WO2020123226A1 - Feuilles de verre à résistance de bord améliorée et leurs procédés de production - Google Patents

Feuilles de verre à résistance de bord améliorée et leurs procédés de production Download PDF

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Publication number
WO2020123226A1
WO2020123226A1 PCT/US2019/064430 US2019064430W WO2020123226A1 WO 2020123226 A1 WO2020123226 A1 WO 2020123226A1 US 2019064430 W US2019064430 W US 2019064430W WO 2020123226 A1 WO2020123226 A1 WO 2020123226A1
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WO
WIPO (PCT)
Prior art keywords
edge surface
edge
glass
plasma
millimeters
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Application number
PCT/US2019/064430
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English (en)
Inventor
Kaveh Adib
Robert Alan Bellman
Ya-Huei Chang
Jiangwei Feng
James Joseph Price
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 WO2020123226A1 publication Critical patent/WO2020123226A1/fr

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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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0005—Other surface treatment of glass not in the form of fibres or filaments by irradiation
    • C03C23/006—Other surface treatment of glass not in the form of fibres or filaments by irradiation by plasma or corona discharge
    • 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
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz

Definitions

  • the present disclosure relates generally to glass sheets with improved edge quality and methods for producing the same and more particularly to glass sheets with greater edge strength and methods for producing the same.
  • glass articles such as glass sheets for display applications, including televisions and hand held devices, such as telephones and tablets
  • processing steps can involve glass particle generation, such as when glass sheets are separated from a glass ribbon as well as when the glass sheets are subject to finishing processes, such as edge grinding and polishing.
  • Such processing steps can also introduce surface flaws and defects along edges of the glass articles.
  • Such flaws and defects can, among other things, adversely affect the mechanical strength and failure resistance of the glass articles.
  • Embodiments disclosed herein include a method for manufacturing a glass article.
  • the method includes forming the glass article, wherein the glass article includes a first major surface, a second major surface parallel to the first major surface, and an edge surface extending between the first major surface and the second major surface in a perpendicular direction to the first and second major surfaces. A distance of the extension direction of the edge between the first and second major surfaces is less than or equal to about 0.5 millimeters.
  • the method also includes directing a flow of plasma toward the edge surface.
  • the plasma includes at least one high thermal conductivity component.
  • An edge strength of the glass article subsequent to directing a flow of plasma toward the edge surface, as measured by the four point bend test, is at least about 250 MPa.
  • Embodiments disclosed herein also include a method for treating a glass article.
  • the glass article includes a first major surface, a second major surface parallel to the first major surface, and an edge surface extending between the first major surface and the second major surface in a perpendicular direction to the first and second major surfaces. A distance of the extension direction of the edge between the first and second major surfaces is less than or equal to about 0.5 millimeters.
  • the method also includes directing a flow of plasma toward the edge surface.
  • the plasma includes at least one high thermal conductivity component.
  • An edge strength of the glass article subsequent to directing a flow of plasma toward the edge surface, as measured by the four point bend test, is at least about 250 MPa.
  • Embodiments disclosed herein also include a glass article.
  • the glass article includes a first major surface, a second major surface parallel to the first major surface, and an edge surface extending between the first major surface and the second major surface in a perpendicular direction to the first and second major surfaces.
  • a distance of the extension direction of the edge between the first and second major surfaces is less than or equal to about 0.5 millimeters.
  • An edge strength of the glass article, as measured by the four point bend test, is at least about 250 MPa.
  • FIG. 1 is a schematic view of an example fusion down draw glass making apparatus and process
  • FIG. 2 is a schematic side view of a stage of an example glass sheet separation process
  • FIG. 3 is a schematic side view of another stage of an example glass sheet separation process
  • FIG. 4 is a schematic side view of yet another stage of an example glass sheet separation process
  • FIG. 5 is a schematic side view of still yet another stage of an example glass sheet separation process
  • FIG. 6 is an perspective view of a glass sheet
  • FIG. 7 is a perspective view of at least a portion of a beveling process of an edge surface of a glass sheet
  • FIG. 8 is a perspective view of at least a portion of an edge treatment process with a plasma jet
  • FIGS. 9A and 9B are, respectively, charts showing edge strength and edge impact strength of glass samples tested according to methods disclosed herein;
  • FIG. 10 is a chart showing edge strength of glass samples tested according to methods disclosed herein;
  • FIGS. 11A and 1 IB are, respectively, charts showing edge strength and edge impact strength of glass samples tested according to methods disclosed herein;
  • FIG. 12 is a chart showing edge strength of glass samples tested according to methods disclosed herein.
