Source: https://patents.google.com/patent/US8341976B2/en
Timestamp: 2019-05-20 05:30:11
Document Index: 726903908

Matched Legal Cases: ['Application No. 61', 'Application No. 61', 'Application No. 61', 'Application No. 61', 'Application No. 61', 'Application No. 61']

US8341976B2 - Method of separating strengthened glass - Google Patents
US8341976B2
US8341976B2 US12/845,066 US84506610A US8341976B2 US 8341976 B2 US8341976 B2 US 8341976B2 US 84506610 A US84506610 A US 84506610A US 8341976 B2 US8341976 B2 US 8341976B2
US12/845,066
US20100291353A1 (en
Daniel R. Harvey
Timothy Michael Gross
2009-08-21 Priority to US23576709P priority
2010-07-28 Application filed by Corning Inc filed Critical Corning Inc
2010-07-28 Assigned to CORNING INCORPORATED reassignment CORNING INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DEJNEKA, MATTHEW JOHN, GOMEZ, SINUE, Gross, Timothy Michael, HARVEY, DANIEL R, STRELTSOV, ALEXANDER MIKHAILOVICH
2010-07-28 Priority to US12/845,066 priority patent/US8341976B2/en
2010-11-18 Publication of US20100291353A1 publication Critical patent/US20100291353A1/en
2013-01-01 Publication of US8341976B2 publication Critical patent/US8341976B2/en
A method of cutting a glass sheet that has been thermally or chemically strengthened along a predetermined line, axis, or direction with high speed and with minimum damage on the cut edges. The strengthened glass sheet may be an aluminoborosilicate glass material having at least one alkali metal oxide modifier, and the ratio
Al 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) + B 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) ∑ ⁢ modifiers ⁢ ⁢ ( mol ⁢ ⁢ % ) > 1.
At least one damage line is formed within the strengthened glass sheet. The at least one damage line is formed outside the strengthened compressive stress surface layers and within the tensile stress layer of the strengthened glass sheet. The at least one damage line may be formed by laser treatment. A crack is initiated in the strengthened glass sheet and propagated along the at least one damage line to separate the strengthened glass sheet along the predetermined line, axis, or direction into at least two pieces.
This application is a continuation-in-part of U.S. patent application Ser. No. 12/388,837, filed Feb. 19, 2009, and entitled “Method of Separating Strengthened Glass.” This application is also related to U.S. Provisional Patent Application Ser. No. 61/235,767, filed Aug. 21, 2009, and entitled “Crack and Scratch Resistant Glass and Enclosures Made Therefrom,” but does not claim priority thereto.
Glasses that are either tempered or chemically strengthened are difficult, if not impossible, to cut or separate into pieces of desired shape and/or sizes. Conventional score-and-break techniques do not work because the initial crack does not propagate along the score line, but instead tends to bifurcate multiple times. Consequently, the glass sample usually breaks into multiple pieces. Cutting operations are therefore performed before carrying out strengthening operations.
A method of cutting a glass sheet that has been thermally or chemically strengthened along a predetermined line, axis, or direction with high speed and with minimum damage on the cut edges is provided. The strengthened glass sheet may be cut into at least two pieces, one of which having a predetermined shape or dimension. At least one damage line is formed within the strengthened glass sheet. The at least one damage line is formed outside the strengthened compressive stress surface layers and within the tensile stress layer of the strengthened glass sheet. The at least one damage line may be formed by laser treatment. In one embodiment, a crack is initiated in the strengthened glass sheet (e.g., as an edge score) and propagated along the at least one damage line to separate the strengthened glass sheet along the predetermined line, axis, or direction into at least two pieces. In another embodiment, crack initiation and propagation is not utilized to separate the strengthened glass sheet but rather a UV-laser may be used without edge scoring.
In one embodiment, a method of separating a strengthened glass sheet, the method includes providing the strengthened glass sheet, the strengthened glass sheet having a first surface and a second surface. Each of the first surface and the second surface has a strengthened surface layer under a compressive stress and extending from the surface to a depth of layer, and a central region under tensile stress. The strengthened glass sheet is an aluminoborosilicate glass material having at least one alkali metal oxide modifier, and the ratio
The method further includes forming at least one damage line in the central region; and initiating and propagating a crack to separate the strengthened glass sheet into at least two pieces along the at least one damage line.
In another embodiment, a method of separating a strengthened glass sheet, the method includes providing the strengthened glass sheet, the strengthened glass sheet having a first surface and a second surface. Each of the first surface and the second surface have a strengthened surface layer under a compressive stress and extending from the surface to a depth of layer, and a central region under a tensile stress. The strengthened glass sheet is an aluminoborosilicate glass material having at least one alkali metal oxide modifier, and the ratio
The method further includes forming a first laser-induced damage line in the central region and forming a second laser-induced damage line. The second laser-induced damage line is located between the strengthened surface layer of the first surface and the first laser-induced damage line, and is parallel to the first laser-induced damage line. The first laser-induced damage line and the second laser-induced damage line define a plane being perpendicular to the first surface and the second surface. The method further includes initiating and propagating a crack to separate the strengthened glass sheet into at least two pieces, wherein at least one of the pieces has at least one of a predetermined shape and a predetermined dimension.
In yet another embodiment, a strengthened glass article includes a first surface, a second surface and at least one edge joining the first and second surfaces. Each of the first surface and the second surface has an ion exchanged strengthened surface layer under a compressive stress and extending from the surface to a depth of layer, and a central region under a tensile stress. The strengthened glass sheet is an aluminoborosilicate glass material having at least one alkali metal oxide modifier, and the ratio
The at least one edge is formed by forming at least one laser-induced damage line in a central region of a strengthened glass sheet comprising the aluminoborosilicate glass material and having the ion exchanged strengthened surface layers, and initiating and propagating a crack along the at least one laser-induced damage line to separate the strengthened glass article from the strengthened glass sheet along the at least one edge to form the at least one edge.
As used herein, the terms “separate,” “divide,” and “cut,” unless otherwise specified, are considered to be equivalent terms that are used interchangeably and refer to the separation or division of a glass article, such as a planar sheet, into one or more pieces by physical means.
