WO2021030098A1 - Verres revêtus ayant une ténacité efficace à la rupture élevée - Google Patents

Verres revêtus ayant une ténacité efficace à la rupture élevée Download PDF

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Publication number
WO2021030098A1
WO2021030098A1 PCT/US2020/044832 US2020044832W WO2021030098A1 WO 2021030098 A1 WO2021030098 A1 WO 2021030098A1 US 2020044832 W US2020044832 W US 2020044832W WO 2021030098 A1 WO2021030098 A1 WO 2021030098A1
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Prior art keywords
glass
equal
mpa
polymer
less
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PCT/US2020/044832
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English (en)
Inventor
Yunfeng Gu
Jian Luo
Weijun Niu
Rui Zhang
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Corning Incorporated
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Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to CN202080057475.8A priority Critical patent/CN114269707B/zh
Publication of WO2021030098A1 publication Critical patent/WO2021030098A1/fr

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    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins

Definitions

  • the present specification generally relates to increasing fracture toughness of glass articles by applying a polymer coating to glass substrates.
  • cover glass when the associated portable device is dropped on a hard surface.
  • One of the modes is flexure failure, which is caused by bending of the glass when the device is subjected to dynamic load from impact with the hard surface.
  • the other mode is sharp contact failure, which is caused by introduction of damage to the glass surface. Impact of the glass with rough hard surfaces, for example asphalt, granite, etc., can result in sharp indentations in the glass surface. These indentations become failure sites in the glass surface from which cracks may develop and propagate.
  • Embodiment 1 A glass-based article comprising: a glass-based substrate comprising opposing first and second surfaces defining a substrate thickness (t s ), a substantially planar central portion, and a perimeter portion; a polymer coating disposed on at least a portion of at least one of the first or the second surfaces; and an effective fracture toughness that is greater than or equal to 1.25 MPa. m° 5 as measured at room temperature.
  • Embodiment 2 The glass-based article of Embodiment 1, wherein the effective fracture toughness of the glass-based article is measured using a double torsion method at a temperature of 20°C.
  • Embodiment 3 The glass-based article of any preceding Embodiment, wherein the perimeter portion comprises finished edges.
  • Embodiment 4 The glass-based article of any preceding Embodiment, wherein an average thickness of the polymer coating (t c ) is greater than or equal to 5 micrometers and/or is less than or equal to 150 micrometers.
  • Embodiment 5 The glass-based article of the preceding Embodiment, wherein the average thickness of the polymer coating (t c ) is greater than or equal to 10 micrometers and/or is less than or equal to 90 micrometers.
  • MIi first material index
  • ME second material index
  • ME third material index
  • Embodiment 9 The glass-based article of any preceding Embodiment, wherein the polymer coating comprises a polymer selected from the group consisting of: polyimides, polyamides, polysulfones, polybenzimidazoles, silicones, epoxies, acrylates, and combinations thereof.
  • Embodiment 10 The glass-based article of the preceding Embodiment, wherein the polymer coating comprises a polyimide.
  • Embodiment 11 The glass-based article of any preceding Embodiment, wherein the glass-based substrate comprises in mole percent: greater than or equal to 55% to less than or equal to 70% SiCE, and greater than or equal to 10% to less than or equal to 20% AhCE.
  • Embodiment 12 The glass-based article of any preceding Embodiment, wherein the glass-based substrate comprises in mole percent: 55 to 70% SiCE, 10 to 20% AhCE, 0 to 7% P2O5, 0 to 20 % LEO, and 0 to 20% NaiO.
  • Embodiment 13 The glass-based article of any preceding Embodiment, wherein the glass-based substrate comprises in mole percent: 60 to 80% SiCE, 10 to 18% AhCE, 0 to 15% B2O3, 0 to 20 % RO, wherein RO is alkaline earth metal oxides and wherein the substrate is substantially free of alkaline metal oxides.
  • Embodiment 14 The glass-based article of any preceding Embodiment, wherein t s is greater than or equal to 0.02 mm and less than or equal to 1.3 mm.
  • Embodiment 15 A consumer electronic product comprising: 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 disposed over the display; wherein a portion of at least one of the housing and the cover comprises the glass- based article of any preceding Embodiment.
