WO2013063002A2 - Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability - Google Patents

Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability Download PDF

Info

Publication number
WO2013063002A2
WO2013063002A2 PCT/US2012/061534 US2012061534W WO2013063002A2 WO 2013063002 A2 WO2013063002 A2 WO 2013063002A2 US 2012061534 W US2012061534 W US 2012061534W WO 2013063002 A2 WO2013063002 A2 WO 2013063002A2
Authority
WO
WIPO (PCT)
Prior art keywords
mol
glass composition
glass
equal
composition
Prior art date
Application number
PCT/US2012/061534
Other languages
French (fr)
Other versions
WO2013063002A3 (en
Inventor
Melinda Ann DRAKE
Robert Michael MORENA
Original Assignee
Corning Incorporated
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
Priority to RU2014116644A priority Critical patent/RU2632084C2/en
Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to EP18205364.5A priority patent/EP3546433A1/en
Priority to MX2014004971A priority patent/MX366947B/en
Priority to EP12781010.9A priority patent/EP2771293B1/en
Priority to CN201910114588.6A priority patent/CN109704566B/en
Priority to KR1020197007397A priority patent/KR102120349B1/en
Priority to JP2014538893A priority patent/JP6204920B2/en
Priority to CN201280052382.1A priority patent/CN104066695B/en
Priority to AU2012328981A priority patent/AU2012328981B2/en
Priority to KR1020147012855A priority patent/KR102068774B1/en
Publication of WO2013063002A2 publication Critical patent/WO2013063002A2/en
Publication of WO2013063002A3 publication Critical patent/WO2013063002A3/en
Priority to AU2016203653A priority patent/AU2016203653B2/en

Links

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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/06—Ampoules or carpules
    • A61J1/065—Rigid ampoules, e.g. glass ampoules
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • 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
    • C03C2203/00—Production processes
    • C03C2203/50—After-treatment
    • 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
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31—Surface property or characteristic of web, sheet or block
    • Y10T428/315—Surface modified glass [e.g., tempered, strengthened, etc.]