A method of controllably separating a strengthened glass sheet into multiple pieces or parts is provided. The method is controllable in the sense that the glass sheet is separated along a predetermined line or plane in a controlled or guided fashion. At least one of the pieces formed by separating the strengthened glass sheet has at least one of a predetermined shape and predetermined dimension. The term predetermined as used herein means that a particular property was determined prior to cutting or separating the strengthened glass sheet. For example, a piece formed by separating the strengthened glass sheet may have a predetermined shape that is circular having a particular radius. The shape and dimension is determined prior to separating the piece from the strengthened glass sheet. The method comprises first providing a strengthened glass sheet having first and second surfaces, strengthened surface layers under compressive stress and extending from each of the first and second surfaces to a depth of layer, and a central region under a tensile stress. At least one damage line is then formed in the central region and outside the strengthened surface layers. A crack is then initiated and propagated along the at least one damage line to separate the strengthened glass sheet into multiple pieces, one of which has at least one of a predetermined shape and predetermined dimension.
Turning to FIG. 1, a cross-sectional view of a strengthened glass sheet is schematically shown. Strengthened glass sheet 100 has a thickness t and length l, a first surface 110 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 is either thermally or chemically strengthened, and has strengthened surface layers 112, 122 extending from first surface 110 and second surface 120, respectively, to depths d1, d2, 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 115 balances the compressive stresses in strengthened surface layers 112, 122, thus maintaining equilibrium within strengthened glass sheet 100. The depths d1, d2 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 0.2 mm up to about 2 mm and, in some embodiments, up to about 3 mm. In one embodiment, thickness t is in a range from about 0.5 mm up to about 1.3 mm.
Strengthened glass sheet 100 comprises, consists essentially of, or consists of an alkali aluminoborosilicate glass having a densification mechanism such that the strengthened glass sheet 100 does not undergo deformation by subsurface shear faulting, but instead undergoes indentation deformation by densification under an indentation load, thereby yielding higher damage resistance. In one embodiment, the strengthened glass sheet 100 undergoes indentation deformation by a densification under an indentation load of at least 500 gf, which may make flaw/crack initiation more difficult. Non-limiting examples of such alkali aluminoborosilicate glasses having a densification mechanism are described in U.S. Patent Application No. 61/235,767, by Kristen L. Barefoot et al., entitled “Crack and Scratch Resistant Glass and Enclosures Made Therefrom,” filed on Aug. 21, 2009, the contents of which are incorporated herein by reference in their entirety.
Cutting a glass after the glass is ion exchanged exposes areas on the edges that are under tension, which reduces the strength of the edge itself. The edge is made more robust—i.e., less susceptible to damage—by providing a glass having higher damage resistance before ion exchange.
In some embodiments, the strengthened glass deforms upon indentation under an indentation load of at least 500 gram force (gf) primarily by a mechanism in which the glass undergoes densification rather than shear faulting. The glass may be free of subsurface faulting and radial cracks upon deformation and may consequently be more resistant to damage than typical ion-exchangeable glasses and, when strengthened by ion exchange, is more resistant to crack initiation by shear faulting. In one embodiment, the strengthened glass sheet is an ion exchanged glass having a Vickers median/radial crack initiation threshold of at least 10 kilogram force (kgf). In a second embodiment, the strengthened glass sheet is an ion exchanged glass having a Vickers median/radial crack initiation threshold of at least about 20 kgf and, in a third embodiment, the strengthened glass sheet is an ion exchanged glass having a Vickers median/radial crack initiation threshold of at least about 30 kgf. Unless otherwise specified, the Vickers median/radial crack threshold is determined by measuring the onset of median or radial cracks in 50% relative humidity at room temperature.
The densification mechanism described above may be attributed to the absence or lack of non-bridging oxygens (NBOs) in the glass structure, high molar volume (at least 27 cm3/mol), and low Young's modulus (less than about 69 GPa) of the glass. In the aluminoborosilicate glasses having the densification mechanism described herein, a structure having substantially no non-bridging oxygens (NBO-free) is achieved and the inequality:
Al 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) + B 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) ∑ ⁢ modifiers ⁢ ⁢ ( mol ⁢ ⁢ % ) > 1 , ( 1 )
where Al2O3 and B2O3 are intermediate glass formers and alkali metal (e.g., Li2O, Na2O, K2O, Rb2O, Cs2O) and alkaline earth metal oxides (e.g., MgO, CaO, SrO, BaO) are modifiers, is satisfied. To obtain sufficient depth of layer and compressive stress by ion exchange, it is preferable that 0.9<R2O/Al2O3<1.3. Given a particular compressive stress and compressive depth of layer, any ion-exchangeable silicate glass composition that is described by equation (1) and contains alkali metals (e.g., Li+, Na+, K+) should have a high resistance to both crack initiation and crack propagation following ion exchange. Prior to ion exchange, such aluminoborosilicate glasses have a Vickers median/radial crack initiation threshold of at least 500 gf and, in one embodiment, the glasses have Vickers median/radial crack initiation threshold of at least 1000 gf.
In one embodiment, the strengthened glass sheet comprises, consists essentially of, or consists of a strengthened glass that, when ion exchanged, is resistant to damage, such as crack initiation and propagation. The glass comprises at least one alkali metal modifier, wherein the ratio (Al2O3+B2O3)/Σ(modifiers)>1. In one embodiment, (Al2O3+B2O3)/Σ(modifiers)≧1.45. As the value of this ratio increases, the damage resistance of the glass increases. In addition, an increase in the ratio or a substitution of B2O3 for Al2O3 results in a decrease in Young's modulus. In one embodiment, the Young's modulus of the aluminoborosilicate glass is less than about 69 GPa. In one embodiment, the Young's modulus of the aluminoborosilicate glass is less than about 65 GPa. In another embodiment, the Young's modulus of the aluminoborosilicate glass is in a range from about 57 GPa up to about 69 GPa. In another embodiment, the strengthened glass sheet has a compressive stress of at least about 400 MPa and a depth of layer of at least about 15 μm, in another embodiment, at least about 25 μm, and, in a third embodiment, at least about 30 μm.
