WO2016049400A1 - Uv blocking for improved transmission glasses - Google Patents

Uv blocking for improved transmission glasses Download PDF

Info

Publication number
WO2016049400A1
WO2016049400A1 PCT/US2015/052103 US2015052103W WO2016049400A1 WO 2016049400 A1 WO2016049400 A1 WO 2016049400A1 US 2015052103 W US2015052103 W US 2015052103W WO 2016049400 A1 WO2016049400 A1 WO 2016049400A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
glass article
glass
zno
sno
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2015/052103
Other languages
English (en)
French (fr)
Inventor
Dana Craig Bookbinder
Nicholas Francis Borrelli
Matthew John Dejneka
Timothy Michael Gross
Xiaoju GUO
Ronald Leroy Stewart
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Inc filed Critical Corning Inc
Priority to KR1020177010799A priority Critical patent/KR102530039B1/ko
Priority to JP2017516308A priority patent/JP6730264B2/ja
Priority to EP15778477.8A priority patent/EP3197841B1/en
Priority to CN201580063781.1A priority patent/CN107001113B/zh
Publication of WO2016049400A1 publication Critical patent/WO2016049400A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087Glass 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C4/00Compositions for glass with special properties
    • C03C4/08Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
    • C03C4/085Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass

Definitions

  • the present disclosure is generally related to glass articles and specifically related to glass articles used as cover or display glass, which are resistant to ultraviolet (UV) photodarkening.
  • UV ultraviolet
  • Glasses for example, strengthened glasses may be used as cover plates or windows for portable or mobile electronic communication and entertainment devices, such as cellular phones, smart phones, tablets, video players, information terminal (IT) devices, laptop computers and the like.
  • cover plate or “cover glass” includes windows or the like for display and touch screen applications, as well as in other applications requiring transparency, high strength and abrasion resistance.
  • cover glass may be used as decorative pieces such as the back and side surfaces of electronic devices.
  • other glasses which have not been chemically strengthened, are utilized as display glasses.
  • Embodiments of the present disclosure are directed to glass articles having UV absorbers that minimally reduce or eliminate UV photodarkening of the glass article.
  • UV photodarkening refers to discoloration in glass articles upon exposure to UV light.
  • a glass article is provided.
  • the glass article has a thickness ⁇ 1 .3 mm and comprises: 54-75 mol% S1O2; 8-17 mol% AI2O3; at least one of B2O3 and P 2 O 5 , wherein 0.1 mol% ⁇ B 2 O 3 + P 2 O 5 ⁇ 19 mol%; 10-20 mol% R 2 O, wherein R 2 O comprises one or more of Na2O, K 2 O, and Li 2 O; above 0 to 1 mol% SnO2; and an inorganic UV absorber.
  • the inorganic UV absorber may comprises: 0.1 -1 .0 mol% of one or more metal ions or oxides thereof, wherein the metal ions are selected from the group consisting of Ti, V, Mn, Fe, Cu, Ce, Ge, and combinations thereof; above 0 to 500 ppm by wt. of one or more metals or oxides thereof, wherein the metals are selected from the group consisting of Mo, Cr, Co and Ni; or combinations thereof.
  • the glass article which has a thickness ⁇ 1 .3 mm, comprises 0-12 mol% B 2 O 3 ; 0-7 mol% P 2 O 5 ; and 3 mol% ⁇ B 2 O 3 + P 2 O 5 ⁇ 15 mol%; and an inorganic UV absorber.
  • a glass article that is substantially free of alkali metals and oxides comprises 65-74 mol% SiO 2; 1 1 -13 mol% AI 2 O 3 ; 1 1 -16 mol% RO, wherein RO is one or more of MgO, CaO, SrO, BaO and ZnO; 2-1 1 mol% B 2 O 3 ; above 0 to 1 mol% SnO 2 ; and an inorganic UV absorber, wherein the inorganic UV absorber comprises: 0.1 -1 .0 mol% of one or more metal ions or oxides thereof, wherein the metal ions are selected from the group consisting of Ti, V, Mn, Fe, Cu, Ce, Ge, and combinations thereof; above 0 to 500 ppm by wt. of one or more metals or oxides thereof, wherein the metals are selected from the group consisting of Mo, Cr, Co and Ni; or combinations thereof.
  • the glass article comprises: 54-75 mol% S1O2; 8-17 mol% AI 2 O 3 ; 0.1 -9 mol% B 2 O 3 ; optionally P 2 O 5 , wherein 0.1 mol% ⁇ B 2 O 3 + P 2 O 5 ⁇ 19 mol%;10-20 mol% R 2 O, wherein R 2 O comprises one or more of Na2O, K 2 O, and Li 2 O; above 0 to 1 mol% SnO 2 ; and 0.5-10 mol % ZnO.
  • the glass article comprises: 54-75 mol% S1O2; 8-14 mol% AI 2 O 3 ; 0-12 mol% B 2 O 3 ; 0.1 -7 mol% P 2 O 5 ; 10-20 mol% R 2 O, wherein R 2 O comprises one or more of Na2O, K 2 O, or Li 2 O; 3 mol% ⁇ B2O3 + P2O 5 ⁇ 15 mol%; and 0.5-10 mol % ZnO.
  • the glass article is substantially free of alkali metals and oxides and comprises: 65-74 mol% S1O2; 1 1 -13 mol% AI2O3; 1 1 -16 mol% RO, wherein RO is one or more of MgO, CaO, SrO, BaO and ZnO, and wherein the glass article comprises 0.5-10 mol % ZnO; 2-1 1 mol% B2O3; and above 0 to 1 mol% SnO 2 .