Definitions

  • the present specification generally relates to glass compositions and, more specifically, to chemically durable glass compositions which are free from boron and compounds of boron and which are suitable for use in pharmaceutical packaging.
  • glass has been used as the preferred material for packaging pharmaceuticals because of its hermetic ity, optical clarity, and excellent chemical durability relative to other materials.
  • the glass used in pharmaceutical packaging must have adequate chemical durability so as to not affect the stability of the pharmaceutical compositions contained therein.
  • Glasses having suitable chemical durability include those glass compositions within the ASTM standard 'Type la' and 'Type lb' glass compositions which have a proven history of chemical durability.
  • Type la and Type lb glass compositions are commonly used in pharmaceutical packages, they do suffer from several deficiencies. Foremost is the tendency of these glasses to phase separate. Specifically, the glass tends to separate on a fine microscopic scale into an alkali borate phase and silica rich phase. This phase separation may be a precursor to the glass flakes and de- lamination phenomena that have been reported in such glasses.
  • a second deficiency is that the low levels of alkali and alumina in Type la and Type lb glass compositions result in only a minimal ability to ion exchange and strengthen these glasses. As a result, pharmaceutical packages made from Type la and lb pharmaceutical glasses offer poor resistance to damage from mechanical events such as impacts and scratches.
  • a glass composition may include from about 67 mol.% to about 75 mol.%> Si0 2 ; from about 6 mol.% to about 10 mol.%> AI2O3; from about 5 mol.% to about 12 mol.% alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide.
  • the alkali oxide comprises at least Na 2 0 and K 2 0.
  • the glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening of glass to improve mechanical durability.
  • a glass composition may include from about 67 mol.% to about 75 mol.% Si0 2 ; from about 6 mol.% to about 10 mol.% ⁇ 1 2 ⁇ 3; from about 5 mol.% to about 12 mol.%) alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide.
  • the alkaline earth oxide comprises at least one of SrO and BaO.
  • the glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening the glass to improve mechanical durability.
  • a pharmaceutical package for a pharmaceutical composition may include a glass composition comprising from about 67 mol.% to about 75 mol.% Si0 2 ; from about 6 mol.% to about 10 mol.% Al 2 (3 ⁇ 4; from about 5 mol.% to about 12 mol.% alkali oxide; and from about 9 mol.%> to about 15 mol.% of alkaline earth oxide.
  • the alkali oxide comprises at least Na 2 0 and K 2 0.
  • the composition is free from boron and compounds of boron and has at least a class S3 acid resistance according to DIN 121 16; a class Al base resistance according to ISO 695; and a type HGA1 hydrolytic resistance according to ISO 720.
  • the pharmaceutical package may be ion exchange strengthened to improve the mechanical durability of the package.
  • FIG. 1 graphically depicts the ion-exchange properties (compressive stress and depth of layer) for inventive glass composition and, for purposes of comparison, Type I B glass compositions.
  • glass compositions which exhibit improved chemical and mechanical durability.
  • Such glass compositions are suitable for use in various applications including, without limitation, as pharmaceutical packaging materials.
  • the glass compositions may also be chemically strengthened thereby imparting increased mechanical durability to the glass.
  • the glass compositions described herein generally comprise silica (S1O2), alumina (AI2O 3 ), alkaline earth oxides, and alkali oxides (such as Na 2 0 and K 2 0) in amounts which impart chemical durability to the glass composition.
  • the alkali oxide present in the glass compositions facilitate chemically strengthening the glass compositions by ion exchange.
  • Various embodiments of the glass compositions will be described herein and further illustrated with reference to specific examples.
  • the term "softening point,” as used herein, refers to the temperature at which the viscosity of the glass composition is lxl 0 76 poise.
  • the term “annealing point,” as used herein, refers to the temperature at which the viscosity of the glass composition is lxlO 13 poise.
  • CTE refers to the coefficient of thermal expansion of the glass composition over a temperature range from about RT to about 300°C.
  • the term "chemical durability,” as used herein, refers to the ability of the glass composition to resist degradation upon exposure to specified chemical conditions. Specifically, the chemical durability of the glass compositions described herein was assessed according to 3 established material testing standards: DIN 121 16 entitled “Testing of glass - Resistance to attack by a boiling aqueous solution of hydrochloric acid - Method of test and classification”; ISO 695: 1991 entitled “Glass— Resistance to attack by a boiling aqueous solution of mixed alkali - Method of test and classification”; and ISO 720: 1985 entitled “Glass - Hydrolytic resistance of glass grains at 121 degrees C ⁇ Method of test and classification.” Each standard and the classifications within each standard are described in further detail herein.
  • the glass compositions described herein are alkaline earth alumino-silicate glass compositions which generally include a combination of Si0 2 , AI2O3, at least one alkaline earth oxide, alkali oxide including at least as Na 2 0 and K 2 0, and are free from boron and compounds containing boron.
  • the combination of these components enables a glass composition which is resistant to chemical degradation and is also suitable for chemical strengthening by ion exchange.
  • the glass compositions may further comprise minor amounts of one or more additional oxides such as, for example, Sn0 2 , Zr0 2 , ZnO, or the like. These components may be added as fining agents and/or to further enhance the chemical durability of the glass composition.
  • Si0 2 is the largest constituent of the composition and, as such, is the primary constituent of the glass network.
  • Si0 2 enhances the chemical durability and, in particular, the resistance of the glass composition to decomposition in acid. Accordingly, a high Si0 2 concentration is generally desired.
  • the formability of the glass may be diminished as higher concentrations of Si0 2 increase the difficulty of melting the glass which, in turn, adversely impacts the formability of the glass.
  • additions of alkali oxide assist in offsetting this effect by decreasing the softening point of the glass.
  • the glass composition generally comprises Si0 2 in an amount greater than or equal to about 67 mol.% and less than or equal to about 75 mol.%.
  • S1O2 is present in the glass composition in an amount greater than or equal to about 67 mol.% and less than or equal to about 73 mol.%.
  • the amount of S1O2 present in the glass composition may be greater than or equal to about 70 mol.% or even greater than or equal to about 72 mol.%.
  • the glass compositions described herein further include AI2O3.
  • additions of AI2O3 to the composition reduce the propensity of alkali constituents (such as Na and K) from leaching out of the glass and, as such, additions of AI2O3 increase the resistance of the composition to hydro lytic degradation.
  • additions of AI2O3 greater than about 10 mol.% may also increase the softening point of the glass thereby reducing the formability of the glass.
  • the glass compositions described herein generally include AI2O3 in an amount greater than or equal to about 6 mol.% and less than or equal to about 10 mol.%. In some embodiments, the amount of AI2O3 in the glass composition is greater than or equal to about 7 mol.%) and less than or equal to about 10 mol.%.
  • the glass compositions also include at least two alkali oxides.
  • the alkali oxides facilitate the ion exchangeability of the glass composition and, as such, facilitate chemically strengthening the glass substrate.
  • the alkali oxides also lower the softening point of the glass thereby offsetting the increase in the softening point due to higher concentrations of Si02 in the glass composition.
  • the alkali oxides also assist in improving the chemical durability of the glass composition.
  • the alkali oxides are generally present in the glass composition in an amount greater than or equal to about 5 mol.% and less than or equal to about 12 mol.%. In some of these embodiments, the amount of alkali oxides may be greater than or equal to about 5 mol.%) and less than or equal to about 10 mol.%.
  • the amount of alkali oxide may be greater than or equal to about 5 mol.% and less than or equal to about 8 mol.%.
  • the alkali oxides comprise at least Na 2 ⁇ 3 and K 2 O.
  • the alkali oxides further comprise L12O.
  • the ion exchangeability of the glass composition is primarily imparted to the glass composition by the amount of the alkali oxide Na 2 0 initially present in the glass composition prior to ion exchange.
  • the glass compositions include Na20 in an amount greater than or equal to about 2.5 mol.% and less than or equal to about 10 mol.% based on the molecular weight of the glass composition.
  • the glass composition may include Na 2 0 in an amount greater than or equal to about 3.5 mol.% and less than or equal to about 8 mol.%.
  • the glass composition may include Na 2 0 in an amount greater than or equal to about 6 mol.%) and less than or equal to about 8 mol.%.
  • the alkali oxides in the glass composition also include K2O.
  • the amount of K2O present in the glass composition also relates to the ion exchangeability of the glass composition. Specifically, as the amount of K2O present in the glass composition increases, the compressive stress obtainable through ion exchange decreases. Accordingly, it is desirable to limit the amount of K2O present in the glass composition. In some embodiments, the amount of K2O is greater than 0 mol.%> and less than or equal to about 2.5 mol.%) by molecular weight of the glass composition. In some of these embodiments, the amount of K2O present in the glass composition is less than or equal to about 0.5 mol.% by molecular weight of the glass composition.
  • the alkali oxide in the glass composition further comprises L12O. Including L12O in the glass composition further decreases the softening point of the glass. In embodiments where the alkali oxide includes L12O, the L12O may be present in an amount greater than or equal to about 1 mol.% and less than or equal to about 3 mol.%. In some embodiments, L12O may be present in the glass composition in an amount which is greater than about 2 mol.% and less than or equal to about 3 mol.%.
  • the alkaline earth oxides present in the composition improve the meltability of the glass batch materials and increase the chemical durability of the glass composition.
  • the presence of alkaline earth oxides in the glass composition also reduce the susceptibility of the glass to de-lamination.
  • the glass compositions generally include from about 9 mol.% to about 15 mol.% of alkaline earth oxide.
  • the amount of alkaline earth oxide in the glass composition may be from about 10 mol.% to about 14 mol.%.
  • the alkaline earth oxide in the glass composition may include MgO, CaO, SrO, BaO or combinations thereof.
  • the alkaline earth oxide includes MgO.
  • MgO is present in the glass composition in an amount which is greater than or equal to about 3 mol.% and less than or equal to about 7 mol.% by molecular weight of the glass composition or even greater than or equal about 2 mol.% and less than or equal to about 5 mol.% by molecular weight of the glass composition.
  • the alkaline earth oxide also includes CaO.
  • CaO is present in the glass composition in an amount from about 3 mol.% to less than or equal to 7 mol.% by molecular weight of the glass composition. In some of these embodiments, CaO may be present in the glass composition in an amount greater than or equal to about 4 mol.% and less than or equal to about 7 mol.%.
  • the alkaline earth oxide further comprises at least one of SrO or BaO.
  • SrO reduces the liquidus temperature of the glass composition and, as a result, improves the formability of the glass composition.
  • the glass composition may include SrO in an amount greater than about 0 mol.% and less than or equal to about 5 mol.%. In some of these embodiments, the glass composition may include from about 1 mol.% to about 2 mol.% SrO.
  • the BaO may be present in an amount greater than about 0 mol.% and less than about 2 mol.%. In some of these embodiments, BaO may be present in the glass composition in an amount less than or equal to about 1.5 mol.% or even less than or equal to about 0.5 mol.%. However, in some other embodiments, the glass composition is free from barium and compounds of barium.
  • the glass compositions are free from boron and compounds of boron such as B2O3. Specifically, it has been determined that forming the glass composition without boron or compounds of boron significantly increases the chemical durability of the glass composition. In addition, it has also been determined that forming the glass composition without boron or compounds of boron improves the ion exchangeability of the glass compositions by reducing the process time and/or temperature required to achieve a specific value of compressive stress and/or depth of layer.
  • the glass compositions described herein may optionally further comprise one or more fining agents such as, for example, Sn0 2 , AS2O3, and/or CI " (from NaCl or the like).
  • a fining agent When a fining agent is present in the glass composition, the fining agent may be present in an amount less than or equal to about 1 mol.% or even less than or equal to about 0.5 mol.%.
  • the glass composition may include SnC>2 as a fining agent.
  • Sn0 2 may be present in the glass composition in an amount greater than about 0 mol.% and less than or equal to about 0.30 mol.%.
  • the glass compositions described herein may comprise one or more additional metal oxides to further improve the chemical durability of the glass composition.
  • the glass composition may further include ZnO or Zr0 2 , each of which further improves the resistance of the glass composition to chemical attack.
  • the additional metal oxide may be present in an amount which is greater than or equal to about 0 mol.% and less than or equal to about 1.5 mol.%.
  • the additional metal oxide when the additional metal oxide is Zr0 2 , the Zr0 2 may be present in an amount less than or equal to about 1.5 mol.%.
  • the glass composition includes from about 67 mol.% to about 75 mol.% Si0 2 ; from about 6 mol.% to about 10 mol.% AI2O3; from about 5 mol.% to about 12 mol.% alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide.
  • the alkali oxide comprises at least Na 2 0 and K 2 0.
  • the glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening the glass to improve the mechanical durability.
  • Na 2 0 may be present in an amount from about 6 mol.%) to about 8 mol.%.
  • the K 2 0 may be present in an amount less than or equal to about 0.5 mol.%).
  • the alkali metal oxide may further comprise Li 2 0 in an amount from about 2 mol.%) to about 3 mol.%.
  • the alkaline earth oxide may be present in an amount from about 10 mol.% to about 14 mol.% and may comprise at least one of SrO and BaO.
  • SrO may be present in an amount greater than or equal to about 1 mol.% and less than or equal to about 2 mol.%.
  • the glass composition is free from barium and compounds of barium.
  • the alkaline earth oxide may also comprise MgO and CaO.
  • the concentration of AI2O3 may be greater than about 7 mol. %.
  • the glass composition may further include Zr0 2 in an amount less than or equal to about 1.5 mol.% and/or Sn0 2 in an amount less than or equal to about 0.3 mol.%.
  • a glass composition may include from about 67 mol.% to about 75 mol.% Si0 2 ; from about 6 mol.% to about 10 mol.% AI2O3; from about 5 mol.%) to about 12 mol.% alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide.
  • the alkaline earth oxide comprises at least one of SrO and BaO.
  • the glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening the glass to improve the mechanical durability.
  • the alkali oxide may include Na 2 0 and K 2 0.
  • the Na 2 0 may be present in an amount from about 6 mol.% to about 8 mol.%.
  • the K 2 0 may be present in an amount less than or equal to about 0.5 mol.%.
  • the alkaline earth oxide comprises SrO
  • SrO may be present in an amount greater than or equal to about 1 mol.% and less than or equal to about 2 mol.%.
  • the glass composition is free from barium and compounds of barium.
  • the alkaline earth oxide may also comprise MgO and CaO.
  • the concentration of Al 2 03 may be greater than about 7 mol. %.
  • the glass composition may further include Zr0 2 in an amount less than or equal to about 1.5 mol.% and/or Sn0 2 in an amount less than or equal to about 0.3 mol.%.
  • the glass compositions generally have softening points of less than about 1040°C or even less than about 950°C. In some embodiments, the softening point of the glass composition is less than about 900°C. These lower softening points improve the ease of formability of the glass composition.
  • the glass compositions have a CTE of less than about 70xlO "7 " ' or even less than about 60xlO "7 ' ' . These lower CTE values improve the survivability of the glass to thermal cycling or thermal stress conditions relative to glass compositions with higher CTEs.
  • the presence of alkali oxides in the glass composition facilitates chemically strengthening the glass by ion exchange. By varying the concentration of alkali oxides in the glass, specifically the concentration of a 2 0 in the glass, a wide range of compressive stresses and depth of layer values are possible for various ion-exchange processing conditions.
  • compressive stress from about 200 MPa to about 850 MPa and depth of layers from about 15 ⁇ to about 50 ⁇ or greater may be obtained in some glass compositions described herein after the glass composition is treated in a salt bath of 100% molten KNO3 at a temperatures from about 400°C to about 500°C for a time period of less than about 30 hours or even less than about 20 hours.
  • the glass compositions described herein can be chemically strengthened by ion exchange. Exemplary depths of layer and the corresponding compressive stress are graphically depicted in FIG. 1. Also, for purposes of comparison, the depth of layer and compressive stress obtainable for Type l b glass are also depicted. As shown in FIG. 1 , the glass compositions described herein may be ion exchanged to achieve a much greater compressive stress and depth of layer than Type 1 b glass.
  • the glass compositions are chemically durable and resistant to degradation as determined by the DIN 121 16 standard, the ISO 695 standard, and the ISO 720 standard.
  • the DIN 121 16 standard is a measure of the resistance of the glass to decomposition when placed in an acidic solution.
  • the DIN 121 16 standard utilizes a polished glass sample of a known surface area which is weighed and then positioned in contact with a proportional amount of boiling 6M hydrochloric acid for 6 hours. The sample is then removed from the solution, dried and weighed again. The glass mass lost during exposure to the acidic solution is a measure of the acid durability of the sample with smaller numbers indicative of greater durability. The results of the test are reported in units of mass per surface area, specifically mg/dm 2 .
  • the DIN 12116 standard is broken into individual classes.
  • Class S I indicates a half weight losses of up to 0.7 mg/dm 2 ; Class S2 indicates a half weight losses from 0.7 mg/dm 2 up to 1.5 mg/dm 2 ; Class S3 indicates a half weight losses from 1.5 mg/dm 2 up to 15 mg dm 2 ; and Class S4 indicates a half weight losses of more than 15 mg/dm 2 .
  • the ISO 695 standard is a measure of the resistance of the glass to decomposition when placed in a basic solution. In brief, the ISO 695 standard utilizes a polished glass sample which is weighed and then placed in a solution of boiling 1M NaOH + 0.5M Na 2 C0 3 for 3 hours. The sample is then removed from the solution, dried and weighed again.
  • the glass mass lost during exposure to the basic solution is a measure of the base durability of the sample with smaller numbers indicative of greater durability.
  • the results of the ISO 695 standard are reported in units of mass per surface area, specifically mg/dm 2 .
  • the ISO 695 standard is broken into individual classes. Class Al indicates weight losses of up to 75 mg/dm 2 ; Class A2 indicates weight losses from 75 mg/dm 2 up to 175 mg/dm 2 ; and Class A3 indicates weight losses of more than 175 mg/dm 2 .
  • the ISO 720 standard is a measure of the resistance of the glass to degradation in distilled water.
  • the ISO 720 standard protocol utilizes crushed grass grains which are placed in contact with 18 ⁇ water under autoclave conditions (121 °C, 2 attn) for 30 minutes. The solution is then titrated colorimetrically with dilute HC1 to neutral pH. The amount of HCL required to titrate to a neutral solution is then converted to an equivalent of Na 2 0 extracted from the glass and reported in ⁇ g of glass with smaller values indicative of greater durability.
  • the ISO 720 standard is broken into individual types.
  • Type HGA1 is indicative of up to 31 ⁇ g extracted equivalent of Na 2 0;
  • Type HGA2 is indicative of more than 31 ⁇ g and up to 62 g extracted equivalent of Na 2 0;
  • Type HGA3 is indicative of more than 62 ⁇ g and up to 264 ⁇ g extracted equivalent of Na 2 0;
  • Type HGA4 is indicative of more than 264 ⁇ g and up to 620 ⁇ g extracted equivalent of Na 2 0;
  • Type HGA5 is indicative of more than 620 g and up to 1085 ⁇ g extracted equivalent of Na 2 0.
  • the glass compositions described herein have an acid resistance of at least class S3 according to DIN 121 16 with some embodiments having an acid resistance of at least class S2 or even class S I . Further, the glass compositions described herein have a base resistance according to ISO 695 of at least class A2 with some embodiments having a class Al base resistance. The glass compositions described herein also have a DIN 121 16 type HGA2 hydrolytic resistance with some embodiments having a type HGA1 hydrolytic resistance.
  • the glass compositions described herein are formed by mixing a batch of glass raw materials (e.g., powders of Si0 2 , Al 2 0 3 , alkali carbonates, alkaline earth carbonates and the like) such that the batch of glass raw materials has the desired composition. Thereafter, the batch of glass raw materials is heated to form a molten glass composition which is subsequently cooled and solidified to form the glass composition. During solidification (i.e., when the glass composition is plastically deformable) the glass composition may be shaped using standard forming techniques to shape the glass composition into a desired final form. Alternatively, the glass article may be shaped into a stock form, such as a sheet, tube or the like, and subsequently reheated and formed into the desired final form.
  • a batch of glass raw materials e.g., powders of Si0 2 , Al 2 0 3 , alkali carbonates, alkaline earth carbonates and the like
  • the batch of glass raw materials is heated to form a molten glass composition
  • the glass compositions described herein may be shaped into various forms such as, for example, sheets, tubes or the like. However, given the chemical durability of the glass composition, the glass compositions described herein are particularly well suited for use in the formation of pharmaceutical packages for containing a pharmaceutical composition, such as liquids, powders and the like. For example, the glass compositions described herein may be used to form vials, ampoules, cartridges, syringe bodies and/or any other glass container for storing pharmaceutical compositions. Moreover, the ability to chemically strengthen the glass compositions through ion exchange can be utilized to improve the mechanical durability of such pharmaceutical packaging. Accordingly, it should be understood that, in at least one embodiment, the glass compositions are incorporated in a pharmaceutical package in order to improve the chemical durability and/or the mechanical durability of the pharmaceutical packaging.
  • Table 1 below contains the composition of Comparative Examples 1-4 and Inventive Examples A-C. The softening point, CTE, and chemical durability of each composition are also listed. Specifically, Comparative Examples 1-4 contained B2O3. Removing B2O3 from the glass composition to improve the chemical durability results in a corresponding undesirable increase in the softening point of the glass. In order to counteract this trend, B2O3 was replaced with alkali oxide, S1O2, ⁇ 3 ⁇ 4 or combinations thereof. The Si0 2 and ⁇ 1 ⁇ 2 improve the chemical durability of the glass. Additions of alkali oxide lowered the softening point pf the glass by as much as 80°C. However, additions of alkali also decreased the hydro lytic durability of the glass while still meeting the ISO 720 Type HGA1 classification.
  • Table 2 shows the composition and properties of inventive Examples D-J. Specifically, the composition of inventive Examples D-J were used to assess the efficacy of further additions of alkali oxide (Na 2 0, K 2 O, Li 2 0) on chemical durability of the glass as well as ion exchange performance. As shown in Table 2, alkali oxide additions as high as 1 1.5 mol.% were examined with slight increases in Si0 2 content to maintain acid durability. The softening points of these glass compositions decreased to as low as 870°C due to the increase in alkali oxide content.
  • alkali oxide Na 2 0, K 2 O, Li 2 0
  • inventive Examples E-J The ion exchangeability of inventive Examples E-J was also investigated. Specifically, samples of the glass compositions of inventive Examples E-J were ion exchanged in a molten salt bath of 100% K O 3 for 15 hours at temperatures of 430°C, 475°C, and 440°C. Thereafter, the surface compression and depth of layer were determined. The chemical durability of the samples was also determined following ion exchange. The results are reported in Table 3 below.
  • Table 3 shows that the ion exchangeability of the glass compositions is strongly dependent on the amount of alkali oxide in the composition.
  • Compressive stress values of 200-350 MPa were reached in glass compositions with alkali oxide levels of 5 mol.% to 6 mol.%.
  • Compressive stress values of 700-825 MPa were reached in glass compositions with alkali oxide levels of 8.5 mol.% to 1 1.5 mol.%.
  • Example H had a compressive stress of 817 MPa with a depth of layer of 48 microns after ion exchange for 15 hours at 440°C for 15 hours, values which are comparable to commercially available ion exchanged damage tolerant glass.
  • Table 3 also shows that ion exchange treatment has minimal effect on chemical durability with the exception of the acid durability of several of the glasses with higher compressive stress values.
  • the glass mass lost following testing increased by a factor of 20 to 200 compared to corresponding non-ion exchanged glass compositions. While not wishing to be bound by theory, this result may be more of a manifestation of chipping of the glass edge during testing due to high compressive stress rather than actual decreased chemical resistance from ion exchange.
  • Table 4 contains the composition and properties of several inventive examples of alkaline earth alumino-silicate glass compositions with intermediate amounts of alkali oxides (i.e., from about 5 mol.% to about 10.5 mol.%).
  • Each of the samples exhibited an acid resistance of at least class S3 according to the DIN 12116 standard.
  • Each of the samples also exhibited a base resistance of class Al according to the ISO 695 standard.
  • Test data for the ISO 720 standard was not available. The softening point of these glass compositions was in the range of 830-940°C.
  • the glass compositions of inventive Examples K-R had compressive stress values in the range of 350-600 MPa and depth of layers up to about 50 ⁇ .
  • the glass compositions described herein exhibit chemical durability as well as mechanical durability following ion exchange. These properties make the glass compositions well suited for use in various applications including, without limitation, pharmaceutical packaging materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Health & Medical Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Hematology (AREA)
  • Surface Treatment Of Glass (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)

