CN115925252B - Ultra-white amorphous aluminum silicon oxide material, preparation method thereof and metal coating product - Google Patents
Ultra-white amorphous aluminum silicon oxide material, preparation method thereof and metal coating product Download PDFInfo
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- CN115925252B CN115925252B CN202310101929.2A CN202310101929A CN115925252B CN 115925252 B CN115925252 B CN 115925252B CN 202310101929 A CN202310101929 A CN 202310101929A CN 115925252 B CN115925252 B CN 115925252B
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- 239000000463 material Substances 0.000 title claims abstract description 104
- -1 aluminum silicon oxide Chemical compound 0.000 title claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011248 coating agent Substances 0.000 title description 5
- 238000000576 coating method Methods 0.000 title description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 17
- 229910002651 NO3 Inorganic materials 0.000 claims description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 13
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims description 5
- 239000004323 potassium nitrate Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 238000005468 ion implantation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000007 visual effect Effects 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 27
- 239000011669 selenium Substances 0.000 description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 7
- 239000000075 oxide glass Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000003426 chemical strengthening reaction Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000003712 decolorant Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000005358 alkali aluminosilicate glass Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/111—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing nitrogen
-
- 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
- C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
-
- 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
- C03C17/40—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 all coatings being metal coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the field of amorphous inorganic oxide materials and metal coated products thereof, and discloses an ultrawhite amorphous aluminum silicon oxide material, a preparation method thereof and a metal coated product. The ultra-white amorphous aluminum silicon oxide material of the application ensures that the transmittance of the ultra-white amorphous aluminum silicon oxide material is more than 92.0 percent by controlling the iron content in raw materials to be less than 120ppm and adding a proper chemical decolorizer and a physical decolorizer and enabling the physical decolorizer to meet a certain proportion relation, and enables chromaticity coordinates to move towards a white point (an original point of 0, 0) according to a uniform chromaticity space standard, and visual materials are whiter.
Description
Technical Field
The application relates to the field of amorphous inorganic oxide materials and metal coated products thereof, in particular to an ultra-white amorphous aluminum silicon oxide material, a preparation method thereof and a metal coated product.
Background
The high-alumina glass is one of the amorphous materials with wider application, can increase the surface hardness through chemical strengthening, improves the scratch resistance, and greatly increases the bending resistance and the impact resistance; in addition, the thickness of the glass is thinner, and the glass can replace thick glass, so that the glass is light, and can be widely applied to display screen protection glass (mobile phones, flat plates, pen-powered, car navigation and the like), transparent parts of vehicles (front-end glass of high-speed rail locomotives, car body glass, airplane transparent parts and the like) and the like. However, these applications require that the glass has high transparency and "whiteness", i.e., not only high transmittance, but also the chromaticity coordinate values of a and b are as close as the origin "0,0", i.e., the more "white", according to the chromaticity space standard of the ICE (International Commission on illumination) for emission control) in 1976.
Raw materials used in the production of high alumina glass inevitably carry iron impurities, the iron oxides are valence-changing oxides in the glass, and Fe is also present 2+ And Fe (Fe) 3+ Iron ions exist, and ferrous iron is green and ferric iron is yellow in the glass.
Reducing the iron oxide content of various raw materials is one of the direct effective methods of increasing the light transmittance of glass and reducing the chromaticity values a, b, but it is known that the lower the iron content of raw materials, the higher the price, for example, the iron content of silica sand is 50ppm and 80ppm, and the cost is greatly increased, as is the other raw materials. Therefore, how to provide an ultra-white glass material with the production cost, light transmittance and chromaticity requirements is a technical problem which needs to be solved at present.
Disclosure of Invention
In view of this, the present application aims to provide an ultra-white amorphous aluminum silicon oxide material and a preparation method thereof, so that chromaticity coordinate values of a and b of the material are closer to an origin "0,0", chromaticity is whiter, and meanwhile, transmittance is higher;
another object of the present application is to provide a metal coated product based on the above ultra-white aluminum silicon oxide material and a method for preparing the same.