In a particular embodiment, the strengthened glass sheet comprises, consists essentially of, or consists of an ion exchangeable aluminoborosilicate glass that has been strengthened, for example, by ion exchange. In a particular embodiment, the aluminoborosilicate glass comprises, consists essentially of, or consists of: 60-72 mol % SiO2; 9-16 mol % Al2O3; 5-12 mol % B2O3; 8-16 mol % Na2O; and 0-4 mol % K2O, wherein (Al2O3+B2O3)/Σ(modifiers)>1, and has a molar volume of at least 27 cm3/mol. In some embodiments, the glass further includes 0-5 mol % of at least one of P2O5, MgO, CaO, SrO, BaO, ZnO, and ZrO2. In other embodiments, the glass is batched with 0-2 mol % of at least one fining agent selected from a group that includes Na2SO4, NaCl, NaF, NaBr, K2SO4, KCl, KF, KBr, and SnO2. The aluminoborosilicate glass is, in some embodiments, substantially free of lithium, whereas in other embodiments, the aluminoborosilicate glass is substantially free of at least one of arsenic, antimony, and barium. In another embodiment, the aluminoborosilicate glass is down-drawable by processes known in the art, such as slot-drawing, fusion drawing, re-drawing, and the like, and has a liquidus viscosity of at least 130 kilopoise.
As previously described herein, the glass, in one embodiment, is chemically strengthened by an ion exchange process in which ions in the surface layer of the glass are replaced by larger ions having the same valence, or oxidation state. In one particular embodiment, the ions in the surface layer and the larger ions are monovalent alkali metal cations, such as Li+ (when present in the glass), Na+, K+, Rb+, and Cs+. Alternatively, monovalent cations in the surface layer may be replaced with monovalent cations other than alkali metal cations, such as Ag+, Cu+, Tl+, or the like.
Ion exchange processes are typically carried out by immersing glass in a molten salt bath containing the larger ions. It will be appreciated by those skilled in the art that 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 strengthened glass that is to be achieved as a result of the strengthening operation. By way of example, ion exchange of alkali metal-containing glasses may be achieved by immersion in at least one molten bath containing a salt such as, but not limited to, nitrates, sulfates, and chlorides of the larger alkali metal ion. The temperature of the molten salt bath is typically in a range from about 370° C. up to about 450° C., while immersion items range from about 15 minutes up to about 16 hours.
Non-limiting examples of ion exchange processes are provided in U.S. Pat. No. 7,666,511, by Adam J. Ellison et al., entitled “Down-Drawable, Chemically Strengthened Glass for Cover Plate,” filed on Jul. 31, 2007, which claims priority from U.S. Provisional Patent Application 60/930,808, filed on May 22, 2007, and having the same title; U.S. patent application Ser. No. 12/277,573, by Matthew J. Dejneka et al., entitled “Glasses Having Improved Toughness and Scratch Resistance,” filed on Nov. 25, 2008, which claims priority from U.S. Provisional Patent Application 61/004,677, filed on Nov. 29, 2007; U.S. patent application Ser. No. 12/392,577, by Matthew J. Dejneka et al., entitled “Fining Agents for Silicate Glasses,” filed Feb. 25, 2009, which claims priority from U.S. Provisional Patent Application No. 61/067,130, filed Feb. 26, 2008; U.S. patent application Ser. No. 12/393,241, by Matthew J. Dejneka et al., entitled “Ion-Exchanged, Fast Cooled Glasses,” filed Feb. 26, 2009, which claims priority from U.S. Provisional Patent Application No. 61/067,732, filed Feb. 29, 2008; and U.S. patent application Ser. No. 12/537,393, by Kristen L. Barefoot et al., entitled “Chemically Tempered Cover Glass,” filed Aug. 7, 2009, which claims priority from U.S. Provisional Patent Application No. 61/087,324, filed Aug. 8, 2008. In addition, non-limiting examples of ion exchange processes in which glass is immersed in multiple ion exchange baths, with washing and/or annealing steps between immersions are described in U.S. patent application Ser. No. 12/500,650, by Douglas C. Allan et al., entitled “Glass with Compressive Surface for Consumer Applications,” filed Aug. 7, 2009, which claims priority from U.S. Provisional Patent Application No. 61/079,995, filed Jul. 11, 2008, in which glass is strengthened by immersion in multiple, successive, ion exchange treatments in salt baths of different concentrations; and U.S. patent application Ser. No. 12/510,599, by Christopher M. Lee et al., entitled “Dual Stage Ion Exchange for Chemical Strengthening of Glass,” filed Jul. 28, 2009, which claims priority from U.S. Provisional Patent Application No. 61/084,398, filed Jul. 29, 2008, in which glass is strengthened by ion exchange in a first bath is diluted with an effluent ion, followed by immersion in a second bath having a smaller concentration of the effluent ion than the first bath. The contents of the patent and patent applications listed above are incorporated herein by reference in their entirety.
Various compositions of the aluminoborosilicate glasses having a deformation mechanism described above are listed in Table 1 and Table 2. Samples a, b, c, and d in Table 1 nominally do not have non-bridging oxygens; i.e., Al2O3+B2O3=Na2O or Al2O3+B2O3−Na2O=0 (i.e., (Al2O3+B2O3)/Σ(modifiers)=1). Regardless of whether B2O3 or Al2O3 is used to consume the NBOs created by the presence of the Na2O modifier in these sample compositions, all of the above samples exhibited low (i.e., 100-300 gf) crack initiation thresholds. In glasses e and f, however, an excess of B2O3 is created by increasing the Al2O3 content while decreasing the concentration of alkali metal oxide modifiers. For samples e and f, (Al2O3+B2O3)/Σ(modifiers)>1.
Table 2 lists additional sample compositions g, h and i that were subjected to various ion exchange processes. For example, the samples g, h, and i were subjected to various KNO3 bath temperatures and exposure durations. Further, some samples were rapidly quenched from above the glass transition temperature (referred to in Table 2 as “fictivated”) prior to the ion exchange process. The compressive stress (CS) and depth of layer (DOL) values were determined for the sample compositions g, h, and i for the different ion exchange processes. The center tension (CT) values provided in Table 2 were calculated based on the CT and DOL values. It should be understood that samples listed in Tables 1 and 2 are for illustrative purposes only, and no particular limitations are intended by such sample composition listings.
Compositions and properties of aluminoborosilicate glasses.