Abstract

Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability and pharmaceutical packages comprising the same are disclosed herein. In one embodiments, a glass composition includes from about 67 mol.% to about 75 mol.% SiO2; from about 6 mol.% to about 10 mol.% Αl2O3; from about 5 mol.% to about 12 mol.% alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide. The alkali oxide comprises at least Νa2O and K2O. The glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening the glass to improve the mechanical durability.

Description

ALKALINE EARTH ALUMINO-SILICATE GLASS COMPOSITIONS WITH IMPROVED CHEMICAL AND MECHANICAL DURABILITY
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority under 35 U.S.C. § 1 19 of U.S. Provisional Application Serial No. 61/551,133 filed on October 25, 2011, the content of which is relied upon and incorporated herein by reference in its entirety.
BACKGROUND
Field
[0002] The present specification generally relates to glass compositions and, more specifically, to chemically durable glass compositions which are free from boron and compounds of boron and which are suitable for use in pharmaceutical packaging.
Technical Background
[0003] Historically, glass has been used as the preferred material for packaging pharmaceuticals because of its hermetic ity, optical clarity, and excellent chemical durability relative to other materials. Specifically, the glass used in pharmaceutical packaging must have adequate chemical durability so as to not affect the stability of the pharmaceutical compositions contained therein. Glasses having suitable chemical durability include those glass compositions within the ASTM standard 'Type la' and 'Type lb' glass compositions which have a proven history of chemical durability.
[0004] Although Type la and Type lb glass compositions are commonly used in pharmaceutical packages, they do suffer from several deficiencies. Foremost is the tendency of these glasses to phase separate. Specifically, the glass tends to separate on a fine microscopic scale into an alkali borate phase and silica rich phase. This phase separation may be a precursor to the glass flakes and de- lamination phenomena that have been reported in such glasses. [0005] A second deficiency is that the low levels of alkali and alumina in Type la and Type lb glass compositions result in only a minimal ability to ion exchange and strengthen these glasses. As a result, pharmaceutical packages made from Type la and lb pharmaceutical glasses offer poor resistance to damage from mechanical events such as impacts and scratches.
[0006] Accordingly, a need exists for glass compositions which are chemically durable and susceptible to chemical strengthening by ion exchange for use in glass pharmaceutical packages and similar applications.
SUMMARY
[0007] According to one embodiment, a glass composition may include from about 67 mol.% to about 75 mol.%> Si02; from about 6 mol.% to about 10 mol.%> AI2O3; from about 5 mol.% to about 12 mol.% alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide. The alkali oxide comprises at least Na20 and K20. The glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening of glass to improve mechanical durability.
[0008] In another embodiment, a glass composition may include from about 67 mol.% to about 75 mol.% Si02; from about 6 mol.% to about 10 mol.% Α12θ3; from about 5 mol.% to about 12 mol.%) alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide. The alkaline earth oxide comprises at least one of SrO and BaO. The glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening the glass to improve mechanical durability.
[0009] In yet another embodiment, a pharmaceutical package for a pharmaceutical composition may include a glass composition comprising from about 67 mol.% to about 75 mol.% Si02; from about 6 mol.% to about 10 mol.% Al2(¾; from about 5 mol.% to about 12 mol.% alkali oxide; and from about 9 mol.%> to about 15 mol.% of alkaline earth oxide. The alkali oxide comprises at least Na20 and K20. The composition is free from boron and compounds of boron and has at least a class S3 acid resistance according to DIN 121 16; a class Al base resistance according to ISO 695; and a type HGA1 hydrolytic resistance according to ISO 720. The pharmaceutical package may be ion exchange strengthened to improve the mechanical durability of the package. [0010] Additional features and advantages of the embodiments will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art fiOin that description or recognized by practicing the embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings.
[0011] It is to be understood that both the foregoing general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate the various embodiments described herein, and together with the description serve to explain the principles and operations of the claimed subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 graphically depicts the ion-exchange properties (compressive stress and depth of layer) for inventive glass composition and, for purposes of comparison, Type I B glass compositions.
DETAILED DESCRIPTION
[0013] Reference will now be made in detail to various embodiments of glass compositions which exhibit improved chemical and mechanical durability. Such glass compositions are suitable for use in various applications including, without limitation, as pharmaceutical packaging materials. The glass compositions may also be chemically strengthened thereby imparting increased mechanical durability to the glass. The glass compositions described herein generally comprise silica (S1O2), alumina (AI2O3), alkaline earth oxides, and alkali oxides (such as Na20 and K20) in amounts which impart chemical durability to the glass composition. Moreover, the alkali oxide present in the glass compositions facilitate chemically strengthening the glass compositions by ion exchange. Various embodiments of the glass compositions will be described herein and further illustrated with reference to specific examples.
[0014] The term "softening point," as used herein, refers to the temperature at which the viscosity of the glass composition is lxl 076 poise. [0015] The term "annealing point," as used herein, refers to the temperature at which the viscosity of the glass composition is lxlO13 poise.
[0016] The term "CTE," as used herein, refers to the coefficient of thermal expansion of the glass composition over a temperature range from about RT to about 300°C.
[0017] The term "chemical durability," as used herein, refers to the ability of the glass composition to resist degradation upon exposure to specified chemical conditions. Specifically, the chemical durability of the glass compositions described herein was assessed according to 3 established material testing standards: DIN 121 16 entitled "Testing of glass - Resistance to attack by a boiling aqueous solution of hydrochloric acid - Method of test and classification"; ISO 695: 1991 entitled "Glass— Resistance to attack by a boiling aqueous solution of mixed alkali - Method of test and classification"; and ISO 720: 1985 entitled "Glass - Hydrolytic resistance of glass grains at 121 degrees C ~ Method of test and classification." Each standard and the classifications within each standard are described in further detail herein.
[0018] The glass compositions described herein are alkaline earth alumino-silicate glass compositions which generally include a combination of Si02, AI2O3, at least one alkaline earth oxide, alkali oxide including at least as Na20 and K20, and are free from boron and compounds containing boron. The combination of these components enables a glass composition which is resistant to chemical degradation and is also suitable for chemical strengthening by ion exchange. In some embodiments the glass compositions may further comprise minor amounts of one or more additional oxides such as, for example, Sn02, Zr02, ZnO, or the like. These components may be added as fining agents and/or to further enhance the chemical durability of the glass composition.
[0019] In the embodiments of the glass compositions described herein Si02 is the largest constituent of the composition and, as such, is the primary constituent of the glass network. Si02 enhances the chemical durability and, in particular, the resistance of the glass composition to decomposition in acid. Accordingly, a high Si02 concentration is generally desired. However, if the content of Si02 is too high, the formability of the glass may be diminished as higher concentrations of Si02 increase the difficulty of melting the glass which, in turn, adversely impacts the formability of the glass. However, additions of alkali oxide assist in offsetting this effect by decreasing the softening point of the glass. In the embodiments described herein, the glass composition generally comprises Si02 in an amount greater than or equal to about 67 mol.% and less than or equal to about 75 mol.%. In some embodiments S1O2 is present in the glass composition in an amount greater than or equal to about 67 mol.% and less than or equal to about 73 mol.%. In each of these embodiments, the amount of S1O2 present in the glass composition may be greater than or equal to about 70 mol.% or even greater than or equal to about 72 mol.%.
[0020] The glass compositions described herein further include AI2O3. AI2O3, in conjunction with alkali oxides present in the glass compositions such as Na20 or the like, improves the susceptibility of the glass to ion exchange strengthening. Moreover, additions of AI2O3 to the composition reduce the propensity of alkali constituents (such as Na and K) from leaching out of the glass and, as such, additions of AI2O3 increase the resistance of the composition to hydro lytic degradation. Moreover, additions of AI2O3 greater than about 10 mol.% may also increase the softening point of the glass thereby reducing the formability of the glass. Accordingly, the glass compositions described herein generally include AI2O3 in an amount greater than or equal to about 6 mol.% and less than or equal to about 10 mol.%. In some embodiments, the amount of AI2O3 in the glass composition is greater than or equal to about 7 mol.%) and less than or equal to about 10 mol.%.
[0021] The glass compositions also include at least two alkali oxides. The alkali oxides facilitate the ion exchangeability of the glass composition and, as such, facilitate chemically strengthening the glass substrate. The alkali oxides also lower the softening point of the glass thereby offsetting the increase in the softening point due to higher concentrations of Si02 in the glass composition. The alkali oxides also assist in improving the chemical durability of the glass composition. The alkali oxides are generally present in the glass composition in an amount greater than or equal to about 5 mol.% and less than or equal to about 12 mol.%. In some of these embodiments, the amount of alkali oxides may be greater than or equal to about 5 mol.%) and less than or equal to about 10 mol.%. In some other embodiments, the amount of alkali oxide may be greater than or equal to about 5 mol.% and less than or equal to about 8 mol.%. In all the glass compositions described herein, the alkali oxides comprise at least Na2<3 and K2O. In some embodiments, the alkali oxides further comprise L12O.
[0022] The ion exchangeability of the glass composition is primarily imparted to the glass composition by the amount of the alkali oxide Na20 initially present in the glass composition prior to ion exchange. Specifically, in order to achieve the desired compressive strength and depth of layer in the glass composition upon ion exchange strengthening, the glass compositions include Na20 in an amount greater than or equal to about 2.5 mol.% and less than or equal to about 10 mol.% based on the molecular weight of the glass composition. In some embodiments the glass composition may include Na20 in an amount greater than or equal to about 3.5 mol.% and less than or equal to about 8 mol.%. In some of these embodiments the glass composition may include Na20 in an amount greater than or equal to about 6 mol.%) and less than or equal to about 8 mol.%.
[0023] As noted above, the alkali oxides in the glass composition also include K2O. The amount of K2O present in the glass composition also relates to the ion exchangeability of the glass composition. Specifically, as the amount of K2O present in the glass composition increases, the compressive stress obtainable through ion exchange decreases. Accordingly, it is desirable to limit the amount of K2O present in the glass composition. In some embodiments, the amount of K2O is greater than 0 mol.%> and less than or equal to about 2.5 mol.%) by molecular weight of the glass composition. In some of these embodiments, the amount of K2O present in the glass composition is less than or equal to about 0.5 mol.% by molecular weight of the glass composition.
[0024] As noted above, in some embodiments, the alkali oxide in the glass composition further comprises L12O. Including L12O in the glass composition further decreases the softening point of the glass. In embodiments where the alkali oxide includes L12O, the L12O may be present in an amount greater than or equal to about 1 mol.% and less than or equal to about 3 mol.%. In some embodiments, L12O may be present in the glass composition in an amount which is greater than about 2 mol.% and less than or equal to about 3 mol.%.
[0025] The alkaline earth oxides present in the composition improve the meltability of the glass batch materials and increase the chemical durability of the glass composition. The presence of alkaline earth oxides in the glass composition also reduce the susceptibility of the glass to de-lamination. In the glass compositions described herein, the glass compositions generally include from about 9 mol.% to about 15 mol.% of alkaline earth oxide. In some of these embodiments, the amount of alkaline earth oxide in the glass composition may be from about 10 mol.% to about 14 mol.%.
[0026] The alkaline earth oxide in the glass composition may include MgO, CaO, SrO, BaO or combinations thereof. For example, in the embodiments described herein the alkaline earth oxide includes MgO. MgO is present in the glass composition in an amount which is greater than or equal to about 3 mol.% and less than or equal to about 7 mol.% by molecular weight of the glass composition or even greater than or equal about 2 mol.% and less than or equal to about 5 mol.% by molecular weight of the glass composition.
[0027] In some embodiments, the alkaline earth oxide also includes CaO. In these embodiments CaO is present in the glass composition in an amount from about 3 mol.% to less than or equal to 7 mol.% by molecular weight of the glass composition. In some of these embodiments, CaO may be present in the glass composition in an amount greater than or equal to about 4 mol.% and less than or equal to about 7 mol.%.
[0028] In some embodiments described herein, the alkaline earth oxide further comprises at least one of SrO or BaO. The inclusion of SrO reduces the liquidus temperature of the glass composition and, as a result, improves the formability of the glass composition. For example, in some embodiments the glass composition may include SrO in an amount greater than about 0 mol.% and less than or equal to about 5 mol.%. In some of these embodiments, the glass composition may include from about 1 mol.% to about 2 mol.% SrO.
[0029] In embodiments where the glass composition includes BaO, the BaO may be present in an amount greater than about 0 mol.% and less than about 2 mol.%. In some of these embodiments, BaO may be present in the glass composition in an amount less than or equal to about 1.5 mol.% or even less than or equal to about 0.5 mol.%. However, in some other embodiments, the glass composition is free from barium and compounds of barium.
[0030] In all the embodiments of the glass compositions described herein, the glass compositions are free from boron and compounds of boron such as B2O3. Specifically, it has been determined that forming the glass composition without boron or compounds of boron significantly increases the chemical durability of the glass composition. In addition, it has also been determined that forming the glass composition without boron or compounds of boron improves the ion exchangeability of the glass compositions by reducing the process time and/or temperature required to achieve a specific value of compressive stress and/or depth of layer.