In order to solve or at least partially solve the above-mentioned problems, as a first aspect of the present application, there is provided an ultrawhite amorphous aluminum silicon oxide material comprising (1) an inorganic oxide, (2) Se and/or Nd 2 O 3 And (3) Co 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Se and/or Nd 2 O 3 0.5-1.5ppm of the total weight of the super Bai Fei crystal aluminum silicon oxide material, and Co 2 O 3 0.3-0.9ppm of the total weight of the super Bai Fei crystalline aluminum silicon oxide material, wherein the inorganic oxide comprises the following components in percentage by weight:
SiO 2 58wt%-62wt%
Al 2 O 3 13%wt-15wt%
Na 2 O 13%wt-16wt%
K 2 O 4wt%-7wt%
MgO 3wt%-4.9wt%
ZrO 2 0.5wt%-1.2wt%
wherein the iron content of the inorganic oxide is less than 120ppm of the total weight of the amorphous aluminum silicon oxide material of Yu Chaobai.
Optionally, the Se, nd 2 O 3 、Co 2 O 3 The content of (2) satisfies the requirement of formula 1:
0.3≤Co 2 O 3 /(Se+Nd 2 O 3 ) And less than or equal to 1 formula 1.
As a second aspect of the present application, there is provided a method for preparing the super Bai Fei crystalline aluminum silicon oxide material, comprising:
and taking various raw materials according to the composition of the super Bai Fei crystal aluminum silicon oxide material, adding sulfate and/or nitrate, mixing to obtain a mixture, and melting, forming, annealing and slicing the mixture to prepare the super Bai Fei crystal aluminum silicon oxide material.
Optionally, the sulfate comprises sodium sulfate and/or potassium sulfate, and the nitrate comprises sodium nitrate and/or potassium nitrate; further alternatively, the sulfate is added in an amount of 0.4-1.6kg per 100kg of the mixture, and the nitrate is added in an amount of 2.0-4.0kg per 100kg of the mixture.
Optionally, the residual oxygen content at the discharge port side in the preparation process is kept to be more than 2%.
As a third aspect of the present application, based on the excellent chemical strengthening performance and efficiency of the super Bai Fei crystalline aluminum silicon oxide material, the application of the super white amorphous aluminum silicon oxide material or the super white amorphous aluminum silicon oxide material prepared by the preparation method in preparing metal coated products is provided.
As a fourth aspect of the present application, a metal-coated article is provided, which includes the ultrawhite amorphous aluminum silicon oxide material described herein or the ultrawhite amorphous aluminum silicon oxide material prepared by the preparation method described herein, and one or more metal films coated on the surface thereof.
Optionally, the metal film includes one or more of a Cr film, a Ni film, a Ti film, an Au film, an Ag film, a Cu film, and an Al film, and is plated by a chemical vapor deposition method, a vacuum evaporation method, a sputtering method, or an ion implantation method.
Compared with the similar amorphous aluminum silicon oxide materials, the ultra-white amorphous aluminum silicon oxide material of the application firstly controls the total introduction amount of ferric oxide impurities in raw materials to be less than 120ppm, and then adds a proper chemical decolorizer and a physical decolorizer to enable the physical decolorizer to accord with a certain proportion relation, thereby ensuring that the light transmittance of the ultra-white amorphous aluminum silicon oxide material is more than 92.0%, and enabling chromaticity coordinates to move towards the direction of white point (original point '0, 0') according to the a-value and the b-value of uniform chromaticity space standard, and visual glass is 'whiter'.
Drawings
FIG. 1 is a flow chart of a preparation process of the ultra-white amorphous aluminum silicon oxide material;
FIG. 2 is a chromaticity coordinate diagram illustrating an embodiment of the present application; the graph of a and b values in a chromaticity control region under the reference thickness of the ultra-white amorphous aluminum silicon oxide material in the embodiment of the application shows that an elliptical region in the graph is a region constructed by (b-0.14) x 2/0.0016+ (a+0.012) x 2/0.000324 =2' required by ICE;
FIG. 3 is a graph showing chromaticity coordinates of a comparative example; that is, the values of a and b are plotted in the chromaticity control region at the reference thickness of the control material, and the oval region in the graph is the region constructed by (b-0.14) ×2/0.0016+ (a+0.012) ×2/0.000324 =2″ required by ICE.