  • FIG. 1 is a graphical illustration depicting the effect of T1O2 on the
  • FIG. 2 is a graphical illustration depicting the effect of T1O2 on the UV induced absorbance of the glasses in Table 1 .
  • FIG. 3 is another graphical illustration depicting the effect of T1O2 on the UV induced absorbance of the glasses in Table 1 .
  • FIG. 4 is a graphical illustration depicting the effect of TiO2 on the UV induced absorbance of the alkali-free display glasses of Table 3.
  • FIG. 5 is a graphical illustration depicting the effect of ZnO on the UV induced absorbance of the alkali aluminophosphosilicate glasses of Table 2.
  • FIG. 6 is a graphical illustration depicting the effect of ZnO on the UV induced absorbance of the alkali aluminoborosilicate glasses of Table 4.
  • FIG. 7 is a graphical illustration depicting the effect of ZnO on the UV induced absorbance of the alkali-free glasses of Table 5.
  • FIG. 8 is a graphical illustration depicting the effect of SnO 2 on the UV induced absorbance of the alkali-free glasses of Table 6.
  • Embodiments of the glass articles comprise UV absorbers suitable to reduce UV photodarkening. Many UV absorbers are contemplated for reducing UV
  • the aluminosilicate glass may be an alkali aluminosilicate, an alkali-free aluminosilicate, an aluminoborosilicate, or an aluminophosphosilicate glass.
  • the inorganic UV absorber may comprise one or more metals or oxides of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ce, Ge, or combinations thereof.
  • the inorganic UV absorber may comprise 0.1 -1 .0 mol% of one or more metal ions or oxides thereof, wherein the metal ions are selected from the group consisting of Ti, V, Mn, Fe, Cu, Ce, Ge, and combinations thereof.
  • the inorganic UV absorber may include above 0 (i.e., greater than zero) to 500 ppm by wt.
  • the inorganic UV absorber may comprise 150 ppm by wt. or less of one or more metals or oxides thereof, wherein the metals are selected from the group consisting of Mo, Cr, Co and Ni.
  • the inorganic UV absorber is T1O2. Various amounts of UV absorber are contemplated herein.
  • the glass article may comprise 0.1 -2 mol% of inorganic UV absorbers, or 0.1 -1 mol% of inorganic UV absorbers, or 0.2-1 mol% of inorganic UV absorbers, or about 0.3-0.9 mol% of inorganic UV absorbers.
  • the glass article may comprise 0.2-1 mol% ⁇ 2, or about 0.3-0.9 mol% ⁇ 2. While most of the examples below depict the impact of ⁇ 2 , it is shown in the accompanying figures and described below that beneficial impacts may be achieved by other UV absorbers such as Sb2O3, CeO2,
  • An alternative approach is doping glass with zinc that is resistant to induced coloration when exposed to ultraviolet (UV) light or plasma cleaning processes.
  • the zinc addition can be applied to any glass composition to prevent the coloration due to color center formation during deep UV exposure or by plasma cleaning. While higher amounts are also contemplated, the glass may comprise 0.5-10 mol % ZnO, or 1 -10 mol% ZnO, or 2-10 mol% ZnO, or 3-10 mol% ZnO, or 5-10 mol% ZnO in one or more embodiments.
  • the glass articles which demonstrate reduced UV photodarkening, have a UV absorbance/mm > 2 at spectrum wavelengths of about 270 nm and an induced absorbance of less than 0.025 in the visible spectrum upon exposure to UV radiation.
  • the visible spectrum encompasses wavelengths between 400 nanometers to 700 nanometers
  • the ultraviolet (UV) spectrum encompasses wavelengths below the visible spectrum (i.e, 400 nm or less), specifically encompassing wavelengths between 100 and 400 nm.
  • UV ultraviolet
  • the glass articles may have a UV absorbance/mm > 2.2 at spectrum wavelengths of about 270 nm, or a UV absorbance/mm > 2.5 at spectrum wavelengths of about 270 nm.
  • the glass may have an induced absorbance of 0.02 or less in the visible spectrum, or 0.01 or less in the visible spectrum.
  • UV radiation wavelengths could cause UV photodarkening in the glass articles unless UV absorbers are utilized.
  • UV absorbers it may be possible to have UV photodarkening upon exposure to UV Ozone radiation having a range of wavelengths delivered for a period of 16 minutes at an irradiance of 28 mW cm-1 .
  • the glass article may comprise a thickness ⁇ 1 .3 mm, or from 0.1 mm to 1 .0 mm, or from 0.2 mm to 0.8 mm.
  • the thickness of the glass sheet is less than 0.7 millimeters and the area of each of the major surfaces are greater than 60 square centimeters.
  • the present glass articles are aluminosilicate glasses, for example, an alkali aluminosilicate glass article.
  • the glass article comprises 54-75 mol% S1O2, and 8-17 mol% AI2O3. Additionally, the glass article comprises at least one of B2O3 and P2O5, wherein 0.1 mol% ⁇ B2O3 + P2O 5 ⁇ 19 mol%. Further, the glass article comprises 12-20 mol% R2O, wherein R 2 O comprises one or more of Na2O, K 2 O, and Li 2 O.