[0031] In addition to the Si02, AI2O3, alkali oxides and alkaline earth oxides, the glass compositions described herein may optionally further comprise one or more fining agents such as, for example, Sn02, AS2O3, and/or CI" (from NaCl or the like). When a fining agent is present in the glass composition, the fining agent may be present in an amount less than or equal to about 1 mol.% or even less than or equal to about 0.5 mol.%. For example, in some embodiments the glass composition may include SnC>2 as a fining agent. In these embodiments Sn02 may be present in the glass composition in an amount greater than about 0 mol.% and less than or equal to about 0.30 mol.%.
[0032] Moreover, the glass compositions described herein may comprise one or more additional metal oxides to further improve the chemical durability of the glass composition. For example, the glass composition may further include ZnO or Zr02, each of which further improves the resistance of the glass composition to chemical attack. In these embodiments, the additional metal oxide may be present in an amount which is greater than or equal to about 0 mol.% and less than or equal to about 1.5 mol.%. For example, when the additional metal oxide is Zr02, the Zr02 may be present in an amount less than or equal to about 1.5 mol.%.
[0033] In a first exemplary embodiment, the glass composition includes from about 67 mol.% to about 75 mol.% Si02; from about 6 mol.% to about 10 mol.% AI2O3; from about 5 mol.% to about 12 mol.% alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide. The alkali oxide comprises at least Na20 and K20. The glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening the glass to improve the mechanical durability.
[0034] In this first exemplary embodiment Na20 may be present in an amount from about 6 mol.%) to about 8 mol.%. The K20 may be present in an amount less than or equal to about 0.5 mol.%). The alkali metal oxide may further comprise Li20 in an amount from about 2 mol.%) to about 3 mol.%.
[0035] In this first exemplary embodiment the alkaline earth oxide may be present in an amount from about 10 mol.% to about 14 mol.% and may comprise at least one of SrO and BaO. When the alkaline earth oxide comprises SrO, SrO may be present in an amount greater than or equal to about 1 mol.% and less than or equal to about 2 mol.%. In some of these embodiments, the glass composition is free from barium and compounds of barium. The alkaline earth oxide may also comprise MgO and CaO. [0036] In this first exemplary embodiment the concentration of AI2O3 may be greater than about 7 mol. %. The glass composition may further include Zr02 in an amount less than or equal to about 1.5 mol.% and/or Sn02 in an amount less than or equal to about 0.3 mol.%.
[0037] In a second exemplary embodiment, a glass composition may include from about 67 mol.% to about 75 mol.% Si02; from about 6 mol.% to about 10 mol.% AI2O3; from about 5 mol.%) to about 12 mol.% alkali oxide; and from about 9 mol.% to about 15 mol.% of alkaline earth oxide. The alkaline earth oxide comprises at least one of SrO and BaO. The glass composition is free from boron and compounds of boron and is susceptible to ion exchange thereby facilitating chemically strengthening the glass to improve the mechanical durability.
[0038] In this second exemplary embodiment the alkali oxide may include Na20 and K20. The Na20 may be present in an amount from about 6 mol.% to about 8 mol.%. The K20 may be present in an amount less than or equal to about 0.5 mol.%.
[0039] In this second exemplary embodiment, when the alkaline earth oxide comprises SrO, SrO may be present in an amount greater than or equal to about 1 mol.% and less than or equal to about 2 mol.%. In some of these embodiments, the glass composition is free from barium and compounds of barium. The alkaline earth oxide may also comprise MgO and CaO.
[0040] In this second exemplary embodiment the concentration of Al203 may be greater than about 7 mol. %. The glass composition may further include Zr02 in an amount less than or equal to about 1.5 mol.% and/or Sn02 in an amount less than or equal to about 0.3 mol.%.
[0041] In the embodiments described herein the glass compositions generally have softening points of less than about 1040°C or even less than about 950°C. In some embodiments, the softening point of the glass composition is less than about 900°C. These lower softening points improve the ease of formability of the glass composition.
[0042] In the embodiments described herein the glass compositions have a CTE of less than about 70xlO"7 "' or even less than about 60xlO"7 '' . These lower CTE values improve the survivability of the glass to thermal cycling or thermal stress conditions relative to glass compositions with higher CTEs. [0043] As noted above, the presence of alkali oxides in the glass composition facilitates chemically strengthening the glass by ion exchange. By varying the concentration of alkali oxides in the glass, specifically the concentration of a20 in the glass, a wide range of compressive stresses and depth of layer values are possible for various ion-exchange processing conditions. For example, compressive stress from about 200 MPa to about 850 MPa and depth of layers from about 15 μιη to about 50 μηι or greater may be obtained in some glass compositions described herein after the glass composition is treated in a salt bath of 100% molten KNO3 at a temperatures from about 400°C to about 500°C for a time period of less than about 30 hours or even less than about 20 hours.
[0044] As graphically illustrated in FIG. 1 , the glass compositions described herein can be chemically strengthened by ion exchange. Exemplary depths of layer and the corresponding compressive stress are graphically depicted in FIG. 1. Also, for purposes of comparison, the depth of layer and compressive stress obtainable for Type l b glass are also depicted. As shown in FIG. 1 , the glass compositions described herein may be ion exchanged to achieve a much greater compressive stress and depth of layer than Type 1 b glass.
[0045] Further, as noted hereinabove, the glass compositions are chemically durable and resistant to degradation as determined by the DIN 121 16 standard, the ISO 695 standard, and the ISO 720 standard.
[0046] Specifically, the DIN 121 16 standard is a measure of the resistance of the glass to decomposition when placed in an acidic solution. In brief, the DIN 121 16 standard utilizes a polished glass sample of a known surface area which is weighed and then positioned in contact with a proportional amount of boiling 6M hydrochloric acid for 6 hours. The sample is then removed from the solution, dried and weighed again. The glass mass lost during exposure to the acidic solution is a measure of the acid durability of the sample with smaller numbers indicative of greater durability. The results of the test are reported in units of mass per surface area, specifically mg/dm2. The DIN 12116 standard is broken into individual classes. Class S I indicates a half weight losses of up to 0.7 mg/dm2; Class S2 indicates a half weight losses from 0.7 mg/dm2 up to 1.5 mg/dm2; Class S3 indicates a half weight losses from 1.5 mg/dm2 up to 15 mg dm2; and Class S4 indicates a half weight losses of more than 15 mg/dm2. [0047] The ISO 695 standard is a measure of the resistance of the glass to decomposition when placed in a basic solution. In brief, the ISO 695 standard utilizes a polished glass sample which is weighed and then placed in a solution of boiling 1M NaOH + 0.5M Na2C03 for 3 hours. The sample is then removed from the solution, dried and weighed again. The glass mass lost during exposure to the basic solution is a measure of the base durability of the sample with smaller numbers indicative of greater durability. As with the DIN 121 16 standard, the results of the ISO 695 standard are reported in units of mass per surface area, specifically mg/dm2. The ISO 695 standard is broken into individual classes. Class Al indicates weight losses of up to 75 mg/dm2; Class A2 indicates weight losses from 75 mg/dm2 up to 175 mg/dm2; and Class A3 indicates weight losses of more than 175 mg/dm2.
[0048] The ISO 720 standard is a measure of the resistance of the glass to degradation in distilled water. In brief, the ISO 720 standard protocol utilizes crushed grass grains which are placed in contact with 18 ΜΩ water under autoclave conditions (121 °C, 2 attn) for 30 minutes. The solution is then titrated colorimetrically with dilute HC1 to neutral pH. The amount of HCL required to titrate to a neutral solution is then converted to an equivalent of Na20 extracted from the glass and reported in μg of glass with smaller values indicative of greater durability. The ISO 720 standard is broken into individual types. Type HGA1 is indicative of up to 31 μg extracted equivalent of Na20; Type HGA2 is indicative of more than 31 μg and up to 62 g extracted equivalent of Na20; Type HGA3 is indicative of more than 62 μg and up to 264 μg extracted equivalent of Na20; Type HGA4 is indicative of more than 264 μg and up to 620 μg extracted equivalent of Na20; and Type HGA5 is indicative of more than 620 g and up to 1085 μg extracted equivalent of Na20.
[0049] The glass compositions described herein have an acid resistance of at least class S3 according to DIN 121 16 with some embodiments having an acid resistance of at least class S2 or even class S I . Further, the glass compositions described herein have a base resistance according to ISO 695 of at least class A2 with some embodiments having a class Al base resistance. The glass compositions described herein also have a DIN 121 16 type HGA2 hydrolytic resistance with some embodiments having a type HGA1 hydrolytic resistance.
[0050] The glass compositions described herein are formed by mixing a batch of glass raw materials (e.g., powders of Si02, Al203, alkali carbonates, alkaline earth carbonates and the like) such that the batch of glass raw materials has the desired composition. Thereafter, the batch of glass raw materials is heated to form a molten glass composition which is subsequently cooled and solidified to form the glass composition. During solidification (i.e., when the glass composition is plastically deformable) the glass composition may be shaped using standard forming techniques to shape the glass composition into a desired final form. Alternatively, the glass article may be shaped into a stock form, such as a sheet, tube or the like, and subsequently reheated and formed into the desired final form.
[0051] The glass compositions described herein may be shaped into various forms such as, for example, sheets, tubes or the like. However, given the chemical durability of the glass composition, the glass compositions described herein are particularly well suited for use in the formation of pharmaceutical packages for containing a pharmaceutical composition, such as liquids, powders and the like. For example, the glass compositions described herein may be used to form vials, ampoules, cartridges, syringe bodies and/or any other glass container for storing pharmaceutical compositions. Moreover, the ability to chemically strengthen the glass compositions through ion exchange can be utilized to improve the mechanical durability of such pharmaceutical packaging. Accordingly, it should be understood that, in at least one embodiment, the glass compositions are incorporated in a pharmaceutical package in order to improve the chemical durability and/or the mechanical durability of the pharmaceutical packaging.
Examples
[0052] The invention will be further clarified by the following examples.
[0053] Table 1 below contains the composition of Comparative Examples 1-4 and Inventive Examples A-C. The softening point, CTE, and chemical durability of each composition are also listed. Specifically, Comparative Examples 1-4 contained B2O3. Removing B2O3 from the glass composition to improve the chemical durability results in a corresponding undesirable increase in the softening point of the glass. In order to counteract this trend, B2O3 was replaced with alkali oxide, S1O2, ΖΓ<¾ or combinations thereof. The Si02 and Ζ ½ improve the chemical durability of the glass. Additions of alkali oxide lowered the softening point pf the glass by as much as 80°C. However, additions of alkali also decreased the hydro lytic durability of the glass while still meeting the ISO 720 Type HGA1 classification.
Table 1: Comparative Examples 1-4 and Inventive Examples A-C
(Mol %) Comp. Comp. Comp. Comp. Ex. A Ex. B Ex. C
Ex. 1 Ex. 2 Ex. 3 Ex. 4
Si02 70.8 69.9 69.3 68.3 68.6 67..7 70.8
Figure imgf000014_0001
[0054] Table 2 shows the composition and properties of inventive Examples D-J. Specifically, the composition of inventive Examples D-J were used to assess the efficacy of further additions of alkali oxide (Na20, K2O, Li20) on chemical durability of the glass as well as ion exchange performance. As shown in Table 2, alkali oxide additions as high as 1 1.5 mol.% were examined with slight increases in Si02 content to maintain acid durability. The softening points of these glass compositions decreased to as low as 870°C due to the increase in alkali oxide content. Moreover, neither the acid, base, nor hydro lytic resistances of these glass compositions were adversely impacted by the higher alkali level with all glasses falling into either the S2 or S3 DIN 12116 classification, the Al ISO 695 classification, and the HGA1 ISO 720 classification.
Table 4: Compositions and Properties of Inventive Exampli
Figure imgf000014_0002
Figure imgf000015_0001
[0055] The ion exchangeability of inventive Examples E-J was also investigated. Specifically, samples of the glass compositions of inventive Examples E-J were ion exchanged in a molten salt bath of 100% K O3 for 15 hours at temperatures of 430°C, 475°C, and 440°C. Thereafter, the surface compression and depth of layer were determined. The chemical durability of the samples was also determined following ion exchange. The results are reported in Table 3 below.
[0056] Table 3 shows that the ion exchangeability of the glass compositions is strongly dependent on the amount of alkali oxide in the composition. Compressive stress values of 200-350 MPa were reached in glass compositions with alkali oxide levels of 5 mol.% to 6 mol.%. Compressive stress values of 700-825 MPa were reached in glass compositions with alkali oxide levels of 8.5 mol.% to 1 1.5 mol.%. Example H had a compressive stress of 817 MPa with a depth of layer of 48 microns after ion exchange for 15 hours at 440°C for 15 hours, values which are comparable to commercially available ion exchanged damage tolerant glass.
[0057] Table 3 also shows that ion exchange treatment has minimal effect on chemical durability with the exception of the acid durability of several of the glasses with higher compressive stress values. In these instances, the glass mass lost following testing increased by a factor of 20 to 200 compared to corresponding non-ion exchanged glass compositions. While not wishing to be bound by theory, this result may be more of a manifestation of chipping of the glass edge during testing due to high compressive stress rather than actual decreased chemical resistance from ion exchange.
Table 3: Ion Exchange Properties of Exampli
Ex. E Ex. Γ Ex. G Ex. H Ex. I Ex. J
Total 5.0 5.0 6.0 (incl. 10.5 8.5 (incl. 1 1.5 (incl.
Figure imgf000016_0001
[0058] Table 4 contains the composition and properties of several inventive examples of alkaline earth alumino-silicate glass compositions with intermediate amounts of alkali oxides (i.e., from about 5 mol.% to about 10.5 mol.%). Each of the samples exhibited an acid resistance of at least class S3 according to the DIN 12116 standard. Each of the samples also exhibited a base resistance of class Al according to the ISO 695 standard. Test data for the ISO 720 standard was not available. The softening point of these glass compositions was in the range of 830-940°C.
[0059] Further, the glass compositions of inventive Examples K-R had compressive stress values in the range of 350-600 MPa and depth of layers up to about 50 μιη.
Table 4: Composition and Properties of Examples K-R
(Mol %) Ex. K Ex. L Ex. M Ex. N Ex. O Ex. P Ex. Q Ex. R
Si02 72.3 72.3 72.3 72.3 71.7 72.2 71.7 71.7
A1203 7.1 7.1 7.1 7.4 7.4 7.4 7.4 7.4
Li20 0 0 0 0 0 0 3 1
NajO 2.5 4.5 5.9 7.7 7.4 10 5 7.2
K2O 2.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Figure imgf000017_0001
[0060] It should now be understood that the glass compositions described herein exhibit chemical durability as well as mechanical durability following ion exchange. These properties make the glass compositions well suited for use in various applications including, without limitation, pharmaceutical packaging materials.
[0061] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus it is intended that the specification cover the modifications and variations of the various embodiments described herein provided such modification and variations come within the scope of the appended claims and their equivalents.