  • Ranges can be expressed herein as from“about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, for example by use of the antecedent“about,” it will be understood that the particular value forms another embodiment It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • high thermal conductivity component refers to a component having a thermal conductivity at 25°C of at least 0.1 W/m-K.
  • plasma refers to an electrically neutral ionized gas comprising positive ions and unbound electrons.
  • the term“atmospheric pressure plasma jet” refers to a flow of plasma discharged from an aperture, wherein the plasma pressure approximately matches that of the surrounding atmosphere, including conditions wherein the plasma pressure is between 90% and 110% of 101.325 kilopascals (standard atmospheric pressure).
  • the term“particles” refers to any type of particles that can be present on a surface, such as glass particles and dust particles.
  • edge strength refers to edge strength at which 10% of samples would be expected to fail using the glass flexure fixture four point test set forth in Suresh T. Gulati and John D. Helfinstine,“Edge Strength Testing of Thin Glasses”, International Journal of Applied Glass Science 2 [1] 39— 46 (2011).
  • two point bend test refers to the edge strength test method set forth in Suresh T. Gulati, Jamie Westbrook, Stephen Carley, Hemanth Vepakomma and Toshihiko Ono,“45.2: Two point bending of thin glass substrates”, SID Conf, 652-654 (201 1)
  • edge impact strength refers to the greatest height at which a 172 gram pendulum can be dropped on an edge of a glass sample with an observed impact diameter of less than 1 millimeter.
  • the glass manufacturing apparatus 10 can comprise a glass melting furnace 12 that can include a melting vessel 14.
  • glass melting furnace 12 can optionally include one or more additional components such as heating elements (e.g., combustion burners or electrodes) that heat raw materials and convert the raw materials into molten glass.
  • heating elements e.g., combustion burners or electrodes
  • glass melting furnace 12 may include thermal management devices (e g., insulation components) that reduce heat lost from a vicinity of the melting vessel.
  • glass melting furnace 12 may include electronic devices and/or electromechanical devices that facilitate melting of the raw materials into a glass melt.
  • glass melting furnace 12 may include support structures (e.g., support chassis, support member, etc.) or other components.
  • Glass melting vessel 14 is typically comprised of refractory material, such as a refractory ceramic material, for example a refractory ceramic material comprising alumina or zirconia. In some examples glass melting vessel 14 may be constructed from refractory ceramic bricks. Specific embodiments of glass melting vessel 14 will be described in more detail below.
  • the glass melting furnace may be incorporated as a component of a glass manufacturing apparatus to fabricate a glass substrate, for example a glass ribbon of a continuous length.
  • the glass melting furnace of the disclosure may be incorporated as a component of a glass manufacturing apparatus comprising a slot draw apparatus, a float bath apparatus, a down-draw apparatus such as a fusion process, an up- draw apparatus, a press-rolling apparatus, a tube drawing apparatus or any other glass manufacturing apparatus that would benefit from the aspects disclosed herein.
  • FIG. 1 schematically illustrates glass melting furnace 12 as a component of a fusion down-draw glass manufacturing apparatus 10 for fusion drawing a glass ribbon for subsequent processing into individual glass sheets.
  • the glass manufacturing apparatus 10 can optionally include an upstream glass manufacturing apparatus 16 that is positioned upstream relative to glass melting vessel 14. In some examples, a portion of, or the entire upstream glass manufacturing apparatus 16, may be incorporated as part of the glass melting furnace 12
  • the upstream glass manufacturing apparatus 16 can include a storage bin 18, a raw material delivery device 20 and a motor 22 connected to the raw material delivery device.
  • Storage bin 18 may be configured to store a quantity of raw materials 24 that can be fed into melting vessel 14 of glass melting furnace 12, as indicated by arrow 26.
  • Raw materials 24 typically comprise one or more glass forming metal oxides and one or more modifying agents.
  • raw material delivery device 20 can be powered by motor 22 such that raw material delivery device 20 delivers a predetermined amount of raw materials 24 from the storage bin 18 to melting vessel 14.
  • motor 22 can power raw material delivery device 20 to introduce raw materials 24 at a controlled rate based on a level of molten glass sensed downstream from melting vessel 14.
  • Raw materials 24 within melting vessel 14 can thereafter be heated to form molten glass 28.
  • Glass manufacturing apparatus 10 can also optionally include a downstream glass manufacturing apparatus 30 positioned downstream relative to glass melting furnace 12.