Detailed Description
The application discloses an ultra-white amorphous aluminum silicon oxide material and a metal coating product thereof, and the technical parameters can be properly improved by a person skilled in the art by referring to the content of the specification. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included herein. The products, processes and applications described herein have been described in terms of preferred embodiments, and it will be apparent to those skilled in the relevant art that variations and modifications can be made in the products, processes and applications described herein without departing from the spirit and scope of the application. It will be apparent that the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
It should be noted that, in this document, relational terms such as "first" and "second," "step 1" and "step 2," and "(1)" and "(2)" and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Meanwhile, the embodiments and features in the embodiments in the present application may be combined with each other without conflict.
In a first aspect of the present application, there is provided an ultrawhite amorphous aluminum silicon oxide material comprising (1) an inorganic oxide, (2) Se or Nd 2 O 3 And (3) Co 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Said Se or Nd 2 O 3 0.5-1.5ppm of the total weight of the super Bai Fei crystal aluminum silicon oxide material, and Co 2 O 3 0.3-0.9ppm of the total weight of the super Bai Fei crystalline aluminum silicon oxide material, wherein the inorganic oxide comprises the following components in percentage by weight:
SiO 2 58wt%-62wt%
Al 2 O 3 13%wt-15wt%
Na 2 O 13%wt-16wt%
K 2 O 4wt%-7wt%
MgO 3wt%-4.9wt%
ZrO 2 0.5wt%-1.2wt%
wherein the content of iron (calculated as ferric oxide) in the inorganic oxide is less than 120ppm of the total weight of the Yu Chaobai amorphous aluminum silicon oxide material.
In certain embodiments of the present application, the SiO 2 58%, 60.5%, 60.7%, 61% or 61.4% by weight of Al 2 O 3 13%, 13.5%, 13.8% or 15% by weight of Na 2 O is 13%, 14%, 15% or 16% by weight, said K 2 4%, 6%, 6.3% or 7% by weight of O, 3%, 4%, 4.5%, 4.8% or 4.9% by weight of MgO, and ZrO 2 The weight percentage is 0.5%, 0.6%, 0.8%, 1.0% or 1.2%.
In certain embodiments of the present application, the Se or Nd 2 O 3 0.5ppm, 0.8ppm, 1.0ppm, 1.1ppm, 1.3ppm or 1.5ppm based on the total weight of the super Bai Fei crystalline aluminum silicon oxide material, the Co 2 O 3 0.3ppm, 0.5ppm, 0.6ppm, 0.7ppm, 0.8ppm or 0.9ppm based on the total weight of the super Bai Fei crystalline aluminum silicon oxide material.
In certain embodiments of the present application, the inorganic oxide has an iron (as ferric oxide) content of less than 120ppm, 110ppm, 100pmm, or 90ppm, such as 82ppm, 85ppm, 90ppm, 100ppm, 112ppm, or 118ppm, based on the total weight of the Yu Chaobai amorphous aluminum silicon oxide material.
In addition, through the experimental verification of the application, the Se and the Nd 2 O 3 、Co 2 O 3 The content of (2) satisfies the requirement of formula 1, the light transmittance can be more than 92.0%, and the chromaticity coordinates can be led to the white point (origin "0, 0") according to the a-x and b-x values of the uniform chromaticity space standard ") And (3) direction movement:
0.3≤Co 2 O 3 /(Se+Nd 2 O 3 ) And less than or equal to 1 formula 1.
In certain embodiments of the present application, the parameter value of formula 1 is 0.375, 0.55, 0.6, 0.62, 0.7 or 1.0.
In certain embodiments of the present application, the thickness of the super Bai Fei crystalline aluminum silicon oxide material is 0.8-4mm, and the super Bai Fei crystalline aluminum silicon oxide material can be specifically an aluminum silicon inorganic oxide glass material, such as a high aluminum glass material.
