WO2020231967A1 - Compositions de verre renforçable à la vapeur à faible teneur en alcali - Google Patents

Compositions de verre renforçable à la vapeur à faible teneur en alcali Download PDF

Info

Publication number
WO2020231967A1
WO2020231967A1 PCT/US2020/032432 US2020032432W WO2020231967A1 WO 2020231967 A1 WO2020231967 A1 WO 2020231967A1 US 2020032432 W US2020032432 W US 2020032432W WO 2020231967 A1 WO2020231967 A1 WO 2020231967A1
Authority
WO
WIPO (PCT)
Prior art keywords
equal
mol
glass
less
mpa
Prior art date
Application number
PCT/US2020/032432
Other languages
English (en)
Inventor
Timothy Michael Gross
Alexandra Lai Ching Kao Andrews MITCHELL
Jingshi WU
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corning Incorporated filed Critical Corning Incorporated
Publication of WO2020231967A1 publication Critical patent/WO2020231967A1/fr
Priority to US17/526,071 priority Critical patent/US20220073426A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/007—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in gaseous phase
    • 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

  • This disclosure relates to glass-based articles strengthened by steam treatment, alkali-free glass compositions utilized to form the glass-based articles, and methods of steam treatment to strengthen the glass-based articles.
  • Portable electronic devices such as, smartphones, tablets, and wearable devices (such as, for example, watches and fitness trackers) continue to get smaller and more complex.
  • materials that are conventionally used on at least one external surface of such portable electronic devices also continue to get more complex.
  • the display covers and housings used in these portable electronic devices also get smaller and thinner, resulting in higher performance requirements for the materials used to form these components.
  • a glass-based article comprises: a hydrogen-containing layer extending from the surface of the glass-based article to a depth of layer, wherein a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of layer; a compressive stress layer extending from the surface of the glass-based article to a depth of compression, wherein the compressive stress layer comprises a compressive stress of greater than or equal to 10 MPa; and a composition at the center of the glass-based article comprising:
  • the glass-based article of aspect (1) is provided, wherein the compressive stress layer comprises a compressive stress of greater than or equal to 200 MPa.
  • the glass-based article of aspect (1) or (2) is provided, wherein the depth of compression is greater than or equal to 5 pm.
  • the glass-based article of any of aspects (1) to (3) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 5 mol% Na 2 0.
  • the glass-based article of any of aspects (1) to (4) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 8 mol% K2O.
  • the glass-based article of any of aspects (1) to (5) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 2 mol% MgO.
  • the glass-based article of any of aspects (1) to (6) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 12 mol% CaO.
  • the glass-based article of any of aspects (1) to (7) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 14 mol% SrO.
  • the glass-based article of any of aspects (1) to (8) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 16 mol% BaO.
  • the glass-based article of any of aspects (1) to (9) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 3 mol% ZnO.
  • the glass-based article of any of aspects (1) to (10) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 0 mol% to less than or equal to 0.5 mol% SnCh.
  • the glass-based article of any of aspects (1) to (11) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 10 mol% BaO and is substantially free of R2O.
  • the glass-based article of any of aspects (1) to (12) is provided, wherein the composition at the center of the glass-based article is substantially free of Na20.
  • the glass-based article of any of aspects (1) to (13) is provided, wherein the composition at the center of the glass-based article comprises greater than or equal to 1 mol% to less than or equal to 9 mol% P2O5.
  • a consumer electronic product comprises: a housing comprising a front surface, a back surface and side surfaces; electrical components at least partially within the housing, the electrical components comprising at least a controller, a memory, and a display, the display at or adjacent the front surface of the housing; and a cover substrate disposed over the display. At least a portion of at least one of the housing and the cover substrate comprises the glass-based article of any of aspects (1) to (14).
  • a glass is provided.
  • the glass comprises:
  • the glass of aspect (16) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 5 mol% Na 2 0.
  • the glass of aspect (16) or (17) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 8 mol% K2O.
  • the glass of any of aspects (16) to (18) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 2 mol% MgO.
  • the glass of any of aspects (16) to (19) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 12 mol% CaO.
  • the glass of any of aspects (16) to (20) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 14 mol% SrO.
  • the glass of any of aspects (16) to (21) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 16 mol% BaO.
  • the glass of any of aspects (16) to (22) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 3 mol% ZnO.
  • the glass of any of aspects (16) to (23) is provided, further comprising greater than or equal to 0 mol% to less than or equal to 0.5 mol% SnCh.
  • the glass of any of aspects (16) to (24) is provided, wherein the glass is substantially free of R2O and further comprises greater than or equal to 10 mol% BaO.
  • the glass of any of aspects (16) to (25) is provided, wherein the glass is substantially free of Na20.
  • the glass of any of aspects (16) to (26) is provided, comprising greater than or equal to 1 mol% to less than or equal to 9 mol% P2O5.
  • the glass of any of aspects (16) to (27) is provided, comprising Young’s modulus of greater than or equal to 65 GPa.
  • a method comprises: exposing a glass- based substrate to an environment comprising steam with a pressure greater than or equal to 0.1 MPa, and a temperature of greater than or equal to 175 °C to form a glass-based article with compressive stress layer extending from the surface of the glass-based article to a depth of compression and a hydrogen-containing layer extending from the surface of the glass- based article to a depth of layer.
  • the compressive stress layer comprises a compressive stress of greater than or equal to 10 MPa.
  • a hydrogen concentration of the hydrogen-containing layer decreases from a maximum hydrogen concentration to the depth of layer.
  • the glass- based substrate comprises:
  • the method of aspect (29) is provided, wherein the environment comprises a temperature of greater than or equal to 300 °C.
  • aspect (31) the method of aspect (29) or (30) is provided, wherein the environment comprises a pressure of greater than or equal to 1 MPa.
  • the method of any of aspects (29) to (33) is provided, wherein the compressive stress layer comprises a compressive stress of greater than or equal to 200 MPa.
  • the method of any of aspects (29) to (34) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 5 mol% Na20.
  • the method of any of aspects (29) to (35) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 8 mol% K2O.
  • the method of any of aspects (29) to (36) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 2 mol% MgO.
  • the method of any of aspects (29) to (37) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 12 mol% CaO.
  • the method of any of aspects (29) to (38) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 14 mol% SrO.
  • the method of any of aspects (29) to (39) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 16 mol% BaO.
  • the method of any of aspects (29) to (40) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 3 mol% ZnO.
  • the method of any of aspects (29) to (41) is provided, wherein the glass-based substrate comprises greater than or equal to 0 mol% to less than or equal to 0.5 mol% SnC .
  • the method of any of aspects (29) to (42) is provided, wherein the glass-based substrate is substantially free of R2O and further comprises greater than or equal to 10 mol% BaO.
