| CN111285621A (en) * | 2020-03-25 | 2020-06-16 | 四川猛犸半导体科技有限公司 | Thin film device |
| CN111886212A (en) * | 2017-12-28 | 2020-11-03 | Ａｇｃ株式会社 | Transparent substrate with laminated film |
| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
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| CN108218253A (en) * | 2018-01-11 | 2018-06-29 | 中建材光电装备（太仓）有限公司 | A kind of high-permeability, tempered three silver medal Low-E glass and preparation method thereof |
| CN108218253B (en) * | 2018-01-11 | 2020-12-11 | 中建材光电装备（太仓）有限公司 | High-permeability tempered three-silver Low-E glass and preparation method thereof |
| CN109987857A (en) * | 2019-04-29 | 2019-07-09 | 布勒莱宝光学设备（北京）有限公司 | Novel Low emissivity energy conservation membrane system and its preparation method and application |
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| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
| US11578386B2 (en) | 2020-08-18 | 2023-02-14 | Enviro Metals, LLC | Metal refinement |
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