  • a portion of downstream glass manufacturing apparatus 30 may be incorporated as part of glass melting furnace 12.
  • first connecting conduit 32 discussed below, or other portions of the downstream glass manufacturing apparatus 30, may be incorporated as part of glass melting furnace 12.
  • Elements of the downstream glass manufacturing apparatus, including first connecting conduit 32 may be formed from a precious metal. Suitable precious metals include platinum group metals selected from the group of metals consisting of platinum, iridium, rhodium, osmium, ruthenium and palladium, or alloys thereof.
  • downstream components of the glass manufacturing apparatus may be formed from a platinum -rhodium alloy including from about 70 to about 90% by weight platinum and about 10% to about 30% by weight rhodium.
  • platinum -rhodium alloy including from about 70 to about 90% by weight platinum and about 10% to about 30% by weight rhodium.
  • suitable metals can include molybdenum, palladium, rhenium, tantalum, titanium, tungsten and alloys thereof.
  • Downstream glass manufacturing apparatus 30 can include a first conditioning (i.e., processing) vessel, such as fining vessel 34, located downstream from melting vessel 14 and coupled to melting vessel 14 by way of the above-referenced first connecting conduit 32.
  • a first conditioning (i.e., processing) vessel such as fining vessel 34
  • molten glass 28 may be gravity fed from melting vessel 14 to fining vessel 34 by way of first connecting conduit 32.
  • gravity may cause molten glass 28 to pass through an interior pathway of first connecting conduit 32 from melting vessel 14 to fining vessel 34.
  • other conditioning vessels may be positioned downstream of melting vessel 14, for example between melting vessel 14 and fining vessel 34.
  • a conditioning vessel may be employed between the melting vessel and the fining vessel wherein molten glass from a primary melting vessel is further heated to continue the melting process, or cooled to a temperature lower than the temperature of the molten glass in the melting vessel before entering the fining vessel.
  • Bubbles may be removed from molten glass 28 within fining vessel 34 by various techniques.
  • raw materials 24 may include multivalent compounds (i.e. fining agents) such as tin oxide that, when heated, undergo a chemical reduction reaction and release oxygen.
  • suitable fining agents include without limitation arsenic, antimony, iron and cerium.
  • Fining vessel 34 is heated to a temperature greater than the melting vessel temperature, thereby heating the molten glass and the fining agent.
  • Oxygen bubbles produced by the temperature-induced chemical reduction of the fining agent(s) rise through the molten glass within the fining vessel, wherein gases in the molten glass produced in the melting furnace can diffuse or coalesce into the oxygen bubbles produced by the fining agent.
  • the enlarged gas bubbles can then rise to a free surface of the molten glass in the fining vessel and thereafter be vented out of the fining vessel.
  • the oxygen bubbles can further induce mechanical mixing of the molten glass in the fining vessel.
  • Downstream glass manufacturing apparatus 30 can further include another conditioning vessel such as a mixing vessel 36 for mixing the molten glass.
  • Mixing vessel 36 may be located downstream from the fining vessel 34.
  • Mixing vessel 36 can be used to provide a homogenous glass melt composition, thereby reducing cords of chemical or thermal inhomogeneity that may otherwise exist within the fined molten glass exiting the fining vessel.
  • fining vessel 34 may be coupled to mixing vessel 36 by way of a second connecting conduit 38.
  • molten glass 28 may be gravity fed from the fining vessel 34 to mixing vessel 36 by way of second connecting conduit 38. For instance, gravity may cause molten glass 28 to pass through an interior pathway of second connecting conduit 38 from fining vessel 34 to mixing vessel 36.
  • mixing vessel 36 is shown downstream of fining vessel 34, mixing vessel 36 may be positioned upstream from fining vessel 34.
  • downstream glass manufacturing apparatus 30 may include multiple mixing vessels, for example a mixing vessel upstream from fining vessel 34 and a mixing vessel downstream from fining vessel 34. These multiple mixing vessels may be of the same design, or they may be of different designs.
  • Downstream glass manufacturing apparatus 30 can further include another conditioning vessel such as delivery vessel 40 that may be located downstream from mixing vessel 36.
  • Delivery vessel 40 may condition molten glass 28 to be fed into a downstream forming device.
  • delivery vessel 40 can act as an accumulator and/or flow controller to adjust and/or provide a consistent flow of molten glass 28 to forming body 42 by way of exit conduit 44.
  • mixing vessel 36 may be coupled to delivery vessel 40 by way of third connecting conduit 46.
  • molten glass 28 may be gravity fed from mixing vessel 36 to delivery vessel 40 by way of third connecting conduit 46.