  • the method of any of aspects (29) to (44) is provided, wherein the glass-based substrate comprises greater than or equal to 1 mol% to less than or equal to 9 mol% P2O5.
  • the method of any of aspects (29) to (45) is provided, wherein the glass-based substrate comprises a Young’s modulus of greater than or equal to 65 GPa.
  • FIG. l is a representation of a cross-section of a glass-based article according to an embodiment.
  • FIG. 2A is a plan view of an exemplary electronic device incorporating any of the glass-based articles disclosed herein.
  • FIG. 2B is a perspective view of the exemplary electronic device of FIG. 2A.
  • FIG. 3 is a plot of the saturation condition for water as a function or pressure and temperature.
  • glass-based is used in its broadest sense to include any objects made wholly or partly of glass, including glass ceramics (which include a crystalline phase and a residual amorphous glass phase). Unless otherwise specified, all compositions of the glasses described herein are expressed in terms of mole percent (mol%), and the constituents are provided on an oxide basis. Unless otherwise specified, all temperatures are expressed in terms of degrees Celsius (°C).
  • the terms “substantially” and “about” may be utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. These terms are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.
  • a glass that is“substantially free of K2O” is one in which K2O is not actively added or batched into the glass but may be present in very small amounts as a contaminant, such as in amounts of less than about 0.01 mol%.
  • the term“about” when the term“about” is used to modify a value, the exact value is also disclosed.
  • the term“greater than about 10 mol%” also discloses“greater than or equal to 10 mol%.”
  • the glass-based articles disclosed herein are formed by steam treating a glass-based substrate to produce a compressive stress layer extending from surface of the article to a depth of compression (DOC).
  • the compressive stress layer includes a stress that decreases from a maximum stress to the depth of compression.
  • the maximum compressive stress may be located at the surface of the glass-based article.
  • depth of compression means the depth at which the stress in the glass-based article changes from compressive to tensile.
  • the glass-based article also contains a tensile stress region having a maximum central tension (CT), such that the forces within the glass- based article are balanced.
  • CT maximum central tension
  • the glass-based articles further include a hydrogen-containing layer extending from a surface of the article to a depth of layer.
  • the hydrogen-containing layer includes a hydrogen concentration that decreases from a maximum hydrogen concentration of the glass-based article to the depth of layer.
  • the maximum hydrogen concentration may be located at the surface of the glass-based article.
  • the glass-based articles may be formed by exposing glass-based substrates to environments containing water vapor, thereby allowing hydrogen species to penetrate the glass-based substrates and form the glass-based articles having a hydrogen-containing layer and/or a compressive stress layer.
  • hydrogen species includes molecular water, hydroxyl, hydrogen ions, and hydronium.
  • the composition of the glass-based substrates may be selected to promote the interdiffusion of hydrogen species into the glass.
  • glass-based substrate refers to the precursor prior to exposure to a water vapor containing environment for the formation of a glass-based article that includes hydrogen-containing layers and/or compressive stress layers.
  • glass-based article refers to the post exposure article that includes a hydrogen-containing layer and/or a compressive stress layer.
  • the glass-based articles disclosed herein may exhibit a compressive stress layer without undergoing conventional ion exchange, thermal tempering, or lamination treatments. Ion exchange processes produces significant waste in the form of expended molten salt baths that require costly disposal, and also are applicable to only some glass compositions.
  • Thermal tempering requires thick glass specimens as a practical matter, as thermal tempering of thin sheets utilizes small air gap quenching processes which results in sheet scratching damage that reduces performance and yield. Additionally, it is difficult to achieve uniform
  • Laminate processes result in exposed tensile stress regions when large sheets are cut to usable sizes, which is undesirable.
  • the water vapor treatment utilized to form the glass-based articles allows for reduced waste and lower cost when compared to ion exchange treatments as molten salts are not utilized, and alkali-free glass-based substrates may be employed.
  • the water vapor treatment is also capable of strengthening thin ( ⁇ 2 mm) low-cost glass that would not be suitable for thermal tempering at such thicknesses. Additionally, the water vapor treatment may be performed at the part level, avoiding the undesirable exposed tensile stress regions associated with laminate processes.
  • the glass-based articles disclosed herein may be produced with a low thickness and at a low cost while exhibiting a high compressive stress and deep depth of compression.
  • a representative cross-section of a glass-based article 100 is depicted in FIG. 1.
  • the glass-based article 100 has a thickness / that extends between a first surface 110 and a second surface 112.
  • a first compressive stress layer 120 extends from the first surface 110 to a first depth of compression, where the first depth of compression has a depth di measured from the first surface 110 into the glass-based article 100.
  • a second compressive stress layer 122 extends from the second surface 112 to a second depth of compression, where the second depth of compression has a depth r/ measured from the second surface 112 into the glass-based article 100.
  • a tensile stress region 130 is present between the first depth of compression and the second depth of compression.
  • the first depth of compression di may be substantially equivalent or equivalent to the second depth of compression
  • the compressive stress layer of the glass-based article may include a compressive stress of at greater than or equal to 10 MPa, such as greater than or equal to 20 MPa, greater than or equal to 30 MPa, greater than or equal to 40 MPa, greater than or equal to 50 MPa, greater than or equal to 60 MPa, greater than or equal to 70 MPa, greater than or equal to 80 MPa, greater than or equal to 90 MPa, greater than or equal to 100 MPa, greater than or equal to 110 MPa, greater than or equal to 120 MPa, greater than or equal to 130 MPa, greater than or equal to 140 MPa, greater than or equal to 145 MPa, greater than or equal to 150 MPa, greater than or equal to 160 MPa, greater than or equal to 170 MPa, greater than or equal to 180 MPa, greater than or equal to 190 MPa, greater than or equal to 200 MPa, greater than or equal to 210 MPa, greater than or equal to 220 MPa, greater than or equal to 230 MPa, greater than or equal to 10 MPa, greater
  • the compressive stress layer may include a compressive stress of from greater than or equal to 10 MPa to less than or equal to 550 MPa, such as from greater than or equal to 20 MPa to less than or equal to 540 MPa, from greater than or equal to 30 MPa to less than or equal to 530 MPa, from greater than or equal to 40 MPa to less than or equal to 520 MPa, from greater than or equal to 50 MPa to less than or equal to 510 MPa, from greater than or equal to 60 MPa to less than or equal to 500 MPa, from greater than or equal to 70 MPa to less than or equal to 490 MPa, from greater than or equal to 80 MPa to less than or equal to 480 MPa, from greater than or equal to 90 MPa to less than or equal to 470 MPa, from greater than or equal to 100 MPa to less than or equal to 460 MPa, from greater than or equal to 110 MPa to less than or equal to 450 MPa, from greater than or equal to 120 MPa to less than or equal to
  • the DOC of the compressive stress layer may be greater than or equal to 5 pm, such as greater than or equal to 7 pm, greater than or equal to 10 pm, greater than or equal to 15 pm, greater than or equal to 20 pm, greater than or equal to 25 pm, greater than or equal to 30 pm, greater than or equal to 35 pm, greater than or equal to 40 pm, or more.