  • Embodiment 16 A process for making a glass-based article based in part on mechanical modeling, the glass-based article comprising an effective fracture toughness (Kc), the process comprising: disposing a polymer precursor on at least a portion of at least one of first and second surfaces of a glass-based substrate that comprises: a substrate thickness (t s ) defined by the first and second surfaces, a glass composition-based fracture toughness (K g ), wherein the polymer precursor delivers a polymer comprising a tensile strength s n in MPa; and curing the polymer precursor to form a polymer coating comprising an average coating thickness (t c ) on the glass-based substrate to form a glass-based article; wherein the Kc is defined by:
  • a is the ratio of coating thickness (t c ) to glass-based substrate thickness (t s )
  • b is the ratio of K m to K g
  • g is the ratio of Young’s Modulus of the polymer (E p ) to Young’s Modulus of the glass (E g )
  • K m is a value of greater than or equal to 0.45 MPa*m° 5 to less than or equal to 10 MPa*m° 5 .
  • Embodiment 17 The process of Embodiment 16, wherein the glass-based article comprises an effective fracture toughness that is greater than or equal to 1.25 MPa.m 05 as measured at room temperature.
  • Embodiment 18 The process of Embodiment 16, wherein the effective fracture toughness is measured using a double torsion method at a temperature of 20°C.
  • MIi first material index
  • ME second material index
  • Embodiment 22 The process of one of Embodiments 16 to 21, wherein the average coating thickness (t c ) is greater than or equal to 5 micrometers and/or is less than or equal to 150 micrometers.
  • Embodiment 23 A method of manufacturing a glass-based article comprising: disposing a polymer precursor on at least a portion of at least one of first and second surfaces of a glass-based substrate that comprises: a substrate thickness (t s ) defined by the first and second surfaces, a substantially planar central portion, and a perimeter portion; and curing the polymer precursor to form a polymer coating on the glass-based substrate to form a glass-based article comprising an effective fracture toughness that is greater than or equal to 1.25 MPa.m 05 as measured at room temperature.
  • Embodiment 24 The method of Embodiment 23, wherein the curing is conducted at a temperature of greater than or equal to 300°C.
  • Embodiment 25 The method of one of Embodiments 23 to 24, wherein applying the polymer precursor comprises applying a solution comprising at least one monomer and at least one solvent.
  • Embodiment 26 The method of one of Embodiments 23 to 25, wherein applying the polymer coating comprises spreading by a doctor blade.
  • Embodiment 27 The method of one of Embodiments 23 to 26, wherein the polymer coating comprises a polymer selected from the group consisting of: polyimides, polyamides, polysulfones, polybenzimidazoles, silicones, epoxies, acrylates, and combinations thereof.
  • Embodiment 28 The method of one of Embodiments 23 to 27, wherein an average thickness of the polymer coating (t c ) is greater than or equal to 5 micrometers and/or is less than or equal to 150 micrometers.
  • FIG. 1 schematically depicts an apparatus for conducting a double torsion (DT) method
  • FIG. 2 is a schematic representation of a cross-section of a glass-based article in accordance with an embodiment
  • FIG. 3A is a plan view of an exemplary electronic device incorporating any of the glass articles disclosed herein;
  • FIG. 3B is a perspective view of the exemplary electronic device of FIG. 3 A;
  • FIG. 4 is a profilometer thickness profile for an exemplary polymer coating
  • FIG. 5 is effective fracture toughness (Kc) MPa*m° 5 by the Double Torsion (DT) method as a function of coating thickness (micrometers) by profilometer for several embodiments; and
  • FIG. 6 is a comparison of Kc versus coating thickness (micrometers) for experimental and modeled fracture toughness.
  • glass-based article and “glass-based substrates” are used to include any object made wholly or partly of glass, including glass-ceramics (including an amorphous phase and a crystalline phase).
  • Laminated glass-based articles include laminates of glass and non-glass materials, laminates of glass and crystalline materials.
  • Glass-based substrates according to one or more embodiments can be selected from soda-lime silicate glass, alkali- alumino silicate glass, alkali-containing borosilicate glass, alkali-containing aluminoborosilicate glass, and alkali-containing glass-ceramics.
  • the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
  • the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.
  • the Kic values measured on glass-based articles are denoted as “K c ” to reflect an effective fracture toughness of the glass articles comprising the combination of a glass-based substrate (having the K g ) and a polymer coating (having a K m ). No ion exchange was conducted on the glass-based substrates herein. Fracture toughness is a measure of a material’s resistance to crack propagation.
  • the DT test apparatus 10 is shown in FIG. 1.
  • the DT configuration comprises a symmetric four-point loading 2 around a notch 4 on one end of a rectangular test plate 6, which produces torsional deformation in the two plate halves, driving the formation of a crack originating from the tip of the notch.
  • the stress intensity factor obtained using this method is independent of crack length in the test specimen.
  • the DT method can be used to test the fracture toughness of thin glass plates for example display glass.
  • the DT method can also be used to evaluate slow crack growth behavior of the material.
  • the DT method is conducted at room temperature, which is nominally in the range of greater than or equal to 20°C to less than or equal to 40°C.