Composition Mol % a b c d e f
SiO2 64 64 64 64 64 64
Al2O3 0 6 9 15 12 13.5
B2O3 18 12 9 3 9 9
Na2O 18 18 18 18 15 13.5
Al2O3 + B2O3 − Na2O 0 0 0 0 6 9
Strain Point (° C.) 537 527 524 570 532 548
Anneal Point (° C.) 575 565 564 619 577 605
Softening Point (° C.) 711 713 730 856 770 878
Coefficient of Thermal Expansion (×10−7/° C.) 81.7 81.8 84.8 88.2 78 74.1
Density (g/cm3) 2.493 2.461 2.454 2.437 2.394 2.353
Pre-Ion Exchange Crack Initiation Load (gf) 100 200 200 300 700 1100
Pre-Ion Exchange Vickers Hardness at 200 gf 511 519 513 489 475
Pre-Ion Exchange Indentation Toughness 0.64 0.66 0.69 0.73 0.77
(MPa m{circumflex over ( )}0.5)
Pre-Ion Exchange Brittleness (μm{circumflex over ( )}0.5) 7.8 7.6 7.3 6.6 6
IX at 410° C. for 8 hrs in 100% KNO3
DOL (μm) 10.7 15.7 20.4 34.3 25.6 35.1
CS (MPa) 874 795 773 985 847 871
Compositions and properties of ion exchanged
aluminoborosilicate glasses.
Glass Sample g h i
Composition SiO2 65.81 64.13 64.29
Mole % Al2O3 10.39 12.54 13.95
B2O3 0.58 9.55 6.94
Na2O 14.18 13.59 14.13
K2O 2.50 0.01 0.51
MgO 5.76 0.01 0.02
CaO 0.58 0.02 0.07
SnO2 0.18 0.12 0.10
Strain 551 529 553
Anneal 600 580 606
Softening 843 817.2 870.7
Exp Coef 91 79.4
Density 2.461 2.356 2.375
Liquidus 860 880
Phase Nepheline Albite
SOC 28.80 35.24 33.80
(nm/cm/MPa)
Fictivated IX CS 370° C. (MPa) 889.1059 743.5641 838.3803
Data 8 Hrs CS 390° C. 841.7913 770.5593
CS 410° C. 799.9036 595.5732 718.1476
DOL 370° C. (μm) 28.146 24 33.973
DOL 390° C. 39.393 48.761
DOL 410° C. 54.545 42 58.692
Fictivated IX CS 370° C. 862.8234 724.6141 811.1667
Data 15 Hrs CS 390° C. 834.1261 732.1668
CS 410° C. 778.422 526.0897 672.7195
DOL 370° C. 39.777 33 46.711
DOL 390° C. 51.534 65.775
DOL 410° C. 67.679 61 82.554
Annealed IX CS 370° C. 952.4398 850.9478 915.0505
Data 8 Hrs CS 390° C. 961.537 862.1435
CS 410° C. 931.2729 723.7117 805.3314
DOL 370° C. 27.341 17 25.379
DOL 390° C. 38.96 40.259
DOL 410° C. 51.557 33 47.798
Annealed IX CS 370° C. 956.374 827.4858 896.5275
Data 15 Hrs CS 390° C. 939.7077 827.4016
CS 410° C. 882.3109 677.6901 755.7468
DOL 370° C. 34.458 23 37.627
DOL 390° C. 53.598 52.224
DOL 410° C. 68.854 66.841
Central CT 370 26.52 18.75 30.56
Tension CT 390 36.00 41.63
8 hr Fict CT 410 48.97 27.31 47.76
Central CT 370 27.55 14.98 24.46
Tension CT 390 40.63 37.75
8 hr Annealed CT 410 53.53 25.57 42.56
After providing the strengthened glass sheet, at least one damage line is formed within strengthened glass sheet 100 in the central region 115, which is under tensile stress, of strengthened glass sheet 100. In the embodiment schematically shown in FIG. 2, first and second damage lines 140, 150 are formed in central region 115. The at least one damage line is formed along a predetermined axis, line, or direction within strengthened glass sheet 100 and is located outside of strengthened surface layers 112, 122. The at least one damage line is formed in a plane that is perpendicular to first surface 110 and second surface 120.
In one embodiment, the damage lines are formed by irradiating strengthened glass sheet 100 with a laser that operates in the window of transparency of the glass transmission spectrum. Damage within the bulk of strengthened glass sheet 100 is generated by nonlinear absorption when the intensity or fluence of the laser beam exceeds a threshold value. Rather than creating damage lines by heating the glass, nonlinear absorption creates damage lines by breaking molecular bonds; the bulk of strengthened glass sheet 100 experiences no excessive heating. In one embodiment, the laser is a nanosecond pulsed Nd laser operating at the fundamental wavelength of 1064 nm, or harmonics thereof (e.g., 532 nm, 355 nm), with a repetition rate of 10-150 kHz. The power of the nanosecond-pulsed Nd laser is in a range from about 1 W up to about 4 W.
The formation of damage lines in strengthened glass sheet 100 by laser irradiation is schematically shown in FIG. 2. A first laser-formed damage line 140 is formed by irradiating strengthened glass sheet 100 with laser beam 160, which is generated by laser 162 and laser optics (not shown) that are needed to focus laser beam 160. Laser beam 160 is focused above second surface 120 and second strengthened surface layer 122 to form first damage line 140. First damage line 140 is formed at a depth d3 from second surface 120, where d3 is greater than depth d2 of second strengthened surface layer 122. Thus, first damage line 140 is located within central region 115, which is under tensile stress, and outside the surface region—i.e., second strengthened surface layer 122—that is under compressive stress. At least one of strengthened glass sheet 100 and laser beam 160 is translated in direction 142 along line l of strengthened glass sheet 100 to form first damage line 140. In one embodiment, strengthened glass sheet 100 is translated with respect to laser beam 160. In another embodiment, laser beam 160 is translated with respect to strengthened glass sheet 100. Such movement may be accomplished using translatable stages, tables, beam scanners, and the like that are known in the art.
After forming first damage line 140, laser beam 160 is refocused below first surface 110 and first strengthened surface layer 112 to form second damage line 150 in central region 115. Second damage line 150 is formed at a depth d4, where d4 is greater than depth d1 of first strengthened surface layer 112, and between first damage line 140 and first strengthened layer 112. Thus, second damage line 150 is located outside the surface region—i.e., first strengthened surface layer 112—that is under compressive stress.
