WO2022265484A1 - Vidrio gris de baja transmisión de luz - Google Patents
Vidrio gris de baja transmisión de luz Download PDFInfo
- Publication number
- WO2022265484A1 WO2022265484A1 PCT/MX2021/050029 MX2021050029W WO2022265484A1 WO 2022265484 A1 WO2022265484 A1 WO 2022265484A1 MX 2021050029 W MX2021050029 W MX 2021050029W WO 2022265484 A1 WO2022265484 A1 WO 2022265484A1
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- WO
- WIPO (PCT)
- Prior art keywords
- glass
- transmission
- oxide
- light transmission
- composition
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims abstract description 112
- 230000005540 biological transmission Effects 0.000 title claims abstract description 75
- 239000011669 selenium Substances 0.000 claims abstract description 36
- 230000005855 radiation Effects 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 22
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000003086 colorant Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000033116 oxidation-reduction process Effects 0.000 claims description 6
- 238000006124 Pilkington process Methods 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000006121 base glass Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 24
- 238000004040 coloring Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- NCXOIRPOXSUZHL-UHFFFAOYSA-N [Si].[Ca].[Na] Chemical compound [Si].[Ca].[Na] NCXOIRPOXSUZHL-UHFFFAOYSA-N 0.000 abstract 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 22
- 229910000428 cobalt oxide Inorganic materials 0.000 description 17
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 13
- 229910017356 Fe2C Inorganic materials 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 235000010344 sodium nitrate Nutrition 0.000 description 11
- 239000004317 sodium nitrate Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 241000549556 Nanos Species 0.000 description 7
- 229910000431 copper oxide Inorganic materials 0.000 description 7
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910001447 ferric ion Inorganic materials 0.000 description 6
- 239000005751 Copper oxide Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 229910001448 ferrous ion Inorganic materials 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 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
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000083869 Polyommatus dorylas Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PCIREHBGYFWXKH-UHFFFAOYSA-N iron oxocobalt Chemical class [Fe].[Co]=O PCIREHBGYFWXKH-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000006062 low-transmittance glass Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
Classifications
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/082—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for infrared absorbing glass
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
Definitions
- the present invention relates to a low transmittance glass, of a neutral gray color and more specifically to a composition of gray glass to produce glass for use in the automotive industry, for the manufacture of panoramic roofs, medallions and rear doors, both laminated as temperate
- Colored glass is a material to which, during the melting process, metal oxides are incorporated.
- metal oxides are incorporated.
- iron-cobalt oxides in combination with selenium, gives the glass shades from greenish gray - neutral gray to yellowish gray depending on the ratio of these.
- Solar control is the ability to modify the amount of solar radiation transmitted or reflected, in the spectral intervals of the near ultraviolet (UV; 300
- the glasses described in almost all the patents that refer to a type of neutral gray glass are based on three main colorants: iron oxide, cobalt oxide and selenium, whose main function is to provide solar control properties to the glass.
- the following prior art patents use various metal oxides as the main colorants to obtain a gray glass and provide the final characteristics of the product.
- These components such as nickel oxide, manganese oxide, chromium oxide or rare earth oxides, are mixed in a base formulation of a silico-soda-calcium glass.
- nickel oxide is used in concentrations of 500 to 1000 ppm, erbium oxide of 0.1 to 0.8% and chromium oxide in contents of 1 to 20 ppm. , in addition to a total content of iron oxide of 0.15 to 0.45%, selenium less than or equal to 3 ppm and cobalt oxide of 120 to 240 ppm.
- the mixture of these oxides is used for the general adjustment of the gray coloration of the glass.
- the light transmission of the glass of this patent is 8 to 25%, with a dominant wavelength of 435 to 570 nm, using a cobalt oxide/nickel oxide ratio of 0.22 to 0.30 and redox values of FeO/Fe2C >3 from 0.20 to 0.40.
- the main disadvantage of these glasses is the high cost of using rare earth oxides in their composition.
- the glasses presented are known to use nickel oxide in concentrations of 400 to 700 ppm or 1500 to 1900 ppm, iron oxide 0.7 to 0.95% with a redox value of 0.40 or less, in addition to 200 to 300 ppm cobalt oxide, to obtain a gray color adjustment and obtain the following physical properties: light transmission under illuminant A (TLA) of 50% or less and an average in the energy transmission (TE) less than 45%, for a glass thickness of 3.85mm.