  • Each coated or uncoated sample was prepared by saw-cutting a notch with a length of about 35% of the sample length and pre-cracking the sample with an initial crack length of about 5% to about 30% of the sample length using a slow pre-loading speed of 0.01 mm/minute (min).
  • the pre-cracked sample was then positioned in a loading fixture and placed in a furnace box. The glass sample was allowed to sit in the furnace until reaching thermal equilibrium at the desired temperature.
  • a motor was then triggered to push the loading rod down at a loading speed of 0.06 mm/min with coating under tension.
  • a load vs. time curve was recorded and the peak load was extracted to calculate the fracture toughness (Kic) value using Equation (A):
  • Average coating thickness of the polymer coating was measured by a profilometer, which was a stylus surface profilometer.
  • Glass-based articles herein exhibit high effective fracture toughness (Kc).
  • glass-based articles disclosed herein comprise a glass-based substrate 102 comprising a first surface 104 opposing a second surface 106, defining a substrate thickness (t s ).
  • the substrate has a substantially planar central portion 108 and a perimeter portion 110 suitable for its applications.
  • the perimeter portion 110 may optionally comprise finished edges, obtained by, for example, edge polishing.
  • a polymer coating 112 having an average coating thickness (t c ) is disposed on at least a portion of at least one of the first or the second surfaces, which in FIG. 2 is exemplified in a non-limiting way by a coating on the entirety of first surface 104.
  • the glass-based article comprises an effective fracture toughness of greater than or equal to 1.25 MPa*m° 5 , for example, greater than or equal to 1.50 MPa* m 0 5 , 2.0 MPa* m 0 5 , or 2.5 MPa* m 0 5 ; and/or a fracture toughness of less than or equal to 5.0 MPa* m 0 5 , for example less than or equal to 4.5 MPa* m 0 5 , 4.0 MPa* m 0 5 , 3.5 MPa* m 0 5 , or 3.0 MPa* m° 5 ; and all values and subranges therebetween.
  • the glass-based article comprises a thickness (/A) that is nominally the thickness of the substrate (Is) plus and the thickness of the coating (/ c ).
  • the /A may be in the range of greater than or equal to 0.025 mm to less than or equal to 1.450 mm, and all values and subranges therebetween; and/or the /A may be less than or equal to 1.2 mm, less than or equal to 1.1 mm, less than or equal to 1.0 mm, less than or equal to 0.9 mm, less than or equal to 0.8 mm, less than or equal to 0.7 mm, less than or equal to 0.6 mm, less than or equal to 0.5 mm, less than or equal to 0.4 mm, less than or equal to 0.3 mm, or less than or equal to 0.2 mm.
  • the article has a thickness (/A) in the range of greater than or equal to 0.2 mm and less than or equal to 0.8 mm. In some embodiments, the / A is in the range of greater than or equal to 30 micrometers and less than or equal to 275 micrometers, which may be used in the formation of ultra-thin, bendable glass articles.
  • the glass articles herein offer the advantage of overall improvement in fracture resistance by applying a polymer coating with selected mechanical properties to increase effective fracture toughness of the underlying glass substrate. Increased effective fracture toughness is expected as coating thickness increases and/or as the mechanical properties of the selected polymer material are improved.
  • the coating may be transparent for some applications.
  • the coating may be applied on glass at room temperature and is feasible for scale-up and mass production. Relative to uncoated substrates, the glass articles herein are improved and can provide 1.2 to 4 times or more fracture toughness.
  • the polymer coating on at least a portion of the first and/or second surfaces can have a thickness of greater than or equal to 5 micrometers (pm) and/or of less than or equal to 150 micrometers (pm), for example ranging: from greater than or equal to 10 pm to less than or equal to 125 pm, greater than or equal to 15 pm to less than or equal to 100 pm, greater than or equal to 20 pm to less than or equal to 90 pm, greater than or equal to 30 pm to less than or equal to 80 pm, greater than or equal to 40 pm to less than or equal to 70 pm, greater than or equal to 50 pm to less than or equal to 60 pm, including all ranges and subranges therebetween.
  • pm micrometers
  • the polymer coating may not have a uniform thickness across the area of application and, in such embodiments, the thickness of the coating can correspond to an average thickness across the coated area.
  • the polymer coating can be formed by multiple applications of polymer sub-coatings and, in such embodiments, the thickness of the coating can correspond to an aggregate thickness of all sub-coatings.
  • the polymer coating is disposed over the entirety of only one surface. In some embodiments, the polymer coating is disposed over the entirety of both surfaces. In other embodiments, the polymer coating is disposed partially over only one surface. In other embodiments, the polymer coating is disposed partially over both surfaces. In other embodiments, the polymer coating is disposed over the entirety of one surface and partially over the other surface.