In certain embodiments of the present application, the super Bai Fei crystalline aluminum silicon oxide material is soaked in pure potassium nitrate (or 99% potassium nitrate+1% sodium nitrate) molten salt at 430 ℃ for 150min, the surface stress CS is not less than 800MPa, and the stress layer depth DOL is not less than 43 μm. In other embodiments of the present application, the ultra-white amorphous aluminum silicon oxide material moves in the direction of "white point" 0,0 "according to the a-x and b-x values of the uniform chromaticity space standard of the ICE (international electroluminescence committee) 1976, specifically, the a-x and b-x values are in the area of the control area constructed by the elliptic equation" (b-0.14) 2/0.0016+ (a+0.012) 2/0.000324 =2 "with the reference thickness being 1.10mm, and the other control materials are outside the area, which indicates that the chromaticity of the material is whiter and the transmittance higher than 92% is better than that of each control material.
In a second aspect of the present application, there is provided a method for preparing the super Bai Fei crystalline aluminosilicate oxide material, comprising:
taking various raw materials according to the composition of the super Bai Fei crystal aluminum silicon oxide material, adding sulfate and nitrate to mix to obtain a mixture, and melting, forming, annealing and slicing the mixture to prepare the super Bai Fei crystal aluminum silicon oxide material, wherein the process flow chart is shown in figure 1.
Wherein, the compounding is to transport various raw materials to the weighing machine through the conveyer belt, put into the blendor after weighing through the weighing machine and heat and add water compounding, after the compounding reaches the requirement of predetermineeing, convey the kiln through the conveyer belt and heat and melt. Heating natural gas in a kiln to melt raw materials and form feed liquid; after the material liquid is clarified through foam removal, the material liquid flows into a tin bath from a kiln, and is drawn into an amorphous aluminum silicon oxide material plate with preset thickness through a edge roller. The amorphous aluminum silicon oxide material plate enters an annealing kiln for annealing treatment after coming out of a tin bath, and after internal stress is eliminated, the amorphous aluminum silicon oxide material plate enters a cold end from the annealing kiln for slicing, split charging and packaging; the amorphous aluminum silicon oxide material of the present application may specifically be a low alkaline earth alkali aluminosilicate glass material, such as a low alkaline earth high alumina glass material.
In certain embodiments of the present application, the sulfate salt comprises sodium sulfate and/or potassium sulfate, and the nitrate salt comprises sodium nitrate and/or potassium nitrate, which are converted to volatile gases and corresponding K during melting of the materials of the present application 2 O and Na 2 O has no influence on the composition of materials; in other embodiments of the present application, the sulfate is added in an amount of 0.4 to 1.6kg, for example 0.40kg, 0.55kg, 0.72kg, 0.92kg, 1.22kg or 1.52kg, per 100kg of the mix, and the nitrate is added in an amount of 2.0 to 4.0kg, for example 2.0kg, 2.6kg, 2.9kg, 3.6kg or 4.0kg, per 100kg of the mix.
In certain embodiments of the present application, the Fe in the material is maintained by controlling the atmosphere during the melting of the material, particularly near the end (outlet side) of the kiln, to maintain a residual oxygen level greater than 2%, i.e., to maintain an oxidizing atmosphere 3+ The ratio of the components is higher than Fe 2+ The color of the material can be made lighter.
In the preparation method, the oxidative raw materials such as nitrate, sulfate and the like are added to improve the oxidation-reduction index of the mixture, and Fe in the material is enabled to be in the melting process 3+ The ratio of the components is higher than Fe 2+ Thereby realizing the effect of chemical decolorization; sulfate and nitrate have not only an oxidizing effect, but also other positive or negative effects on the melting of materials, so that the use amount of the sulfate and the nitrate in the materials has respective upper limits. For example, sulfate is a clarifier, and a proper amount can play a role in eliminating bubbles of glass, but excessive use of sulfate can cause bubble increase on one hand and can corrode kiln refractory on the other hand, and the sulfate is generally used in an amount of 0.4% -1.6% in the mixture. The nitrate is usually mixed in the amount ofThe proportion of the mixture is 2.0-4.0%. The amount of sulfate and nitrate used is preferably such that the redox index of the mixture is adjusted to +25 or higher, for example +25.7, +25.9, +26.8, +27.4, +27.9, etc.