In one embodiment, laser beam 160 is translated in direction 152 along line l of strengthened glass sheet 100 to form second damage line 150 by moving at least one of strengthened glass sheet 100 and laser beam 160. In one embodiment, direction 152 of translation of laser beam 160 or strengthened glass sheet 100 that is used to form second damage line 150 is opposite to direction 142 of translation that is used to form first damage line 140. In one embodiment, first damage line 140, which is furthest from laser 162 and the associated laser optics, is formed first, followed by formation of second damage line 150, which is closer to laser 162 and associated laser optics. In one embodiment, first and second damage lines 140, 150 are formed by laser beam 160 at a rate ranging from about 30 cm/s up to about 50 cm/s. In another embodiment, first damage line 140 and second damage line 150 may be formed simultaneously by splitting laser beam 160.
In one embodiment, formation of first and second damage lines 140, 150 includes overwriting, or making at least two passes, with laser beam 160 along each damage line; i.e., laser beam 160 is translated along each damage line at least two times, preferably in succession (e.g., within 0.2-5 seconds) of each other. This may be accomplished by splitting laser beam 160 or by other means known in the art, so as to make multiple passes simultaneously with only a slight delay of about 0.1 second
For a strengthened glass sheet 100 having a thickness t of about 1 mm, the depths d3, d4 of first and second damage lines 140, 150 below first and second surfaces 110, 120, respectively, are in a range form about 50 μm up to about 350 μm. In one embodiment, depths d3, d4 are in a range from about 100 μm up to about 150 μM.
Table 3 lists the laser power and laser translation speed when using a 355-nm laser for separating four exemplary strengthened glass sheets having the deformation mechanism described hereinabove. Samples j, k, l, and m have different thicknesses and/or strength properties. It should be understood that the results and information provided in Table 3 are for illustrative purposes only.
Exposure conditions for separating strengthened glass sheets.
Glass Type CS DOL CT (est., Power Speed
(thickness) (MPa) (um) MPa) (W) (cm/s)
Sample j (0.2 mm) 765 20 96 1.4 30
Sample k (1.0 mm) 615 59 37 3.0-3.5 30
Sample l (1.0 mm) 843 50 42 3.2 30
Sample m (1.0 mm) 685 65 46 3.2 30
The glass composition for sample j, k, l, and m were the same as sample h listed in Table 2. A single damage line was scanned twice with a 1.4 W laser to separate sample j, while two damage lines were formed within the 1.0 mm samples, with a laser power of 3.0-3.5 W. It is noted that the laser translation speed was hardware-limited and not limited by the process. As such, faster translation speeds may be utilized.
Final and/or complete glass separation may be accomplished by those means known in the art such, but not limited to, as manual or mechanical flexion of strengthened glass sheet 100 on opposite sides of the plane formed by the damage lines. In one embodiment, the glass separation is accomplished by manual or mechanical flexion of the glass after the damage line or lines are inscribed with the laser. In another embodiment, a scribe may be used to introduce a flaw on either first or second surface 110, 120 to initiate the crack, which then propagates along first and second damage lines 140, 150. In another embodiment, mechanical scribes of about 2-3 mm in length may be made on edge 130 of strengthened glass sheet 100 to facilitate crack initiation. In another embodiment, glass separation is achieved by immersing strengthened glass sheet 100 in a liquid, such as water. In still another embodiment, self-separation may be achieved by repeated overwriting of first and second damage lines 140,150 with laser beam 160. For example, strengthened glass sheets of some alkali aluminoborosilicate glasses may be self-separated by overwriting first and second damage lines 140,150 at least twice with laser beam 160. Alternatively, the power of laser beam 162 may be increased to a level that is sufficient to affect separation. Strengthened alkali aluminoborosilicate glass sheets may, for example, be completely separated by using a 355 nm nanosecond pulsed Nd laser having a power of at least 1 W.
The strengthened glass article may be any glass that is either chemically or thermally strengthened, as described hereinabove. In one embodiment, the glass is an alkali aluminoborosilicate glass, such as those previously described herein.
A glass sample having the composition 64.13 mol % SiO2; 12.55 mol % Al2O3; 9.55 mol % B2O3; 13.59 mol % Na2O; 0.01 mol % K2O; 0.01 mol % MgO; 0.02 mol % CaO; and 0.12 mol % SnO2 underwent ion-exchange by immersion in a molten KNO3 bath for fifteen hours at 410° C. The resulting thickness of the ion-exchanged layer on the surface of the glass was about 59 μm, and the compressive stress within the strengthened surface layers was about 615 MPa. The glass sample had a thickness of about 1.0 mm.
The glass sample was mounted on a computer-controlled XYZ stage and was translated at speed of about 30 cm/s. The output from a 355-nm nanosecond Nd laser was first focused about 130 μm above the rear surface (i.e., the surface of the glass farthest from the laser; e.g., second surface 120 in FIGS. 1 and 2) with a 0.27-NA lens. The mean power of the laser beam was 3.0 W, and the repetition rate was 150 kHz. After the first damage line was written near the rear surface, the beam was refocused about 130 μm below the front surface of the glass and the sample was traversed again to write the second damage line near the front surface. Each damage line was scanned twice with the laser, although a single pass may have also been sufficient. The two damage lines formed in the glass allowed the strengthened glass sheet to be divided by manual snapping or flexion.
providing the strengthened glass sheet, the strengthened glass sheet having a first surface and a second surface, wherein:
each of the first surface and the second surface has a strengthened surface layer under a compressive stress and extending from the surface to a depth of layer, and wherein the strengthened glass sheet has a central region under tensile stress; and
the strengthened glass sheet comprises an aluminoborosilicate glass material having at least one alkali metal oxide modifier, and the ratio
Al 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) + B 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) ∑ ⁢ modifiers ⁢ ⁢ ( mol ⁢ ⁢ % ) > 1 ;
forming at least one laser-induced damage line in the central region at a predetermined depth below the first surface by irradiating the strengthened glass sheet with a nanosecond pulsed laser, wherein the nanosecond pulsed laser is operated at a power of less than about 4W; and
initiating and propagating a crack to separate the strengthened glass sheet into at least two pieces along the at least one damage line.
2. The method of claim 1, wherein forming the at least one damage line in the central region comprises forming a first damage line and a second damage line in the central region, the second damage line being located between the strengthened surface layer of the first surface and the first damage line, the first damage line and the second damage line defining a plane perpendicular to the first surface and the second surface.