  • gravity may drive molten glass 28 through an interior pathway of third connecting conduit 46 from mixing vessel 36 to delivery vessel 40.
  • Downstream glass manufacturing apparatus 30 can further include forming apparatus 48 comprising the above-referenced forming body 42 and inlet conduit 50.
  • Exit conduit 44 can be positioned to deliver molten glass 28 from delivery vessel 40 to inlet conduit 50 of forming apparatus 48.
  • exit conduit 44 may be nested within and spaced apart from an inner surface of inlet conduit 50, thereby providing a free surface of molten glass positioned between the outer surface of exit conduit 44 and the inner surface of inlet conduit 50.
  • Forming body 42 in a fusion down draw glass making apparatus can comprise a trough 52 positioned in an upper surface of the forming body and converging forming surfaces 54 that converge in a draw direction along a bottom edge 56 of the forming body.
  • Molten glass delivered to the forming body trough via delivery vessel 40, exit conduit 44 and inlet conduit 50 overflows side walls of the trough and descends along the converging forming surfaces 54 as separate flows of molten glass.
  • the separate flows of molten glass join below and along bottom edge 56 to produce a single ribbon of glass 58 that is drawn in a draw or flow direction 60 from bottom edge 56 by applying tension to the glass ribbon, such as by gravity, edge rolls 72 and pulling rolls 82, to control the dimensions of the glass ribbon as the glass cools and a viscosity of the glass increases. Accordingly, glass ribbon 58 goes through a visco-elastic transition and acquires mechanical properties that give the glass ribbon 58 stable dimensional characteristics.
  • Glass ribbon 58 may, in some embodiments, be separated into individual glass sheets 62 by a glass separation apparatus 100 in an elastic region of the glass ribbon.
  • a robot 64 may then transfer the individual glass sheets 62 to a conveyor system using gripping tool 65, whereupon the individual glass sheets may be further processed.
  • FIG 2 shows a schematic side view of a stage of an example glass sheet separation process.
  • glass separation apparatus 100 includes scoring mechanism 102 and nosing 104, wherein scoring mechanism 102 and nosing 104 are positioned on opposite sides of glass ribbon 58.
  • scoring mechanism 102 moves across the glass ribbon 58 in the widthwise direction (in a direction into and out of the plane of FIG. 2 as shown) and imparts a widthwise score line across the glass ribbon 58.
  • gripping tool 65 has not yet engaged glass ribbon 58, although engagement while scoring is also known in the art and commonly practiced.
  • scoring mechanism 102 is shown in FIG.2 as a mechanical scoring mechanism, such as a mechanism comprising a score wheel, it is to be understood that embodiments herein include other types of scoring mechanism, such as, for example, laser scoring mechanisms.
  • scoring mechanism 102 comprises a score wheel
  • the score wheel may be mounted on a ball bearing pivot which is secured to a shaft which is in turn mounted on a linear actuator (air cylinder) that moves the score wheel towards the glass ribbon 58 so it can be drawn across and score a side of the ribbon.
  • Nosing 104 may comprise a resilient material, such as silicon mbber.
  • nosing 104 may be a conformable nosing that has a bowed shape of the glass ribbon 58 as disclosed, for example, in U.S. patent no. 8,051,681, the entire disclosure of which is incorporated by reference.
  • Nosing 104 may also be in fluid communication with a vacuum source (not shown) to enhance engagement between the glass ribbon 58 and the nosing, as disclosed, for example, in U.S. patent no. 8,245,539, the entire disclosure of which is incorporated herein by reference.
  • FIG. 3 shows a schematic side view of another stage of an example glass sheet separation process wherein scoring mechanism 102 has disengaged glass ribbon 58 and gripping tool 65, including gripping elements 66, is actuated by robot 64 to engage glass ribbon 58.
  • Gripping elements 66 may, for example, comprise a resilient material, such as silicone rubber, and may, in certain exemplary embodiments, comprise a cup-shaped resilient material that may be in fluid communication with a vacuum source (not shown) to enhance engagement between the glass ribbon 58 and the gripping elements 66 (gripping elements comprising cup-shaped material in fluid communication with a vacuum source are hereinafter referred to as vacuum cups).
  • FIG. 4 shows a schematic side view of yet another stage of an example glass sheet separation process wherein gripping tool 65 has been further actuated by robot 64, thereby imparting a pulling force that is sufficient to begin to bend the portion of glass ribbon 58 extending below nosing 104 away from the draw or flow direction 60.