In the preparation method, selenium and/or neodymium oxide are adopted to counteract Fe 2+ Ion color, counteracting Fe with cobalt oxide 3+ Ion color. However, physical decolorants decrease the "brightness" of the glass, i.e., decrease the light transmittance of the glass, while removing the original color of the material, and thus it is necessary to control the amount of "cancelled" primary color elements and the amount of physical decolorants added. Namely, the content of iron (calculated by ferric oxide) in the material is controlled to be less than 120ppm, the amount of selenium powder added is controlled to be 0.8-1.5ppm, the amount of neodymium oxide added is controlled to be 0.5-1.0ppm, the amount of cobalt oxide added is controlled to be 0.3-0.9ppm, and meanwhile, the requirement of the formula 1 is met, so that the light transmittance of the glass can be kept to be more than 92.0 percent, and the effect of basically counteracting the requirement of Fe is achieved 2+ And Fe (Fe) 3+ Yellow and green color induced in the glass.
In a third aspect of the present application, based on the excellent properties of the ultrawhite amorphous aluminum silicon oxide material of the present application, the application of the ultrawhite amorphous aluminum silicon oxide material or the ultrawhite amorphous aluminum silicon oxide material prepared by the preparation method in preparing a metal coated product is provided.
In a fourth aspect of the present application, a metal-coated article is provided, including the ultrawhite amorphous aluminum silicon oxide material described herein or the ultrawhite amorphous aluminum silicon oxide material prepared by the preparation method described herein, and one or more than two metal films coated on the surface thereof. The amorphous aluminum silicon oxide material is used as ingredients, and is plated with a metal material, so that various application purposes such as privacy, sunshade, heat insulation and the like are realized on the basis of excellent performance.
In certain embodiments of the present application, the metal film comprises one or more of a Cr film, a Ni film, a Ti film, an Au film, an Ag film, a Cu film, and an Al film; the Cr film, the Ni film and the Ti film have better adhesiveness with the amorphous aluminum silicon oxide material, but the infrared reflectivity is inferior to that of an Au film, an Ag film, a Cu film and an Al film, so in other embodiments of the application, the amorphous aluminum silicon oxide material can be coated with one or more layers of the Cr film, the Ni film or the Ti film firstly and then one or more layers of the Au film, the Ag film, the Cu film or the Al film, thereby better adhesiveness and heat insulation property are realized;
in certain embodiments of the present application, the Cr, ni or Ti film has a thickness of 1-10nm, e.g., 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm or 10nm, and the Au, ag, cu or Al film has a thickness of 20-50nm, e.g., 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm; in other embodiments of the present application, the amorphous aluminum silicon oxide material is first coated with a Ti film having a thickness of 5nm, and then coated with a Cu film having a thickness of 30nm.
In certain embodiments of the present application, the metal film is plated by chemical vapor deposition, vacuum evaporation, sputtering, or ion implantation. In other embodiments of the present application, the metal film is plated by magnetron sputtering.
In certain embodiments of the present application, the magnetron sputtering method has a sputtering power of 1.5-10kW and a sputtering rate of 1.5-5.0nm/s; in other embodiments of the present application, the sputtering power is 1.5-1.7kW and the sputtering rate is 1.5-2.0nm/s when the first Cr film, ni film or Ti film is plated; when plating the second Au film, ag film, cu film or Al film, the sputtering power is 5-10kW, and the sputtering rate is 3.0-5.0nm/s.
In each of the comparative experiments provided herein, unless specifically indicated otherwise, other experimental conditions, materials, etc. were consistent for comparison, except for the differences noted in each group. The experimental materials and reagents used in the examples were obtained from commercial sources unless otherwise specified.
The following further describes an ultra-white amorphous aluminum silicon oxide material and a metal coated product thereof.
Examples 1 to 6:
1. preparation method
And taking various raw materials according to the composition of the super Bai Fei crystal aluminum silicon oxide material, adding sulfate and nitrate, mixing to obtain a mixture, and melting, forming, annealing and slicing the mixture to prepare the super Bai Fei crystal aluminum silicon oxide glass material, wherein the preparation process flow is shown in figure 1.