Claims

CLAIMS What is claimed is:
1. A glass composition comprising:
from about 65 mol.% to about 75 mol.% Si02;
from about 6 mol.% to about 12.5 mol.% AI2O3;
from about 5 mol.% to about 12 mol.% alkali oxide, wherein the alkali oxide comprises Na20 and K20 and the K20 is present in an amount less than or equal to 0.5 mol.%; and
from about 8.0 mol.% to about 15 mol.% of at least one alkaline earth oxide, wherein the glass composition is susceptible to strengthening by ion-exchange.
2. A glass composition comprising:
from about 67 mol.% to about 75 mol.% Si02;
from about 6 mol.% to about 10 mol.% AI2O3;
from about 5 mol.% to about 12 mol.% alkali oxide, wherein the alkali oxide comprises K20 in an amount less than or equal to about 0.5 mol.%;
from about 8 mol.% to about 15 mol.% of alkaline earth oxide, wherein the at least one alkaline earth oxide comprises at least one of SrO and BaO, wherein:
the glass composition is free from boron and compounds of boron;
the glass composition is free from phosphorous and compounds of phosphorous; and
the glass composition is ion exchangeable to a depth of layer greater than or equal to about 15 μιη with a corresponding compressive stress greater than or equal to about 250 MPa.
3. The glass composition of claim 1 wherein Si02 is present in the glass composition in a concentration from about 67 mol.% to about 75 mol.%.
4. The glass composition of claim 1 , wherein AI2O3 is present in the glass composition in a concentration from about 6 mol.% to about 10 mol.%.
5. The glass composition of claim 1 , wherein the glass composition comprises less than about 1 mol.% B203.
6. The glass composition of claim 1 , wherein the glass composition is free from boron and compounds of boron.
7. The glass composition of claim 1, wherein the alkaline earth oxide comprises at least one of SrO and BaO.
8. The glass composition of claim 2 or claim 7, wherein the alkaline earth oxide comprises SrO in an amount greater than or equal to about 1 mol.% and less than or equal to about 2 mol.%.
9. The glass composition of claim 8, wherein the alkaline earth oxide comprises SrO in an amount greater than 0 mol.% and less than or equal to about 6 mol.%.
10. The glass composition of claim 1 or claim 2, wherein the glass composition is free from barium and compounds of barium.
1 1. The glass composition of claim 1 or claim 2, wherein a concentration of AI2O3 is greater than about 7 mol. %.
12. The glass composition of claim 1 or claim 2, wherein the alkali metal oxide further comprises Li20 in an amount from about 1 mol.% to about 3 mol.%.
13. The glass composition of claim 1, wherein the Na20 is present in an amount from about 3.5 mol.% to about 8 mol.%.
14. The glass composition of claim 1 or claim 2, wherein the alkaline earth oxide is present in an amount from about 10 mol.% to about 14 mol.%.
15. The glass composition of claim 1 or claim 2, wherein the alkaline earth oxide comprises MgO and CaO.
16. The glass composition of claim 15, wherein MgO is present in an amount greater than 0 mol.% and less than or equal to 3.5 mol.%.
17. The glass composition of claim 1 or claim 2 further comprising Zr02 in an amount less than or equal to about 1.5 mol.%.
18. The glass composition of claim 1 or claim 2, further comprising ZnO in an amount less than or equal to about 2.0 mol.%.
19. The glass composition of claim 1 or claim 2, further comprising Sn02 in an amount less than or equal to about 0.3 mol.%.
20. The glass composition of claim 1 , wherein the glass composition is substantially free from phosphorous and compounds of phosphorous.
21. The glass composition of claim 1 or claim 2, wherein the glass composition has a liquidus viscosity greater than or equal to 85 kP.
22. The glass composition of claim 1 or claim 2, wherein a ratio MgO:∑RO is less than 0.3.
23. The glass composition of claim 1 or claim 2, wherein the glass composition has at least a class S3 acid resistance according to DIN 121 16 both before and after ion-exchange strengthening.
24. The glass composition of claim 1 or claim 2, wherein the glass composition has a class Al base resistance according to ISO 695 both before and after ion-exchange strengthening.
25. The glass composition of claim 1 or claim 2, wherein the glass composition has a type HGA1 hydro lytic resistance according to ISO 720 after ion exchange strengthening.
26. The glass composition of claim 1 or claim 2, wherein the glass composition has a Type HGA1 hydro lytic resistance according to ISO 720 before strengthening by ion exchange and after strengthening by ion exchange.
27. The glass composition of claim 2, wherein the alkali oxide comprises Na20 in an amount from about 3.5 mol.% to about 8 mol.%.
28. The glass composition of claim 16, wherein the glass composition further comprises ZnO in an amount less than or equal to 2.0 mol.%.
29. The glass composition of claim 16, wherein the glass composition is free from zinc and compounds containing zinc.
30. The glass composition of claim 16, wherein the glass composition further comprises L12O in an amount greater than or equal to 1 mol.% and less than or equal to 3 mol.%.
31. The glass composition of claim 16, wherein the glass composition is free from lithium and compounds containing lithium.
32. The glass composition of claim 16, wherein the glass composition comprises:
from about 5 mol.% to about 6 mol.% CaO; and
from about 2 mol.% to about 4 mol.% SrO.
33. The glass composition of claim 2, wherein the glass composition comprises:
from about 2 mol.% to about 5 mol.% CaO; and
from about 3 mol.% to about 6 mol.% SrO.
34. A glass article formed from glass having a composition comprising:
from about 67 mol.% to about 75 mol.% S1O2;
from about 6 mol.% to about 10 mol.% AI2O3;
from about 5 mol.% to about 12 mol.% alkali oxide, wherein the alkali oxide comprises Na20 and K2O and the K2O is present in an amount less than or equal to 0.5 mol.%;
from about 8 mol.% to about 15 mol.% of the at least one alkaline earth oxide, wherein the composition is free from boron and compounds of boron and the glass article has: at least a class S3 acid resistance according to DIN 121 16;
a class Al base resistance according to ISO 695; and
a type HGAl hydro lytic resistance according to ISO 720.
35. A glass article comprising:
a compressive stress layer with a compressive stress greater than or equal to about 250 MPa and depth of layer greater than or equal to about 15 μιη; and
a type HGAl hydro lytic resistance according to ISO 720, wherein the glass article is formed from a glass composition which is free of boron and compounds of boron and free from phosphorous and compounds of phosphorous.
36. The glass article of claim 34, wherein the glass article has a compressive stress greater than or equal to about 250 MPa.
37. The glass article of claim 34, wherein the glass article has a depth of layer greater than or equal to about 15 μπι.
38. The glass article of claim 34 or claim 35, wherein the glass article has a coefficient of thermal expansion less than or equal to 70xlO"7K_1.
39. The glass composition of claim 34, wherein the glass composition is substantially free from phosphorous and compounds of phosphorous.
40. The glass article of claim 35 wherein the glass composition has a class SI base resistance according to ISO 695.
41. The glass composition of claim 35, the glass composition has at least a class S3 acid resistance according to DIN 21 16.
42. The glass article of claim 35, wherein the glass composition comprises:
from about 67 mol.% to about 75 mol.% S1O2;
from about 6 mol.% to about 10 mol.% AI2O3; from about 5 mol.% to about 12 mol.% alkali oxide, wherein the alkali oxide comprises Na20 and ¾0 and the K20 is present in an amount less than or equal to 0.5 mol.%; and
from about 8.0 mol.% to about 15 mol.% of at least one alkaline earth oxide.
43. The glass composition of claim 34 or 42, wherein a ratio MgO:∑RO is less than 0.3.
PCT/US2012/061534 2011-10-25 2012-10-24 Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability WO2013063002A2 (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
KR1020197007397A KR102120349B1 (en) 2011-10-25 2012-10-24 Alkaline Earth Alumino-Silicate Glass Compositions with Improved Chemical And Mechanical Durability
EP18205364.5A EP3546433A1 (en) 2011-10-25 2012-10-24 Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
MX2014004971A MX366947B (en) 2011-10-25 2012-10-24 Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability.
EP12781010.9A EP2771293B1 (en) 2011-10-25 2012-10-24 Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
CN201910114588.6A CN109704566B (en) 2011-10-25 2012-10-24 Alkaline earth aluminosilicate glass compositions having improved chemical and mechanical durability
RU2014116644A RU2632084C2 (en) 2011-10-25 2012-10-24 Alkaline-earth aluminosilicate glass compositions with improved chemical and mechanical stability
JP2014538893A JP6204920B2 (en) 2011-10-25 2012-10-24 Alkaline earth aluminosilicate glass composition with improved chemical and mechanical durability
KR1020147012855A KR102068774B1 (en) 2011-10-25 2012-10-24 Alkaline Earth Alumino-Silicate Glass Compositions with Improved Chemical And Mechanical Durability
AU2012328981A AU2012328981B2 (en) 2011-10-25 2012-10-24 Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
CN201280052382.1A CN104066695B (en) 2011-10-25 2012-10-24 The alkaline earth metal aluminosilicate glass composition of chemistry and mechanical endurance with improvement
AU2016203653A AU2016203653B2 (en) 2011-10-25 2016-06-01 Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161551133P 2011-10-25 2011-10-25
US61/551,133 2011-10-25