  • the pulling force is not yet sufficient to substantially separate the portion of the glass ribbon 58 extending below nosing 104 from the rest of the glass ribbon 58.
  • FIG. 5 shows a schematic side view of still yet another stage of an example glass sheet separation process wherein gripping tool 65 has been further actuated by robot 65, thereby imparting a pulling force that is sufficient to separate the portion of the glass ribbon 58 extending below nosing 104 (i.e., glass sheet) from the rest of the glass ribbon 58.
  • the glass sheet may then be transferred to, for example, a conveyor system for further processing.
  • FIG. 6 shows a perspective view of a glass sheet 62 having a first major surface 162, a second major surface 164 extending in a generally parallel direction to the first major surface 162 (on the opposite side of the glass sheet 62 as the first major surface) and an edge surface 166 extending between the first major surface 162 and the second major surface 164 and extending in a generally perpendicular direction to the first and second major surfaces 162, 164.
  • FIG. 7 shows a perspective view of at least a portion of a beveling process of an edge surface 166 of a glass sheet 62.
  • beveling process includes applying a grinding wheel 200 to edge surface 166, wherein the grinding wheel 200 moves relative to edge surface 166 in the direction indicated by arrow 300.
  • Beveling process may further include applying at least one polishing wheel (not shown) to edge surface 166.
  • Such beveling process can lead to the presence of numerous glass particles, as well as surface and sub surface damage (i.e., irregular topography), on edge surface 166.
  • Downstream processing of glass sheet 62 may involve application of mechanical or chemical treatments on edge surfaces 166, which can result in additional particle generation due to the presence of irregular edge surface topography. Such particles may migrate to at least one surface of glass sheets 62. Accordingly, embodiments disclosed herein include those in which irregular edge surface topography is removed, while at the same time removing and/or reducing particles present on the edge surfaces 166 (i.e.,“edge particles”) as well as removing reaction by-products that may be formed upon removal of the irregular edge surface topography.
  • FIG. 8 shows a perspective view of at least a portion of a treatment process of an edge surface 166 of a glass sheet 62 with a plasma jet 402.
  • treatment process includes directing a flow of plasma, via plasma jet 402, toward edge surface 166, wherein plasma jet head 400 moves relative to edge surface 166 in the direction indicated by arrow 500.
  • plasma jet 402 comprises an atmospheric pressure plasma jet.
  • Embodiments disclosed herein include those in which the plasma comprises at least one high thermal conductivity component.
  • embodiments disclosed herein include those in which the plasma comprises at least one component selected from hydrogen and helium.
  • Plasma jet 402 can be directed toward edge surface 166 under a variety of processing parameters.
  • plasma jet 402 can be generated at a power of at least about 300 watts, such as a power of at least about 500 watts, including a power of from about 300 watts to about 800 watts and further including a power of from about 500 watts to about 800 watts.
  • plasma jet 402 is generated via a direct current high voltage discharge that generates a pulsed electric arc, such as a voltage discharge of at least about 5 kV, such as from about 5 kV to about 15 kV.
  • a direct current high voltage discharge that generates a pulsed electric arc, such as a voltage discharge of at least about 5 kV, such as from about 5 kV to about 15 kV.
  • plasma jet 402 is generated at a frequency of at least about 10 kHz, such as from about 10 kHz to about 1,000 kHz.
  • plasma jet can have a beam length of from about 5 millimeters to about 40 millimeters and a widest beam width of from about 0.5 millimeters to about 15 millimeters.
  • the distance between the portion of plasma jet head 400 that is closest to edge surface 166 is at least about 1 millimeter, such as at least about 2 millimeters, and further such as at least about 4 millimeters, and yet further such as at least about 5 millimeters, such as from about 1 millimeter to about 10 millimeters, including from about 5 millimeters to about 10 millimeters.
  • the number of times that the plasma jet head 400 moves relative to the entire length of edge surface 166 can be at least 1 pass, such as at least 2 passes, and further such as at least 3 passes, and yet further such as at least 4 passes, including from 1 pass to 10 passes, and further including from 2 passes to 6 passes.
  • the speed of relative movement between plasma jet head 400 and edge surface 166 can be a function of the thickness of edge surface 166 (i.e., the distance of the extension direction of the edge surface 166 between the first major surface 162 and the second major surface 164).
  • a scan speed of the flow of plasma along the edge surface 166 in millimeters per second is from about 1 to about 50, such as from about 2 to about 20, of the inverse of the thickness of the edge surface 166 in millimeters.