2. Formula and performance index detection thereof
(1) Method for testing chromaticity coordinates and light transmittance
(1) The thickness of the glass material to be measured is accurately measured and is recorded as "d", and the unit is "mm".
(2) The full-band light transmittance of the glass material at 190nm-900nm was measured using a spectrophotometer.
Wherein the light transmittance at 550nm is denoted as "T%" of the light transmittance of the glass material.
(3) And (3) processing by using color analysis software ColorAnalysis of the instrument to obtain chromaticity coordinate values a and b of the glass material under the original thickness.
(4) The values of a and b at the original thickness are converted into values of a and b at a reference thickness of 1.10mm by the following formula:
a*=a÷d×1.10；b*=b÷d×1.10
wherein: a. b-the chromaticity coordinate values a, b measured at the original thickness;
d-the actual thickness of the glass (mm);
(2) Formula and detection result
TABLE 1
Filling the values of a and b into a coordinate graph of a pre-drawn chromaticity control region, see fig. 2;
as can be seen from table 1 and fig. 2, the transmittance of the ultra-white amorphous aluminum silicon oxide glass materials prepared in the present application is 92% or more, and the values of a and b are shifted to the directions of "white point" and "0,0", and are in the control region constructed by the elliptic equation "(b-0.14) ×2/0.0016+ (a+0.012) ×2/0.000324 =2", and are visually whiter.
Comparative examples 1 to 6:
preparation and detection methods of reference examples were performed according to the following table 2;
TABLE 2
Filling the values of a and b into a coordinate graph of a pre-drawn chromaticity control region, see fig. 3;
as can be seen from table 2 and fig. 3, the transmittance of the comparative amorphous aluminum silicon oxide glass material did not reach 92%, and the values of a and b were not within the control region constructed by the elliptic equation "(b-0.14) ×2/0.0016+ (a+0.012) ×2/0.000324 =2", which is inferior to the chromaticity and transmittance of the examples of the present application.
Example 7:
baking the ultra-white amorphous aluminum silicon oxide glass material for 15min at 90 ℃ before plating the metal film, and then performing plasma cleaning;
placing the ultra-white amorphous aluminum silicon oxide glass material into a magnetron sputtering coating device for coating, and setting the linear speed of a machine table: 50+ -5 mm/sec, vacuum degree < 8.0X10 -6 Pa, using inert gas as working gas, such as argon, krypton, xenon, etc., with gas flow rate of 100+ -10 sccm; firstly, plating a first layer of Ti metal film by utilizing a metal Ti target, wherein the sputtering power is 1.5kW, the sputtering rate is 1.8nm/s, and the thickness of the obtained first layer of Ti metal film is 5nm; plating a second layer of Cu metal film by utilizing a metal Cu target, wherein the sputtering power is 7.5kW, the sputtering rate is 4nm/s, and the thickness of the obtained second layer of Cu metal film is 30nm; obtaining the ultra-white amorphous aluminum silicon oxide glass material plated by the double-layer metal material.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. An ultrawhite amorphous aluminum silicon oxide material is characterized by comprising inorganic oxide, se and/or Nd 2 O 3 And Co 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Se and/or Nd 2 O 3 0.5-1.5ppm of the total weight of the super Bai Fei crystal aluminum silicon oxide material, and Co 2 O 3 0.3-0.9ppm of the total weight of the super Bai Fei crystalline aluminum silicon oxide material, wherein the inorganic oxide comprises the following components in percentage by weight:
SiO 2 58wt%-62wt%
Al 2 O 3 13%wt-15wt%
Na 2 O13%wt-16wt%
K 2 O 4wt%-7wt%
MgO 3wt%-4.9wt%
ZrO 2 0.5wt%-1.2wt%
wherein, the iron content in the inorganic oxide is less than 120ppm of the total weight of the amorphous aluminum silicon oxide material of Yu Chaobai;
the Se, nd 2 O 3 、Co 2 O 3 The content of (2) satisfies the requirement of formula 1:
0.3≤Co 2 O 3 /(Se+Nd 2 O 3 ) Less than or equal to 1, 1
In the preparation process, various raw materials are taken according to the composition of the super Bai Fei crystal aluminum silicon oxide material, sulfate and/or nitrate are added for mixing to obtain a mixture, and the super Bai Fei crystal aluminum silicon oxide material is prepared by melting, forming, annealing and slicing the mixture; the sulfate comprises sodium sulfate and/or potassium sulfate, the nitrate comprises sodium nitrate and/or potassium nitrate, and the sulfate and/or nitrate can be converted into volatile gas and corresponding K in melting 2 O and Na 2 O has no influence on the material composition.