Publications (2)

Publication Number Publication Date
WO2013063002A2 true WO2013063002A2 (en) 2013-05-02
WO2013063002A3 WO2013063002A3 (en) 2013-08-15

Family

ID=47116506

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/061534 WO2013063002A2 (en) 2011-10-25 2012-10-24 Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability

Country Status (9)

Country Link
US (4) US9145329B2 (en)
EP (2) EP3546433A1 (en)
JP (2) JP6204920B2 (en)
KR (2) KR102068774B1 (en)
CN (2) CN109704566B (en)
AU (2) AU2012328981B2 (en)
MX (1) MX366947B (en)
RU (2) RU2691186C2 (en)
WO (1) WO2013063002A2 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015013793A (en) * 2013-06-06 2015-01-22 日本電気硝子株式会社 Glass for pharmaceutical containers
EP2876092A4 (en) * 2012-07-18 2016-01-06 Nippon Electric Glass Co Glass for pharmaceutical product container, pharmaceutical product container glass tube using same, method for manufacturing pharmaceutical product container, and pharmaceutical product container
WO2015195435A3 (en) * 2014-06-19 2016-03-24 Corning Incorporated Aluminosilicate glasses
DE102015116097A1 (en) * 2015-09-23 2017-03-23 Schott Ag Chemically resistant glass and its use
WO2017151771A1 (en) * 2016-03-04 2017-09-08 Corning Incorporated Ion-exchangeable glass with high surface compressive stress
JP2017214285A (en) * 2011-10-25 2017-12-07 コーニング インコーポレイテッド Alkaline earth aluminosilicate glass composition having improved chemical and mechanical durability
JP2018145093A (en) * 2012-12-21 2018-09-20 日本電気硝子株式会社 Strengthened glass, strengthened glass plate, strengthened glass container, and glass for strengthening
WO2018183444A3 (en) * 2017-03-31 2018-12-13 Corning Incorporated High transmission glasses
EP4385957A1 (en) * 2022-12-13 2024-06-19 Schott Ag Aluminosilicate glass

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009070237A1 (en) 2007-11-29 2009-06-04 Corning Incorporated Glasses having improved toughness and scratch resistance
US9474688B2 (en) 2011-10-25 2016-10-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9517966B2 (en) 2011-10-25 2016-12-13 Corning Incorporated Glass compositions with improved chemical and mechanical durability
WO2013063238A1 (en) 2011-10-25 2013-05-02 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US10350139B2 (en) 2011-10-25 2019-07-16 Corning Incorporated Pharmaceutical glass packaging assuring pharmaceutical sterility
US9359251B2 (en) 2012-02-29 2016-06-07 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
US10273048B2 (en) 2012-06-07 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US9034442B2 (en) * 2012-11-30 2015-05-19 Corning Incorporated Strengthened borosilicate glass containers with improved damage tolerance
US10117806B2 (en) 2012-11-30 2018-11-06 Corning Incorporated Strengthened glass containers resistant to delamination and damage
DE102013103573B4 (en) * 2013-04-10 2016-10-27 Schott Ag Chemically toughened glass element with high scratch tolerance, and method for producing the glass element
US9849066B2 (en) * 2013-04-24 2017-12-26 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707153B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9713572B2 (en) 2013-04-24 2017-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700486B2 (en) * 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9603775B2 (en) 2013-04-24 2017-03-28 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700485B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717648B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717649B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707155B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9839579B2 (en) 2013-04-24 2017-12-12 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707154B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
EP3140116B1 (en) * 2014-05-07 2022-02-23 Corning Incorporated Laminated glass article and method for forming the same
TWI773291B (en) 2014-06-19 2022-08-01 美商康寧公司 Glasses having non-frangible stress profiles
US11097974B2 (en) 2014-07-31 2021-08-24 Corning Incorporated Thermally strengthened consumer electronic glass and related systems and methods
US10730791B2 (en) 2014-10-08 2020-08-04 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
JP6791851B2 (en) 2014-10-31 2020-11-25 コーニング インコーポレイテッド Dimensionally stable, fast-etched glass
BR112017014200A2 (en) 2014-12-31 2018-03-06 Corning Incorporated ? methods for treating glassware?
US9701569B2 (en) 2015-07-21 2017-07-11 Corning Incorporated Glass articles exhibiting improved fracture performance
US11613103B2 (en) 2015-07-21 2023-03-28 Corning Incorporated Glass articles exhibiting improved fracture performance
EP3383809A4 (en) * 2015-12-01 2019-12-11 Kornerstone Materials Technology Co., Ltd Low-boron, barium-free, alkaline earth aluminosilicate glass and its applications
DK3386930T3 (en) 2015-12-11 2021-07-26 Corning Inc FUSION-MOLDABLE, GLASS-BASED ARTICLES INCLUDING A METAL OXIDE CONCENTRATION GRADIENT
EP3402762B1 (en) 2016-01-12 2023-11-08 Corning Incorporated Thin thermally and chemically strengthened glass-based articles
TWI750807B (en) 2016-04-08 2021-12-21 美商康寧公司 Glass-based articles including a metal oxide concentration gradient
KR20210122313A (en) 2016-04-08 2021-10-08 코닝 인코포레이티드 Glass-based articles including a stress profile comprising two regions, and methods of making
US20170320769A1 (en) * 2016-05-06 2017-11-09 Corning Incorporated Glass compositions that retain high compressive stress after post-ion exchange heat treatment
CA3025663A1 (en) 2016-05-31 2017-12-07 Corning Incorporated Anti-counterfeiting measures for glass articles
CN109715574B (en) * 2016-09-16 2022-04-05 康宁股份有限公司 High transmission glass with alkaline earth oxide as modifier
US10640415B2 (en) 2016-11-30 2020-05-05 Corning Incorporated Lithium containing aluminosilicate glasses
WO2019209201A2 (en) * 2018-02-05 2019-10-31 Turkiye Sise Ve Cam Fabrikalari Anonim Sirketi Chambered thin glass product with complex shape and with increased resistance and the production method of said glass product
DE102018116460A1 (en) 2018-07-06 2020-01-09 Schott Ag Highly resistant and chemically toughened glasses
US12037282B2 (en) 2018-11-01 2024-07-16 Corning Incorporated Strengthened glass articles with reduced delayed breakage and methods of making the same
CN113227008B (en) * 2018-12-27 2023-08-15 日本电气硝子株式会社 Glass for medical container, glass tube for medical container, and medical container using same
CN109796130B (en) * 2019-03-05 2021-12-03 宜昌南玻光电玻璃有限公司 Medium-alumina glass with high permeability and improved ion exchange depth
BR112021018300A2 (en) 2019-03-15 2021-11-23 Corning Inc Chemically durable aluminosilicate glass compositions and glass articles formed therefrom
CN113727954A (en) 2019-04-23 2021-11-30 康宁股份有限公司 Glass laminates having defined stress profiles and methods of making same
KR20220002360A (en) * 2019-04-30 2022-01-06 코닝 인코포레이티드 Chemically durable, lithium-free glass composition
US11697617B2 (en) 2019-08-06 2023-07-11 Corning Incorporated Glass laminate with buried stress spikes to arrest cracks and methods of making the same
CN115720574A (en) * 2020-06-30 2023-02-28 康宁股份有限公司 Method for regenerating a poisoned molten salt bath, and glass and related glass compositions
MX2023000918A (en) 2020-07-20 2023-04-14 Corning Inc Stress features for crack redirection and protection in glass containers.
CN111995243A (en) * 2020-09-04 2020-11-27 彩虹集团（邵阳）特种玻璃有限公司 High-strength and low-brittleness aluminosilicate glass and strengthening method and application thereof
US11642280B2 (en) 2020-11-10 2023-05-09 Corning Incorporated Glass containers and sealing assemblies for maintaining seal integrity at low storage temperatures
MX2023012677A (en) 2021-04-26 2023-11-07 Corning Inc Container closure system and sealing assemblies for maintaining seal integrity at low storage temperatures.
DE112022002228T5 (en) * 2021-06-30 2024-02-29 AGC Inc. GLASS PANEL, LAMINATED GLASS, WINDOW PANE FOR VEHICLES AND WINDOW PANE FOR BUILDINGS
WO2023009321A1 (en) 2021-07-27 2023-02-02 Corning Incorporated Pharmaceutical containers comprising necks with non-uniform outer surfaces and methods regarding the same
EP4396104A1 (en) 2021-08-31 2024-07-10 Corning Incorporated Container closure system and sealing assemblies for maintaining seal integrity at low storage temperatures
CN118043017A (en) 2021-09-30 2024-05-14 康宁公司 Glass container for storing pharmaceutical compositions
KR20240064724A (en) 2021-09-30 2024-05-13 코닝 인코포레이티드 Glass container for storing pharmaceutical compositions
WO2023086251A1 (en) 2021-11-09 2023-05-19 Corning Incorporated Pharmaceutical containers including sealing assembly with filler material
CN118488918A (en) 2021-11-22 2024-08-13 康宁股份有限公司 Cap design for a medicament container closure system
WO2024118413A1 (en) 2022-11-30 2024-06-06 Corning Incorporated Reusable pharmaceutical containers and processes of reusing the same

