WO2011149740A1 - Glasses having low softening temperatures and high toughness - Google Patents
Glasses having low softening temperatures and high toughness Download PDFInfo
- Publication number
- WO2011149740A1 WO2011149740A1 PCT/US2011/037036 US2011037036W WO2011149740A1 WO 2011149740 A1 WO2011149740 A1 WO 2011149740A1 US 2011037036 W US2011037036 W US 2011037036W WO 2011149740 A1 WO2011149740 A1 WO 2011149740A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glass
- alkali aluminoborosilicate
- mol
- glasses
- alkali
- Prior art date
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
- C03C3/089—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
-
- 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
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
Definitions
- the disclosure relates to glasses having a low softening point and high damage resistance.
- Magnesium alkali alumino silicate and soda lime glasses are currently being used in consumer electronic products.
- Magnesium alkali alumino silicate glasses often have softening points that are so high as to damage steel molds that are used for sagging the glass into the desired contour for selected applications, whereas soda lime glasses cannot be adequately strengthened by ion exchange.
- the coefficient of thermal expansion of such glasses tends to be high, thus making these glasses prone to cracking during rapid thermal changes.
- the glasses are alkali aluminoborosilicate glasses having softening points of less than 900°C and in some embodiments, in a range from about 650°C up to about 825°C.
- the glasses have an indenter damage threshold of at least 300 g and, when strengthened by ion exchange, have a damage threshold of at least 3000 g.
- the glasses are free of alkaline earth metals, lead, arsenic, and antimony, in some embodiments, lithium.
- one aspect of the disclosure is to provide an alkali aluminoborosilicate glass having a softening point in a range from 650°C up to 825°C and an indenter damage threshold of at least 300 g.
- the glass is free of alkaline earth metals, lead, arsenic, and antimony.
- a second aspect of the disclosure is to provide an alkali aluminoborosilicate glass having a surface layer under compressive stress, a softening point of less than 900°C, and an indenter damage threshold of at least 5 kg.
- the glass is free of alkaline earth metals, lead, arsenic, and antimony.
- FIGURE 1 is a schematic cross-sectional view of a glass sheet strengthened by ion exchange
- FIGURE 2 is a plot of softening points of glasses as a function of the
- FIGURE 3 is a plot of damage threshold loads for various glasses before ion exchange (pre-IX) and after ion exchange (post-IX);
- FIGURE 4 is a plot of damage threshold as a function of the molar ratio ⁇ R' 2 0 3 / ⁇ R 2 0;
- FIGURE 5 is a plot of indentation threshold as a function of the molar ratio ⁇ R 2 0/A1 2 0 3 .
- the terms “softening point” and “softening temperature” refer to the temperature at which a glass flows and has a viscosity of 10 7'6 poise (P).
- the term “indenter threshold” refers to the load on a Vickers indenter that is needed to initiate Vickers (i.e., radial) cracks at the corners of the indent.
- glass such as magnesium alkali aluminosilicate glasses, that can be strengthened by ion exchange.
- Such glasses have softening points that are so high as to damage steel molds that are used for sagging the glass into the desired contour or three-dimensional shape for selected applications.
- the coefficient of thermal expansion (CTE) of such glasses tends to be high (e.g., about 91 x 10 ⁇ 7 /°C), thus making these glasses prone to cracking during rapid thermal changes.
- CTE coefficient of thermal expansion
- the glass has excellent ion exchange properties, a high resistance to crack initiation, and is fusion formable.
- the glass article comprises an alkali aluminoboro silicate glass having, in some embodiments, a softening point of less than about 900°C, in other embodiments, a softening point of less than about 825°C and, in still other embodiments, in a range from about 650°C up to about 825°C.
- the alkali aluminoborosilicate glass has an indenter damage threshold of at least 300 g without chemical strengthening by ion exchange.
- the alkali aluminoborosilicate glass is free of alkaline earth metals and lead. In some embodiments, the alkali aluminoborosilicate glass is free of at least one of lithium, arsenic, antimony, lead, and/or transition metals.
- the alkali aluminoborosilicate glass is strengthened by ion exchange.
- ions in the surface layer of the glass are replaced by - or exchanged with - larger ions having the same valence or oxidation state as the ions present in the glass.
- Ions in the surface layer of the alkali aluminoborosilicate glass and the larger ions are monovalent metal cations such as, but not limited to, Na + , K + , Rb + , Cs + , Ag + , Tl + , Cu + , and the like.
- Ion exchange processes typically comprise immersing the alkali aluminoborosilicate glass in a molten salt bath containing the larger ions to be exchanged with the smaller ions in the glass.
- parameters for the ion exchange process including, but not limited to, bath composition and temperature, immersion time, the number of immersions of the glass in a salt bath (or baths), use of multiple salt baths, additional steps such as annealing, washing, and the like, are generally determined by the composition of the glass and the desired depth of layer and compressive stress of the glass to be achieved by the strengthening operation.
- ion exchange of alkali metal-containing glasses can be achieved by immersion in at least one molten salt bath containing a salt such as, but not limited to, nitrates, sulfates, and chlorides of the larger alkali metal ion.