  • the DOC of the compressive stress layer may be from greater than or equal to 5 pm to less than or equal to 55 pm, such as from greater than or equal to 7 pm to less than or equal to 50 pm, from greater than or equal to 10 pm to less than or equal to 45 pm, from greater than or equal to 15 pm to less than or equal to 40 pm, from greater than or equal to 20 pm to less than or equal to 35 pm, from greater than or equal to 25 pm to less than or equal to 30 pm, or any and all sub-ranges that may be formed from any of these endpoints.
  • the glass-based articles may have a DOC greater than or equal to 0.05/, wherein / is the thickness of the glass-based article, such as greater than or equal to 0.06/, greater than or equal to 0.07/, greater than or equal to 0.08/, greater than or equal to 0.09/, greater than or equal to 0.10/, greater than or equal to 0.11/, greater than or equal to 0.12/, greater than or equal to 0.13/, greater than or equal to 0.14/, greater than or equal to 0.15/, greater than or equal to 0.16/, greater than or equal to 0.17/, greater than or equal to 0.18/, greater than or equal to 0.19/, or more.
  • the glass-based articles may have a DOC from greater than or equal to 0.05/ to less than or equal to 0.20/, such as from greater than or equal to 0.06/ to less than or equal to 0.19/, from greater than or equal to 0.07/ to less than or equal to 0.18/, from greater than or equal to 0.08/ to less than or equal to 0.17/, from greater than or equal to 0.09/ to less than or equal to 0.16/, from greater than or equal to 0.10/ to less than or equal to 0.15/, from greater than or equal to 0.11/ to less than or equal to 0.14/, from greater than or equal to 0.12/ to less than or equal to 0.13/, or any sub-ranges formed from any of these endpoints.
  • a DOC from greater than or equal to 0.05/ to less than or equal to 0.20/, such as from greater than or equal to 0.06/ to less than or equal to 0.19/, from greater than or equal to 0.07/ to less than or equal to 0.18/, from greater than or equal to 0.08/
  • Compressive stress is measured by surface stress meter using commercially available instruments such as the FSM-6000 (FSM), manufactured by Orihara Industrial Co., Ltd. (Japan).
  • FSM FSM-6000
  • SOC stress optical coefficient
  • ASTM standard C770-16 ASTM standard C770-16, entitled“Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety.
  • DOC is measured by FSM.
  • the maximum central tension (CT) values are measured using a scattered light polariscope (SCALP) technique known in the art.
  • the hydrogen-containing layer of the glass-based articles may have a depth of layer (DOL) greater than 5 pm.
  • the depth of layer may be greater than or equal to 10 pm, such as greater than or equal to 15 pm, greater than or equal to 20 pm, greater than or equal to 25 pm, greater than or equal to 30 pm, greater than or equal to 35 pm, greater than or equal to 40 pm, greater than or equal to 45 pm, greater than or equal to 50 pm, greater than or equal to 55 pm, greater than or equal to 60 pm, greater than or equal to 65 pm, greater than or equal to 70 pm, greater than or equal to 75 pm, greater than or equal to 80 pm, greater than or equal to 85 pm, greater than or equal to 90 pm, greater than or equal to 95 pm, or more.
  • the depth of layer may be from greater than 5 pm to less than or equal to 100 pm, such as from greater than or equal to 10 pm to less than or equal to 95 pm, from greater than or equal to 15 pm to less than or equal to 90 pm, from greater than or equal to 20 pm to less than or equal to 85 pm, from greater than or equal to 25 pm to less than or equal to 80 pm, from greater than or equal to 30 pm to less than or equal to 75 pm, from greater than or equal to 35 pm to less than or equal to 70 pm, from greater than or equal to 40 pm to less than or equal to 65 pm, from greater than or equal to 45 pm to less than or equal to 60 pm, from greater than or equal to 50 pm to less than or equal to 55 pm, or any sub-ranges formed by any of these endpoints.
  • the depth of layer exhibited by the glass-based articles is greater than the depth of layer that may be produced by exposure to the ambient environment.
  • the hydrogen-containing layer of the glass-based articles may have a depth of layer (DOL) greater than 0.005/, wherein / is the thickness of the glass-based article.
  • the depth of layer may be greater than or equal to 0.010/, such as greater than or equal to 0.015/, greater than or equal to 0.020/, greater than or equal to 0.025/, greater than or equal to 0.030/, greater than or equal to 0.035/, greater than or equal to 0.040/, greater than or equal to 0.045/, greater than or equal to 0.050/, greater than or equal to 0.055/, greater than or equal to 0.060/, greater than or equal to 0.065/, greater than or equal to 0.070/, greater than or equal to 0.075/, greater than or equal to 0.080/, greater than or equal to 0.085/, greater than or equal to 0.090/, greater than or equal to 0.095/, greater than or equal to 0.10/, greater than or equal to 0.
  • DOL depth of
  • the DOL may be from greater than 0.005/ to less than or equal to 0.205/, such as from greater than or equal to 0.010/ to less than or equal to 0.200/, from greater than or equal to 0.015/ to less than or equal to 0.195/, from greater than or equal to 0.020/ to less than or equal to 0.190/, from greater than or equal to 0.025/ to less than or equal to 0.185/, from greater than or equal to 0.030/ to less than or equal to 0.180/, from greater than or equal to 0.035/ to less than or equal to 0.175/, from greater than or equal to 0.040/ to less than or equal to 0.170/, from greater than or equal to 0.045/ to less than or equal to 0.165/, from greater than or equal to 0.050/ to less than or equal to 0.160/, from greater than or equal to 0.055/ to less than or equal to 0.155/, from greater than or equal to 0.060/ to less than or equal to 0.150/, from greater than or
  • the depth of layer and hydrogen concentration are measured by a secondary ion mass spectrometry (SIMS) technique that is known in the art.
  • SIMS secondary ion mass spectrometry
  • the SIMS technique is capable of measuring the hydrogen concentration at a given depth but is not capable of distinguishing the hydrogen species present in the glass-based article. For this reason, all hydrogen species contribute to the SIMS measured hydrogen concentration.
  • the depth of layer refers to the first depth below the surface of the glass-based article where the hydrogen concentration is equal to the hydrogen concentration at the center of the glass-based article. This definition accounts for the hydrogen concentration of the glass-based substrate prior to treatment, such that the depth of layer refers to the depth of the hydrogen added by the treatment process.
  • the hydrogen concentration at the center of the glass-based article may be approximated by the hydrogen concentration at the depth from the surface of the glass-based article where the hydrogen concentration becomes substantially constant, as the hydrogen concentration is not expected to change between such a depth and the center of the glass-based article. This approximation allows for the determination of the DOL without measuring the hydrogen concentration throughout the entire depth of the glass- based article.
  • the hydrogen-containing layer of the glass-based articles may be the result of an interdiffusion of hydrogen species for ions contained in the compositions of the glass-based substrate.
  • Hydrogen-containing species such as 3 ⁇ 40 + , H2O, and/or H + , may diffuse into the glass-based substrate to form the glass- based article.
  • Water could penetrate the glass-based substrates by forming silanol groups, breaking the network structure and causing a volume expansion of the glass. Such a volume expansion may generate a compressive stress layer in the glass-based articles.
  • compressive stress and depth of compression of the compressive stress layer may depend on the composition of the glass-based substrate utilized to form the glass-based article, and the water vapor treatment conditions, such as temperature, pressure, water content, and duration.
  • the stress profile of the glass-based articles produced by the water vapor treatment may be similar to stress profiles produced by potassium for sodium ion exchange strengthening processes.