Family Cites Families (151)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE25456E (en) 1963-10-08 Ultraviolet light absorbing glass
US3054686A (en) 1960-05-18 1962-09-18 Owens Illinois Glass Co Glass composition having high chemical durability
NL279298A (en) 1962-03-23
US3351474A (en) 1963-12-16 1967-11-07 Owens Illinois Inc Glass compositions resistant to discoloration, method of making and articles produced therefrom
US3524738A (en) * 1965-12-07 1970-08-18 Owens Illinois Inc Surface stressed mineral formed glass and method
US3900329A (en) * 1965-12-07 1975-08-19 Owens Illinois Inc Glass compositions
US3844754A (en) 1966-02-23 1974-10-29 Owens Illinois Inc Process of ion exchange of glass
US3490885A (en) 1966-12-30 1970-01-20 Owens Illinois Inc Manufacture of chemically-strengthened glass articles
FR2051664B1 (en) 1969-07-10 1974-10-11 Asahi Glass Co Ltd
US4065317A (en) 1971-10-28 1977-12-27 Nippon Electric Glass Company, Ltd. Novel glass compositions
DE2609931C3 (en) 1975-03-13 1978-07-20 Owens-Illinois, Inc., Toledo, Ohio (V.St.A.) Process for producing a protective polymeric coating on a glass surface, which holds glass fragments in place, as well as glass containers
SU990700A1 (en) 1980-03-03 1983-01-23 Белорусский технологический институт им.С.М.Кирова Glass for chemical laboratory glassware
US4312953A (en) 1981-01-29 1982-01-26 Owens-Illinois, Inc. Olive-green glass compositions
RO83460B1 (en) 1981-11-17 1984-03-30 Institutul De Chimie Packaging bottles showing a high fastness to acids
JPS6144735A (en) * 1984-08-10 1986-03-04 Narumi China Corp Method of decorating crystallized glass having low expansion
US4689085A (en) 1986-06-30 1987-08-25 Dow Corning Corporation Coupling agent compositions
US5114757A (en) 1990-10-26 1992-05-19 Linde Harold G Enhancement of polyimide adhesion on reactive metals
JP3079579B2 (en) 1990-12-18 2000-08-21 日本電気硝子株式会社 Medical UV absorbing glass
DE4113655A1 (en) 1991-04-26 1992-10-29 Basf Lacke & Farben HAFTVERMITTLER
JP2871440B2 (en) 1994-02-15 1999-03-17 日本板硝子株式会社 Manufacturing method of chemically strengthened glass
WO1995031418A1 (en) 1994-05-17 1995-11-23 Asahi Chemical Company, Limited Glazing layer forming composition for hot coating of oven refractory and method of forming glazing layer
EP0757020B1 (en) 1995-02-10 2001-06-20 Asahi Glass Company Ltd. Scratch-resistant glass
KR970702221A (en) 1995-02-10 1997-05-13 세야 히로미찌 SCRATCH-RESISTANT GLASS
JPH09124339A (en) 1995-08-28 1997-05-13 Asahi Glass Co Ltd Curved-face glass
JPH09124338A (en) 1995-08-28 1997-05-13 Asahi Glass Co Ltd Tempered glass
DE19536708C1 (en) 1995-09-30 1996-10-31 Jenaer Glaswerk Gmbh Boro-silicate glass contg. zirconium and lithium oxide(s)
IL116815A0 (en) 1996-01-18 1996-05-14 Hadasit Med Res Service Carpule for an interligamentary syringe
JPH09241033A (en) 1996-03-11 1997-09-16 Asahi Glass Co Ltd Glass vessel for hermetical sealing
US5908794A (en) 1996-03-15 1999-06-01 Asahi Glass Company Ltd. Glass composition for a substrate
US6214429B1 (en) 1996-09-04 2001-04-10 Hoya Corporation Disc substrates for information recording discs and magnetic discs
US5854153A (en) 1997-01-09 1998-12-29 Corning Incorporated Glasses for display panels
DE29702816U1 (en) 1997-02-18 1997-04-10 Schott Glaswerke, 55122 Mainz Sterilizable glass container for medical purposes, in particular for storing pharmaceutical or diagnostic products
DE19706255C2 (en) 1997-02-18 2000-11-30 Schott Glas Sterilizable glass container for medical purposes, in particular for storing pharmaceutical or diagnostic products
FR2761978B1 (en) 1997-04-11 1999-05-07 Saint Gobain Vitrage GLASS COMPOSITION AND CHEMICALLY TEMPERED GLASS SUBSTRATE
JP3384286B2 (en) 1997-06-20 2003-03-10 日本板硝子株式会社 Glass substrate for magnetic recording media
JP4077536B2 (en) * 1997-07-11 2008-04-16 日本無機株式会社 Extra fine glass fiber
JP4016455B2 (en) 1997-07-23 2007-12-05 旭硝子株式会社 Substrate glass composition
GB9715446D0 (en) 1997-07-23 1997-09-24 British Ceramic Res Ltd Glazes
JPH11180727A (en) 1997-12-22 1999-07-06 Central Glass Co Ltd Substrate glass composition for display device
JPH11180728A (en) 1997-12-22 1999-07-06 Central Glass Co Ltd Substrate glass composition for display device
JPH11240735A (en) 1998-02-27 1999-09-07 Asahi Glass Co Ltd Glass composition for use as substrate
GB2335423A (en) 1998-03-20 1999-09-22 Pilkington Plc Chemically toughenable glass
JPH11328601A (en) * 1998-05-12 1999-11-30 Asahi Techno Glass Corp Glass board for recording medium, recording medium using glass board and manufacture of glass board for recording medium
JPH11335133A (en) 1998-05-27 1999-12-07 Central Glass Co Ltd Substrate glass for display device
JP2000007372A (en) 1998-06-19 2000-01-11 Asahi Techno Glass Corp Glass for chemical tempering and glass base for magnetic recording medium
JP4497591B2 (en) * 1998-09-11 2010-07-07 Ｈｏｙａ株式会社 Glass composition, substrate for information recording medium and information recording medium using the same
JP3657453B2 (en) 1999-02-04 2005-06-08 日本板硝子株式会社 Information processing recording medium
DE19906240A1 (en) 1999-02-15 2000-08-17 Schott Glas Glass composition used, e.g., as container glass for chemically aggressive liquids contains a high amount of zirconium oxide
CZ20012687A3 (en) 1999-02-15 2002-03-13 Schott Glas Glass with high content of zirconium oxide and use thereof
JP4161509B2 (en) * 1999-04-13 2008-10-08 旭硝子株式会社 Glass for information recording medium substrate and glass substrate for information recording medium
US6387510B1 (en) * 1999-04-13 2002-05-14 Asahi Glass Company, Limited Glass for a data storage medium substrate and glass substrate for data storage media
US6277777B1 (en) 1999-08-03 2001-08-21 Johns Manville International, Inc. Boron-free glass composition and filtration media
JP2001076336A (en) * 1999-09-08 2001-03-23 Hoya Corp Glass substrate for information recording medium and information recording medium using the same
JP2001192239A (en) 1999-12-28 2001-07-17 Asahi Techno Glass Corp Method for manufacturing strengthened glass, strengthened glass and glass substrate
JP2001180969A (en) 1999-12-28 2001-07-03 Central Glass Co Ltd Manufacturing method of lithium-containing glass with high young's modulus and its glass product
JP4389257B2 (en) 2000-03-06 2009-12-24 日本電気硝子株式会社 Glass substrate for flat panel display
JP2002003241A (en) 2000-06-19 2002-01-09 Central Glass Co Ltd Glass for press molding and glass substrate for information recording media
JP2002025762A (en) 2000-07-04 2002-01-25 Nippon Electric Glass Co Ltd Glass board for inorganic el display
DE10035801B4 (en) 2000-07-22 2008-04-03 Schott Ag Borosilicate glass of high chemical resistance and its uses
EP1193185A1 (en) 2000-10-02 2002-04-03 Heineken Technical Services B.V. Glass container with improved coating
US6472068B1 (en) 2000-10-26 2002-10-29 Sandia Corporation Glass rupture disk
RU2173673C1 (en) * 2000-11-04 2001-09-20 Валеев Макарим Ямгутдинович Medical glass
JP4686858B2 (en) 2000-12-26 2011-05-25 日本電気硝子株式会社 Glass substrate for flat panel display
JP2001236634A (en) 2001-01-04 2001-08-31 Nippon Sheet Glass Co Ltd Magnetic disk substrate comprising glass composition for chemical strengthening and magnetic disk medium
JP2001229526A (en) 2001-01-04 2001-08-24 Nippon Sheet Glass Co Ltd Magnetic disk substrate consisting of glass composition for chemical strengthening and magnetic disk medium
JP3995902B2 (en) 2001-05-31 2007-10-24 Ｈｏｙａ株式会社 Glass substrate for information recording medium and magnetic information recording medium using the same
EP1443029A4 (en) 2001-11-05 2007-08-01 Asahi Glass Co Ltd Glass ceramic composition
GB0127942D0 (en) 2001-11-21 2002-01-16 Weston Medical Ltd Needleless injector drug capsule and a method for filing thereof
JP2002249340A (en) 2001-11-30 2002-09-06 Hoya Corp Cover glass for semiconductor package
EP1460044B2 (en) 2001-12-28 2016-10-26 Nippon Sheet Glass Company, Limited Sheet glass and photoelectric converter-use sheet glass
DE20220582U1 (en) 2002-08-24 2003-11-13 Schott Glas, 55122 Mainz Aluminum-free borosilicate glass used in the production of ampoules and bottles in the pharmaceutical industry and for laboratory devices and equipment includes oxides of silicon and boron
JP2004131314A (en) 2002-10-09 2004-04-30 Asahi Glass Co Ltd Chemically strengthened glass substrate with transparent conductive film and its manufacturing process
JP4252956B2 (en) * 2002-10-29 2009-04-08 Ｈｏｙａ株式会社 Glass for chemical strengthening, substrate for information recording medium, information recording medium, and method for producing information recording medium
JPWO2004041740A1 (en) * 2002-11-07 2006-03-09 Hoya株式会社 SUBSTRATE FOR INFORMATION RECORDING MEDIUM, INFORMATION RECORDING MEDIUM, AND ITS MANUFACTURING METHOD
CN1753840A (en) 2003-02-25 2006-03-29 肖特股份公司 Antimicrobial active borosilicate glass
JP2004315317A (en) 2003-04-17 2004-11-11 Nippon Sheet Glass Co Ltd Glass composition, sealed container formed of glass composition thereof, and quartz resonator using the sealed container
JP2005048142A (en) * 2003-07-31 2005-02-24 Nippon Sheet Glass Co Ltd Solution for forming colored film and method for producing glass base having colored film formed by using the same
WO2005042437A2 (en) * 2003-09-30 2005-05-12 Schott Ag Antimicrobial glass and glass ceramic surfaces and their production
JP5373267B2 (en) 2003-10-29 2013-12-18 サン−ゴバン グラス フランス Reinforced pane for insulation
DE102004011009A1 (en) 2004-03-08 2005-09-29 Schott Ag Surface-modified, multi-component glass articles, e.g. light bulbs, optical elements or containers, having surface atoms replaced by other atoms to improve properties, e.g. chemical resistance or hardness
KR20070083838A (en) 2004-09-29 2007-08-24 니폰 덴키 가라스 가부시키가이샤 Glass for semiconductor sealing, sheath tube for semiconductor sealing and semiconductor electronic part
CN100519458C (en) * 2005-04-02 2009-07-29 中国洛阳浮法玻璃集团有限责任公司 Single-slice fireproof glass
EP1920010B1 (en) 2005-09-02 2013-01-16 Basf Se Process for preparation of a novel pigmented composition for use in gravure inks
US20070123410A1 (en) 2005-11-30 2007-05-31 Morena Robert M Crystallization-free glass frit compositions and frits made therefrom for microreactor devices
CN103172259B (en) 2006-02-10 2015-10-21 康宁股份有限公司 There is glass composition of high thermostability and chemical stability and preparation method thereof
KR100630309B1 (en) 2006-04-13 2006-10-02 (주)한국나노글라스 The tempered glass for protecting a portable telephone LCD and the manufacturing method the tempered glass
JP3961560B1 (en) 2006-05-19 2007-08-22 東洋佐々木ガラス株式会社 Crystal glass articles
MY152135A (en) 2006-06-08 2014-08-15 Hoya Corp Glass for use in substrate for information recording medium, substrate for information recording medium and information recording medium, and their manufacturing method
US20070293388A1 (en) 2006-06-20 2007-12-20 General Electric Company Glass articles and method for making thereof
WO2008050500A1 (en) 2006-09-29 2008-05-02 Nippon Electric Glass Co., Ltd. Protective plate for portable equipment display device
CN101522584B (en) * 2006-10-10 2012-12-05 日本电气硝子株式会社 Reinforced glass substrate
MY157935A (en) 2006-11-22 2016-08-15 Asahi Glass Co Ltd Glass for information recording media substrate
JP2008195602A (en) 2007-01-16 2008-08-28 Nippon Electric Glass Co Ltd Method for manufacturing tempered glass substrate and tempered glass substrate
JP5808069B2 (en) 2007-02-16 2015-11-10 日本電気硝子株式会社 Glass substrate for solar cell
US7666511B2 (en) 2007-05-18 2010-02-23 Corning Incorporated Down-drawable, chemically strengthened glass for cover plate
WO2009002660A2 (en) 2007-06-15 2008-12-31 Mayaterials, Inc. Multi-functional silsesquioxanes for novel coating applications
JP2010202413A (en) 2007-06-27 2010-09-16 Asahi Glass Co Ltd Method for producing glass, method for producing glass raw material, and glass raw material
JP5467490B2 (en) 2007-08-03 2014-04-09 日本電気硝子株式会社 Method for producing tempered glass substrate and tempered glass substrate
EP2031124A1 (en) 2007-08-27 2009-03-04 Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO Coating having low friction characteristics
JP5743125B2 (en) * 2007-09-27 2015-07-01 日本電気硝子株式会社 Tempered glass and tempered glass substrate
DE102007063463B4 (en) 2007-12-20 2010-06-10 Schott Ag Core glass in the alkali-zinc-silicate glass system for a fiber optic light guide and the use of the core glass in a light guide
KR101579308B1 (en) 2008-02-25 2015-12-21 가부시키가이샤 노리타케 캄파니 리미티드 Ceramic product and ceramic member bonding method
EP2262551A1 (en) * 2008-03-10 2010-12-22 S.E.A. Medical Systems, Inc. Intravenous fluid monitoring
CN101977860B (en) * 2008-03-19 2013-08-21 Hoya株式会社 Glasses for substrate for magnetic recording medium, substrates for magnetic recording medium, magnetic recording media, and processes for producing these
JP5568551B2 (en) 2008-05-23 2014-08-06 ホスピラ・インコーポレイテツド Packaged iron sucrose products
JP5444846B2 (en) 2008-05-30 2014-03-19 旭硝子株式会社 Glass plate for display device
JP5867953B2 (en) 2008-06-27 2016-02-24 日本電気硝子株式会社 Tempered glass and tempered glass
JP5614607B2 (en) * 2008-08-04 2014-10-29 日本電気硝子株式会社 Tempered glass and method for producing the same
US8075999B2 (en) * 2008-08-08 2011-12-13 Corning Incorporated Strengthened glass articles and methods of making
CN102123960A (en) * 2008-08-21 2011-07-13 康宁股份有限公司 Durable glass housings/enclosures for electronic devices
US8966941B2 (en) 2008-09-01 2015-03-03 Saint-Gobain Glass France Process for obtaining glass and glass obtained
JP5622069B2 (en) 2009-01-21 2014-11-12 日本電気硝子株式会社 Tempered glass, tempered glass and method for producing tempered glass
US8535761B2 (en) 2009-02-13 2013-09-17 Mayaterials, Inc. Silsesquioxane derived hard, hydrophobic and thermally stable thin films and coatings for tailorable protective and multi-structured surfaces and interfaces
JP5699434B2 (en) 2009-04-02 2015-04-08 旭硝子株式会社 Glass for information recording medium substrate, glass substrate for information recording medium and magnetic disk
JP5791878B2 (en) 2009-06-12 2015-10-07 ショット・アーゲー Boron-deficient neutral glass with titanium oxide and zirconium oxide
JP5659544B2 (en) * 2009-07-03 2015-01-28 旭硝子株式会社 Glass for information recording medium substrate, glass substrate for information recording medium and magnetic disk
JP2012184118A (en) 2009-07-16 2012-09-27 Asahi Glass Co Ltd Glass plate for display device
US8647995B2 (en) 2009-07-24 2014-02-11 Corsam Technologies Llc Fusion formable silica and sodium containing glasses
EP2465828A4 (en) 2009-08-10 2014-03-26 Hoya Corp Glass for magnetic recording medium substrate, magnetic recording medium substrate and method for producing same, and magnetic recording medium
DE102009038475B4 (en) 2009-08-21 2011-07-07 Schott Ag, 55122 Use of a glass for glass-metal connections
US8802581B2 (en) 2009-08-21 2014-08-12 Corning Incorporated Zircon compatible glasses for down draw
CN101717189B (en) 2009-08-28 2011-06-08 武汉力诺太阳能集团股份有限公司 High chemical resistance borosilicate glass and purpose thereof
JP5115545B2 (en) * 2009-09-18 2013-01-09 旭硝子株式会社 Glass and chemically tempered glass
JP5613164B2 (en) 2009-09-28 2014-10-22 Hoya株式会社 Glass substrate for information recording medium and information recording medium
JP5761025B2 (en) 2009-10-19 2015-08-12 旭硝子株式会社 Glass plate for substrate, method for producing the same, and method for producing TFT panel
JPWO2011049146A1 (en) 2009-10-20 2013-03-14 旭硝子株式会社 Glass plate for Cu-In-Ga-Se solar cell and solar cell using the same
JP5621239B2 (en) 2009-10-20 2014-11-12 旭硝子株式会社 GLASS PLATE FOR DISPLAY DEVICE, PLATE GLASS FOR DISPLAY DEVICE, AND METHOD FOR PRODUCING THE SAME
DE102009051852B4 (en) 2009-10-28 2013-03-21 Schott Ag Borless glass and its use
CN102092940A (en) 2009-12-11 2011-06-15 肖特公开股份有限公司 Aluminum silicate glass for touch screen
JP2011132061A (en) 2009-12-24 2011-07-07 Asahi Glass Co Ltd Glass substrate for information recording medium and magnetic disk
CN102167507B (en) 2010-02-26 2016-03-16 肖特玻璃科技(苏州)有限公司 For the thin lithium aluminosilicate glass of 3D tight mould pressing
CN102167509A (en) 2010-02-26 2011-08-31 肖特玻璃科技(苏州)有限公司 Chemical toughened glass capable of carrying out subsequent cutting
KR20130072187A (en) 2010-05-19 2013-07-01 아사히 가라스 가부시키가이샤 Glass for chemical strengthening and glass plate for display device
JP5838967B2 (en) 2010-08-24 2016-01-06 旭硝子株式会社 Cover glass for flat panel display and manufacturing method
IT1402048B1 (en) 2010-10-19 2013-08-28 Bormioli Luigi Spa ITEM IN MATERIAL OVERLAPPED COMPOSITE AND ITS PREPARATION PROCEDURE
DE102010054967B4 (en) 2010-12-08 2014-08-28 Schott Ag Boreless universal glass and its use
JP5834793B2 (en) 2010-12-24 2015-12-24 旭硝子株式会社 Method for producing chemically strengthened glass
CN102173580A (en) * 2011-02-24 2011-09-07 北京工业大学 High-alkali magnesium aluminum silicate glass applicable to chemical tempering
FR2972446B1 (en) 2011-03-09 2017-11-24 Saint Gobain SUBSTRATE FOR PHOTOVOLTAIC CELL
TW201245080A (en) 2011-03-17 2012-11-16 Asahi Glass Co Ltd Glass for chemical strengthening
TWI591039B (en) 2011-07-01 2017-07-11 康寧公司 Ion exchangeable glass with high compressive stress
US8866762B2 (en) * 2011-07-01 2014-10-21 Pixart Imaging Inc. Method and apparatus for arbitrating among contiguous buttons on a capacitive touchscreen
WO2013021975A1 (en) 2011-08-10 2013-02-14 旭硝子株式会社 Glass to be chemically reinforced and glass housing
US9474688B2 (en) 2011-10-25 2016-10-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9517966B2 (en) 2011-10-25 2016-12-13 Corning Incorporated Glass compositions with improved chemical and mechanical durability
WO2013063238A1 (en) 2011-10-25 2013-05-02 Corning Incorporated Glass compositions with improved chemical and mechanical durability
JP6204920B2 (en) * 2011-10-25 2017-09-27 コーニング インコーポレイテッド Alkaline earth aluminosilicate glass composition with improved chemical and mechanical durability
US9139469B2 (en) 2012-07-17 2015-09-22 Corning Incorporated Ion exchangeable Li-containing glass compositions for 3-D forming
JP2014037343A (en) * 2012-07-18 2014-02-27 Nippon Electric Glass Co Ltd Glass for medicine container and glass tube using the same
JP6220053B2 (en) 2013-04-29 2017-10-25 コーニング インコーポレイテッド Solar cell module package
DE102015116097B4 (en) * 2015-09-23 2017-09-21 Schott Ag Chemically resistant glass and its use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017214285A (en) * 2011-10-25 2017-12-07 コーニング インコーポレイテッド Alkaline earth aluminosilicate glass composition having improved chemical and mechanical durability
EP2876092A4 (en) * 2012-07-18 2016-01-06 Nippon Electric Glass Co Glass for pharmaceutical product container, pharmaceutical product container glass tube using same, method for manufacturing pharmaceutical product container, and pharmaceutical product container
JP2018145093A (en) * 2012-12-21 2018-09-20 日本電気硝子株式会社 Strengthened glass, strengthened glass plate, strengthened glass container, and glass for strengthening
US10450217B2 (en) 2013-06-06 2019-10-22 Nippon Electric Glass Co., Ltd. Glass for pharmaceutical containers
JP2015013793A (en) * 2013-06-06 2015-01-22 日本電気硝子株式会社 Glass for pharmaceutical containers
US10384975B2 (en) 2013-06-06 2019-08-20 Nippon Electric Glass Co., Ltd. Glass for pharmaceutical containers
US10173920B2 (en) 2014-06-19 2019-01-08 Corning Incorporated Aluminosilicate glasses
WO2015195435A3 (en) * 2014-06-19 2016-03-24 Corning Incorporated Aluminosilicate glasses
EP3971147A1 (en) * 2014-06-19 2022-03-23 Corning Incorporated Aluminosilicate glasses
US11001521B2 (en) 2014-06-19 2021-05-11 Corning Incorporated Aluminosilicate glasses
CN106573820A (en) * 2014-06-19 2017-04-19 康宁股份有限公司 Aluminosilicate glasses
US9902644B2 (en) 2014-06-19 2018-02-27 Corning Incorporated Aluminosilicate glasses
DE102015116097B4 (en) * 2015-09-23 2017-09-21 Schott Ag Chemically resistant glass and its use
EP3147265A1 (en) * 2015-09-23 2017-03-29 Schott AG Chemically resistant glass and its use
EP3392217A1 (en) * 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
DE102015116097A1 (en) * 2015-09-23 2017-03-23 Schott Ag Chemically resistant glass and its use
EP3392218A1 (en) * 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
US10336646B2 (en) 2015-09-23 2019-07-02 Schott Ag Chemically resistant glass
EP3392216A1 (en) * 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
EP3392219A1 (en) * 2015-09-23 2018-10-24 Schott AG Chemically resistant glass and its use
WO2017151771A1 (en) * 2016-03-04 2017-09-08 Corning Incorporated Ion-exchangeable glass with high surface compressive stress
US11746045B2 (en) 2016-03-04 2023-09-05 Corning Incorporated Ion-exchangeable glass with high surface compressive stress
CN110944952A (en) * 2017-03-31 2020-03-31 康宁股份有限公司 High transmission glass
US11040907B2 (en) 2017-03-31 2021-06-22 Corning Incorporated High transmission glasses
TWI753147B (en) * 2017-03-31 2022-01-21 美商康寧公司 High transmission glasses
WO2018183444A3 (en) * 2017-03-31 2018-12-13 Corning Incorporated High transmission glasses
US11746038B2 (en) 2017-03-31 2023-09-05 Corning Incorporated High transmission glasses
EP4385957A1 (en) * 2022-12-13 2024-06-19 Schott Ag Aluminosilicate glass

