This disclosure relates to improved thermally tempered glass and more specifically to thermally strengthened glass sheets having both higher overall uniformity and smaller-scale index or birefringence patterns than generally producible by standard thermal tempering.
Commonly-assigned U.S. Pat. No. 9,296,638 (the '638 patent) entitled “Thermally Tempered Glass and Method and Apparatuses for Thermal Tempering of Glass” discloses methods and apparatuses for heating and/or thermally tempering glass sheets. The contents of the '638 patent are relied upon and incorporated herein by reference in their entirety for purposes of U.S. law.
The phrases “glass sheet(s)” and “glass ribbon(s)” are used broadly in the specification and in the claims and include sheet(s) and ribbon(s) that comprise one or more glasses and/or one or more glass-ceramics, as well as laminates or other composites that include one or more glass and/or one or more glass-ceramic components. The phrase “glass sheet(s)” is used to refer to glass sheet(s) and glass ribbon(s) collectively. “Glass” includes glass and materials known as glass ceramics.
According to embodiments, a strengthened glass sheet comprises a first major surface, a second major surface opposite the first major surface, an interior region located between the first and second major surfaces, and an outer edge surface extending between and bordering the first and second major surfaces such that the outer edge surface defines the perimeter of the sheet, wherein the sheet comprises a glass and is thermally strengthened; and wherein the first major surface has a roughness in the range of from 0.05 to 0.8 nm Ra over an area of 10 μm×10 μm; and wherein, excluding areas within three sheet thicknesses of the outer edge surface of the sheet, the slope of a measured value of a thermally generated or thermally affected property of glass over distance along the first major surface of the sheet is higher bordering one or more lower-cooling-rate-effect-exhibiting areas on the first surface of the sheet than elsewhere on the first surface of the sheet, and at least one of said one or more areas has a shortest linear dimension, in a direction parallel to the first major surface, of less than 100000 μm, or as little as only or only 3000, 2000, 1000, 500, 400, 300, 200, 150, 100, 70, 50, 40 or even 30 μm.
According to embodiments, the thermally generated or affected property is through-sheet retardation measured in transmission normal to the first major surface according to ASTM F218. The slope of said retardation may be at least 5 nm per mm, 10 nm per mm, 20 nm per mm, 30 nm per mm, or even 40, 50, 60, 80 or 100 nm per mm, all per mm thickness of the sheet.
According to embodiments, the thermally generated or affected property may be optical index of refraction, measured in transmission through the sheet normal to the first major surface. The slope of said index of refraction may be positive in the direction into said one or more areas, and may be as great as at least 0.00001 per mm, or at least 0.0001, 0.001, 0.01, or even 0.1 per mm.
According to embodiments, the thermally generated or affected property may be fictive temperature. For measuring purposes, fictive temperature is determined by temper-stress compensated Raman spectroscopy shift, as disclosed and described in the '638 patent. The slope of said fictive temperature bordering said one or more areas may be negative in the direction into said one or more areas. The slope of said fictive temperature may be at least 5° C. per mm, or 10, 15, 20, 25, 30, 40, 50, 70 or even 100° C. per mm.
According to still further embodiments compatible with all others above, the one or more areas on the first surface of the strengthened glass sheet can be arranged in a pattern corresponding to a pattern of through holes in a heat sink gas bearing surface. They also can be arranged in a pattern corresponding only in part to a pattern of through holes in a heat sink gas bearing surface. They also can be arranged in a pattern not corresponding to a pattern of through holes in a heat sink gas bearing surface.
According to embodiments, potentially useful applications include applications in the pattern of the one or more areas forms a logo or other recognizable symbol, or a machine-readable pattern.
According to embodiments, in areas of the first major surface not forming part of said one or more areas, a normalized standard deviation Sn
of differential retardance measurement samples taken according to ASTM F218 through the first major surface of the sheet in a series of samples N=10 at locations distributed at intervals of distance d with 0.01 mm≤d≤1000 mm mm along the first major surface and along a center line between borders of the one or more areas and/or between borders of the one or more areas and the outer edge surface of the sheet, but not within 3 times the thickness of the sheet distance to the outer edge surface, is less than or equal to 0.05, or to 0.02, 0.015, 0.01, 0.005, 0.002, or even less than or equal to 0.001. The distance d may be 0.1 mm≤d≤100 mm, 0.1 mm≤d≤100 mm, and 1 mm≤d≤10 mm, the number of samples N may be 10, 100, 500, 1000, 10000.
Apparatus and methods for producing the glass sheets are also disclosed.
The reference characters used are only for the convenience of the reader and are not intended to and should not be interpreted as limiting the scope of the invention. More generally, it is to be understood that both the foregoing general description and the following detailed description are merely exemplary of the invention and are intended to provide an overview or framework for understanding the nature and character of the invention.
Additional features and advantages of the invention are set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the invention as exemplified by the description herein. The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. It is to be understood that the various features of the invention disclosed in this specification and in the drawings (which are not to scale) can be used individually and in any and all combinations.