  • the glass-based articles that have compressive stress layers also exhibit weight gain when compared to the glass-based substrates prior to the water vapor treatment process.
  • the weight gain of the glass-based articles indicates the formation of a hydrogen-containing layer as a result of the water vapor treatment.
  • the glass-based articles disclosed herein may be incorporated into another article such as an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, computers, navigation systems, wearable devices (e.g., watches) and the like), architectural articles, transportation articles (e.g., automotive, trains, aircraft, sea craft, etc.), appliance articles, or any article that requires some transparency, scratch- resistance, abrasion resistance or a combination thereof.
  • a display or display articles
  • FIGS. 2A and 2B An exemplary article incorporating any of the glass-based articles disclosed herein is shown in FIGS. 2A and 2B. Specifically, FIGS.
  • FIGS. 2A and 2B show a consumer electronic device 200 including a housing 202 having front 204, back 206, and side surfaces 208; electrical components (not shown) that are at least partially inside or entirely within the housing and including at least a controller, a memory, and a display 210 at or adjacent to the front surface of the housing; and a cover substrate 212 at or over the front surface of the housing such that it is over the display.
  • electrical components not shown
  • At least a portion of at least one of the cover substrate 212 and the housing 202 may include any of the glass-based articles disclosed herein.
  • the glass- based articles disclosed herein may be utilized in electronic displays, such as curved and/or bendable displays.
  • the glass-based articles may be formed from glass-based substrates having any appropriate composition.
  • the composition of the glass-based substrate may be specifically selected to promote the diffusion of hydrogen-containing species, such that a glass-based article including a hydrogen-containing layer and a compressive stress layer may be formed efficiently.
  • the glass-based substrates are substantially free or free of alkali metal oxides.
  • the use of glass-based substrates that are substantially free of alkali metal oxides allows the glass-based articles to be employed in applications such as semi-conductor or display related products where alkali cations may migrate into electronic components and“poison” transistors.
  • the glass-based substrates may have a composition that includes SiC , AI2O3, P2O5, and alkaline earth metal oxide (R’O).
  • the hydrogen species does not diffuse to the center of the glass-based article. Stated differently, the center of the glass-based article is the area least affected by the water vapor treatment. For this reason, the center of the glass-based article may have a composition that is substantially the same, or the same, as the composition of the glass-based substrate prior to treatment in the water containing environment.
  • the glass-based substrate may include any appropriate amount of SiC .
  • S1O2 is the largest constituent and, as such, S1O2 is the primary constituent of the glass network formed from the glass composition. If the concentration of S1O2 in the glass composition is too high, the formability of the glass composition may be diminished as higher concentrations of S1O2 increase the difficulty of melting the glass, which, in turn, adversely impacts the formability of the glass.
  • the glass-based substrate may include S1O2 in an amount from greater than or equal to 55 mol% to less than or equal to 70 mol%, such as from greater than or equal to 56 mol% to less than or equal to 69 mol%, from greater than or equal to 57 mol% to less than or equal to 68 mol%, from greater than or equal to 58 mol% to less than or equal to 67 mol%, from greater than or equal to 59 mol% to less than or equal to 66 mol%, from greater than or equal to 60 mol% to less than or equal to 65 mol%, from greater than or equal to 61 mol% to less than or equal to 64 mol%, from greater than or equal to 62 mol% to less than or equal to 63 mol%, 62 mol%, or any sub-ranges formed by any of these endpoints.
  • the glass-based substrate may include any appropriate amount of AI2O3.
  • AI2O3 may serve as a glass network former, similar to SiCh.
  • AI2O3 may increase the viscosity of the glass composition due to its tetrahedral coordination in a glass melt formed from a glass composition, decreasing the formability of the glass composition when the amount of AI2O3 is too high.
  • AI2O3 can reduce the liquidus temperature of the glass melt, thereby enhancing the liquidus viscosity and improving the compatibility of the glass composition with certain forming processes, such as the fusion forming process.
  • the inclusion of AI2O3 in the glass-based substrate prevents phase separation and reduces the number of non-bridging oxygens (NBOs) in the glass.
  • NBOs non-bridging oxygens
  • the glass-based substrate may include AI2O3 in an amount of from greater than or equal to 12 mol% to less than or equal to 21 mol%, such as from greater than or equal to 13 mol% to less than or equal to 20 mol%, from greater than or equal to 14 mol% to less than or equal to 19 mol%, from greater than or equal to 15 mol% to less than or equal to 18 mol%, from greater than or equal to 16 mol% to less than or equal to 17 mol%, or any sub-ranges formed by any of these endpoints.
  • the glass-based substrate may include any appropriate amount of P2O5.
  • P2O5 may include any appropriate amount of P2O5.
  • the inclusion of phosphorous in the glass-based substrate promotes faster interdiffusion.
  • the phosphorous containing glass-based substrates allow the efficient formation of glass- based articles including a hydrogen-containing layer.
  • the inclusion of P2O5 also allows for the production of a glass-based article with a deep depth of layer (e.g., greater than about 10 pm) in a relatively short treatment time.
  • the glass-based substrate may include P2O5 in an amount of from greater than or equal to 0 mol% to less than or equal to 9 mol%, such as from greater than or equal to 1 mol% to less than or equal to 8 mol%, from greater than or equal to 2 mol% to less than or equal to 7 mol%, from greater than or equal to 3 mol% to less than or equal to 6 mol%, from greater than or equal to 4 mol% to less than or equal to 5 mol%, or any sub-ranges formed by any of these endpoints.
  • the glass-based substrate may be substantially free or free of P2O5.
  • the glass-based substrate includes any appropriate amount of alkaline metal oxide.
  • the total alkaline metal oxide content of the glass-based substrate is referred to herein as the R’O content.
  • the R’O content is the sum total of the content of BaO, MgO, SrO, and CaO in the glass-based substrate.
  • the glass-based substrate may include RO in an amount of from greater than or equal to 2 mol% to less than or equal to 16 mol%, such as from greater than or equal to 3 mol% to less than or equal to 15 mol%, from greater than or equal to 4 mol% to less than or equal to 14 mol%, from greater than or equal to 5 mol% to less than or equal to 13 mol%, from greater than or equal to 6 mol% to less than or equal to 12 mol%, from greater than or equal to 7 mol% to less than or equal to 11 mol%, from greater than or equal to 8 mol% to less than or equal to 10 mol%, 9 mol%, or any and all sub-ranges formed from any of these endpoints.
  • the glass-based substrates may include BaO.
  • the inclusion of BaO has been demonstrated to reduce the dependence of the specific volume of the glass- based substrate on fictive temperature, which may be especially desirable for display glass applications.
  • BaO may also increase the openness of the glass network which increases the susceptibility of the glass-based substrates to steam strengthening. Additionally, the low ionic field strength of barium compared to other alkaline earth cations leads to a comparably low oxygen packing density, further enabling steam strengthening of glass-based substrates that include BaO.
  • the glass-based substrates may include BaO in an amount from greater than or equal to 0 mol% to less than or equal to 16 mol%, such as from greater than or equal to 1 mol% to less than or equal to 15 mol%, from greater than or equal to 2 mol% to less than or equal to 14 mol%, from greater than or equal to 3 mol% to less than or equal to 13 mol%, from greater than or equal to 4 mol% to less than or equal to 12 mol%, from greater than or equal to 5 mol% to less than or equal to 11 mol%, from greater than or equal to 6 mol% to less than or equal to 10 mol%, from greater than or equal to 7 mol% to less than or equal to 9 mol%, 8 mol%, or any and all sub-ranges formed from these endpoints.