  • a polymer coating disposed partially over a surfaces may cover greater than or equal to 1% and/or less than or equal to 99% of the surface area of the surface, including greater than or equal to 5%, greater than or equal to 10%, greater than or equal to 15%, greater than or equal to 20%, greater than or equal to 25%, greater than or equal to 30%, greater than or equal to 35%, greater than or equal to 40%, greater than or equal to 45%, greater than or equal to 50%, and/or less than or equal to 55%, less than or equal to 60%, less than or equal to 65%, less than or equal to 70%, less than or equal to 75%, less than or equal to 80%, less than or equal to 85%, less than or equal to 90%, or less than or equal to 95%.
  • suitable polymer compositions can be chosen from polyimides, polyamides, polysulfones, polybenzimidazoles, silicones, epoxies, acrylates, and any other polymers that provide effective mechanical properties.
  • the polymer composition may be a thermoplastic polymer.
  • the polymer composition may be a thermally curable polymer, e.g., undergoing a crosslinking reaction at elevated temperatures, for example at temperatures equal to or greater than about 300°C.
  • exemplary compositions suitable for use as a polymer precursor can include polymers that are thermally stable at temperatures equal to or greater than 300°C, for example ranging from about 300°C to about 600°C, from about 325°C to about 550°C, from about 350°C to about 500°C, or from about 400°C to about 450°C, including all ranges and subranges therebetween.
  • thermally stable and variations thereof is intended to denote that the onset point of thermal degradation of the composition, as indicated by the beginning of weight loss.
  • polyimides for example aromatic polyimides
  • aromatic polyimides are thermally curable thermoplastic polymers that are thermally stable at temperatures equal to or greater than about 400°C.
  • Aromatic polyimides may also exhibit at least one of chemical and/or mechanical robustness, high ductility, low CTE, low dielectric constant, and/or low flammability.
  • Two exemplary aromatic polyimides, and their respective crosslinking reactions (A) and (B), are produced below for illustrative purposes.
  • polyamic acid (PAA) is thermally cured to produce polyimide (PI).
  • poly(pyromellitic dianhydride-co-4,4’-oxydianiline), amic acid (PMDA-ODA PAA) is thermally cured to form Kapton®, which is a polyimide available from DuPont that is stable across a wide range of temperatures from -269°C to greater than 400°C.
  • the polymer coating may be applied directly to a glass-based substrate surface and may, as discussed above, be thermally stable at the surface temperature of the substrate.
  • the precursor(s) of a thermally curable polymer for example the polyamic acid precursors depicted above, can be applied to a surface at room temperature or higher, and subsequently cured in situ to form the polymer coating.
  • the surface temperature of the glass-based substrate may be greater than or equal to 20°C and/or less than or equal to 600°C, for example greater than or equal to 25°C, greater than or equal to 50°C, greater than or equal to 75°C, greater than or equal to 100°C, greater than or equal to 125°C, greater than or equal to 150°C, greater than or equal to 175°C, greater than or equal to 200°C, greater than or equal to 225°C, greater than or equal to 250°C, greater than or equal to 275°C, greater than or equal to 300°C, and/or less than or equal to 550°C, less than or equal to 500°C, less than or equal to 450°C, less than or equal to 400°C, less than or equal to 350°C, including all ranges and subranges therebetween.
  • Methods of application of the precursor compositions include spray-coating, casting, and/or printing. Methods of application of the precursor compositions are amenable to mass production. In some embodiments, casting by use of doctor blades at varying gaps (e.g., 5 mil, 10 mil, 25 mil, 50 mil, wherein one mil is one thousandth of an inch or 0.0254 mm) allows for application of coatings having thicknesses of greater than or equal to 5 micrometers. In some embodiments, spray-coating using diluted precursor compositions allows for application of coatings having thicknesses of less than 5 micrometers. Curing can occur in-situ or off-line.
  • gaps e.g., 5 mil, 10 mil, 25 mil, 50 mil, wherein one mil is one thousandth of an inch or 0.0254 mm
  • spray-coating using diluted precursor compositions allows for application of coatings having thicknesses of less than 5 micrometers. Curing can occur in-situ or off-line.
  • Specific examples of glass-based substrates that may be used include but are not limited to a soda-lime silicate glass, an alkali-alumino silicate glass, an alkali-containing borosilicate glass, an alkali-alumino borosilicate glass, an alkali-containing lithium alumino silicate glass, or an alkali-containing phosphate glass.
  • the glass-based substrates have base compositions that may be characterized as ion exchangeable.
  • ion exchangeable means that a substrate comprising the composition is capable of exchanging cations located at or near the surface of the substrate with cations of the same valence that are either larger or smaller in size.