  • the aluminosilicate glass article may comprise about 54-72 mol% S1O2, or about 54-70 mol% S1O2, or about 54-65 mol% S1O2.
  • the glass article may comprise about 63-75 mol% S1O2 .
  • the aluminosilicate glass article may comprise 8-14% AI2O3 , or alternatively, other contemplated ranges such as 1 1 -17 mol% AI2O3, or 1 1 -13 mol% AI2O3 .
  • the aluminosilicate glass article may comprise alkali amounts ranging from 13-19 mol% R2O, or 14-18 mol% R2O.
  • the aluminosilicate glass article may comprise 0.1 mol% ⁇ B2O3 + P2O 5 ⁇ 19; however, for aluminoborosilicates or
  • the glass articles may comprise 1 mol% ⁇ B2O3 + P2O 5 ⁇ 15, or 3 mol% ⁇ B 2 O 3 + P 2 O 5 ⁇ 15 mol%, or 2 mol% ⁇ B 2 O 3 + P 2 O 5 ⁇ 10, or 3 mol% ⁇ B 2 O 3 + P 2 O 5 ⁇ 8.
  • the aluminoborosilicates may comprise up to 8 mol% B 2 O 3 , or 2-8 mol% B 2 O 3
  • the aluminophosphosilicates may comprise up to 7 mol% P 2 O 5 , or 0.1 -7 mol % P 2 O 5 , or 2-7 mol% P 2 O 5 .
  • the glass articles may define a sum of AI 2 O 3 + B 2 O 3 + P 2 O 5 > 12 mol%, or a sum of AI 2 O 3 + B 2 O 3 + P 2 O 5 > 16 mol%, or a sum of AI 2 O 3 + B 2 O 3 + P 2 O 5 > 19 mol%.
  • the glass articles may comprise alkaline earth components. These alkaline earth components may be included at amounts up to 17 mol% RO, wherein RO is one or more of MgO, CaO, SrO, BaO and ZnO. In further embodiments, the glass articles may comprise 0-7 mol% RO, or 0-4 mol% RO.
  • the glass article composition may be defined by the equation: -3.5 ⁇ R 2 O+RO-AI 2 O 3 ⁇ 10.
  • the glass article may be defined by the equation: -3.5 ⁇ R 2 O+RO-AI 2 O 3 ⁇ 3.5.
  • the glass articles may comprise above 0 to 1 mol% Sn or SnO 2 , or from 0.05-1 mol% Sn or SnO 2 or from 0.1 -1 mol% Sn or SnO 2 , or from 0.1 -0.5 mol% Sn or SnO 2 .
  • Sn based fining agents it is contemplated to use other fining agents such as CeO 2 .
  • the glass article may be substantially free of at least one of As 2 O 3 or Sb 2 O 3 .
  • embodiments may also be substantially free of other fining agents such as fluorine.
  • SnO 2 also is effective at reducing
  • the inclusion of SnO 2 results in an induced absorbance of about 0.02 at 400 nm.
  • the improved resistance to UV photodarkening may also be achieved for alkali-free aluminosilicate glass articles.
  • These alkali-free aluminosilicate glass compositions may include 65-72 mol% SiO 2 , 1 1 -13 mol% AI 2 O 3 , 1 1 -16 mol% RO, wherein RO is one or more of MgO, CaO, SrO, BaO and ZnO, 2-1 1 mol% B 2 O 3 ; above 0 to 1 mol% Sn or SnO 2 ; and 0.1 -1 mol% of the inorganic UV absorbers listed above.
  • the alkali-free aluminosilicate glass articles may comprise 0-3 mol% P 2 O 5 or 0-2 mol% P 2 O 5 .
  • glass articles of the present disclosure are strengthened glass articles.
  • glass articles specifically alkali aluminosilicate glass articles, may be chemically strengthened by ion exchange.
  • ions in the surface layer of the glass are replaced by - or exchanged with - larger ions having the same valence or oxidation state.
  • both the ions in the surface layer of the glass and the larger ions are monovalent alkali metal cations, such as Li + (when present in the glass), Na + , K + , Rb + , and Cs + .
  • monovalent cations in the surface layer may be replaced with monovalent cations other than alkali metal cations, such as Ag + or the like.
  • Ion exchange processes are typically carried out by immersing a glass article in a molten salt bath containing the larger ions to be exchanged with the smaller ions in the glass.
  • parameters for the ion exchange process including, but not limited to, bath composition and temperature, immersion time, the number of immersions of the glass in a salt bath (or baths), use of multiple salt baths, additional steps such as annealing, washing, and the like, are generally determined by the composition of the glass and the desired depth of layer and compressive stress of the glass that result from the strengthening operation.
  • ion exchange of alkali metal-containing glasses may be achieved by immersion in at least one molten bath containing a salt such as, but not limited to, nitrates, sulfates, and chlorides of the larger alkali metal ion.
  • a salt such as, but not limited to, nitrates, sulfates, and chlorides of the larger alkali metal ion.
  • the temperature of the molten salt bath typically is in a range from about 380°C up to about 450°C, while immersion times range from about 15 minutes up to about 40 hours. However, temperatures and immersion times different from those described above may also be used.
  • Patent Application No. 12/500,650 and U.S. Patent No. 8,312,739 are incorporated herein by reference in their entirety.
  • the glass compositions of the present disclosure are down-drawable by processes known in the art, such as slot-drawing, fusion drawing, re-drawing, and the like, and have a liquidus viscosity of at least 130 kilopoise.