  • the glass-based substrates may be substantially free or free of BaO.
  • the glass-based substrate may include SrO.
  • SrO has been demonstrated to reduce the dependence of the specific volume of the glass-based substrate on fictive temperature, which may be especially desirable for display glass applications. SrO may also increase the openness of the glass network which increases the susceptibility of the glass-based substrates to steam strengthening.
  • the glass-based substrates may include SrO in an amount from greater than or equal to 0 mol% to less than or equal to 14 mol%, such as from greater than or equal to 1 mol% to less than or equal to 13 mol%, from greater than or equal to 2 mol% to less than or equal to 12 mol%, from greater than or equal to 3 mol% to less than or equal to 11 mol%, from greater than or equal to 4 mol% to less than or equal to 10 mol%, from greater than or equal to 5 mol% to less than or equal to 9 mol%, from greater than or equal to 6 mol% to less than or equal to 8 mol%,
  • the glass- based substrates may be substantially free or free of SrO.
  • the glass-based substrate may additionally include MgO.
  • the glass-based substrates may include MgO in an amount from greater than or equal to 0 mol% to less than or equal to 2 mol%, such as from greater than or equal to 1 mol% to less than or equal to 2 mol%, or any and all sub-ranges formed from these endpoints.
  • the glass-based substrates may be substantially free or free of MgO.
  • the glass-based substrate may additionally include CaO.
  • the glass-based substrates may include CaO in an amount from greater than or equal to 0 mol% to less than or equal to 12 mol%, such as from greater than or equal to 1 mol% to less than or equal to 11 mol%, from greater than or equal to 2 mol% to less than or equal to 10 mol%, from greater than or equal to 3 mol% to less than or equal to 9 mol%, from greater than or equal to 4 mol% to less than or equal to 8 mol%, from greater than or equal to 5 mol% to less than or equal to 7 mol%, 6 mol%, or any and all sub-ranges formed from these endpoints.
  • the glass-based substrates may be substantially free or free of CaO.
  • the glass-based substrate may additionally include alkali metal oxides.
  • the total content of alkali metal oxides in the glass-based substrate may be referred to as the R2O content.
  • the R2O content may be the sum total content of LhO, Na 2 0, K2O, Rb 2 0, and CS2O.
  • the inclusion of R2O in the glass-based substrate may increase the susceptibility of the glass-based substrate to steam strengthening. When the glass-based substrate includes R2O, it is included in a low amount.
  • the glass-based substrate contains R2O in an amount from greater than or equal to 0 mol% to less than or equal to 9 mol%, such as from greater than or equal to 1 mol% to less than or equal to 8 mol%, from greater than or equal to 2 mol% to less than or equal to 7 mol%, from greater than or equal to 3 mol% to less than or equal to 6 mol%, from greater than or equal to 4 mol% to less than or equal to 5 mol%, or any and all sub-ranges formed from these endpoints.
  • the glass-based substrate may be substantially free or free of R2O.
  • a glass-based substrate may be substantially free or free of R2O and include greater than or equal to 10 mol% BaO to maintain a high degree of steam strengthening susceptibility.
  • the glass-based substrate may include Na 2 0 in any appropriate amount.
  • the glass-based substrate may include Na20 in an amount of from greater than or equal to 0 mol% to less than or equal to 5 mol%, such as from greater than or equal to 1 mol% to less than or equal to 4 mol%, from greater than or equal to 2 mol% to less than or equal to 3 mol%, or any and all sub-ranges formed from these endpoints.
  • the glass-based substrate may be substantially free or free of Na 2 0. The inclusion of Na 2 0 in the glass-based substrate may be especially undesirable for display glass applications.
  • the glass-based substrate may include K2O in any appropriate amount.
  • K2O in any appropriate amount.
  • the inclusion of K2O in the glass-based substrate increases the steam strengthening susceptibility of the glass-based article to a greater degree than other alkali metal oxides.
  • the glass-based substrate may include K2O in an amount of from greater than or equal to 0 mol% to less than or equal to 8 mol%, such as from greater than or equal to 1 mol% to less than or equal to 7 mol%, from greater than or equal to 2 mol% to less than or equal to 6 mol%, from greater than or equal to 3 mol% to less than or equal to 5 mol%,
  • the glass- based substrate may be substantially free or free of K2O.
  • K2O may be acceptable for display glass applications, as K + ions are large enough that they will not readily migrate through the glass-based articles under an applied voltage.
  • the glass-based substrate may additionally include ZnO.
  • the glass-based substrates may include ZnO in an amount from greater than or equal to 0 mol% to less than or equal to 3 mol%, such as from greater than or equal to 1 mol% to less than or equal to 2 mol%, or any and all sub-ranges formed from these endpoints.
  • the glass-based substrates may be substantially free or free of ZnO.
  • the glass-based substrates may additionally include a fining agent.
  • the fining agent may include tin.
  • the glass-based substrate may include SnC in an amount from greater than or equal to 0 mol% to less than or equal to 0.5 mol%, such as from greater than 0 mol% to less than or equal to 0.1 mol%.
  • the glass-based substrate may be substantially free or free of SnC .
  • the glass-based substrates may have a Young’s modulus that is greater than or equal to 65 GPa.
  • the high Young’s modulus of the glass-based substrates increases the efficiency of the conversion of strain to stress, such that the strain generated by water vapor treatment produces a higher compressive stress in glass-based articles formed from the glass-based substrates.
  • the glass-based substrates have a Young’s modulus that is greater than or equal to 66 GPa, such as greater than or equal to 67 GPa, greater than or equal to 68 GPa, greater than or equal to 69 GPa, greater than or equal to 70 GPa, greater than or equal to 71 GPa, greater than or equal to 72 GPa, greater than or equal to 73 GPa, greater than or equal to 74 GPa, greater than or equal to 75 GPa, greater than or equal to 76 GPa, greater than or equal to 77 GPa, greater than or equal to 78 GPa, greater than or equal to 79 GPa, or more.
  • the glass-based substrates may have a Young’s modulus in the range from greater than or equal to 65 GPa to less than or equal to 80 GPa, such as from greater than or equal to 66 GPa to less than or equal to 79 GPa, from greater than or equal to 67 GPa to less than or equal to 78 GPa, from greater than or equal to 68 GPa to less than or equal to 77 GPa, from greater than or equal to 69 GPa to less than or equal to 76 GPa, from greater than or equal to 70 GPa to less than or equal to 75 GPa, from greater than or equal to 71 GPa to less than or equal to 74 GPa, from greater than or equal to 72 GPa to less than or equal to 73 GPa, or any and all sub-ranges formed from these endpoints.
  • a Young’s modulus in the range from greater than or equal to 65 GPa to less than or equal to 80 GPa, such as from greater than or equal
  • the glass-based substrate may have any appropriate geometry. In some embodiments,
  • the glass-based substrate may have a thickness of less than or equal to 2 mm, such as less than or equal to 1.9 mm, less than or equal to 1.8 mm, less than or equal to 1.7 mm, less than or equal to 1.6 mm, less than or equal to 1.5 mm, less than or equal to 1.4 mm, less than or equal to 1.3 mm, less than or equal to 1.2 mm, less than or equal to 1.1 mm, less than or equal to 1 mm, less than or equal to 900 pm, less than or equal to 800 pm, less than or equal to 700 pm, less than or equal to 600 pm, less than or equal to 500 pm, less than or equal to 400 pm, less than or equal to 300 pm, or less.