- the temperature of the molten salt bath is typically in a range from about 380°C up to about 450°C, and immersion times range up to about 16 hours. However, temperatures and immersion times that are different from those described above can also be used.
- Such ion exchange treatments typically result in strengthened alkali aluminoborosilicate glasses having an outer surface layer (also referred to herein a "depth of layer" or "DOL”) that is under compressive stress.
- DOL depth of layer
- FIG.l A cross-sectional view of an alkali aluminoborosilicate glass sheet strengthened by ion exchange is schematically shown in FIG.l .
- Strengthened glass sheet 100 has a thickness t, a first surface 1 10 and second surface 120 that are substantially parallel to each other, central portion 115, and edges 130 joining first surface 110 to second surface 120.
- Strengthened glass sheet 100 has strengthened surface layers 112, 122 extending from first surface 110 and second surface 120, respectively, to depths di, d 2 , below each surface.
- Strengthened surface layers 112, 122 are under a compressive stress, while central portion 115 is under a tensile stress, or in tension.
- the tensile stress in central portion 1 15 balances the compressive stresses in strengthened surface layers 112, 122, thus maintaining equilibrium within strengthened glass sheet 100.
- the depths di, d 2 to which the strengthened surface layers 112, 122 extend are generally referred to individually as the "depth of layer.”
- a portion 132 of edge 130 may also be strengthened as a result of the strengthening process.
- Thickness t of strengthened glass sheet 100 is generally in a range from about 0.1 mm up to about 2 mm. In one embodiment, thickness t is in a range from about 0.5 mm up to about 1.3 mm.
- the ion exchanged glass sheet 100 has an indenter damage threshold of at least 3000 g.
- the indenter threshold of the alkali aluminoborosilicate glass is in a range from about 3000 g up to about 10,000 g.
- ion exchanged surface layers 112, 122 each have a depth of layer of at least 20 ⁇ and a compressive stress of at least about 600 MPa.
- the alkali aluminoborosilicate glass comprises, consists essentially of, or consists of: 50-70 mol% Si0 2 ; 5-15 mol% A1 2 0 3 ; 5-20 mol% B 2 0 3 ; 0-15 mol% Li 2 0; 0-20 mol% Na 2 0; and 0-10 mol% K 2 0; and is substantially free of alkaline earth oxides (i.e., alkaline earth oxides are not actively or intentionally added to the glass, but may be present in small amounts as minor contaminants).
- the glass can further comprise up to 10 mol% P2O5 and/or up to 3.3 mol% of Sn0 2 can be added as a fining agent.
- the alkali aluminoborosilicate glass is also substantially free of at least one of lithium, antimony, arsenic, lead, silver, and copper.
- halogens such as fluorine, chlorine, and bromine can be added as fining agents to the alkali aluminoborosilicate glass.
- up to 3.3 mol% of Sn0 2 can be added as a fining agent.
- the alkali aluminoborosilicate glass is down- drawn, using those methods known in the art such as, but not limited to fusion- drawing, slot-drawing, re-drawing, and the like, and has a liquid viscosity of at least 135 kpoise (KP).
- KP kpoise
- the alkali aluminoborosilicate glass has a viscosity of at least 1 Mpoise (MP).
- the alkali aluminoborosilicate glass is, in some embodiments, inert with respect to zircon at those temperatures where the viscosity of the glass has a viscosity of at least 5 kpoise.
- compositions and physical properties of the alkali aluminoborosilicate glasses described herein are listed in Tables la and lb. Properties such as strain point, anneal point, and softening point were determined by fiber elongation. Ion exchange (IX) properties such as depth of layer and surface compressive stress (CS) were obtained by polarized microscopy and/or surface stress meter, respectively, with central tension or central tensile stress (CT) being calculated from DOL and CS values.
- IX ion exchange
- CS surface compressive stress
- the ion exchange properties listed in Table la were obtained using single-step ion exchange treatments (i.e., immersion of the glass in a single ion exchange or salt bath of either 100% NaN0 3 or mixtures (60/40, 80/20, or 90/10 by weight) of NaN0 3 and K 0 3 ).
- the alkali aluminoborosilicate glasses described herein are characterized by high DOL (generally greater than 100 ⁇ ) and relatively low CS ( ⁇ 50 MPa).
- the two step ion exchange process can include immersion in a first bath, having a composition of either 100% NaN0 3 or a mixture of 60% KNO 3 /40% NaN0 3 by weight, at a temperature in a range from 390°C up to 410°C for 2 to 15 hours, followed by immersion in a second bath of either 100% KN0 3 or a salt of a larger cation (e.g., RbN0 3 ) at a temperature in a range from 390°C up to 410°C for a time period ranging from 5 minutes up to 15 hours.