3. The method of claim 1, wherein the strengthened surface layers of the first surface and the second surfaces are chemically strengthened surfaces.
4. The method of claim 1, wherein the strengthened surface layers are ion exchanged chemically strengthened surfaces.
5. The method of claim 4, wherein the strengthened surface layers of the first surface and the second surfaces have a compressive stress of at least about 400 MPa, the depth of layer is at least about 15 μm, and the central region has a tensile stress greater than about 15 MPa.
6. The method of claim 4, wherein the aluminoborosilicate glass material comprises:
60-72 mol % SiO2; 9-16 mol % Al2O3; 5-12 mol % B2O3; 8-16 mol % Na2O; and 0-4 mol % K2O.
Al 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) + B 2 ⁢ O 3 ⁡ ( mol ⁢ ⁢ % ) ∑ ⁢ modifiers ⁢ ⁢ ( mol ⁢ ⁢ % ) > 1.45 .
8. The method of claim 1, wherein the strengthened glass sheet has a Vickers median/radial crack initiation threshold of at least 10 kgf.
9. A method of separating a strengthened glass sheet, the method comprising:
each of the first surface and the second surface have a strengthened surface layer under a compressive stress and extending from the surface to a depth of layer, and wherein the strengthened glass sheet has a central region under a tensile stress; and
forming a first laser-induced damage line in the central region at a predetermined depth below the first surface;
forming a second laser-induced damage line, wherein:
the second laser-induced damage line is located between the strengthened surface layer of the first surface and the first laser- induced damage line;
the second laser-induced damage line is parallel to the first laser-induced damage line; and
the first laser-induced damage line and the second laser-induced damage line define a plane being perpendicular to the first surface and the second surface; and
wherein the first and second laser-induced damage lines are formed by irradiating the strengthened glass sheet with a nanosecond pulsed laser, wherein the nanosecond pulsed laser is operated at a power of less than about 4W; and
initiating and propagating a crack to separate the strengthened glass sheet into at least two pieces, wherein at least one of the pieces has at least one of a predetermined shape and a predetermined dimension.
10. The method of claim 9, wherein the strengthened surface layers are ion exchanged chemically strengthened surfaces.
11. The method of claim 10, wherein the strengthened surface layers of the first surface and the second surfaces have a compressive stress of at least about 400 MPa, the depth of layer is at least about 15 μm, and the central region has a tensile stress greater than about 15 MPa.
12. The method of claim 11, wherein the aluminoborosilicate glass material comprises: 60-72 mol % SiO2; 9-16 mol % Al2O3; 5-12 mol % B2O3; 8-16 mol % Na2O; and 0-4 mol % K2O.
US12/845,066 2009-02-19 2010-07-28 Method of separating strengthened glass Active 2030-02-24 US8341976B2 (en)
US23576709P true 2009-08-21 2009-08-21
US12/388,837 Continuation-In-Part US8327666B2 (en) 2009-02-19 2009-02-19 Method of separating strengthened glass
US20100291353A1 US20100291353A1 (en) 2010-11-18
US8341976B2 true US8341976B2 (en) 2013-01-01
ID=43033185
US12/845,066 Active 2030-02-24 US8341976B2 (en) 2009-02-19 2010-07-28 Method of separating strengthened glass
US12/858,490 Active 2030-12-01 US8586492B2 (en) 2009-08-21 2010-08-18 Crack and scratch resistant glass and enclosures made therefrom
US14/082,847 Active US9290407B2 (en) 2009-08-21 2013-11-18 Crack and scratch resistant glass and enclosures made therefrom
US (3) US8341976B2 (en)
EP (1) EP2467340A2 (en)
JP (3) JP2013502371A (en)
KR (2) KR101823163B1 (en)
CN (2) CN102762508B (en)
IN (1) IN2012DN01533A (en)
TW (1) TWI576324B (en)
WO (1) WO2011022661A2 (en)
US9299613B2 (en) 2013-10-21 2016-03-29 Samsung Display Co., Ltd. Method for cutting substrate
DE102014116798A1 (en) 2014-11-17 2016-05-19 Schott Ag Chemically prestressed or toughened glass and process for its preparation
WO2009070237A1 (en) * 2007-11-29 2009-06-04 Corning Incorporated Glasses having improved toughness and scratch resistance
TWI398423B (en) * 2010-05-28 2013-06-11 Wintek Corp Method for strengthening glass and glass using the same
US20130059157A1 (en) * 2010-05-28 2013-03-07 Dana Craig Bookbinder Transparent laminates comprising intermediate or anomalous glass
WO2013116420A1 (en) * 2012-02-01 2013-08-08 Corning Incorporated Method of producing constancy of compressive stress in glass in an ion-exchange process
US20130136909A1 (en) * 2011-11-30 2013-05-30 John Christopher Mauro Colored alkali aluminosilicate glass articles
US9701580B2 (en) * 2012-02-29 2017-07-11 Corning Incorporated Aluminosilicate glasses for ion exchange
TWI593644B (en) 2012-05-09 2017-08-01 Corning Inc Method of making a cover glass
US9517967B2 (en) * 2012-05-31 2016-12-13 Corning Incorporated Ion exchangeable glass with high damage resistance
US9145333B1 (en) * 2012-05-31 2015-09-29 Corning Incorporated Chemically-strengthened borosilicate glass articles
WO2013181134A1 (en) * 2012-05-31 2013-12-05 Corning Incorporated Zircon compatible, ion exchangeable glass with high damage resistance
KR20150028786A (en) * 2012-05-31 2015-03-16 코닝 인코포레이티드 Ion exchangeable transition metal-containing glasses
CN104125935A (en) * 2012-06-08 2014-10-29 日本电气硝子株式会社 Tempered glass, tempered glass plate, and glass for tempering