  • the experimental test samples which include the compositions listed in Tables 1 -5, were cut into 1 mm thick 1 " diameter discs and the faces were polished. Spectra of the samples were taken via spectrophotometer before and after 16 min UV exposure (UVO cleaner model 7576 Jelight Co., Irvine CA.). The graphical depictions of FIGS. 1 -7 depict the visible spectra after UV exposure for various glasses.
  • the glass samples are compared based on the absorbance and induced absorbance metrics.
  • Example 1 -9 there is a compositional increase in ⁇ 2 from Example 1 to Example 9.
  • the addition of 0.1 TiO2 in Example 1 increases the absorbance/mm at the UV wavelength of 270 nm from approximately 1 .0 to 1 .5 as compared to the ⁇ 2 free Comparative Example 1 .
  • the increase in ⁇ 2 from Example 1 to Examples 2-9 increases the absorbance/mm at the UV wavelength of 270 nm from approximately 1 .0 to at least 2.0.
  • the addition of ⁇ 2 shows significant improvement in induced
  • the addition of TiO2 greatly and desirably reduces the induced absorbance.
  • the induced absorbance at 400 nm is close to 0.0, as compared to Comparative Example 1 .
  • Table 2 Alkaline earth aluminosilicate glass samples containing various amounts of TiO2.
  • FIG. 4 depicts the impact of TiO? content is plotted for these samples.
  • Examples 10-16 in Table 2 above the increase in ⁇ 2 also reduces UV photodarkening in non-strengthened alkali-free display glass. As shown, there is a compositional increase in ⁇ 2 from Example 10 to Example 16. Referring to FIG. 4, the addition of TiO2 in Examples 10-16 reduces the UV induced absorbance to less than 0.01 (1 %) in the visible range of 400-450 nm whereas the ⁇ 2 free
  • Comparative Example 2 is above 0.01 at 400 nm and only decreases to below 0.01 at longer visible wavelengths.
  • FIG. 5 depicts the impact on UV photodarkening for ZnO content for the samples in Table 3.
  • Examples 17-19 in Table 3 above the increase in ZnO reduces UV photodarkening.
  • the addition of ZnO in Examples 17-19 reduces the UV induced absorbance to less than 0.01 (1 %) in the visible range of 400- 700 nm whereas the ZnO-free Comparative Example 3 is above 0.01 at 400 nm and only decreases to below 0.01 at longer visible wavelengths; i.e., at about 600 nm and greater.
  • Table 4 Alkali-free glass samples containing various amounts of ZnO.
  • FIG. 6 depicts the impact on UV photodarkening for ZnO content for the samples in Table 4.
  • the increase in ZnO also reduces UV photodarkening in non-strengthened alkali-free display glasses.
  • the addition of ZnO in Examples 20-26 reduces the UV induced absorbance to less than 0.01 (1 %) in the visible range of 400-700 nm, whereas the induced absorbance of ZnO-free Comparative Example 4 is above 0.01 at 400 nm and only decreases to below 0.01 at longer visible wavelengths
  • FIG. 7 depicts the impact of ZnO and T1O2 on the alkali
  • Zn containing phosphate glasses may be very stable when exposed to UV light, as well as X-ray radiation.
  • Comparative Example 5 contains MgO, which is replaced primarily with ZnO.
  • UV exposure photoreduces Fe3+ to Fe2+ by accepting an electron.
  • the MgO may then stabilize the yielded Fe2+ and detrimentally promotes phosphorus-oxygen hole center (POHC) generation.
  • POHC phosphorus-oxygen hole center
  • these electrons may be excited, then forming electron color centers and/or hole centers. These color centers will absorb light in specific wavelengths, especially the visible range thereby resulting in discoloration.
  • the POHC population may also significantly increase after treatment with an oxygen plasma process.
  • this MgO stabilization of Fe2+ is minimized, thereby substantially minimizing the number of electron color centers which lead to discoloration in the visible range.
  • FIG. 8 depicts the impact of SnO 2 on the alkali aluminophosphosilicate glasses of Table 6.
  • sample 36 which includes 0 mol% SnO2
  • sample 37 which includes 0.2 mol% SnO 2
  • alkali aluminoborosilicate glass sample 38 which includes 0 mol% SnO 2
  • alkali aluminoborosilicate glass sample 39 which includes 0.2 mol% SnO 2
  • alkali aluminoborosilicate glass sample 39 which includes 0.2 mol% SnO 2
  • sample 40 which includes 0 mol% SnO 2 , has an induced absorbance of about 0.16 at 400 nm, whereas alkali
  • aluminophosphosilicate glass sample 41 which includes 0.1 mol% SnO 2 , has an induced absorbance of about 0.04 at 400 nm.
  • alkali aluminophosphosilicate glass sample 42 which includes even more SnO 2 , 0.2 mol% SnO 2 , has an induced absorbance of about 0.02 at 400 nm.
  • the SnO 2 also reduces photodarkening in alkali-free non- strengthened display glasses (Examples 43 and 44).
  • sample 43 which includes 0 mol% SnO 2
  • display glass sample 44 which includes 0.2 mol% SnO 2