- a first bath having a composition of either 100% NaN0 3 or a mixture of 60% KNO 3 /40% NaN0 3 by weight, at a temperature in a range from 390°C up to 410°C for 2 to 15 hours
- immersion in a second bath of either 100% KN0 3 or a salt of a larger cation e.g., RbN0 3
- Table lb lists compositions and thermal and mechanical properties of additional alkali aluminoborosilicate glasses. Depths of layer and indentation damage thresholds are reported for glasses that had been ion exchanged using either a 100% NaN0 3 bath or a bath comprising 60%> K 0 3 and 40% NaN0 3 by weight. Ion- exchange in mixed K /Na + baths allows not only for Li + in the glass to be replaced with Na + from the bath, but also allows Na + in the glass to be replaced with K + from the bath, thus increasing the compressive stress at the glass surface. The increase in CS at the surface in turn contributes to the damage resistance of the glass.
- Damage thresholds that were measured for the base glasses i.e., before ion exchange, labeled "Pre-IX" in Table lb) are also listed. Ion exchange in a 100% NaN0 3 bath produces depths of layer that are comparable, if not identical, to those obtained using a mixed salt bath of a 60:40 weight percent mixture of KN0 3 :NaN0 3 .
- the damage threshold for glasses ion exchanged in NaN0 3 is at least three times greater than that measured for the base glasses before ion exchange.
- the damage threshold for glasses ion exchanged in the mixed KN0 3 :NaN0 3 bath is at least five times greater than that measured before ion exchange for the base glasses.
- Table la Representative compositions and physical properties of alkali aluminoborosilicate glasses described herein.
- Table lb Representative compositions and physical properties of the alkali aluminoborosilicate glasses described herein.
- the ratio B 2 O 3 /AI 2 O 3 in the alkali aluminoboro silicate glass has been found to be a factor in lowering the softening point of the glasses described herein.
- the softening points of the glasses listed in Table la are plotted as a function of the B 2 O 3 /AI 2 O 3 molar ratio in FIG. 2.
- 200P temperatures i.e., the temperature at which the glass has a viscosity of 200 poise
- a B 2 O 3 /AI 2 O 3 molar ratio of greater than 1.2 is necessary to achieve a softening point of less than 750°C for the alkali aluminoborosilicate glasses described herein.
- the alkali aluminoborosilicate glasses described herein are more damage resistant than alkali alumino silicate and soda-lime glasses.
- the intrinsically higher damage resistance of these alkali aluminoborosilicate glasses is associated with the lack of non-bridging oxygens in the structure. This intrinsic damage resistance is further improved by adding a compressive layer to the glass via ion exchange. Damage threshold loads obtained for various glasses before ion exchange (pre-IX) and after ion exchange (post-IX) are compared in FIG. 3.
- Alkali alumino silicate and soda-lime glasses have damage thresholds before ion exchange of 100 g and 300 g, respectively, whereas the alkali aluminoborosilicate glasses described herein have pre-ion exchange damage thresholds of at least 500 g and, in some instances, at least 1000 g (see examples in tables).
- some embodiments of the alkali aluminoborosilicate glasses described herein exhibit damage thresholds as high as 7000 g.
- ion exchanged soda-lime glass having a depth of compressive layer of about 10 ⁇ and a compressive stress of about 650 MPa, reaches a maximum damage threshold of about 800 g.
- Damage thresholds as high as 5000 g can be achieved in ion exchanged alkali alumino silicate glasses having a DOL of about 50 ⁇ and a compressive stress of about 750 MPa.
- the alkali aluminoboro silicate glass in some embodiments, has a surface layer under compressive stress, a softening point of less than 900°C and an indenter damage threshold of at least 5 kg when the glass is strengthened by ion exchange.
- the glass comprises, consists essentially of, or consists of: 50-70 mol% Si0 2 ; 5-15 mol% A1 2 0 3 ; 5-20 mol% B 2 0 3 ; 0-15 mol% Li 2 0; 0-20 mol% Na 2 0; and 0-10 mol% K 2 0; and is substantially free of alkaline earth oxides.
- the glass can further comprise up to 10 mol% P 2 0 5 and/or up to 3.3 mol% of Sn0 2 can be added as a fining agent.
- the alkali aluminoborosilicate glass is also substantially free of at least one of lithium, antimony, arsenic, lead, silver, and copper.
- halogens such as fluorine, chlorine, and bromine can be added as fining agents to the alkali aluminoborosilicate glass.
- Greater toughness (i.e., higher damage threshold) following strengthening of the glass by ion exchange can be achieved by adjusting the concentrations of alumina and B 2 0 3 (together referred to herein as R' 2 0 3 ) and the alkali metal oxides (together referred to herein as R 2 0) so that the molar ratio ⁇ R' 2 0 3 / ⁇ R 2 0 is in the range from about 1.5 up to about 1.7 and the molar ratio ⁇ R 2 0/A1 2 0 3 is less than or equal to 1.12.
- the effect of the ratio ⁇ R' 2 0 3 / ⁇ R 2 0 on damage threshold is shown in FIG. 4.
- the damage threshold falls off rapidly as the value of the ratio moves outside the range 1.5 ⁇ R' 2 0 3 / ⁇ R 2 0 ⁇ 1.7.
- the effect of the ratio ⁇ R 2 0/A1 2 0 3 on indentation load is shown in FIG. 5. Indentation load increases rapidly as this ratio approaches the charge balance composition (1.00) from higher values. Greater depths of layer and surface compressive stresses are achievable through ion exchange by increasing the alumina content and/or lowering the boron content of the glass.