  • a scan speed of the flow of plasma along the edge surface 166 in millimeters per second can be from about 2 to about 100 millimeters per second, such as from about 4 to about 40 millimeters per second.
  • a scan speed of the flow of plasma along the edge surface 166 in millimeters per second can be from about 10 to about 500 millimeters per second, such as from about 20 to about 200 millimeters per second.
  • Applicants have specifically found that when a flow of plasma comprising at least one high thermal conductivity component, such as a flow of plasma comprising an atmospheric pressure plasma jet comprising at least one high thermal conductivity component is directed toward a glass edge surface, an edge strength of the edge surface may be improved.
  • an edge impact strength of the edge surface may be improved.
  • Such edge strength and/or edge impact strength may be further improved when the scan speed is controlled as a function of the thickness of the edge surface as described herein.
  • embodiments disclosed herein include directing a flow of plasma toward the edge surface of a glass article, such as glass sheet 62, wherein a thickness (i.e., distance of the extension direction) of the edge surface 166 between the first major surface 162 and the second major surface 164 is less than or equal to about 0.5 millimeters, such as from about 0.1 millimeters to about 0.5 millimeters, and further such as from about 0.2 millimeters to about 0.4 millimeters, and wherein the plasma comprises at least one high thermal conductivity component, such as at least one of hydrogen and helium, and an edge strength of the glass article subsequent to directing a flow of plasma toward the edge surface 166, as measured by the four point bend test, is at least about 250 MPa, such as at least about 300 MPa, and further such as at least about 350 MPa, and yet further such as at least about 400 MPa, and still yet further such as at least about 450 MPa, including from about 250 MPa to about 500 MPa, such
  • Embodiments disclosed herein also include directing a flow of plasma toward the edge surface of a glass article, such as glass sheet 62, wherein a thickness (i.e., distance of the extension direction) of the edge surface 166 between the first major surface 162 and the second major surface 164 is less than or equal to about 0.5 millimeters and wherein the plasma comprises at least one high thermal conductivity component, such as at least one of hydrogen and helium, and an edge impact strength of the glass article subsequent to directing a flow of plasma toward the edge surface 166 as measured by the pendulum drop test, is at least about 20 millimeters, such as at least about 25 millimeters, and further such as at least about 30 millimeters, and yet further such as at least about 35 millimeters, and still yet further such as at least about 40 millimeters, including from about 20 millimeters to about 50 millimeters, such as from about 25 millimeters to about 45 millimeters.
  • Such embodiments can include those in which a scan
  • Applicants have found including at least one high thermal conductivity component in the plasma can be particularly beneficial, for example, in generating a compressive stress in the edge surface of glasses having a coefficient of thermal expansion (CTE) of at least about 3 ppm/K in the range between about 25°C and about 300°C.
  • CTE coefficient of thermal expansion
  • Embodiments disclosed herein can also be used to generate a compressive stress in the edge surface of glasses having a CTE of less than about 3 ppm/K in the range between about 25°C and about 300°C.
  • the plasma may, for example, comprise at least one component selected from nitrogen, argon, oxygen, and neon that is excited and at least partially converted to the plasma state.
  • the plasma comprises hydrogen and at least one of nitrogen, argon, oxygen, and neon.
  • the plasma comprises helium and at least one of nitrogen, argon, oxygen, and neon.
  • the plasma comprises hydrogen and at least two of nitrogen, argon, oxygen, and neon.
  • the plasma comprises at helium and at least two of nitrogen, argon, oxygen, and neon.
  • the plasma comprises hydrogen, nitrogen, and at least one of argon, oxygen, and neon. In certain exemplary embodiments, the plasma comprises helium, nitrogen, and at least one of argon, oxygen, and neon. In certain exemplary embodiments, the plasma comprises hydrogen and nitrogen. In certain exemplary embodiments, the plasma comprises helium and nitrogen.
  • the plasma comprises at least about 1 mol%, such as at least about 3 mol%, and further such as at least about 5 mol% of at least one high thermal conductivity component, such as at least one of hydrogen and helium.
  • plasma comprises from about 1 mol% to about 10%, such as from about 2 mol% to about 8 mol%, and further such as from about 3 mol% to about 6 mol% of at least one high thermal conductivity component, such as at least one of hydrogen and helium.
  • the nitrogen content can, for example, range from about 50 mol% to about 99 mol%
  • the argon content can, for example, range from about 0 mol% to about 25 mol%
  • the oxygen content can, for example, range from about 0 mol% to about 25 mol%
  • the neon content can, for example, range from about 0 mol% to about 25 mol%.