  • the glass-based substrates may be formed from any composition capable of being ion exchanged to form a desired stress profile.
  • the glass-based substrates may be formed from the glass compositions described in U.S. Provisional Application No. 62/591,953 titled “Glasses with Low Excess Modifier Content,” filed November 29, 2017, the entirety of which is incorporated herein by reference.
  • the glass articles may be formed from the glass compositions described in U.S. Provisional Application No. 62/591,958 titled “Ion-Exchangeable Mixed Alkali Aluminosilicate Glasses,” filed November 29, 2017, the entirety of which is incorporated herein by reference.
  • the glass-based substrates may be characterized by the manner in which it may be formed.
  • the glass-based substrates may be characterized as float-formable (i.e., formed by a float process), down-drawable and, in particular, fusion-formable or slot- drawable (i.e., formed by a down draw process for example a fusion draw process or a slot draw process).
  • Some embodiments of the glass-based substrates described herein may be formed by a down-draw process. Down-draw processes produce glass-based substrates having a uniform thickness that possess relatively pristine surfaces. Because the average flexural strength of the glass article is controlled by the amount and size of surface flaws, a pristine surface that has had minimal contact has a higher initial strength. In addition, down drawn glass articles have a very flat, smooth surface that can be used in its final application without costly grinding and polishing.
  • Some embodiments of the glass-based substrates may be described as fusion- formable (i.e., formable using a fusion down-draw process).
  • the fusion process uses a drawing tank that has a channel for accepting molten glass raw material.
  • the channel has weirs that are open at the top along the length of the channel on both sides of the channel.
  • the molten glass overflows the weirs. Due to gravity, the molten glass flows down the outside surfaces of the drawing tank as two flowing glass films. These outside surfaces of the drawing tank extend down and inwardly so that they join at an edge below the drawing tank. The two flowing glass films join at this edge to fuse and form a single flowing glass article.
  • a fusion drawn glass article has a fusion line at its center where the two glass films came together, wherein the fusion line is detectable by microscope.
  • the fusion draw method offers the advantage that, because the two glass films flowing over the channel fuse together, neither of the outside surfaces of the resulting glass article comes in contact with any part of the apparatus. Thus, the surface properties of the fusion drawn glass article are not affected by such contact.
  • Some embodiments of the glass-based substrates described herein may be formed by a slot draw process.
  • the slot draw process is distinct from the fusion draw method.
  • the molten raw material glass is provided to a drawing tank.
  • the bottom of the drawing tank has an open slot with a nozzle that extends the length of the slot.
  • the molten glass flows through the slot and/or nozzle and is drawn downward as a continuous glass article and into an annealing region.
  • Slot-drawn substrates do not have a fusion line.
  • the glass-based substrates described herein may exhibit an amorphous microstructure and may be substantially free of crystals or crystallites.
  • the glass-base substrates exclude glass-ceramic materials in some embodiments.
  • the concentration of constituent components are given in mole percent (mol%) on an oxide basis, unless otherwise specified. It should be understood that any of the variously recited ranges of one component may be individually combined with any of the variously recited ranges for any other component.
  • the glass-based substrates comprise a glass composition- based fracture toughness (K g ) of greater than or equal to 0.8 MPa*m° 5 , for example, greater than or equal to 0.85 MPa* m 0 5 , 0.9 MPa* m 05 , or 0.95 MPa* m 05 ; and/or a fracture toughness of less than or equal to 1.25 MPa* m° 5 , for example less than or equal to 1.2 MPa* m 05 , 1.15 MPa* m 0 5 , 1.1 MPa* m 0 5 , or 1.0 MPa* m 0 5 ; and all values and subranges therebetween.
  • K g glass composition- based fracture toughness
  • the glass-based substrate comprises t s in the range of greater than or equal to 0.02 mm to less than or equal to 1.3 mm, and all values and subranges therebetween; and/or t s may be less than or equal to 1.2 mm, less than or equal to 1.1, less than or equal to 1.0 mm, less than or equal to 0.9 mm, less than or equal to 0.8 mm, less than or equal to 0.7 mm, less than or equal to 0.6 mm, less than or equal to 0.5 mm, less than or equal to 0.4 mm, less than or equal to 0.3 mm, or less than or equal to 0.2 mm.
  • the substrate is in the range of greater than or equal to 0.2 mm and less than or equal to 0.8 mm. In some embodiments, the substrate has a thickness in the range of greater than or equal to 25 micrometers and less than or equal to 125 micrometers, which may be used in the formation of ultra-thin, bendable glass articles.