JP2014031305A (en) * 2012-07-11 2014-02-20 Asahi Glass Co Ltd Glass for chemical strengthening and chemically strengthened glass
US20140098472A1 (en) * 2012-10-04 2014-04-10 Corning Incorporated Glass enclosure body having mechanical resistance to impact damage
WO2014120628A2 (en) * 2013-01-31 2014-08-07 Corning Incorporated Fictivated glass and method of making
US9714192B2 (en) * 2013-02-08 2017-07-25 Corning Incorporated Ion exchangeable glass with advantaged stress profile
JP2016513055A (en) * 2013-02-11 2016-05-12 コーニング インコーポレイテッド Antibacterial glass article and a manufacturing method and using the same
WO2014127108A1 (en) 2013-02-15 2014-08-21 Corning Incorporated High volume production of display quality glass sheets having low zirconia levels
DE102013103573B4 (en) * 2013-04-10 2016-10-27 Schott Ag Chemically toughenable glass member with high scratch tolerance, and methods for producing the glass member
US9371248B2 (en) * 2013-04-10 2016-06-21 Schott Ag Glass element with high scratch tolerance
TWI631049B (en) 2013-05-07 2018-08-01 康寧公司 The method of manufacturing a glass cover 3d and 3d computer for estimating a shape of the embodiment of the method of the cover glass
CN105377781B (en) 2013-05-07 2019-04-16 康宁股份有限公司 The method and apparatus of preparation molding glassware
CN104150765A (en) * 2013-08-27 2014-11-19 东旭集团有限公司 High-silicon high-aluminum cover plate glass for touch screen
US9714188B2 (en) * 2013-09-13 2017-07-25 Corning Incorporated Ion exchangeable glasses with high crack initiation threshold
KR20160085839A (en) * 2013-11-19 2016-07-18 코닝 인코포레이티드 Ion Exchangeable High Damage Resistance Glasses
WO2015080893A1 (en) * 2013-11-26 2015-06-04 Corning Incorporated Fast ion exchangeable glasses with high indentation threshold
WO2015123077A1 (en) 2014-02-13 2015-08-20 Corning Incorporated Glass with enhanced strength and antimicrobial properties, and method of making same
KR20160133501A (en) 2014-03-13 2016-11-22 코닝 인코포레이티드 Glass Article and Method for Forming the Same
US10144198B2 (en) 2014-05-02 2018-12-04 Corning Incorporated Strengthened glass and compositions therefor
WO2015184527A1 (en) * 2014-06-06 2015-12-10 The Royal Institution For The Advancement Of Learning/Mc Gill University Methods and systems relating to enhancing material toughness
TW201605614A (en) * 2014-06-19 2016-02-16 Corning Inc Glasses having non-frangible stress profiles
JP2017530383A (en) 2014-07-30 2017-10-12 コーニング インコーポレイテッド High-contrast, writable / erasable front projection screen based on the glass
US9902641B2 (en) 2015-03-20 2018-02-27 Corning Incorporated Molds for shaping glass-based materials and methods for making the same
EP3286152A1 (en) 2015-04-21 2018-02-28 Corning Incorporated Edge and corner-strengthened articles and methods for making same
US20170044045A1 (en) 2015-08-14 2017-02-16 Corning Incorporated Molds and methods to control mold surface quality
WO2017087204A1 (en) 2015-11-18 2017-05-26 Corning Incorporated Powder, process of making the powder, and articles made therefrom
US20170144923A1 (en) 2015-11-23 2017-05-25 Corning Incorporated Removal of inorganic coatings from glass substrates
US10181017B2 (en) 2015-12-09 2019-01-15 Lenovo (Singapore) Pte. Ltd. Swipe mechanism
DE202016103452U1 (en) 2016-06-29 2016-07-12 Irlbacher Blickpunkt Glas Gmbh Operating terminal with a protected glass surface
WO2018022453A1 (en) 2016-07-28 2018-02-01 Corning Incorporated Glasses having resistance to photo-darkening
US3524737A (en) 1967-06-01 1970-08-18 Corning Glass Works Method for thermochemical strengthening of glass articles
US4166745A (en) * 1977-12-16 1979-09-04 Corning Glass Works Refractive index-corrected copper-cadmium halide photochromic glasses
DE2756555C3 (en) * 1977-12-19 1982-12-02 Schott Glaswerke, 6500 Mainz, De
JPS6049145B2 (en) * 1980-01-26 1985-10-31 Nippon Electric Glass Co
JPS60141642A (en) * 1983-12-28 1985-07-26 Tdk Corp Low expansion glass having stability at high temperature
US4549894A (en) 1984-06-06 1985-10-29 Corning Glass Works Ultraviolet absorbing photochromic glass of low silver content
JPH0146460B2 (en) * 1984-08-21 1989-10-09 Central Glass Co Ltd
JP2589986B2 (en) * 1987-08-10 1997-03-12 旭硝子株式会社 Magnetic recording media
JPH03177333A (en) * 1989-12-06 1991-08-01 Nippon Electric Glass Co Ltd Crystallized glass having pinky color tone
JP2577493B2 (en) * 1990-07-23 1997-01-29 ホーヤ株式会社 Glass silicon base, a silicon base material type sensors, and the silicon substrate type pressure sensor
JPH04119942A (en) * 1990-09-11 1992-04-21 Nippon Electric Glass Co Ltd Crystallized glass showing light green color tone
GB9106086D0 (en) * 1991-03-22 1991-05-08 Pilkington Plc Glass composition
DE4241411C2 (en) 1992-12-09 1995-05-11 Schott Glaswerke On borosilicate glass or glass-ceramic substrates coated decorative layers of ceramic paints and processes for their preparation
JP3431279B2 (en) * 1993-06-08 2003-07-28 旭テクノグラス株式会社 Low expansion glass used in anodic bonding
US5489558A (en) 1994-03-14 1996-02-06 Corning Incorporated Glasses for flat panel display
DE69508706T2 (en) * 1994-11-30 1999-12-02 Asahi Glass Co Ltd Alkali-free glass and flat screen TV
WO1996024559A1 (en) 1995-02-10 1996-08-15 Asahi Glass Company Ltd. Scratch-resistant glass
US5674790A (en) * 1995-12-15 1997-10-07 Corning Incorporated Strengthening glass by ion exchange
DE19603698C1 (en) 1996-02-02 1997-08-28 Schott Glaswerke Alkali-free aluminoborosilicate glass and the use thereof