  • the plasma comprises from about 1 mol% to about 10%, such as from about 2 mol% to about 8 mol%, and further such as from about 3 mol% to about 6 mol% of hydrogen and from about 50 mol% to about 99 mol% of nitrogen, from about 0 mol% to about 25 mol% of argon, from about 0 mol% to about 25 mol% of oxygen, and from about 0 mol% to about 10 mol% of neon.
  • the plasma comprises from about 1 mol% to about 10%, such as from about 2 mol% to about 8 mol%, and further such as from about 3 mol% to about 6 mol% of helium and from about 50 mol% to about 99 mol% of nitrogen, from about 0 mol% to about 25 mol% of argon, from about 0 mol% to about 25 mol% of oxygen, and from about 0 mol% to about 10 mol% of neon.
  • the plasma comprises from about 1 mol% to about 10%, such as from about 2 mol% to about 8 mol%, and further such as from about 3 mol% to about 6 mol% of hydrogen, from about 75 mol% to about 99 mol% of nitrogen, and from about 0 mol% to about 25 mol% of argon.
  • the plasma comprises from about 1 mol% to about 10%, such as from about 2 mol% to about 8 mol%, and further such as from about 3 mol% to about 6 mol% of helium, from about 75 mol% to about 99 mol% of nitrogen, and from about 0 mol% to about 25 mol% of argon.
  • treatment process comprising directing a flow of plasma, via plasma jet 402, toward edge surface 166, can result in a substantial reduction of particle density on edge surface 166, such as a particle density reduction of at least 1 order of magnitude, and further such as a particle density reduction of at least 2 orders of magnitude, and yet further such as a particle density reduction of at least 3 orders of magnitude.
  • directing a flow of plasma toward edge surface 166 can reduce a density of particles on edge surface 166 to less than about 10 per 0.1 square millimeter, such as less than about 8 per 0.1 square millimeter, and further such as less than about 5 per 0.1 square millimeter, and yet further such as less than about 2 per 0.1 square millimeter, including from about 0 to about 10 particles per 0.1 square millimeter, and further including from about 1 to about 8 particles per 0.1 square millimeter, and yet further from about 2 to about 5 particles per 0.1 square millimeter.
  • a compressive stress can be generated in edge surface 166 subsequent to directing a flow of plasma toward the edge surface.
  • stress in edge surface 166 can be determined by the de Senarmont and Friedel optical birefringence method described in Schott AG,“TIE-27: Stress in Optical Glass”, Technical Information: Advanced Optics July 2004. When a negative stress value (in MPa) is observed in a sample using this method, then the stress in the edge surface 166 is said to be compressive.
  • embodiments disclosed herein include those having a compressive stress in edge surface 166 subsequent to directing a flow of plasma toward the edge surface, wherein the measured stress value, according to the above referenced optical birefringence method is less than about -1 MPa, such as less than about -5 MPa, and further such as less than about -10 MPa, and further such as less than about -20 MPa, and yet further such as less than about -30 MPa, such as from about -1 MPa to about -100 MPa, and further such as from about -10 MPa to about -60 MPa, and yet further such as from about -20 MPa to about -40 MPa.
  • the measured stress value according to the above referenced optical birefringence method is less than about -1 MPa, such as less than about -5 MPa, and further such as less than about -10 MPa, and further such as less than about -20 MPa, and yet further such as less than about -30 MPa, such as from about -1 MPa to about -100 MPa, and further such as
  • methods disclosed herein including directing a flow of plasma toward edge surface 166, wherein the plasma comprises at least one high thermal conductivity component, can enable temperature of edge surface 166 at a time of at least one second subsequent to directing a flow of plasma toward edge surface 166 to be less than a temperature of a portion of the glass article that is at least about 5 millimeters away from edge surface 166 This can, in turn, generate a compressive stress in edge surface 166.
  • Generation of a compressive stress in edge surface 166 can contribute to higher edge strength of glass articles, such as an edge strength of at least about 250 MPa, as measured by the four point bend test.
  • Generation of a compressive stress in edge surface 166 can also contribute to higher edge impact strength of glass articles, such as an edge impact strength of at least about 20 millimeters, as measured by the pendulum drop test.
  • directing a flow of plasma toward the edge surface can result in a composition of the edge surface 166 differing from that of the glass that is at least about 5 millimeters away from the edge surface.
  • embodiments disclosed herein include those in which directing a flow of plasma toward the edge surface 166 results in an edge surface 166 comprising a silica content that is at least about 10 mol% higher, such as at least about 20 mol% higher, including from about 10 mol% higher to about 40 mol% higher than a silica content of the glass that is at least about 5 millimeters away from the edge surface 166.