2. The ultra-white amorphous aluminum silicon oxide material according to claim 1, wherein the sulfate is added in an amount of 0.4-1.6kg per 100kg of the mixture, and the nitrate is added in an amount of 2.0-4.0kg per 100kg of the mixture.
3. The ultra-white amorphous aluminum silicon oxide material according to claim 1, wherein the residual oxygen content is maintained to be more than 2% at the discharge port side during the preparation process.
4. Use of the ultrawhite amorphous aluminum silicon oxide material according to any one of claims 1 to 3 for preparing a metal-plated product.
5. A metal-coated article comprising the ultrawhite amorphous aluminum silicon oxide material according to any one of claims 1 to 3, and one or more metal films coated on the surface thereof.
6. The metal-plated article according to claim 5, wherein the metal film comprises one or more of a Cr film, a Ni film, a Ti film, an Au film, an Ag film, a Cu film, and an Al film.
7. The metal-coated article according to claim 5 or 6, wherein the metal film is coated by a chemical vapor deposition method, a vacuum evaporation method, a sputtering method, or an ion implantation method.
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| US5681782A (en) * | 1996-02-28 | 1997-10-28 | Corning Incorporated | Light pink glassware |
| WO2017185288A1 (en) * | 2016-04-28 | 2017-11-02 | 中国南玻集团股份有限公司 | Aluminosilicate glass and preparation method therefor, and glass plate |
| CN108821566A (en) * | 2016-04-28 | 2018-11-16 | 中国南玻集团股份有限公司 | Alumina silicate glass, preparation method and application |
| US20200002216A1 (en) * | 2018-06-27 | 2020-01-02 | Vitro Flat Glass Llc | High Alumina Low Soda Glass Compositions |
| CN111559875A (en) * | 2020-06-19 | 2020-08-21 | 广东旗滨节能玻璃有限公司 | Coated glass and preparation method thereof |
| EP3872042A1 (en) * | 2020-02-28 | 2021-09-01 | Schott AG | Cooking surface made of a las glass ceramic plate |
| CN115140949A (en) * | 2022-06-29 | 2022-10-04 | 天津旗滨节能玻璃有限公司 | Low-reflectivity LOW-transmittance LOW-E coated glass and manufacturing method thereof |
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- 2023-02-13 CN CN202310436524.4A patent/CN116693191A/en active Pending
- 2023-02-13 CN CN202310101929.2A patent/CN115925252B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5681782A (en) * | 1996-02-28 | 1997-10-28 | Corning Incorporated | Light pink glassware |
| WO2017185288A1 (en) * | 2016-04-28 | 2017-11-02 | 中国南玻集团股份有限公司 | Aluminosilicate glass and preparation method therefor, and glass plate |
| CN108821566A (en) * | 2016-04-28 | 2018-11-16 | 中国南玻集团股份有限公司 | Alumina silicate glass, preparation method and application |
| US20200002216A1 (en) * | 2018-06-27 | 2020-01-02 | Vitro Flat Glass Llc | High Alumina Low Soda Glass Compositions |
| EP3872042A1 (en) * | 2020-02-28 | 2021-09-01 | Schott AG | Cooking surface made of a las glass ceramic plate |
| CN111559875A (en) * | 2020-06-19 | 2020-08-21 | 广东旗滨节能玻璃有限公司 | Coated glass and preparation method thereof |
| CN115140949A (en) * | 2022-06-29 | 2022-10-04 | 天津旗滨节能玻璃有限公司 | Low-reflectivity LOW-transmittance LOW-E coated glass and manufacturing method thereof |
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