  • the glass-based substrate comprises in mole percent: greater than or equal to 55% to less than or equal to 70% S1O2, and greater than or equal to 10% to less than or equal to 20% AI2O3. In some embodiments, the glass-based substrate comprises in mole percent: 55 to 70% S1O2, 10 to 20% AI2O3, 0 to 7% P2O5, 0 to 20 % LhO, and 0 to 20% Na 2 0. In some embodiments, the glass-based substrate comprises in mole percent: 60 to 80% S1O2, 10 to 18% AI2O3, 0 to 15% B2O3, 0 to 20 % RO, wherein RO is alkaline earth metal oxides and wherein the substrate is substantially free of alkaline metal oxides.
  • the glass-based substrate is not exposed to any IOX treatment prior to coating with the polymer precursor.
  • optional chemical strengthening of glass substrates having base compositions is done by placing the ion-exchangeable glass substrates in a molten bath containing cations (e.g., K+, Na+, Ag+, etc.) that diffuse into the glass while the smaller alkali ions (e.g., Na+, Li+) of the glass diffuse out into the molten bath.
  • cations e.g., K+, Na+, Ag+, etc.
  • the smaller alkali ions e.g., Na+, Li+
  • ion exchange processes they may independently be a thermal- diffusion process or an electro-diffusion process.
  • 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. Pat. No. 8,561,429, by Douglas C. Allan et al., issued on Oct. 22, 2013, entitled “Glass with Compressive Surface for Consumer Applications,” and claiming 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. Pat. No. 8,312,739, by Christopher M.
  • a composition at the surface of a glass article may be different than the composition of the as-formed glass article (i.e., the glass article before it undergoes an ion exchange process).
  • the glass composition at or near the center of the depth of the glass article will, in embodiments, still have the composition of the as-formed glass article.
  • the glass-based articles disclosed herein may be incorporated into another article for example an article with a display (or display articles) (e.g., consumer electronics, including mobile phones, tablets, watches, computers, navigation systems, and the like), architectural articles, transportation articles (e.g., automobiles, trains, aircraft, sea craft, etc.), appliance articles, or any article that would benefit from some transparency, scratch- resistance, abrasion resistance or a combination thereof.
  • a display or display articles
  • FIGS. 3A and 3B An exemplary article incorporating any of the glass articles disclosed herein is shown in FIGS. 3A and 3B. Specifically, FIGS.
  • FIG. 3 A and 3B 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.
  • the cover substrate 212 may include any of the glass articles disclosed herein.
  • K g is the fracture toughness of the glass-based substrate
  • a is the ratio of coating thickness (t c ) to glass-based substrate thickness (t s )
  • b is the ratio of K m to K g
  • g is the ratio of Young’s Modulus of the polymer (E p ) to Young’s Modulus of the glass (E g ).
  • K m is the effective fracture toughness of the polymer at the micro-scale.
  • K m was obtained by fitting the experimental data in accordance with Equation (I). It was found that K m was in the range of 1.45 to 4.23 MPa*m 0 5 in order to fit the data.
  • K m could be in the range of greater than or equal to 0.45 MPa*m° 5 to less than or equal to 10 MPa*m° 5 .
  • Equation (II) is informative to show that K m is proportional to the polymer’s yield strength (s n ).
  • the Kc value may be increased by: increasing coating thickness (thus a) and/or increasing polymer yield strength o y or/and increasing stretching distance r p.
  • a material selection index (MI) identifies a suitable coating polymer to achieve a maximum effective fracture toughness improvement based on polymer characteristics of yield (or tensile) strength o y and elongation Q.
  • ASTM D882-02 can be used to measure tensile strength and elongation.
  • effective fracture toughness of a glass-based article may be modeled for a starting glass-based substrate having a glass composition-based fracture toughness (K g ) (MPa*m° 5 ) by selecting a polymer having a tensile strength s n (MPa) and elongation Q and optionally having a Young’s Modulus E p.
  • K g glass composition-based fracture toughness
  • MIi first material index
  • Suitable ME values are greater than or equal to 35 MPa and/or less than or equal to 100 MPa, including greater than or equal to 39 MPa and/or less than or equal to 95 MPa, including greater than or equal to 39 MPa and/or less than or equal to 95 MPa, including greater than or equal to 45 MPa and/or less than or equal to 90 MPa, including greater than or equal to 50 MPa and/or less than or equal to 85 MPa, including greater than or equal to 55 MPa and/or less than or equal to 80 MPa, including greater than or equal to 60 MPa and/or less than or equal to 75 MPa, including greater than or equal to 65 MPa and/or less than or equal to 70 MPa, and including all values and subranges therebetween.