  • the glass-based substrate may have a thickness from greater than or equal to 300 pm to less than or equal to 2 mm, such as from greater than or equal to 400 pm to less than or equal to 1.9 mm, from greater than or equal to 500 pm to less than or equal to 1.8 mm, from greater than or equal to 600 mih to less than or equal to 1.7 mm, from greater than or equal to 700 pm to less than or equal to 1.6 mm, from greater than or equal to 800 pm to less than or equal to 1.5 mm, from greater than or equal to 900 pm to less than or equal to 1.4 mm, from greater than or equal to 1 mm to less than or equal to 1.3 mm, from greater than or equal to 1.1 mm to less than or equal to 1.2 mm, or any and all sub-ranges formed from these endpoints.
  • a thickness from greater than or equal to 300 pm to less than or equal to 2 mm, such as from greater than or equal to 400 pm to less than or equal to 1.9 mm, from greater than or equal to 500 pm to
  • the glass-based substrate may have a plate or sheet shape. In some other embodiments, the glass-based substrates may have a 2.5D or 3D shape. As utilized herein, a “2.5D shape” refers to a sheet shaped article with at least one major surface being at least partially nonplanar, and a second major surface being substantially planar. As utilized herein, a“3D shape” refers to an article with first and second opposing major surfaces that are at least partially nonplanar.
  • the glass-based articles may have dimensions and shapes substantially similar or the same as the glass-based substrates from which they are formed.
  • the glass-based articles may be produced from the glass-based substrate by exposure to water vapor under any appropriate conditions.
  • the exposure may be carried out in any appropriate device, such as a furnace with relative humidity control.
  • the exposure may also be carried out at an elevated pressure, such as a furnace or autoclave with relative humidity and pressure control.
  • the glass-based articles may be produced by exposing a glass-based substrate to an environment with a pressure greater than or equal to ambient pressure and containing water vapor.
  • the environment may have a pressure greater than or equal to 0.1 MPa, and a temperature greater than 100°C.
  • the use of an elevated pressure allows in the exposure environment allows for a higher concentration of water vapor in the environment, especially as temperatures are increased. As the temperature increases the amount of water available for diffusion into the glass-based substrates to form glass-based articles decreases for a fixed volume, such as the interior of a furnace or autoclave.
  • the regions above the curve will result in condensation of water vapor into liquid which is undesirable.
  • the water vapor treatment conditions utilized herein may preferably fall on or under the curve in FIG. 3, with further preferred conditions being on or just under the curve to maximize water vapor content.
  • the water vapor treatment of the glass-based substrates may be carried out at elevated pressure.
  • the glass-based substrates may be exposed to an
  • a pressure greater than or equal to 0.1 MPa such as greater than or equal to 0.2 MPa, greater than or equal to 0.3 MPa, greater than or equal to 0.4 MPa, greater than or equal to 0.5 MPa, greater than or equal to 0.6 MPa, greater than or equal to 0.7 MPa, greater than or equal to 0.8 MPa, greater than or equal to 0.9 MPa, greater than or equal to 1.0 MPa, greater than or equal to 1.1 MPa, greater than or equal to 1.2 MPa, greater than or equal to 1.3 MPa, greater than or equal to 1.4 MPa, greater than or equal to 1.5 MPa, greater than or equal to 1.6 MPa, greater than or equal to 1.7 MPa, greater than or equal to 1.8 MPa, greater than or equal to 1.9 MPa, greater than or equal to 2.0 MPa, greater than or equal to 2.1 MPa, greater than or equal to 2.2 MPa, greater than or equal to 2.3 MPa, greater than or equal to 2.4 MPa, greater than or equal to 2.5 MPa, greater than or
  • the glass-based substrates may be exposed to an environment at a pressure of from greater than or equal to 0.1 MPa to less than or equal to 8 MPa, such as from greater than or equal to 0.2 MPa to less than or equal to 7.5 MPa, from greater than or equal to 0.3 MPa to less than or equal to 7.0 MPa, from greater than or equal to 0.4 MPa to less than or equal to 6.5 MPa, from greater than or equal to 0.5 MPa to less than or equal to 6.0 MPa, from greater than or equal to 0.6 MPa to less than or equal to 5.9 MPa, from greater than or equal to 0.7 MPa to less than or equal to 5.8 MPa, from greater than or equal to 0.8 MPa to less than or equal to 5.7 MPa, from greater than or equal to 0.9 MPa to less than or equal to
  • the glass-based substrates may be exposed to an environment at a pressure of from greater than or equal to 1 MPa to less than or equal to 8 MPa, such as greater than or equal to 2.6 MPa.
  • the glass-based substrates may be exposed to an
  • a water partial pressure greater than or equal to 0.05 MPa such as greater than or equal to 0.075 MPa, greater than or equal to 0.1 MPa, greater than or equal to 0.2 MPa, greater than or equal to 0.3 MPa, greater than or equal to 0.4 MPa, greater than or equal to 0.5 MPa, greater than or equal to 0.6 MPa, greater than or equal to 0.7 MPa, greater than or equal to 0.8 MPa, greater than or equal to 0.9 MPa, greater than or equal to 1.0 MPa, greater than or equal to 1.1 MPa, greater than or equal to 1.2 MPa, greater than or equal to 1.3 MPa, greater than or equal to 1.4 MPa, greater than or equal to 1.5 MPa, greater than or equal to 1.6 MPa, greater than or equal to 1.7 MPa, greater than or equal to 1.8 MPa, greater than or equal to 1.9 MPa, greater than or equal to 2.0 MPa, greater than or equal to 2.1 MPa, greater than or equal to 2.2 MPa, greater than or equal to 2.3
  • the glass-based substrates may be exposed to an
  • the glass-based substrate may be exposed to an environment with 100% relative humidity.
  • the environment may be a saturated steam environment.
  • the glass-based substrates may be exposed to an
  • a temperature of greater than or equal to 175°C such as greater than or equal to 180°C, greater than or equal to 185°C, greater than or equal to 190°C, greater than or equal to 195°C, greater than or equal to 200°C, greater than or equal to 205°C, greater than or equal to 210°C, greater than or equal to 215°C, greater than or equal to 220°C, greater than or equal to 225°C, greater than or equal to 230°C, greater than or equal to 235°C, greater than or equal to 240°C, greater than or equal to 245°C, greater than or equal to 250°C, greater than or equal to 255°C, greater than or equal to 260°C, greater than or equal to 265°C, greater than or equal to 270°C, greater than or equal to 275°C, greater than or equal to 280°C, greater than or equal to 285°C, greater than or equal to 290°C, greater than or equal to 295°C, such as
  • the glass- based substrates may be exposed to an environment with a temperature from greater than or equal to 175°C to less than or equal to 400°C, such as from greater than or equal to 180°C to less than or equal to 390°C, from greater than or equal to 185°C to less than or equal to 380°C, from greater than or equal to 190°C to less than or equal to 370°C, from greater than or equal to 195°C to less than or equal to 360°C, from greater than or equal to 200°C to less than or equal to 350°C, from greater than or equal to 205°C to less than or equal to 340°C, from greater than or equal to 210°C to less than or equal to 330°C, from greater than or equal to 215°C to less than or equal to 320°C, from greater than or equal to 220°C to less than or equal to 310°C, from greater than or equal to 225°C to less than or equal to 300°C, from greater than or equal to
  • the glass-based substrate may be exposed to the water vapor containing environment for a time period sufficient to produce the desired degree of hydrogen-containing species diffusion and the desired compressive stress layer.
  • the glass-based substrate may be exposed to the water vapor containing environment for greater than or equal to 2 hours, such as greater than or equal to 4 hours, greater than or equal to 6 hours, greater than or equal to 8 hours, greater than or equal to 10 hours, greater than or equal to 12 hours, greater than or equal to 14 hours, greater than or equal to 16 hours, greater than or equal to 18 hours, greater than or equal to 20 hours, greater than or equal to 22 hours, greater than or equal to 24 hours, greater than or equal to 30 hours, greater than or equal to 36 hours, greater than or equal to 42 hours, greater than or equal to 48 hours, greater than or equal to 54 hours, greater than or equal to 60 hours, greater than or equal to 66 hours, greater than or equal to 72 hours, greater than or equal to 78 hours, greater than or equal to 84 hours, greater than or equal to 2 hours, such as greater than or