Also Published As

Publication number Publication date
US20170327407A1 (en) 2017-11-16
KR20140084175A (en) 2014-07-04
CN109704566A (en) 2019-05-03
JP2015501280A (en) 2015-01-15
RU2017132271A (en) 2019-02-06
US20150344350A1 (en) 2015-12-03
RU2017132271A3 (en) 2019-02-06
JP6204920B2 (en) 2017-09-27
KR20190031586A (en) 2019-03-26
CN104066695A (en) 2014-09-24
KR102068774B1 (en) 2020-01-21
RU2632084C2 (en) 2017-10-02
US9718721B2 (en) 2017-08-01
WO2013063002A3 (en) 2013-08-15
RU2014116644A (en) 2015-12-10
JP6646636B2 (en) 2020-02-14
CN109704566B (en) 2022-08-26
MX2014004971A (en) 2014-05-22
AU2012328981A1 (en) 2014-05-22
JP2017214285A (en) 2017-12-07
RU2691186C2 (en) 2019-06-11
US20200140319A1 (en) 2020-05-07
CN104066695B (en) 2019-02-12
AU2012328981B2 (en) 2016-07-07
US9145329B2 (en) 2015-09-29
US11168017B2 (en) 2021-11-09
EP2771293A2 (en) 2014-09-03
US20130101853A1 (en) 2013-04-25
MX366947B (en) 2019-07-30
EP3546433A1 (en) 2019-10-02
KR102120349B1 (en) 2020-06-09
AU2016203653A1 (en) 2016-06-23
AU2016203653B2 (en) 2018-04-12
EP2771293B1 (en) 2019-01-16
US10577274B2 (en) 2020-03-03

Similar Documents

Publication Publication Date Title
US11168017B2 (en) Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
JP6972207B2 (en) Glass composition with improved chemical and mechanical durability
WO2015080893A1 (en) Fast ion exchangeable glasses with high indentation threshold
WO2013181134A1 (en) Zircon compatible, ion exchangeable glass with high damage resistance

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: 12781010

Country of ref document: EP

Kind code of ref document: A2

ENP Entry into the national phase

Ref document number: 2014538893

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: MX/A/2014/004971

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2012781010

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20147012855

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2012328981

Country of ref document: AU

Date of ref document: 20121024

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2014116644

Country of ref document: RU

Kind code of ref document: A