Landscapes

  • 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)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Liquid Crystal (AREA)
PCT/US2015/052103 2014-09-25 2015-09-25 Uv blocking for improved transmission glasses Ceased WO2016049400A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020177010799A KR102530039B1 (ko) 2014-09-25 2015-09-25 개선된 투과 유리용 uv 차단
JP2017516308A JP6730264B2 (ja) 2014-09-25 2015-09-25 ガラスの透過性改良のためのuv遮断
EP15778477.8A EP3197841B1 (en) 2014-09-25 2015-09-25 Uv blocking for improved transmission glasses
CN201580063781.1A CN107001113B (zh) 2014-09-25 2015-09-25 用于具有改善的透光性的玻璃的uv阻隔

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462055275P 2014-09-25 2014-09-25
US62/055,275 2014-09-25

Publications (1)

Publication Number Publication Date
WO2016049400A1 true WO2016049400A1 (en) 2016-03-31

Family

ID=54291647

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2015/052103 Ceased WO2016049400A1 (en) 2014-09-25 2015-09-25 Uv blocking for improved transmission glasses

Country Status (7)

Country Link
US (3) US10501365B2 (enExample)
EP (1) EP3197841B1 (enExample)
JP (1) JP6730264B2 (enExample)
KR (1) KR102530039B1 (enExample)
CN (1) CN107001113B (enExample)
TW (2) TWI771589B (enExample)
WO (1) WO2016049400A1 (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018022453A1 (en) * 2016-07-28 2018-02-01 Corning Incorporated Glasses having resistance to photo-darkening
US10550029B2 (en) 2015-12-17 2020-02-04 Corning Incorporated Ion exchangeable glass with fast diffusion
KR20200036810A (ko) * 2017-04-18 2020-04-07 퉁수 테크놀로지 그룹 컴퍼니 리미티드 유리용 조성물, 알칼리 토류 알루미늄 규산염 유리 및 그 제조 방법과 적용
EP3212588B1 (en) * 2014-10-31 2021-04-07 Corning Incorporated Dimensionally stable fast etching glasses