  • the glass-based substrate may be exposed to the water vapor containing environment for a time period from greater than or equal to 2 hours to less than or equal to 10 days, such as from greater than or equal to 4 hours to less than or equal to 9 days, from greater than or equal to 6 hours to less than or equal to 8 days, from greater than or equal to 8 hours to less than or equal to 168 hours, from greater than or equal to 10 hours to less than or equal to 162 hours, from greater than or equal to 12 hours to less than or equal to 156 hours, from greater than or equal to 14 hours to less than or equal to 150 hours, from greater than or equal to 16 hours to less than or equal to 144 hours, from greater than or equal to 18 hours to less than or equal to 138 hours, from greater than or equal to 20 hours to less than or equal to 132 hours, from greater than or equal to 22 hours to less than or equal to 126 hours, from greater than or equal to 24 hours to less than or equal to 120 hours, from greater than or equal to 30 hours to less than or equal to 114
  • the glass-based substrates may be exposed to multiple water vapor containing environments.
  • the glass-based substrate may be exposed to a first environment to form a first glass-based article with a first compressive stress layer extending from a surface of the first glass-based article to a first depth of compression, and the first glass-based article may then be exposed to a second environment to form a second glass-based article with a second compressive stress layer extending from a surface of the second glass-based article to a second depth of compression.
  • the first environment has a first water partial pressure and a first temperature
  • the glass-based substrate is exposed to the first environment for a first time period.
  • the second environment has a second water partial pressure and a second temperature, and the first glass-based article is exposed to the second environment for a second time period.
  • the first water partial pressure and the second water partial pressure may be any appropriate partial pressure, such as greater than or equal to 0.05 MPa or greater than or equal to 0.075 MPa.
  • the first and second partial pressure may be any of the values disclosed herein with respect to the water partial pressures employed in the elevated pressure method.
  • the first and second environments may have, independently, a relative humidity of greater than or equal to 10%, such as greater than or equal to 25%, greater than or equal to 50%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 90%, greater than or equal to 95%, or equal to 100%.
  • at least one of the first environment and the second environment has a relative humidity of 100%.
  • the first compressive stress layer includes a first maximum compressive stress
  • the second compressive stress layer includes a second maximum compressive stress.
  • the first maximum compressive stress is less than the second maximum compressive stress.
  • the second maximum compressive stress may be compared to a compressive stress“spike” of the type formed through multi-step or mixed bath ion exchange techniques.
  • the first and second maximum compressive stress may have any of the values disclosed herein with respect to the compressive stress of the glass-based article.
  • the second maximum compressive stress may be greater than or equal to 50 MPa.
  • the first depth of compression may be less than or equal to the second depth of compression. In some embodiments, the first depth of compression is less than the second depth of compression.
  • the first depth of compression and the second depth of compression may have any of the values disclosed herein with respect to the depth of compression. In embodiments, the second depth of compression is greater than 5 pm.
  • the first temperature may be greater than or equal to the second temperature. In embodiments, the first temperature is greater than the second temperature.
  • the first and second temperatures may be any of the temperatures disclosed in connection with the elevated pressure method.
  • the first time period may be less than or equal to the second time period. In embodiments, the first time period is less than the second time period.
  • the first and second time periods may be any of the time periods disclosed in connection with the elevated pressure method.
  • any or all of the multiple exposures to a water vapor containing environment may be performed at an elevated pressure.
  • at least one of the first environment and the second environment may have a pressure greater than 0.1 MPa.
  • the first and second environments may have any pressure disclose in connection with the elevated pressure method.
  • the multiple water vapor environment exposure technique may include more than two exposure environments.
  • the second glass-based article may be exposed to a third environment to form a third glass-based article.
  • the third environment has a third water partial pressure and a third temperature, and the second glass- based article is exposed to the third environment for a third time period.
  • the third glass-based article includes a third compressive stress layer extending from a surface of the article to a third depth of compression and having a third maximum compressive stress.
  • the third water partial pressure may be greater than or equal to 0.05 MPa or greater than or equal to
  • the first glass-based article may be cooled to ambient temperature or otherwise removed from the first environment after the conclusion of the first time period and prior to being exposed to the second environment. In some embodiments, the first glass-based article may remain in the first environment after the conclusion of the first time period, and the first environment conditions may be changed to the second environment conditions without cooling to ambient temperature or removing the first glass-based article from the water vapor containing environment.
  • the methods of producing the glass-based articles disclosed herein may be free of an ion exchange treatment with an alkali ion source.
  • the glass-based articles are produced by methods that do not include an ion exchange with an alkali ion source.
  • the glass-based substrates and glass-based articles are not subjected to an ion exchange treatment with an alkali ion source.
  • the exposure conditions may be modified to reduce the time necessary to produce the desired amount of hydrogen-containing species diffusion into the glass-based substrate.
  • the temperature and/or relative humidity may be increased to reduce the time required to achieve the desired degree of hydrogen-containing species diffusion and depth of layer into the glass-based substrate.
  • Low alkali glass compositions that are particularly suited for formation of the glass- based articles described herein were formed into glass-based substrates, and the glass compositions are provided in Table I below.
  • the density of the glass compositions was determined using the buoyancy method of ASTM C693-93(2013).
  • the strain point and anneal point were determined using the beam bending viscosity method of ASTM C598- 93(2013).
  • the Young's modulus, shear modulus, and Poisson’s ratio values refer to values as measured by a resonant ultrasonic spectroscopy technique of the general type set forth in ASTM E2001-13, titled“Standard Guide for Resonant Ultrasound Spectroscopy for Defect Detection in Both Metallic and Non-metallic Parts.”
  • the stress optical coefficient (SOC) was measured according to Procedure C (Glass Disc Method) described in ASTM standard C770- 16, entitled“Standard Test Method for Measurement of Glass Stress-Optical Coefficient.”
  • the refractive index was measured at a wavelength of 589.3 nm. Table I
  • compositions F-J demonstrate that increased K2O, increased P2O5, and increased total alkali content (R2O) all appear to improve the depth of compression for a given treatment condition.