  • Embodiments disclosed herein can also include those in which directing a flow of plasma toward the edge surface 166 results in an edge surface 166 comprising an alumina content that is at least about 25 mol% lower, such as at least about 50 mol% lower, including from about 25 mol% lower to about 75 mol% lower than an alumina content of the glass that is at least about 5 millimeters away from the edge surface 166.
  • the glass composition comprises one or more alkali metal oxides, such as sodium oxide or potassium oxide
  • directing a flow of plasma toward an edge surface 166 can result in an edge surface 166 comprising an alkali metal oxide content that is at least about 25 mol% lower, such as at least about 50 mol% lower, including from about 25 mol% lower to about 75 mol% lower than an alkali metal oxide content of the glass that is at least about 5 millimeters away from the edge surface 166.
  • Embodiments disclosed herein include those in which plasma jet 402 is applied toward edge surface 166 after or in lieu of an edge beveling process, such as the exemplary edge beveling process shown in FIG. 7.
  • plasma jet 402 may be applied toward edge surface 166 of glass sheet 62 immediately following separation of glass sheet 62 from glass ribbon 58, as shown, for example, in FIG. 5.
  • subsequent processing steps such as the exemplary edge beveling process shown in FIG. 7, may be applied to glass sheet 62, prior to application of plasma jet 402 toward edge surface 166 of glass sheet 62.
  • edge surface 166 may be heated, for example, by an electrical resistance heater or an induction heater, to a temperature of at least about 100°C, such as at least about 200°C, and further such as at least about 300°C, and yet further such as at least about 400°C, and still yet further such as at least about 500°C, including a temperature ranging from about 100°C to about 600°C prior to directing the flow of plasma toward the edge surface 166.
  • exemplary embodiments also include those in which temperature of edge surface 166 is maintained in the above-referenced ranges for a period of time subsequent to directing a flow of plasma toward the edge surface 166. Such heat treatment can potentially reduce any edge tensile stress.

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Abstract

L'invention concerne un procédé de fabrication et de traitement d'un article en verre, le traitement de l'article consistant à diriger un flux de plasma, tel qu'un flux de plasma comprenant un jet de plasma à pression atmosphérique comprenant au moins un composant à conductivité thermique élevée, vers une surface de bord de l'article. Un tel traitement peut augmenter la résistance de bord de l'article. Un tel traitement peut également augmenter la résistance aux chocs du bord de l'article. Un tel traitement peut en outre réduire une densité de particules sur une surface de bord de l'article.
PCT/US2019/064430 2018-12-13 2019-12-04 Feuilles de verre à résistance de bord améliorée et leurs procédés de production WO2020123226A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024102286A1 (fr) * 2022-11-08 2024-05-16 Corning Incorporated Appareil et procédé d'amélioration de la qualité de surface d'une feuille de verre

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US8938993B2 (en) * 2010-11-30 2015-01-27 Ut-Battelle, Llc Glass strengthening and patterning methods
US20160137549A1 (en) * 2013-07-24 2016-05-19 Schott Ag Composite Element and Use Thereof
US9533910B2 (en) * 2009-08-28 2017-01-03 Corning Incorporated Methods for laser cutting glass substrates
US9557773B2 (en) * 2014-01-29 2017-01-31 Corning Incorporated Bendable glass stack assemblies, articles and methods of making the same
US20180009697A1 (en) * 2015-03-20 2018-01-11 Schott Glass Technologies (Suzhou) Co. Ltd. Shaped glass article and method for producing such a shaped glass article

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US9533910B2 (en) * 2009-08-28 2017-01-03 Corning Incorporated Methods for laser cutting glass substrates
US8938993B2 (en) * 2010-11-30 2015-01-27 Ut-Battelle, Llc Glass strengthening and patterning methods
US20160137549A1 (en) * 2013-07-24 2016-05-19 Schott Ag Composite Element and Use Thereof
US9557773B2 (en) * 2014-01-29 2017-01-31 Corning Incorporated Bendable glass stack assemblies, articles and methods of making the same
US20180009697A1 (en) * 2015-03-20 2018-01-11 Schott Glass Technologies (Suzhou) Co. Ltd. Shaped glass article and method for producing such a shaped glass article

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024102286A1 (fr) * 2022-11-08 2024-05-16 Corning Incorporated Appareil et procédé d'amélioration de la qualité de surface d'une feuille de verre

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