- the compositions of the alkali aluminoborosilicate glasses described herein can be categorized according to the combination of softening temperature and toughness exhibited by each glass.
- One such group of glasses is deemed "soft and tough" when the glasses possess a softening point in a range from about 725°C up to about 775°C and a 200 poise (200P) temperature in a range from about 1550°C up to about 1600°C.
- these glasses When strengthened by ion exchange, these glasses have a damage threshold loading in a range from about 5 kg up to about 15 kg.
- the ratio ⁇ R' 2 03/ ⁇ R 2 0 for these soft and tough glasses is less than 1.5 and the ratio ⁇ R 2 0/A1 2 03 is greater than 1.12.
- soft and tough glasses have a liquidus viscosity of greater than 1 MP (megapoise) and a zircon breakdown viscosity in a range from about 5 kP (kpoise) up to about 15 kP.
- the properties and representative compositions of soft and tough alkali aluminoborosilicate glasses are listed in Table 2.
- the alkali aluminoborosilicate glasses described herein having intermediate softness and toughness have a softening point in a range from about 800°C up to about 825°C, a 200P temperature in a range from approximately 1600°C up to about 1650°C, and a damage threshold loading in a range from about 25 kg up to about 40 kg when strengthened by ion exchange.
- the glasses in this intermediate group of alkali aluminoborosilicate glasses have a liquidus viscosity of greater than 1 MP and a zircon breakdown viscosity in a range from about 15 kP (kpoise) up to about 40 kP.
- the molar ratio R 2 O 3 /R 2 O for these glasses is in a range from about 1.5 up to about 1.7, and the molar ratio R 2 O/AI 2 O 3 is in a range from about 1.1 up to about 1.2.
- Representative compositions of alkali aluminoborosilicate glasses having intermediate softness and toughness are listed in Table 3.
- Extremely tough alkali alummoborosilicate glasses that are described herein have a softening point in a range from about 850°C up to about 900°C and a 200P temperature in a range from about 1650°C up to about 1700°C. When ion exchanged, these glasses have a damage threshold loading of at least about 45 kg. These glasses each have a liquidus viscosity of greater than 1 MP and a zircon breakdown viscosity in a range from about 35 kP up to about 50 kP.
- the molar ratio R' 2 0 3 /R 2 0 is in a range from about 1.5 up to about 1.7, and the molar ratio R 2 O/AI 2 O 3 in a range from about 0.95 up to about 1.10 for these glasses.
- Representative compositions of extremely tough alkali alummoborosilicate glasses are listed in Table 4.
- the alkali aluminoborosilicate glass articles described herein can be formed into planar sheets for use as display windows, cover plates, screens, structural features, and the like, in applications such as, but not limited to, touch screens and mobile electronic devices, including telephones and other communication devices, entertainment devices, and hand-held, laptop and notebook computers.
- such alkali aluminoborosilicate glass articles are planar (i.e., substantially flat) in shape.
- these glass articles can be formed by sagging, molding, polishing, grinding, or other means known in the art into non- planar or three-dimensional shapes having some degree of curvature, contour, or a radius profiled portion.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020127033855A KR101765975B1 (en) | 2010-05-27 | 2011-05-18 | Glasses having low softening temperatures and high toughness |
JP2013512087A JP5948321B2 (en) | 2010-05-27 | 2011-05-18 | Glass with low softening temperature and high toughness |
CN201180025885.5A CN102971266B (en) | 2010-05-27 | 2011-05-18 | There is the glass of low softening temperature and high tenacity |
EP11721694.5A EP2576467A1 (en) | 2010-05-27 | 2011-05-18 | Glasses having low softening temperatures and high toughness |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/788,559 | 2010-05-27 | ||
US12/788,559 US8778820B2 (en) | 2010-05-27 | 2010-05-27 | Glasses having low softening temperatures and high toughness |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011149740A1 true WO2011149740A1 (en) | 2011-12-01 |
Family
ID=44121326
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/037036 WO2011149740A1 (en) | 2010-05-27 | 2011-05-18 | Glasses having low softening temperatures and high toughness |
Country Status (7)
Country | Link |
---|---|
US (1) | US8778820B2 (en) |
EP (1) | EP2576467A1 (en) |
JP (2) | JP5948321B2 (en) |
KR (1) | KR101765975B1 (en) |
CN (1) | CN102971266B (en) |
TW (1) | TWI557087B (en) |
WO (1) | WO2011149740A1 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013130653A2 (en) | 2012-02-29 | 2013-09-06 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