  • Suitable MI2 values are greater than or equal to 12 MPa and/or less than or equal to 75 MPa, including greater than or equal to 17 MPa and/or less than or equal to 60 MPa, including greater than or equal to 20 MPa and/or less than or equal to 55 MPa, including greater than or equal to 25 MPa and/or less than or equal to 50 MPa, including greater than or equal to 30 MPa and/or less than or equal to 45 MPa, including greater than or equal to 35 MPa and/or less than or equal to 40 MPa, including all values and subranges therebetween.
  • a third material index is MI3:
  • Suitable MI3 values are greater than or equal to 0.5 MPa and/or less than or equal to 5 MPa, including greater than or equal to 0.8 MPa and/or less than or equal to 2.75 MPa, including greater than or equal to 0.9 MPa and/or less than or equal to 2.5 MPa, including greater than or equal to 1.0 MPa and/or less than or equal to 2.25 MPa, including greater than or equal to 1.25 MPa and/or less than or equal to 2.00 MPa, including greater than or equal to 1.50 MPa and/or less than or equal to 1.75 MPa, including all values and subranges therebetween.
  • Glass substrates were obtained comprising a composition according to Composition A, Composition B, or Composition C.
  • Glass Composition A was a soda-lime silicate composition nominally comprising ( ⁇ 0.75 wt%): 73.5 wt% Si0 2 , 1.7 wt% AI2O3, 12.28 wt% Na 2 0, 0.24 wt% K 2 0, 4.5 wt% MgO, 7.45 wt% CaO, 0.017 wt% Zr0 2 , 0.032 wt% Ti0 2 , 0.002 wt% Sn0 2 , 0.093 wt% Fe 2 C> 3 , 0.001 HfO l , 0.028 wt% Cl oxides, and 0.203 wt% SO3.
  • Glass Composition B was a lithium aluminoborosilicate composition nominally comprising ( ⁇ 0.75 mol%): 63 mol% SiCh, 7 mol% B2O3, 15 mol% AI2O3, 4 mol% Na 2 0, 7 mol% L12O, 1 MgO, 0.02 mol% Fe 2 0 3 , 1 mol% SrO, 2 mol% CaO and 0.07 mol% Sn0 2.
  • Glass Composition C was an aluminosilicate composition (lithium-free) nominally comprising ( ⁇ 0.75 mol%): 57 mol% S1O2, 16 mol% AI2O3, 17 mol% Na 2 0, 3 MgO, 0.003 mol% T1O2, 0.07 mol% Sn0 2 , and 7 mol% P2O5.
  • Glass Composition C has a Young’s Modulus (Eg) of 65 GPa.
  • Polymer precursor compositions for forming polymer coatings were obtained comprising compositions according to Precursor Composition I, Precursor Composition II, and Precursor Composition III.
  • Precursor Composition I is a polyimide precursor sold under the tradename Kapton® by DuPont, which is a solution of 15.0 wt.% poly(pyromellitic dianhydride-co-4,4’- oxydianiline) amic acid (PMDA-ODA PAA) in 85.0 wt.% 1-m ethyl -2-pyrrolidinone (NMP).
  • Kapton® poly(pyromellitic dianhydride-co-4,4’- oxydianiline) amic acid
  • NMP 1-m ethyl -2-pyrrolidinone
  • Precursor Composition II is a polyimide precursor sold under the tradename VT300A-G008 PI from FlexUp Technologies Co., which contains 5 wt.%-20 wt.% of modified polyimide and 80-95 wt.% of gamma-Butyrolactone (GBL). The resulting coatings were transparent.
  • Precursor Composition III is a polyimide precursor sold under the tradename PI- 2574 from HD MicroSystems, which includes an adhesion promotor.
  • Table 1 compares the tensile strength s and elongation Q of these three different types of polyimide coating material.
  • the MIi material index is calculated by s* Q 05 shown in the table.
  • the MI2 material index is calculated by s* Q shown in the table.
  • the MI3 material index is calculated by s 2 * Q/E r shown in the table.
  • the properties of Precursor Composition I coating were measured by ASTM D882-02.
  • the properties of Precursor Compositions II and III are as reported by the supplier.
  • the material index can be used to rank the resulting composite fracture toughness. As will be shown in the following Example 5, Precursor Composition III Polymer has the highest MIi, and correspondingly generated a glass article having the highest effective fracture toughness.
  • glass articles were made from substrates having a dimension of 20Wx40Lx0.7T mm, each of which was coated on one side at room temperature (e.g. 20-40°C) with one of the precursor compositions.
  • the precursor composition was cast at room temperature (20-40°C) by using a doctor blade, utilizing a gap ranging from about 5 mil. Thereafter, the samples were thermally cured in an oven (in air) at 300°C for 1 hour.
  • NMP was further added to the precursor solution to form a diluted solution for application.