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI771589B (zh) * 2014-09-25 2022-07-21 美商康寧公司 玻璃製品
TWI789367B (zh) * 2016-11-07 2023-01-11 美商康寧公司 含有鋰的玻璃
CN106746601B (zh) * 2016-12-30 2019-06-04 东旭集团有限公司 用于制备玻璃的组合物、玻璃制品及用途
CN107226614A (zh) * 2017-05-16 2017-10-03 东旭科技集团有限公司 一种玻璃用组合物和玻璃及其制备方法和应用
US11028007B2 (en) 2017-06-22 2021-06-08 Corning Incorporated Automotive glass compositions, articles and hybrid laminates
EP3810558B1 (en) 2018-06-19 2023-04-26 Corning Incorporated High strain point and high young's modulus glasses
DE102018116483A1 (de) * 2018-07-06 2020-01-09 Schott Ag Chemisch vorspannbare Gläser mit hoher chemischer Resistenz und Rißbeständigkeit
EP4355702A1 (en) 2021-06-18 2024-04-24 Corning Incorporated Colored glass articles having improved mechanical durability
CN116854366A (zh) 2021-06-18 2023-10-10 康宁股份有限公司 具有改善的机械耐久性的着色玻璃制品
US11634354B2 (en) 2021-06-18 2023-04-25 Corning Incorporated Colored glass articles having improved mechanical durability
US11802072B2 (en) 2021-06-18 2023-10-31 Corning Incorporated Gold containing silicate glass
US11597674B2 (en) 2021-06-18 2023-03-07 Corning Incorporated Colored glass articles having improved mechanical durability
US12454479B2 (en) 2021-06-18 2025-10-28 Corning Incorporated Gold containing silicate glass
US11560329B1 (en) 2021-10-04 2023-01-24 Corning Incorporated Colored glass articles having improved mechanical durability
US12378152B2 (en) 2021-06-18 2025-08-05 Corning Incorporated Colored glass articles having improved mechanical durability
US12054422B2 (en) 2021-06-18 2024-08-06 Corning Incorporated Colored glass articles having improved mechanical durability
US12240782B2 (en) 2022-05-31 2025-03-04 Corning Incorporated Ion exchangeable yellow glass articles

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19939789A1 (de) * 1999-08-21 2001-02-22 Schott Glas Alkalifreie Aluminoborosilicatgläser und deren Verwendungen
EP2075237A1 (en) * 2006-10-10 2009-07-01 Nippon Electric Glass Co., Ltd. Reinforced glass substrate
WO2010128673A1 (ja) * 2009-05-07 2010-11-11 日本電気硝子株式会社 ガラス基板及びその製造方法
US8312739B2 (en) 2008-07-29 2012-11-20 Corning Incorporated Dual stage ion exchange for chemical strengthening of glass
WO2013191110A1 (ja) * 2012-06-18 2013-12-27 日本電気硝子株式会社 非接触給電用支持部材
WO2014120641A2 (en) * 2013-01-31 2014-08-07 Corning Incorporated Transition metal-containing, ion exchangeable colored glasses