JP2015527970A (en) * | 2012-07-17 | 2015-09-24 | コーニング インコーポレイテッド | Ion-exchangeable Li-containing glass composition for 3D molding |
WO2016191676A1 (en) * | 2015-05-28 | 2016-12-01 | Corning Incorporated | Strengthened glass with deep depth of compression |
US9593042B2 (en) | 2014-10-08 | 2017-03-14 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US9908811B2 (en) | 2015-12-11 | 2018-03-06 | Corning Incorporated | Fusion formable glass-based articles including a metal oxide concentration gradient |
US10017417B2 (en) | 2016-04-08 | 2018-07-10 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
US10472272B2 (en) | 2016-01-21 | 2019-11-12 | AGC Inc. | Chemically strengthened glass, and glass for chemical strengthening |
US10579106B2 (en) | 2015-07-21 | 2020-03-03 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
EP3798196A1 (en) * | 2014-06-19 | 2021-03-31 | Corning Incorporated | Glasses having non-frangible stress profiles |
US11021393B2 (en) | 2014-11-04 | 2021-06-01 | Corning Incorporated | Deep non-frangible stress profiles and methods of making |
US11365149B2 (en) | 2016-01-21 | 2022-06-21 | AGC Inc. | Chemically strengthened glass and method for manufacturing chemically strengthened glass |
US11613103B2 (en) | 2015-07-21 | 2023-03-28 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
US11634359B2 (en) | 2014-02-24 | 2023-04-25 | Corning Incorporated | Strengthened glass with deep depth of compression |
US11746046B2 (en) | 2014-10-31 | 2023-09-05 | Corning Incorporated | Strengthened glass with ultra deep depth of compression |
US11963320B2 (en) | 2016-04-08 | 2024-04-16 | Corning Incorporated | Glass-based articles including a stress profile comprising two regions |
Families Citing this family (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8778820B2 (en) * | 2010-05-27 | 2014-07-15 | Corning Incorporated | Glasses having low softening temperatures and high toughness |
US20120052271A1 (en) | 2010-08-26 | 2012-03-01 | Sinue Gomez | Two-step method for strengthening glass |
US9346703B2 (en) | 2010-11-30 | 2016-05-24 | Corning Incorporated | Ion exchangable glass with deep compressive layer and high damage threshold |
US8889575B2 (en) * | 2011-05-31 | 2014-11-18 | Corning Incorporated | Ion exchangeable alkali aluminosilicate glass articles |
US9517966B2 (en) | 2011-10-25 | 2016-12-13 | Corning Incorporated | Glass compositions with improved chemical and mechanical durability |
US11707409B2 (en) | 2011-10-25 | 2023-07-25 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
EP3992161A3 (en) | 2012-05-31 | 2022-06-08 | Corning Incorporated | Zircon compatible, ion exchangeable glass with high damage resistance |
US9512029B2 (en) | 2012-05-31 | 2016-12-06 | Corning Incorporated | Cover glass article |
MX2014015003A (en) * | 2012-06-07 | 2015-03-05 | Corning Inc | Delamination resistant glass containers. |
US20140087193A1 (en) * | 2012-09-26 | 2014-03-27 | Jeffrey Scott Cites | Methods for producing ion exchanged glass and resulting apparatus |
US9387651B2 (en) | 2012-09-26 | 2016-07-12 | Corning Incorporated | Methods for producing ion exchanged glass and resulting apparatus |
US10202303B2 (en) * | 2012-10-04 | 2019-02-12 | Corning Incorporated | Compressively stressed laminated glass article via photosensitive glass and method of making the article |
JP2014133683A (en) * | 2013-01-10 | 2014-07-24 | Central Glass Co Ltd | Method for manufacturing a chemically strengthened glass plate |
US9717649B2 (en) | 2013-04-24 | 2017-08-01 | 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 |
US9700485B2 (en) | 2013-04-24 | 2017-07-11 | 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 |
US9717648B2 (en) | 2013-04-24 | 2017-08-01 | 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 |
US9707155B2 (en) | 2013-04-24 | 2017-07-18 | 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 |
US9849066B2 (en) | 2013-04-24 | 2017-12-26 | 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 |
US9707153B2 (en) | 2013-04-24 | 2017-07-18 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
KR102144705B1 (en) * | 2013-05-24 | 2020-08-14 | 니폰 덴키 가라스 가부시키가이샤 | Method for producing toughened glass plate |
US9512035B2 (en) * | 2013-06-17 | 2016-12-06 | Corning Incorporated | Antimicrobial glass articles with improved strength and methods of making and using same |
US11079309B2 (en) | 2013-07-26 | 2021-08-03 | Corning Incorporated | Strengthened glass articles having improved survivability |
KR102236063B1 (en) * | 2013-08-06 | 2021-04-06 | 삼성디스플레이 주식회사 | Optical coating structure |
EP3038983B1 (en) | 2013-08-27 | 2021-10-20 | Corning Incorporated | Damage resistant glass with high coefficient of thermal expansion |