- TLA light transmission under illuminant A
- TE energy transmission
- nickel oxide used as a colorant in some of the previous patents, has the disadvantage that nickel sulfide inclusions can form (a defect that is not easily detectable) that can cause the glass sheets to break due to to the difference in the coefficient of thermal expansion of this material with the rest of the glassy matrix.
- the glasses described in US Patent No. 8,551,899 by Kim, et al. have a dark neutral gray-green coloration, due to the dyes used, such as Fe2C>3 at 1.4 to 2.5%, CoO at 0.02 to 0.04%. , Se from 0.0001 to 0.004%, MnO from 0.005 to 0.5 and CeO from 0.05 to 1% with an illuminant light transmission A of less than 15%.
- US Patent No. 8,785,338 to Tsuzuki, et al refers to a composition of a silico-sodic-lime glass with contents of 0.70 to 1.70% by mass of Fe2Ü3 (total iron), 0.15 to 0.45% by mass of FeO (oxide ferrous), 0-0.8% by mass of T1O2, 100 to 350 ppm of CoO, 0 to 60 ppm of Se, 100 to 700 ppm of Q2O3 and 3 to 150 ppm of MnO, which has a ratio (Fe 2+ /Fe 3+ ) from ferrous ion to ferric ion from 0.20 to 0.80.
- the glass exhibits a transmittance of visible light (TLA) of 15% or less, a transmittance of direct solar energy (TDS) of 16% or less, and a transmittance of ultraviolet radiation (Tuv) of 3% or less, measured for a thickness 4mm reference.
- TLA visible light
- TDS direct solar energy
- Tiv ultraviolet radiation
- US patent No. 7,902,097 B2 by Cid-Aguilar et al. uses concentrations of: 0 to 30 ppm of C03O4, 1 to 20 ppm of Se, 20 to 200 ppm of CuO and 0.30 to 0.70% of Fe2Ü3 to obtain a glass neutral gray, with optical characteristics of light transmission with illuminant A greater than 65%, transmission of total solar energy equal to or less than 60%, transmission of ultraviolet radiation less than 46% and a dominant wavelength of 490 to 600 nm .
- This patent adds components such as carbon from 0.01 to 0.07% or sodium nitrate from 0.2 to 1.2% to modify the oxidation-reduction state of iron and copper oxide, since, in combination with the other dyes, it is used as a alternative for obtaining the gray hue, partially substituting the addition of titanium oxide and cobalt oxide.
- iron is present in glass (silico-sodic-calcic) in two compounds that depend on the oxidation state of the iron: if the iron is found as Fe 2+ , the compound formed is ferrous oxide (Ugly). If iron is found as Fe 3+ , ferric oxide (Fe2C>3) would be found. each ion confers different properties; the ferrous ion has a broad and strong absorption band centered at 1050 nm, which results in a decrease in infrared radiation. Furthermore, this band extends into the visible region, decreasing light transmission and imparting a bluish tint to the glass.
- the ferric ion presents a strong absorption band located in the ultraviolet region, which obviously prevents its transmission through the glass and, in addition, it presents two other weak bands in the visible region located between 420 and 440 nm, which cause a slight decrease in light transmission and a yellowing in the glass.
- the iron in the glass and its amount of ferrous oxide are expressed in the form of Fe2C>3. Being common in the industry to express the amount of ferrous or ferric oxide as the percentage of total iron. The balance between ferrous and ferric oxide has a direct effect on the color and transmittance characteristics of the glass, represented as:
- titanium oxide also acts as a colorant and when used in combination with Fe203, it is possible to obtain a further reduction of ultraviolet radiation transmission up to a point where the desired visibility transmission is achieved.
- TiCh titanium oxide
- TiCh titanium oxide
- the most stable form of titanium in glasses is tetravalent (T ⁇ 4+ ).
- the trivalent form could confer coloration, however, this effect is not observed in silico-sodic-calcic glass.