  • the glass substrate was heated to 300-400°C before application of the solution.
  • the diluted solution was applied by spraying with use of an air brush under a pressure of 15-30 psi. In-situ curing occurred for 5- 15 minutes at 300-400°C.
  • the glass articles including a coating according to Table 2 were analyzed for effective fracture toughness (Kc) by the Double Torsion (DT) method defined herein at room temperature, and for average coating thickness (t c ) measured by a profilometer.
  • Kc effective fracture toughness
  • DT Double Torsion
  • t c average coating thickness
  • Examples 4-6 show the impact of polyimide coating with different mechanical properties as described in Table 1 on the effective fracture toughness of the resulting glass articles.
  • Table 4 summarizes the glass composition and precursor compositions.
  • the glass articles of Glass Composition C and polymer delivered by Precursor Composition III showed the best effective fracture toughness.
  • the effective fracture toughness (Kc) at room temperature was 4.05 MPa*m° 5 and at a thickness of 81 micrometers, the effective fracture toughness (Kc) at room temperature was 4.7 MPa*m° 5
  • K c K g * (l + ab 2 /g)
  • K g is a glass composition-based fracture toughness at a temperature
  • a is the ratio of coating thickness (t c ) to glass-based substrate thickness (t s )
  • b is the ratio of K m to K g
  • g is the ratio of Young’s Modulus of the polymer (E p ) to Young’s Modulus of the glass (Eg).
  • FIG. 6 The comparison of Kc versus coating thickness (micrometers) for experimental and modeled fracture toughness of Examples 4-6 is shown in FIG. 6, which includes the data of FIG. 5.
  • “Comp 1” denotes Precursor Composition I
  • “Comp 2” denotes Precursor Composition II
  • “Comp 3” denotes Precursor Composition III.
  • E g was 65 GPa for Examples 4-6.
  • K g was 0.5 MPa*m 05 and K m was 1.45 MPa*m 05 for Example 4.
  • K g was 0.599 MPa*m° 5 and K m was 2.35 MPa*m° 5 for Example 5.
  • K g was 0.599 MPa*m° 5 and K m was 4.23 MPa*m° 5 for Example 6.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Glass Compositions (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne des articles à base de verre présentant une ténacité efficace à la rupture élevée. Les articles à base de verre comprennent : un substrat à base de verre comprenant des première et seconde surfaces opposées définissant une épaisseur de substrat (ts), une partie centrale sensiblement plane et une partie périphérique ; un revêtement polymère disposé sur au moins une partie de la première et/ou de la seconde surface ; et une ténacité efficace à la rupture qui est supérieure ou égale à 1,25 MPa.m0,5 telle que mesurée à température ambiante.
PCT/US2020/044832 2019-08-12 2020-08-04 Verres revêtus ayant une ténacité efficace à la rupture élevée WO2021030098A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8312739B2 (en) 2008-07-29 2012-11-20 Corning Incorporated Dual stage ion exchange for chemical strengthening of glass
US8561429B2 (en) 2008-07-11 2013-10-22 Corning Incorporated Glass with compressive surface for consumer applications
EP3330235A1 (fr) * 2016-12-02 2018-06-06 Samsung Display Co., Ltd. Article de verre flexible ayant une courbure de flexion ré?duite et son procé?dé? de fabrication
WO2019100049A1 (fr) * 2017-11-20 2019-05-23 Corning Incorporated Procédé pour l'augmentation de la ténacité à la rupture de rubans de verre

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104271346B (zh) * 2012-02-28 2017-10-13 康宁股份有限公司 具有低摩擦涂层的玻璃制品
EP3872047A1 (fr) * 2012-10-12 2021-09-01 Corning Incorporated Articles ayant une résistance conservée
CN107848876A (zh) * 2015-04-30 2018-03-27 康宁股份有限公司 具有中等粘附性、保留强度和光学透射率的膜的玻璃制品
EP3402667A1 (fr) * 2016-01-15 2018-11-21 Corning Incorporated Ensembles dispositif électronique pliable et leurs éléments couvercle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8561429B2 (en) 2008-07-11 2013-10-22 Corning Incorporated Glass with compressive surface for consumer applications
US8312739B2 (en) 2008-07-29 2012-11-20 Corning Incorporated Dual stage ion exchange for chemical strengthening of glass
EP3330235A1 (fr) * 2016-12-02 2018-06-06 Samsung Display Co., Ltd. Article de verre flexible ayant une courbure de flexion ré?duite et son procé?dé? de fabrication
WO2019100049A1 (fr) * 2017-11-20 2019-05-23 Corning Incorporated Procédé pour l'augmentation de la ténacité à la rupture de rubans de verre

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