US10209419B2 (en) | 2013-09-17 | 2019-02-19 | Corning Incorporated | Broadband polarizer made using ion exchangeable fusion drawn glass sheets |
WO2015046113A1 (en) * | 2013-09-25 | 2015-04-02 | 旭硝子株式会社 | Glass plate and chemically strengthened glass plate |
WO2015077109A1 (en) * | 2013-11-20 | 2015-05-28 | Corning Incorporated | Scratch-resistant boroaluminosilicate glass |
CN114230176A (en) * | 2013-11-26 | 2022-03-25 | 康宁股份有限公司 | Fast ion-exchangeable glass with high indentation threshold |
EP3110769B1 (en) * | 2014-02-27 | 2023-04-05 | Corning Incorporated | Ion exchangeable glass article for three-dimensional forming |
CN108609866B (en) * | 2014-07-25 | 2021-12-07 | 康宁股份有限公司 | Strengthened glass with deep depth of compression |
WO2016085778A1 (en) * | 2014-11-26 | 2016-06-02 | Corning Incorporated | Thin glass sheet and system and method for forming the same |
CN107873021A (en) | 2015-02-27 | 2018-04-03 | 康宁股份有限公司 | Cryochemistry reinforcement process for glass |
CN104843977A (en) * | 2015-05-04 | 2015-08-19 | 山东华芯富创电子科技有限公司 | Method for material changing and reprocessing of touch panel tempered glass |
US11104602B2 (en) * | 2015-06-26 | 2021-08-31 | Corning Incorporated | Glass with high surface strength |
JP6511166B2 (en) | 2015-06-26 | 2019-05-15 | コーニング インコーポレイテッド | Glass with high surface strength |
CN108463439B (en) | 2016-01-08 | 2022-07-22 | 康宁股份有限公司 | Chemically strengthenable lithium aluminosilicate glass with inherent damage resistance |
CN108883975A (en) * | 2016-01-13 | 2018-11-23 | 康宁股份有限公司 | Ultra-thin, non fragile glass and its manufacturing method |
WO2017205605A1 (en) * | 2016-05-27 | 2017-11-30 | Corning Incorporated | Fracture and scratch resistant glass articles |
US10065880B2 (en) | 2016-11-07 | 2018-09-04 | Corning Incorporated | Lithium containing glasses |
EP3535220B1 (en) * | 2016-11-07 | 2021-11-17 | Corning Incorporated | Low viscosity glasses |
US11152294B2 (en) | 2018-04-09 | 2021-10-19 | Corning Incorporated | Hermetic metallized via with improved reliability |
WO2019226485A1 (en) | 2018-05-22 | 2019-11-28 | Corning Incorporated | Low temperature moldable sheet forming glass compositions |
WO2020171940A1 (en) | 2019-02-21 | 2020-08-27 | Corning Incorporated | Glass or glass ceramic articles with copper-metallized through holes and processes for making the same |
WO2021211284A1 (en) * | 2020-04-13 | 2021-10-21 | Corning Incorporated | K 2o-containing display glasses |
JPWO2022004892A1 (en) * | 2020-07-03 | 2022-01-06 | ||
US20220396519A1 (en) * | 2021-06-11 | 2022-12-15 | Corning Incorporated | Glass compositions having improved mechanical durability and low characteristic temperatures |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1246384A (en) * | 1968-02-01 | 1971-09-15 | Jenaer Glaswerk Schott & Gen | Improvements in or relating to glass |
WO2009041348A1 (en) * | 2007-09-27 | 2009-04-02 | Nippon Electric Glass Co., Ltd. | Reinforced glass, reinforced glass substrate, and method for producing the same |
US20090142568A1 (en) * | 2007-11-29 | 2009-06-04 | Matthew John Dejneka | Glasses having improved toughness and scratch resistance |
EP2075237A1 (en) * | 2006-10-10 | 2009-07-01 | Nippon Electric Glass Co., Ltd. | Reinforced glass substrate |
US20100047521A1 (en) * | 2008-08-21 | 2010-02-25 | Jaymin Amin | Durable glass housings/enclosures for electronic devices |
WO2011022661A2 (en) * | 2009-08-21 | 2011-02-24 | Corning Incorporated | Crack and scratch resistant glass and enclosures made therefrom |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6036349A (en) * | 1983-08-05 | 1985-02-25 | Ngk Spark Plug Co Ltd | Glass composition |
US4792535A (en) * | 1987-09-02 | 1988-12-20 | Corning Glass Works | UV-transmitting glasses |
US4925814A (en) * | 1989-02-27 | 1990-05-15 | Corning Incorporated | Ultraviolet transmitting glasses for EPROM windows |
US5733622A (en) * | 1995-06-07 | 1998-03-31 | International Business Machines Corporation | Edge strengthened substrate of a data storage disk and method for fabricating same |
EP0980341B1 (en) * | 1997-05-07 | 2003-07-16 | Corning S.A. | Organic lens molds in inorganic glass and novel inorganic glasses |
JPH11153705A (en) * | 1997-11-20 | 1999-06-08 | Nippon Sheet Glass Co Ltd | Lens with distribution of refractive index in axial direction |
JP2005162600A (en) * | 2003-11-11 | 2005-06-23 | Nippon Electric Glass Co Ltd | Cover glass plate for semiconductor package |
DE10361555A1 (en) * | 2003-12-19 | 2005-07-28 | Grintech Gmbh | Aluminoborosilicate glass and process for producing crystallite-free gradient index lenses |
JP2006298691A (en) * | 2005-04-20 | 2006-11-02 | Hitachi Ltd | Flat-panel type image display device |