- T ⁇ C>2 greatly increases the refractive index, increases the absorption of light in the ultraviolet region, and that the viscosity and surface tension are reduced.
- Selenium is one of the most widely used physical bleaches for glass with traces of iron coming as an undesirable impurity in the raw materials, because its coloration neutralizes the ferrous and ferric ions present in the glass.
- the combination of iron oxide and selenium in the silico-soda-lime glass confers a reddish-brown coloration and a decrease in light transmission, due to an absorption band located in the visible region between 490 and 500nm (band similar to selenium atomic). This band extends into the ultraviolet region, also causing a decrease in this type of transmission in the glass.
- the intensity of the coloration and the final properties of the glass are a function of the concentration of iron oxide and selenium in the glass.
- Copper has been used in glass compositions, not only in those of the silico-sodic-calcic type, but in some others, such as those that contain borosilicate, for example. Therefore, the color developed depends on the base of the glass, its concentration and its oxidation state.
- copper in oxide form imparts a blue coloration of a greenish tone, specifically turquoise, however, in glass, copper can be in its monovalent state, which is not imparts color.
- the blue-green coloration depends not only on the amount of copper present, but also on the ionic balance between the cuprous and cupric states.
- the maximum absorption of copper oxide is in a band centered at 780 nm and a secondary weak maximum peak is present at 450 nm, which disappears at high soda contents (around 40 wt%) (CR Bamford Color Generation and Control in Glass, Glass Science and Technology, Elsevier Scientific Publishing Company, P.48-50, Amsterdam, 1977).
- Glass can also be manufactured in smaller thicknesses, such as the glass used in the manufacture of laminated systems. If higher concentrations of CuO are present, during the formation process inside the float chamber, a reduction process attributable to the atmosphere of the process could occur, presenting a reddish coloration on the glass surface, which is observed by reflection. This effect is related to the residence time and the advance speed of the glass batten, which means that, at lower speeds, it will be necessary to reduce the CuO content in glass or adjust the reducing conditions in the float chamber.
- a main objective of the present invention is a gray glass with low illuminating light transmission A (TLA) not greater than 15%, a direct solar energy transmission (TDS) not greater than 14%, a transmission of near infrared radiation (T IR) not more than 14%, a transmission of ultraviolet radiation (Tuv) not more than 8%, a transmission of total solar energy (TTS) not more than 38%, a purity not more than 50% and a dominant wavelength of 480-590 nm when it has a nominal thickness of 3.85 mm, manufactured by the float process.
- TLA gray glass with low illuminating light transmission A
- TDS direct solar energy transmission
- T IR near infrared radiation
- T IR transmission of ultraviolet radiation
- TTS total solar energy
- Another objective of the present invention is the use of copper oxide as a partial replacement for cobalt oxide (C03O4).
- C03O4 cobalt oxide
- T1O2 is incorporated as an additional element to the iron oxide to provide an additional reduction in the transmission of ultraviolet radiation.
- An additional objective of the present invention is also to obtain a gray glass composition with low light transmission, which includes additional elements such as carbon or sodium nitrate to modify the oxidation-reduction state of iron oxide.
- the glass of this invention avoids the use of coloring compounds such as nickel, chromium, manganese or rare earth oxides, mainly erbium oxide (Er 2 0s).
- coloring compounds such as nickel, chromium, manganese or rare earth oxides, mainly erbium oxide (Er 2 0s).
- the present invention relates to a gray glass composition that, even though its use in the automotive field is mentioned as the main application, its use in other fields such as the construction industry or other applications such as, for example, it can be used as a substrate to be coated by single or thin multi-layers applied via vacuum cathodic erosion process (MSVD), chemical vapor deposition (CVD) or other techniques.
- MSVD vacuum cathodic erosion process
- CVD chemical vapor deposition
- composition of a silico-soda-calcium glass formed by the float glass process for the automotive industry is characterized by the following formulation based on the percentage by weight with respect to the total weight of the glass:
- the glass composition of this invention is based on a silica-soda-calcium glass to which the following colorants were added to obtain a gray color:
- the main objective of adding sodium nitrate (NaNOs) and carbon to the composition is to modify the oxidation state of the iron to reach the optimal level of direct heat transfer (TDS).