The sheet 10 can be stationary or in motion between the sinks or sources Si/So. The sheet 10 can be smaller (in one dimension or both) than the extent of the sinks or sources Si/So or larger (preferably in one dimension only, in which case continuous processing in the larger direction is preferred). The sheet 10 can be multiple sheets heated or cooled together at the same time. The gas in the first and second gaps 20a and 20b can be the same or different, and both or either can be gas mixtures or essentially pure gases. Generally, gases or gas mixtures with relatively higher thermal conductivity are preferred. Use of gas bearings allows robustly maintaining the desired size of the gaps 20a and 20b, which enables relatively homogeneous heat transfer rates over all areas of the gaps 20, in comparison to cooling or heating by direct contact with liquids or with solids, and in comparison to cooling by forced air convection.
As represented in the diagrammatic cross section of
Gas bearings, as alternative embodiments, may take either of the forms shown in
Because of the non-contact treatment and handling possible in the thermal strengthening apparatus of
Achieving uniformity of cooling effects in the cooling zone 40 over the area of the sheet 10 requires maintaining the desired size of the gaps 20. It has also been found that maintaining the homogeneity of the gas in the gaps 20a, 20b within the cooling zone is important. If different gases are used in the heat source So gaps and the heat sink Si gaps, gas can be drawn away by a suitable suction or vacuum means at a position between the sources So and the sinks Si, as indicated by the arrows A in
For good homogeneity of heat transfer rates during heating and resulting homogeneous temperature profiles and final properties of sheet 10, it is also desirable to provide a heat source So providing for a non-uniform distribution of heating energy.
With good control of the thermal profile of the sheet just before cooling, such as may be achieved by the heat source So of
For example, a sheet processed according to this disclosure in combination with the disclosure of the '638 patent can achieve a desirable low deviation of membrane stress, such that, in areas of the first major surface not forming part of said one or more areas, a normalized standard deviation Sn
of differential retardance measurement samples taken according to ASTM F218 through the first major surface of the sheet in a series of samples N=10 at locations distributed at intervals of distance d with 0.01 mm≤d≤1000 mm mm along the first major surface and along a center line between borders of the one or more areas and/or between borders of the one or more areas and the outer edge surface of the sheet, but not within 3 times the thickness of the sheet distance to the outer edge surface, is less than or equal to 0.05, or to 0.02, 0.015, 0.01, 0.005, 0.002, or even less than or equal to 0.001. The distance d may be 0.1 mm≤d≤100 mm, 0.1 mm≤d≤100 mm, and 1 mm≤d≤10 mm, the number of samples N may be 10, 100, 500, 1000, 10000.
By employing the gas bearing embodiment of
A plane view of an embodiment of a sink Si is shown in
The embodiment of
The patterns are subtle because they are produced by non-contact thermal effects, namely, by one or more lower-cooling-rate-effect-exhibiting areas corresponding the discrete holes, or to the holes or depressions, or to the lines or trenches or other patterns, and so are detectable through measurements that are able to detect the differing local thermal histories on the sheet. These include birefringence measurements such as retardance through the sheet or observation by the human eye in polarized light; measurements of index of refraction such as through-sheet inteferometry (where oil-on-flats techniques may be used to avoid the need to polish the specimen under test); measurement of fictive temperature variations, and the like.
Although the patterns are typically subtle to the unaided human eye, they are unusual in thermally strengthened glass sheets in that the slope of a given measured property over distance across the first major surface of the sheet is unusually high (meaning unusually steep, meaning unusually high in absolute value) relative to glass sheets strengthened by other methods, at the locations and in the directions crossing the borders of the one or more areas which make up the patterns.
The patterns are also unusual in thermally strengthened glass sheets in that the one or more areas which make up the patterns can be very thin, or more technically expressed, the shortest linear dimension of at least one of the one or more areas, in a direction parallel to the first major surface of the sheet, may be very small relative to patterns produced by other thermal strengthening methods, though it may be also be large if desired.
The product that results may be characterized as a strengthened glass sheet comprising a first major surface, a second major surface opposite the first major surface, an interior region located between the first and second major surfaces, an outer edge surface extending between and surrounding the first and second major surfaces such that the outer edge surface defines the perimeter of the sheet, wherein the first major surface has a roughness of greater than 0.05 nm and less than 0.8 nm Ra over an area of 10 μm×10 μm; and wherein, excluding areas within three sheet thicknesses of the outer edge surface of the sheet (to avoid edge effects), the slope of a measured value of a thermally generated or thermally or affected property of glass over distance along the first major surface of the sheet is higher bordering one or more areas on the first surface of the sheet than elsewhere on the first surface of the sheet, and said areas have a shortest linear dimension, in a direction parallel to the first major surface, of less than 100000 μm, or only 3000, 2000, 1000, 500, 400, 300, 200, 150, 100, 70, 50, 40 or even 30 μm.
According to embodiments, the thermally generated or affected property is through-sheet retardation measured in transmission normal to the first major surface according to ASTM F218. The slope of said retardation may be at least 5 nm per mm, 10 nm per mm, 20 nm per mm, 30 nm per mm, or even 40, 50, 60, 80 or 100 nm per mm, all per mm thickness of the sheet.