CN102898023B (en) | 2006-05-25 | 2016-11-23 | 日本电气硝子株式会社 | Strengthening glass and manufacture method thereof |
JP5875133B2 (en) * | 2006-10-10 | 2016-03-02 | 日本電気硝子株式会社 | Tempered glass substrate |
JP2008201654A (en) * | 2007-02-23 | 2008-09-04 | Hitachi Ltd | Display |
JP2008273782A (en) * | 2007-04-27 | 2008-11-13 | Ohara Inc | Glass |
JP5339173B2 (en) | 2007-09-27 | 2013-11-13 | 日本電気硝子株式会社 | Tempered glass substrate, glass and method for producing tempered glass substrate |
CN101939267B (en) * | 2008-02-08 | 2014-09-17 | 康宁股份有限公司 | Damage resistant chemically-toughened protective cover glass |
RU2010154445A (en) * | 2008-05-30 | 2012-07-10 | Фостер Вилер Энергия Ой (Fi) | METHOD AND SYSTEM FOR ENERGY GENERATION BY BURNING IN PURE OXYGEN |
JP5867953B2 (en) * | 2008-06-27 | 2016-02-24 | 日本電気硝子株式会社 | Tempered glass and tempered glass |
EP2307328A1 (en) * | 2008-07-11 | 2011-04-13 | Corning Incorporated | Glass with compressive surface for consumer applications |
JP5777109B2 (en) * | 2008-07-29 | 2015-09-09 | コーニング インコーポレイテッド | Two-stage ion exchange for chemical strengthening of 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 |
US8778820B2 (en) * | 2010-05-27 | 2014-07-15 | Corning Incorporated | Glasses having low softening temperatures and high toughness |
-
2010
- 2010-05-27 US US12/788,559 patent/US8778820B2/en active Active
-
2011
- 2011-05-17 TW TW100117130A patent/TWI557087B/en not_active IP Right Cessation
- 2011-05-18 JP JP2013512087A patent/JP5948321B2/en not_active Expired - Fee Related
- 2011-05-18 KR KR1020127033855A patent/KR101765975B1/en active IP Right Grant
- 2011-05-18 EP EP11721694.5A patent/EP2576467A1/en not_active Withdrawn
- 2011-05-18 WO PCT/US2011/037036 patent/WO2011149740A1/en active Application Filing
- 2011-05-18 CN CN201180025885.5A patent/CN102971266B/en active Active
-
2016
- 2016-06-06 JP JP2016112642A patent/JP6776010B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1246384A (en) * | 1968-02-01 | 1971-09-15 | Jenaer Glaswerk Schott & Gen | Improvements in or relating to glass |
EP2075237A1 (en) * | 2006-10-10 | 2009-07-01 | Nippon Electric Glass Co., Ltd. | Reinforced glass substrate |
WO2009041348A1 (en) * | 2007-09-27 | 2009-04-02 | Nippon Electric Glass Co., Ltd. | Reinforced glass, reinforced glass substrate, and method for producing the same |
US20090142568A1 (en) * | 2007-11-29 | 2009-06-04 | Matthew John Dejneka | Glasses having improved toughness and scratch resistance |
US20100047521A1 (en) * | 2008-08-21 | 2010-02-25 | Jaymin Amin | Durable glass housings/enclosures for electronic devices |
WO2011022661A2 (en) * | 2009-08-21 | 2011-02-24 | Corning Incorporated | Crack and scratch resistant glass and enclosures made therefrom |
Cited By (43)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11492291B2 (en) | 2012-02-29 | 2022-11-08 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
EP2819966A2 (en) * | 2012-02-29 | 2015-01-07 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
EP2819966B1 (en) * | 2012-02-29 | 2021-08-25 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
WO2013130653A2 (en) | 2012-02-29 | 2013-09-06 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
EP3792228A1 (en) * | 2012-02-29 | 2021-03-17 | Corning Incorporated | Ion exchanged glasses via non-error function compressive stress profiles |
US11124444B2 (en) | 2012-07-17 | 2021-09-21 | Corning Incorporated | Ion exchangeable Li-containing glass compositions for 3-D forming |
US10150691B2 (en) | 2012-07-17 | 2018-12-11 | Corning Incorporated | Ion exchangeable Li-containing glass compositions for 3-D forming |
US10183887B2 (en) | 2012-07-17 | 2019-01-22 | Corning Incorporated | Ion exchangeable Li-containing glass compositions for 3-D forming |
US11814316B2 (en) | 2012-07-17 | 2023-11-14 | Corning Incorporated | Ion exchangeable Li-containing glass compositions for 3-D forming |
JP2015527970A (en) * | 2012-07-17 | 2015-09-24 | コーニング インコーポレイテッド | Ion-exchangeable Li-containing glass composition for 3D molding |
US11634359B2 (en) | 2014-02-24 | 2023-04-25 | Corning Incorporated | Strengthened glass with deep depth of compression |
US11878941B2 (en) | 2014-06-19 | 2024-01-23 | Corning Incorporated | Glasses having non-frangible stress profiles |
EP3798196A1 (en) * | 2014-06-19 | 2021-03-31 | Corning Incorporated | Glasses having non-frangible stress profiles |