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)

Abstract

Des articles à base de verre qui comprennent une couche de contrainte de compression s'étendant d'une surface de l'article à base de verre à une profondeur de compression sont formés par exposition de substrats à base de verre à des environnements contenant de la vapeur d'eau. Les substrats à base de verre comprennent de faibles quantités d'oxydes alcalins. Les procédés de formation des articles à base de verre peuvent comprendre des pressions élevées et/ou de multiples expositions à des environnements contenant de la vapeur d'eau.
PCT/US2020/032432 2019-05-16 2020-05-12 Compositions de verre renforçable à la vapeur à faible teneur en alcali WO2020231967A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/526,071 US20220073426A1 (en) 2019-05-16 2021-11-15 Steam strengthenable glass compositions with low phosphorous content

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201962848805P 2019-05-16 2019-05-16
US62/848,805 2019-05-16

Related Child Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2020/032424 Continuation-In-Part WO2020231963A1 (fr) 2019-05-16 2020-05-12 Compositions de verre renforçable à la vapeur à faible teneur en phosphore

Publications (1)

Publication Number Publication Date
WO2020231967A1 true WO2020231967A1 (fr) 2020-11-19

Family

ID=70919166

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2020/032432 WO2020231967A1 (fr) 2019-05-16 2020-05-12 Compositions de verre renforçable à la vapeur à faible teneur en alcali

Country Status (1)

Country Link
WO (1) WO2020231967A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376402B1 (en) * 1999-04-20 2002-04-23 Schott Glas Glasses and glass-ceramics with high specific young's modulus and their applications
US20120277085A1 (en) * 2011-04-28 2012-11-01 Dana Craig Bookbinder Methods for enhancing strength and durability of a glass article
DE202018102537U1 (de) * 2017-12-22 2018-05-22 Schott Ag Einrichtungs- und Ausstattungsgegenstände für Küchen oder Labore mit Leuchtelement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376402B1 (en) * 1999-04-20 2002-04-23 Schott Glas Glasses and glass-ceramics with high specific young's modulus and their applications
US20120277085A1 (en) * 2011-04-28 2012-11-01 Dana Craig Bookbinder Methods for enhancing strength and durability of a glass article
DE202018102537U1 (de) * 2017-12-22 2018-05-22 Schott Ag Einrichtungs- und Ausstattungsgegenstände für Küchen oder Labore mit Leuchtelement

Similar Documents

Publication Publication Date Title
EP3313795B1 (fr) Verre présentant une résistance de surface élevée
EP3400202B1 (fr) Verres en aluminosilicate de lithium pouvant être renforcés chimiquement à résistance intrinsèque aux dommages
US11104602B2 (en) Glass with high surface strength
EP3142975B1 (fr) Objets transparents en vitrocéramique, verres précurseurs en vitrocéramique et leurs procédés de formation
TWI696592B (zh) 基於玻璃的製品與其製造方法及包含其之產品
US20230391667A1 (en) Glass compositions and methods for strengthening via steam treatment
KR102217784B1 (ko) 높은 표면 압축 응력을 가지는 이온 교환 가능 유리
US11767255B2 (en) Glass compositions and methods with steam treatment haze resistance
TW201742841A (zh) 在後離子交換熱處理之後保留高壓縮應力的玻璃組成物
WO2020009957A1 (fr) Articles à base de verre à profils de contrainte améliorés
TW202027986A (zh) 包括含氫玻璃核心層之積層玻璃製品及其形成方法
CN112533881A (zh) 能够实现高压缩应力的玻璃组合物
US20220242777A1 (en) Fusion formable and steam strengthenable glass compositions with platinum compatibility
WO2020231963A1 (fr) Compositions de verre renforçable à la vapeur à faible teneur en phosphore
US20220073426A1 (en) Steam strengthenable glass compositions with low phosphorous content
WO2022169701A1 (fr) Verres à faible module et à capacité d'échange d'ions ayant une aptitude à la fabrication améliorée
WO2020231967A1 (fr) Compositions de verre renforçable à la vapeur à faible teneur en alcali
WO2020102125A1 (fr) Compositions de verre sans alcali pouvant être renforcées à la vapeur d'eau
US20220204386A1 (en) Glasses with modified young's modulus profile

Legal Events

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

Ref document number: 20729476

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20729476

Country of ref document: EP

Kind code of ref document: A1