According to embodiments, the thermally generated or affected property may be optical index of refraction, measured in transmission through the sheet normal to the first major surface. The slope of said index of refraction may be positive in the direction into said one or more areas, and may be as great as at least 0.00001 per mm, or at least 0.0001, 0.001, 0.01, or even 0.1 per mm.
According to embodiments, the thermally generated or affected property may be fictive temperature, measured at the first surface of the sheet according to the method disclosed in U.S. Pat. No. 9,296,638. The slope of said fictive temperature bordering said one or more areas may be negative in the direction into said one or more areas. The slope of said fictive temperature may be at least 5° C. per mm, or 10, 15, 20, 25, 30, 40, 50, 70 or even 100° C. per mm.
As will be understood from the foregoing, according to still further embodiments compatible with all others above, the one or more areas on the first surface of the strengthened glass sheet can be arranged in a pattern corresponding to a pattern of through holes in a heat sink gas bearing surface. They also can be arranged in a pattern corresponding only in part to a pattern of through holes in a heat sink gas bearing surface. They also can be arranged in a pattern not corresponding to a pattern of through holes in a heat sink gas bearing surface.
Potentially useful applications include applications in the pattern of the one or more areas forms a logo or other recognizable symbol, or a machine-readable pattern.
In areas of the first major surface not forming part of said one or more areas, the good uniformity produced by the apparatuses and methods of the present disclosure can result in areas of the first major surface centered between borders of said one or more areas (and also not within three thicknesses of the outer edge surface) having the a desirable low deviation of membrane stress mentioned above, such that a normalized standard deviation Sn
of a sample of either membrane stress or differential retardance measurement samples, taken according to ASTM F218 through the first major surface 12 of the sheet 10 in a series of samples N=100 at locations distributed along the first major surface and centered between borders of the one or more areas, is low (when edge effects of measuring too close—i.e., within 3 times the thickness of the sheet to the outer edge surface 16 are not included)—as low as 0.02, 0.015, 0.01, 0.005, 0.002, 0.001 or even lower.
A variety of modifications that do not depart from the scope and spirit of the invention will be evident to persons having ordinary skill in the art from the foregoing disclosure.
This application claims the benefit of priority of U.S. Provisional Application No. 62/289,334, filed on Jan. 31, 2016, and of U.S. Provisional Application No. 62/428,263, filed on Nov. 30, 2016, the content of which is relied upon and incorporated herein by reference in its entirety. This application is related to and hereby incorporates herein by reference in full the following applications: Provisional Application Ser. No. 62/288,177 filed on Jan. 28, 2016, U.S. Provisional Application Ser. No. 62/288,615 filed on Jan. 29, 2016, U.S. Provisional Application Ser. No. 62/428,142 filed on Nov. 30, 2016, and U.S. Provisional Application Ser. No. 62/428,168, filed on Nov. 30, 2016, U.S. Provisional Application Ser. No. 62/288,851, filed on Jan. 29, 2016, U.S. application Ser. No. 14/814,232, filed on Jul. 30, 2015; U.S. application Ser. No. 14/814,181, filed on Jul. 30, 2015; U.S. application Ser. No. 14/814,274, filed on Jul. 30, 2015; U.S. application Ser. No. 14/814,293, filed on Jul. 30, 2015; U.S. application Ser. No. 14/814,303, filed on Jul. 30, 2015; U.S. application Ser. No. 14/814,363, filed on Jul. 30, 2015; U.S. application Ser. No. 14/814,319, filed on Jul. 30, 2015; U.S. application Ser. No. 14/814,335, filed on Jul. 30, 2015; U.S. Provisional Application No. 62/031,856, filed Jul. 31, 2014; U.S. Provisional Application No. 62/074,838, filed Nov. 4, 2014; U.S. Provisional Application No. 62/031,856, filed Apr. 14, 2015; U.S. application Ser. No. 14/814,232, filed Jul. 30, 2015; U.S. application Ser. No. 14/814,181, filed Jul. 30, 2015; U.S. application Ser. No. 14/814,274, filed Jul. 30, 2015; U.S. application Ser. No. 14/814,293, filed Jul. 30, 2015; U.S. application Ser. No. 14/814,303, filed Jul. 30, 2015; U.S. application Ser. No. 14/814,363, filed Jul. 30, 2015; U.S. application Ser. No. 14/814,319, filed Jul. 30, 2015; U.S. application Ser. No. 14/814,335, filed Jul. 30, 2015; U.S. Provisional Application No. 62/236,296, filed Oct. 2, 2015; U.S. Provisional Application No. 62/288,549, filed Jan. 29, 2016; U.S. Provisional Application No. 62/288,566, filed Jan. 29, 2016; U.S. Provisional Application No. 62/288,615, filed Jan. 29, 2016; U.S. Provisional Application No. 62/288,695, filed on Jan. 29, 2016; U.S. Provisional Application No. 62/288,755, filed on Jan. 29, 2016.
Filing Document | Filing Date | Country | Kind |
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PCT/US17/15828 | 1/31/2017 | WO | 00 |
Number | Date | Country | |
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62289334 | Jan 2016 | US | |
62428263 | Nov 2016 | US |