US10266447B2 (en) | 2014-10-08 | 2019-04-23 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US10364182B2 (en) | 2014-10-08 | 2019-07-30 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US11459270B2 (en) | 2014-10-08 | 2022-10-04 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US9593042B2 (en) | 2014-10-08 | 2017-03-14 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US10730791B2 (en) | 2014-10-08 | 2020-08-04 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US11220456B2 (en) | 2014-10-08 | 2022-01-11 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US10532947B2 (en) | 2014-10-08 | 2020-01-14 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US11465937B2 (en) | 2014-10-08 | 2022-10-11 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US10259746B2 (en) | 2014-10-08 | 2019-04-16 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US10294151B2 (en) | 2014-10-08 | 2019-05-21 | Corning Incorporated | Glasses and glass ceramics including a metal oxide concentration gradient |
US11746046B2 (en) | 2014-10-31 | 2023-09-05 | Corning Incorporated | Strengthened glass with ultra deep depth of compression |
US11021393B2 (en) | 2014-11-04 | 2021-06-01 | Corning Incorporated | Deep non-frangible stress profiles and methods of making |
US11377388B2 (en) | 2014-11-04 | 2022-07-05 | Corning Incorporated | Deep non-frangible stress profiles and methods of making |
WO2016191676A1 (en) * | 2015-05-28 | 2016-12-01 | Corning Incorporated | Strengthened glass with deep depth of compression |
US11613103B2 (en) | 2015-07-21 | 2023-03-28 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
US11267228B2 (en) | 2015-07-21 | 2022-03-08 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
US10579106B2 (en) | 2015-07-21 | 2020-03-03 | Corning Incorporated | Glass articles exhibiting improved fracture performance |
US10787387B2 (en) | 2015-12-11 | 2020-09-29 | Corning Incorporated | Fusion-formable glass-based articles including a metal oxide concentration gradient |
US11878936B2 (en) | 2015-12-11 | 2024-01-23 | Corning Incorporated | Fusion-formable glass-based articles including a metal oxide concentration gradient |
US11472734B2 (en) | 2015-12-11 | 2022-10-18 | Corning Incorporated | Fusion-formable glass-based articles including a metal oxide concentration gradient |
US9908811B2 (en) | 2015-12-11 | 2018-03-06 | Corning Incorporated | Fusion formable glass-based articles including a metal oxide concentration gradient |
US11390560B2 (en) | 2016-01-21 | 2022-07-19 | AGC Inc. | Chemically strengthened glass and method for manufacturing chemically strengthened glass |
US11365149B2 (en) | 2016-01-21 | 2022-06-21 | AGC Inc. | Chemically strengthened glass and method for manufacturing chemically strengthened glass |
US10472272B2 (en) | 2016-01-21 | 2019-11-12 | AGC Inc. | Chemically strengthened glass, and glass for chemical strengthening |
US10017417B2 (en) | 2016-04-08 | 2018-07-10 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
US11691913B2 (en) | 2016-04-08 | 2023-07-04 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
US11174197B2 (en) | 2016-04-08 | 2021-11-16 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
US10570059B2 (en) | 2016-04-08 | 2020-02-25 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
US11279652B2 (en) | 2016-04-08 | 2022-03-22 | Corning Incorporated | Glass-based articles including a metal oxide concentration gradient |
US11963320B2 (en) | 2016-04-08 | 2024-04-16 | Corning Incorporated | Glass-based articles including a stress profile comprising two regions |
Also Published As
Publication number | Publication date |
---|---|
JP2016155759A (en) | 2016-09-01 |
US8778820B2 (en) | 2014-07-15 |
US20110294649A1 (en) | 2011-12-01 |
JP2013527115A (en) | 2013-06-27 |
KR101765975B1 (en) | 2017-08-23 |
CN102971266B (en) | 2016-05-25 |
TW201204670A (en) | 2012-02-01 |
CN102971266A (en) | 2013-03-13 |
TWI557087B (en) | 2016-11-11 |
KR20130098894A (en) | 2013-09-05 |
EP2576467A1 (en) | 2013-04-10 |
JP6776010B2 (en) | 2020-10-28 |
JP5948321B2 (en) | 2016-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2576467A1 (en) | Glasses having low softening temperatures and high toughness | |
KR101797264B1 (en) | Ion Exchangeable Glasses | |
JP6732823B2 (en) | Two-step method of strengthening glass | |
KR102322091B1 (en) | Scratch-resistant boroaluminosilicate glass | |
EP2874959B1 (en) | Ion exchangeable li-containing glass compositions for 3-d forming | |
US8561429B2 (en) | Glass with compressive surface for consumer applications | |
US20140308526A1 (en) | Ion exchangeable glasses | |
WO2017192533A1 (en) | Glass compositions that retain high compressive stress after post-ion exchange heat treatment | |
KR20180096723A (en) | Low alkali content borosilicate glass |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180025885.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11721694 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2013512087 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011721694 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20127033855 Country of ref document: KR Kind code of ref document: A |