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1393118A (en) 1971-09-16 1975-05-07 Pilkington Brothers Ltd Manufacture of flat glass
US4287380A (en) 1979-09-18 1981-09-01 Emhart Industries, Inc. Electrode assembly for molten glass forehearth
US4429402A (en) 1981-11-04 1984-01-31 Corning Glass Works Devices for use in a glass-melting furnace
US4433419A (en) 1982-04-23 1984-02-21 Owens-Corning Fiberglas Corporation Electrode purge sleeve for glass melting furnaces
US4862477A (en) 1988-09-01 1989-08-29 Manville Corporation Apparatus and method for melting and homogenizing batch material
US5151918A (en) 1990-08-28 1992-09-29 Argent Ronald D Electrode blocks and block assemblies
US5153151A (en) * 1991-05-06 1992-10-06 Corning Incorporated High index fluorine-free phosphate glasses
US5851939A (en) 1995-09-28 1998-12-22 Nippon Electric Glass Co., Ltd. Alkali-free glass substrate
WO1997014661A1 (en) 1995-10-18 1997-04-24 Corning Incorporated High-index glasses that absorb uv radiation
DE19616633C1 (de) 1996-04-26 1997-05-07 Schott Glaswerke Chemisch vorspannbare Aluminosilicatgläser und deren Verwendung
DE19916296C1 (de) 1999-04-12 2001-01-18 Schott Glas Alkalifreies Aluminoborosilicatglas und dessen Verwendung
DE19934072C2 (de) 1999-07-23 2001-06-13 Schott Glas Alkalifreies Aluminoborosilicatglas, seine Verwendungen und Verfahren zu seiner Herstellung
JP2001316128A (ja) 2000-03-02 2001-11-13 Nippon Sheet Glass Co Ltd 淡色着色高透過ガラスおよびその製造方法
CN1307116C (zh) * 2002-05-16 2007-03-28 肖特股份有限公司 防uv硼硅玻璃、其应用以及一种荧光灯
DE102004007436B4 (de) 2004-02-16 2017-11-16 Schott Ag Verwendung eines B2O3 - freien kristallisationsstabilen Aluminosilikatglases und dessen Herstellung
DE102004022629B9 (de) * 2004-05-07 2008-09-04 Schott Ag Gefloatetes Lithium-Aluminosilikat-Flachglas mit hoher Temperaturbeständigkeit, das chemisch und thermisch vorspannbar ist und dessen Verwendung
US7435696B2 (en) 2005-07-15 2008-10-14 Vidrio Plano De Mexico, S.A. De C.V. Glass composition with high visible light transmission and low ultraviolet light transmission
CN101541697A (zh) 2006-11-10 2009-09-23 旭硝子株式会社 平板显示器用玻璃基板及其制造方法以及采用该玻璃基板的显示面板
FR2909374B1 (fr) 2006-11-30 2016-11-25 Soc En Nom Collectif Dite : Eurokera Vitroceramiques de beta-quartz, transparentes et incolores, a faible teneur en tio2; articles en lesdites vitroceramiques ; verres precurseurs, procedes d'elaboration
US7666511B2 (en) 2007-05-18 2010-02-23 Corning Incorporated Down-drawable, chemically strengthened glass for cover plate
CN101074146B (zh) 2007-06-16 2010-10-06 成都光明光电股份有限公司 吸收紫外光的低膨胀系数玻璃
JP5467490B2 (ja) 2007-08-03 2014-04-09 日本電気硝子株式会社 強化ガラス基板の製造方法及び強化ガラス基板
KR20110036828A (ko) 2008-07-11 2011-04-11 코닝 인코포레이티드 소비자 어플리케이션용 압축 표면을 구비한 유리
US8504330B2 (en) 2008-07-14 2013-08-06 Nec Laboratories America, Inc. Parallelizing bounded model checking using tunnels over a distributed framework
US8341976B2 (en) 2009-02-19 2013-01-01 Corning Incorporated Method of separating strengthened glass
US8361915B2 (en) 2009-05-22 2013-01-29 Vidrio Plano De Mexico, S.A. De C.V. Glass composition
US8759238B2 (en) 2010-05-27 2014-06-24 Corning Incorporated Ion exchangeable glasses
WO2011158366A1 (ja) 2010-06-17 2011-12-22 旭硝子株式会社 ガラス基板及びその製造方法
JP5837492B2 (ja) 2010-06-30 2015-12-24 Hoya株式会社 情報記録媒体用ガラス基板
US20120052271A1 (en) * 2010-08-26 2012-03-01 Sinue Gomez Two-step method for strengthening glass
TW201245080A (en) * 2011-03-17 2012-11-16 Asahi Glass Co Ltd Glass for chemical strengthening
CN102690059B (zh) * 2011-03-23 2016-08-03 肖特玻璃科技(苏州)有限公司 用于化学钢化的铝硅酸盐玻璃和玻璃陶瓷
WO2013074779A1 (en) 2011-11-16 2013-05-23 Corning Incorporated Ion exchangeable glass with high crack initiation threshold
CN104619664A (zh) * 2012-09-14 2015-05-13 旭硝子株式会社 化学强化用玻璃、化学强化玻璃以及化学强化用玻璃的制造方法
US9403716B2 (en) * 2012-09-27 2016-08-02 Corning Incorporated Glass-ceramic(s); associated formable and/or color-tunable, crystallizable glass(es); and associated process(es)
CN103641309B (zh) 2013-11-01 2018-10-16 何开生 吸收紫外线和红外线的玻璃组合物及其应用
US9834473B2 (en) 2014-02-20 2017-12-05 Corning Incorporated UV photobleaching of glass having UV-induced colorization
TWI771589B (zh) * 2014-09-25 2022-07-21 美商康寧公司 玻璃製品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19939789A1 (de) * 1999-08-21 2001-02-22 Schott Glas Alkalifreie Aluminoborosilicatgläser und deren Verwendungen
EP2075237A1 (en) * 2006-10-10 2009-07-01 Nippon Electric Glass Co., Ltd. Reinforced glass substrate
US8312739B2 (en) 2008-07-29 2012-11-20 Corning Incorporated Dual stage ion exchange for chemical strengthening of glass
WO2010128673A1 (ja) * 2009-05-07 2010-11-11 日本電気硝子株式会社 ガラス基板及びその製造方法
WO2013191110A1 (ja) * 2012-06-18 2013-12-27 日本電気硝子株式会社 非接触給電用支持部材
WO2014120641A2 (en) * 2013-01-31 2014-08-07 Corning Incorporated Transition metal-containing, ion exchangeable colored glasses