- TDS direct heat transfer
- Sodium Nitrate helps to optimize selenium retention in the glass.
- This gray glass has an Illuminant Light Transmission A (TLA) not greater than
- TDS direct solar energy
- TIR near infrared radiation
- TMS transmission of energy total solar
- the glass of this invention avoids the use of coloring compounds such as nickel, chromium, manganese or rare earth oxides, mainly erbium oxide (Er203).
- TLA Illuminant A Light Transmission
- TDS Direct Solar Power Transmission
- TIR Near Infrared Radiation Transmission
- Tuv Ultraviolet Radiation Transmission
- TTS Total Solar Power Transmission
- Tables 1 and 2 show the experimental results of the composition of the present invention with the combination of iron oxide (Fe2C>3), cobalt oxide (C03O4), selenium (Se), oxide copper and titanium oxide (Ti0 ).
- Fe2C>3 iron oxide
- C03O4 cobalt oxide
- Se selenium
- Si0 oxide copper
- Ti0 titanium oxide
- NaNOs sodium nitrate
- Table 3 (examples 15 to 18) show the experimental results of the composition of the present invention with the combination of iron oxide (Fe 2 C> 3 ), cobalt oxide (C0 3 O 4 ), selenium (Se ), copper oxide and titanium oxide
- Tables 4 and 5 show the experimental results of the composition of the present invention with the combination of iron oxide (Fe2C>3), cobalt oxide (C03O4), selenium (Se), oxide copper and titanium oxide (TiCh). Likewise, they contain 0.16% sodium nitrate (NaNOs) and 0.02% carbon in the mixture.
- Table 6 shows the experimental results of the composition of the present invention with the combination of iron oxide (Fe 2 C> 3 ), cobalt oxide (C0 3 O 4 ), selenium (Se ), copper oxide and titanium oxide
- T1O2 (T1O2). In addition, they contain 0.16% sodium nitrate (NaNOs) and 0.030% carbon.
- the main objective of adding sodium nitrate (NaNOs) and carbon to the composition is to modify the oxidation state of the iron to reach the optimal level of direct heat transfer (TDS).
- Sodium Nitrate helps to optimize selenium retention in the glass. Color and privacy are adjusted by optimizing the percentages of dyes described in this invention.
- the physical properties of the glasses obtained were evaluated according to internationally accepted standards. Specifications for color determination such as dominant wavelength and excitation purity have been derived from Tristimulus (X, Y, Z) values which have been adopted by the International Commission on Illumination (CIE) as a standard. direct result of experiments involving many observers.
- CIE International Commission on Illumination
- These specifications can be determined by calculating the trichromatic coefficients x, y, z of the Tristimulus values that correspond to the colors red, green and blue respectively.
- the trichromatic values are plotted on the chromaticity diagram and compared with the coordinates of the illuminant D65, considered as a lighting standard.
- the comparison provides the information to determine the color excitation purity and its dominant wavelength.
- the dominant wavelength defines the wavelength of the color and its value is in the visible range, from 380 to 780 nm, while for excitation purity, the lower its value, the closer it tends to be. neutral colour.
- illuminant "A” TLA was used, in the wavelength range of 400 to 800 nanometers, integrating values in 10nm intervals.
- Color transmission (L*, a* and b*) was calculated according to ASTM E308 (CIE D65 observer at 10°).
- TDS direct solar energy
- T IR In the infrared transmission (T IR) the range included in the radiation of the solar spectrum is contemplated, having a range of 800 to 2500 nm, with intervals of 50 nm, using the values of the ISO/DIS 13837 standard.
- the total solar energy transmission (TTS) was evaluated in the range from 300 to 2500 nm considering a wind speed of 4 m/s (stationary), according to the ISO/DIS 13837 standard.
- the neutral gray glass of this invention can be manufactured by the float glass process from a thickness of 1.4 mm to 6 mm, however, it is not limited only to this range of thicknesses and can be processed as tempered, in window glazing systems. double, laminate process or as a substrate covered by one or more layers.