DE19643870C2 (en) 1996-10-30 1999-09-23 Schott Glas Use of a glass body to produce a chemically tempered glass body
DE19739912C1 (en) 1997-09-11 1998-12-10 Schott Glas New alkali-free aluminoborosilicate glass
JPH11153705A (en) * 1997-11-20 1999-06-08 Nippon Sheet Glass Co Ltd Lens with distribution of refractive index in axial direction
JPH11310431A (en) * 1998-04-27 1999-11-09 Asahi Glass Co Ltd Glass composition for substrate board
DE69902839T2 (en) 1998-04-28 2003-05-28 Asahi Glass Co Ltd Flat glass and glass substrate for electronics
CN1160268C (en) 1998-11-30 2004-08-04 康宁股份有限公司 Glasses for flat panel displays
DE19916296C1 (en) 1999-04-12 2001-01-18 Schott Glas Alkali-free aluminoborosilicate glass and the use thereof
JP2001106545A (en) * 1999-07-30 2001-04-17 Hoya Corp Glass substrate, method for manufacturing semiconductor sensor and semiconductor sensor
JP3637261B2 (en) * 2000-04-20 2005-04-13 大阪特殊硝子株式会社 Reflector
JP2002265233A (en) 2001-03-05 2002-09-18 Nippon Sheet Glass Co Ltd Glass preform for laser beam machining and glass for laser beam machining
EP1426345A1 (en) * 2002-12-03 2004-06-09 Corning Incorporated Borosilicate glass compositions and uses therof
DE10361555A1 (en) 2003-12-19 2005-07-28 Grintech Gmbh Aluminoborosilicate glass and process for producing gradient index kristallitfreier
JP2006002929A (en) 2004-06-14 2006-01-05 Yutaka Minegishi Double block switching valve
JP2006062929A (en) * 2004-08-30 2006-03-09 Nippon Electric Glass Co Ltd Crystallized glass article and method for manufacturing the same
WO2006064878A1 (en) * 2004-12-16 2006-06-22 Nippon Sheet Glass Company, Limited Glass composition and process for producing the same
JP2006298691A (en) * 2005-04-20 2006-11-02 Hitachi Displays Ltd Flat-panel type image display device
WO2007004683A1 (en) * 2005-07-06 2007-01-11 Asahi Glass Company, Limited Process for production of non-alkaline glass and non-alkaline glass
JP2009528673A (en) * 2006-01-03 2009-08-06 コーニング インコーポレイテッド Glass and glass ceramic on the germanium structure
JP2008201654A (en) * 2007-02-23 2008-09-04 Hitachi Displays Ltd Display
CN101626993B (en) 2007-05-14 2013-03-20 日本电气硝子株式会社 Laminated glass for window and glass window member
DE102008056323B8 (en) 2007-11-21 2019-01-03 Schott Ag Use of alkali-free Aluminoborosilikatgläsern for lamps with external or internal contact
JP5397593B2 (en) * 2007-12-19 2014-01-22 日本電気硝子株式会社 Glass substrate
JP2009203154A (en) * 2008-01-31 2009-09-10 Ohara Inc Glass
JP2011510903A (en) * 2008-02-08 2011-04-07 コーニング インコーポレイテッド Chemically strengthened protective cover glass of damage-resistant
US8232218B2 (en) * 2008-02-29 2012-07-31 Corning Incorporated Ion exchanged, fast cooled glasses
JP5683971B2 (en) * 2010-03-19 2015-03-11 石塚硝子株式会社 Chemically strengthening the glass composition and the chemical strengthened glass material
2010-07-28 US US12/845,066 patent/US8341976B2/en active Active
2010-08-18 US US12/858,490 patent/US8586492B2/en active Active
2010-08-19 TW TW099127636A patent/TWI576324B/en active
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2010-08-20 KR KR1020187001976A patent/KR20180011352A/en not_active Application Discontinuation
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2016-11-08 JP JP2016218026A patent/JP2017081817A/en active Pending
U.S. Appl. No. 12/277,573, by Matthew J. Dejneka et al, titled "Glasses Having Improved Toughness and Scratch Resistance", filed Nov. 25, 2008.
U.S. Appl. No. 61/067,130; by Matthew J. Dejneka et al, titled "Fining Agents for Silicate Glasses", filed on Feb. 26, 2008.
U.S. Appl. No. 61/067,732; by Matthew J. Dejneka et al, titled "Ion-Exchanged, Fast Cooled Glasses" filed on Feb. 29, 2008.
U.S. Appl. No. 61/079,995, by Douglas C. Allan et al, titled "Glass With Compressive Surface for Consumer Applications", filed Jul. 11, 2008.
U.S. Appl. No. 61/084,398, by Christopher M. Lee et al, titled "Dual Stage Ion Exchnage for Chemical Strengthening of Glass", filed Jul. 29, 2008.
U.S. Appl. No. 61/087,324; by Kristen L. Barefoot et al, titled "Chemically Tempered Cover Glass", filed Aug. 8, 2008.
US9688094B2 (en) 2013-10-21 2017-06-27 Samsung Display Co., Ltd. Method for cutting substrate
JP2013502371A (en) 2013-01-24
CN102762508B (en) 2017-05-31
US8586492B2 (en) 2013-11-19
CN107032605A (en) 2017-08-11
IN2012DN01533A (en) 2015-06-05
US20100291353A1 (en) 2010-11-18
US9290407B2 (en) 2016-03-22
KR20180011352A (en) 2018-01-31
KR101823163B1 (en) 2018-03-08
JP2017081817A (en) 2017-05-18
US20140329660A1 (en) 2014-11-06
TWI576324B (en) 2017-04-01
JP6128401B2 (en) 2017-05-17
US20110201490A1 (en) 2011-08-18
JP2015231945A (en) 2015-12-24
WO2011022661A2 (en) 2011-02-24
KR20120089472A (en) 2012-08-10
CN102762508A (en) 2012-10-31
EP2467340A2 (en) 2012-06-27
TW201127771A (en) 2011-08-16
WO2011022661A3 (en) 2011-05-12
US8304078B2 (en) 2012-11-06 Chemically strengthened lithium aluminosilicate glass having high strength effective to resist fracture upon flexing
JP5907160B2 (en) 2016-04-20 Glass for chemical strengthening
US20130302617A1 (en) 2013-11-14 Glass for chemical tempering and glass plate for display device
CN102320741B (en) 2015-08-19 The tempered glass substrate and manufacturing method
JP2016216358A (en) 2016-12-22 Chemically strengthened glass laminate
JP5152706B2 (en) 2013-02-27 Reinforced plate glass
EP1714947B1 (en) 2016-04-13 Method of forming a cased glass stream in preparing the production of glass articles
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