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3212588B1 (en) * 2014-10-31 2021-04-07 Corning Incorporated Dimensionally stable fast etching glasses
US10550029B2 (en) 2015-12-17 2020-02-04 Corning Incorporated Ion exchangeable glass with fast diffusion
US11932577B2 (en) 2015-12-17 2024-03-19 Corning Incorporated Ion exchangeable glass with fast diffusion
WO2018022453A1 (en) * 2016-07-28 2018-02-01 Corning Incorporated Glasses having resistance to photo-darkening
CN109476530A (zh) * 2016-07-28 2019-03-15 康宁股份有限公司 具有抗光致暗化性的玻璃
US11407675B2 (en) 2016-07-28 2022-08-09 Corning Incorporated Glasses having resistance to photo-darkening
KR20200036810A (ko) * 2017-04-18 2020-04-07 퉁수 테크놀로지 그룹 컴퍼니 리미티드 유리용 조성물, 알칼리 토류 알루미늄 규산염 유리 및 그 제조 방법과 적용
EP3613710A4 (en) * 2017-04-18 2020-04-29 Tunghsu Technology Group Co., Ltd. COMPOSITION FOR GLASS, ALKALIALUMINOSILICATE GLASS AND PRODUCTION METHOD THEREFOR AND APPLICATIONS THEREOF
JP2020517563A (ja) * 2017-04-18 2020-06-18 トンシュー テクノロジー グループ カンパニー リミテッドTunghsu Technology Group Co., Ltd. ガラス用組成物、アルカリ土類アルミノシリケートガラス、その製造方法及び応用
KR102282396B1 (ko) * 2017-04-18 2021-07-28 퉁수 테크놀로지 그룹 컴퍼니 리미티드 유리용 조성물, 알칼리 토류 알루미늄 규산염 유리 및 그 제조 방법과 적용
US11407674B2 (en) 2017-04-18 2022-08-09 Tunghsu Technology Group Co., Ltd. Composition for glass, alkaline-earth aluminosilicate glass, and preparation method and application thereof

Also Published As

Publication number Publication date
TW201940447A (zh) 2019-10-16
EP3197841B1 (en) 2021-12-08
TW201619089A (zh) 2016-06-01
US20160090321A1 (en) 2016-03-31
KR20170058423A (ko) 2017-05-26
CN107001113B (zh) 2021-09-10
KR102530039B1 (ko) 2023-05-08
JP6730264B2 (ja) 2020-07-29
TWI695821B (zh) 2020-06-11
JP2017533877A (ja) 2017-11-16
TWI771589B (zh) 2022-07-21
US20200079682A1 (en) 2020-03-12
US20230061747A1 (en) 2023-03-02
CN107001113A (zh) 2017-08-01
US10501365B2 (en) 2019-12-10
EP3197841A1 (en) 2017-08-02
US11498865B2 (en) 2022-11-15

Similar Documents

Publication Publication Date Title
US20230061747A1 (en) Uv blocking for improved transmission glasses
JP5689075B2 (ja) ディスプレイカバーガラス用ガラス基板及びその製造方法
CN107223116B (zh) 玻璃或玻璃-陶瓷制品中的由x射线引发的着色
JP5589379B2 (ja) ディスプレイカバーガラス用ガラス基板の製造方法
JP2017511785A (ja) 強度および抗菌性を高めたガラス、およびそれを製造する方法
US10723652B2 (en) Tempered and colorless antimicrobial soda lime glass and methods of making and using same
WO2016028554A1 (en) Antimicrobial articles with copper nanoparticles and methods of making and using same
JP2013071878A (ja) 抗菌性ガラス及び該抗菌性ガラスの製造方法
CN106458704B (zh) 抗微生物玻璃制品的制造方法
US20190270666A1 (en) Glasses having resistance to photo-darkening

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15778477

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017516308

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2015778477

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015778477

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20177010799

Country of ref document: KR

Kind code of ref document: A