- This glass has the following properties: transmission of light with illuminant A (TLA) not greater than 15%, transmission of direct solar energy (TDS) not greater than 14%, transmission of near infrared radiation (TIR) not greater than 14 %, ultraviolet radiation transmission (Tuv) not greater than 8%, total solar energy transmission (TTS) not greater than 38% and purity not greater than 50%.
- TLA transmission of light with illuminant A
- TDS direct solar energy
- TIR near infrared radiation
- TTS total solar energy transmission
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2023577822A JP2024521976A (ja) | 2021-06-18 | 2021-06-18 | 低光透過率のグレーガラス |
EP21946187.8A EP4357308A1 (en) | 2021-06-18 | 2021-06-18 | Grey glass having low light transmission |
CN202180100903.5A CN117715877A (zh) | 2021-06-18 | 2021-06-18 | 具有低透光率的灰色玻璃 |
KR1020247001651A KR20240023120A (ko) | 2021-06-18 | 2021-06-18 | 낮은 광 투과율을 갖는 회색 유리 |
PCT/MX2021/050029 WO2022265484A1 (es) | 2021-06-18 | 2021-06-18 | Vidrio gris de baja transmisión de luz |
BR112023026662A BR112023026662A2 (pt) | 2021-06-18 | 2021-06-18 | Vidro cinza com baixa transmissão de luz |
MX2023015549A MX2023015549A (es) | 2021-06-18 | 2021-06-18 | Vidrio gris de baja transmision de luz. |
CA3223298A CA3223298A1 (en) | 2021-06-18 | 2021-06-18 | Grey glass having low light transmission |
Applications Claiming Priority (1)
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PCT/MX2021/050029 WO2022265484A1 (es) | 2021-06-18 | 2021-06-18 | Vidrio gris de baja transmisión de luz |
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WO2022265484A1 true WO2022265484A1 (es) | 2022-12-22 |
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PCT/MX2021/050029 WO2022265484A1 (es) | 2021-06-18 | 2021-06-18 | Vidrio gris de baja transmisión de luz |
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EP (1) | EP4357308A1 (es) |
JP (1) | JP2024521976A (es) |
KR (1) | KR20240023120A (es) |
CN (1) | CN117715877A (es) |
BR (1) | BR112023026662A2 (es) |
CA (1) | CA3223298A1 (es) |
MX (1) | MX2023015549A (es) |
WO (1) | WO2022265484A1 (es) |
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EP1036045A1 (en) * | 1997-12-02 | 2000-09-20 | Vidrio Plano de Mexico, S.A. de C.V. | Low light-transmitting neutral grey glass composition |
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US8785338B2 (en) | 2010-06-03 | 2014-07-22 | Central Glass Company, Limited | Glass with low solar transmittance |
US9120695B2 (en) | 2011-08-05 | 2015-09-01 | Kcc Corporation | Dark neutral gray glass composition with low transmittance, and glass formed therefrom |
US9617182B2 (en) | 2013-01-07 | 2017-04-11 | KKC Corporation | Low-transmission dark mist green glass composition |
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-
2021
- 2021-06-18 MX MX2023015549A patent/MX2023015549A/es unknown
- 2021-06-18 EP EP21946187.8A patent/EP4357308A1/en active Pending
- 2021-06-18 CN CN202180100903.5A patent/CN117715877A/zh active Pending
- 2021-06-18 WO PCT/MX2021/050029 patent/WO2022265484A1/es active Application Filing
- 2021-06-18 BR BR112023026662A patent/BR112023026662A2/pt unknown
- 2021-06-18 CA CA3223298A patent/CA3223298A1/en active Pending
- 2021-06-18 JP JP2023577822A patent/JP2024521976A/ja active Pending
- 2021-06-18 KR KR1020247001651A patent/KR20240023120A/ko active Search and Examination
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Also Published As
Publication number | Publication date |
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CN117715877A (zh) | 2024-03-15 |
EP4357308A1 (en) | 2024-04-24 |
CA3223298A1 (en) | 2022-12-22 |
JP2024521976A (ja) | 2024-06-04 |
BR112023026662A2 (pt) | 2024-03-05 |
KR20240023120A (ko) | 2024-02-20 |
MX2023015549A (es) | 2024-04-09 |
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