JP2021529718A - A method for continuously manufacturing a glass ribbon and a stretched glass article manufactured from the glass ribbon. - Google Patents

Abstract

A method (100) for producing a glass ribbon (30b), wherein the cast glass (30a) is formed with a width of about 100 mm to about 5 m (Wcast) and a thickness of about 1 mm to about 500 mm (t). The glass (30) is poured into the caster (20) having (), the cast glass (30a) in the caster (20) is cooled to a viscosity of at least 108 pores (107 Pa · s), and the caster (20) is used. ), And the cast glass is heated to an average viscosity of less than 107 pores (106 Pa · s) to make the cast glass 30a a glass ribbon 30b having a width smaller than Wcast (Wribbon). A method (100) comprising stretching the cast glass (30a), comprising stretching to, followed by cooling the glass ribbon (30b) to ambient temperature. Further, the cast glass (30a) during the cooling, transporting and stretching steps is above about 50 ° C. Disclosed are glass articles that include an unpolished glass ribbon having a thickness of 1 to 25 mm and can be cut into wafers with small thickness variations and small warpage.

Description

Related application

This application claims the priority benefit of US Provisional Patent Application No. 62 / 691,031 filed June 28, 2018. The interests of the priority of the specification shall be claimed, the contents of which shall be relied upon, and the entire contents shall be incorporated herein by reference.

The present disclosure generally relates to a method of producing a glass ribbon, more particularly a method of continuously producing a glass ribbon having high dimensional stability from a glass composition having a relatively low liquidus viscosity.

Conventional methods of producing lenses and other optics from low liquidus viscous glass compositions containing high refractive index compositions are very costly and the utilization of molten glass obtained from these methods is low. .. Typically, these methods involve casting the composition into long bars that are significantly larger in thickness than the final final product. That is, these molding methods produce cast bars that require additional processing to obtain the shape and dimensions of the final product.

The additional processing of these cast bars is often large. Specifically, the cast bar is sewn onto a disc. The disc is then ground to grind to match the outer diameter to the final outer dimensions of the final product lens. The disc is then wire-sewn to the approximate thickness of the final lens final product and then subjected to a significant number of grinding and polishing steps to obtain the warpage and dimensional uniformity required for the final product lens. Served. As a result, the conventional process of forming lenses and other optics from these glass compositions is costly and results in low utilization of molten glass.

According to some aspects of the present disclosure, a method of making a glass ribbon, for forming cast glass, a width of _{about 100 mm to about 5 m (W cast} ) and a thickness of about 1 mm to about 500 mm (W cast). and pouring a glass in a caster having t), and cooling to a viscosity of at least 10 ⁸ poise cast glass in the caster (10 7 ^Pa · s), and conveying the cast glass from the caster, the cast glass is heated to an average viscosity of less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s) and the cast _glass, comprising the step of stretching the glass ribbon having a width less _{(W ribbon)} than _{W cast,} the cast glass A method is provided that includes a step of stretching and then cooling the glass ribbon to ambient temperature. In addition, the cast glass during the cooling, transporting and stretching steps is above about 50 ° C.

According to some aspects of the present disclosure, there is provided a glass article comprising an unpolished glass ribbon having a thickness of about 1 mm to about 25 mm and a width of 25 mm to about 200 mm. Ribbons are borosilicate glass, aluminhosilicate glass, aluminosilicate glass, fluorosilicate glass, phosphate glass, fluorophosphate glass, sulfophosphate glass, germanate glass, vanadate glass. , Includes glass selected from the group consisting of phosphate glass and borate glass. In addition, the composition comprises an upper liquid phase viscosity of less than ^{5 × 10 5} poise (5 × 10 ^{4 Pa · s).} In addition, the glass ribbon can be cut into glass wafers with a thickness variation of about 0.01 μm to about 50 μm and a warp of about 0.01 μm to about 200 μm.

According to some aspects of the present disclosure, there is provided a glass article comprising an unpolished glass wafer having a thickness of about 1 mm to about 25 mm and a width of 100 mm to about 200 mm. Ribbons are borosilicate glass, aluminhosilicate glass, aluminosilicate glass, fluorosilicate glass, phosphate glass, fluorophosphate glass, sulfophosphate glass, germanate glass, vanadate glass. , Includes glass selected from the group consisting of phosphate glass and borate glass. In addition, the composition comprises an upper liquid phase viscosity of less than ^{5 × 10 5} poise (5 × 10 ^{4 Pa · s).} In addition, glass wafers have a thickness variation of about 0.01 μm to about 50 μm and a warp of about 0.01 μm to about 200 μm.

Additional features and advantages are described in the detailed description below, which will be readily apparent to those skilled in the art, or the following detailed description, claims and accompanying drawings. It will be recognized by implementing the embodiments described herein, including.

Both the schematic description described above and the detailed description below describe various embodiments, which provide an overview or framework for understanding the nature and characteristics of the subject matter of the claims. It should be understood that it is intended to be done.

The accompanying drawings are included to provide a detailed understanding of the various embodiments, are incorporated herein by reference, and form part of this specification. The drawings show various embodiments described herein and serve to explain, along with description, the principles and processes of the subject matter of the claims.

The following is a description of the figures in the accompanying drawings. The figures are not necessarily to scale, and certain features and indications of the figure may be exaggerated in scale or schematic for clarity and brevity.
It is the schematic of the method of manufacturing the glass ribbon by one Embodiment. FIG. 5 is a schematic view of a melting device comprising an orifice, casters, and a heating device, which can be used according to a method of manufacturing a glass ribbon according to one embodiment. FIG. 5 is a schematic view of an overflow forming apparatus comprising an isopipe for fluidized glass used in a method of manufacturing a glass ribbon according to one embodiment. FIG. 5 is a schematic view of an overflow forming apparatus comprising an isopipe for fluidized glass used in a method of manufacturing a glass ribbon according to one embodiment.

The above overview and the following detailed description of the particular invention will be easier to understand when read in conjunction with the figures. It should be understood that the claims are not limited to the arrangements and means shown in the figure. Moreover, the appearance shown in the figure is one of many decorative appearances that can be employed to achieve the specified function of the device.

Additional features and advantages are described in the detailed description below, which will be apparent to those skilled in the art or described in the following description along with the claims and accompanying drawings. Will be recognized by implementing certain embodiments.

As used herein, the term "and / or", when used in the enumeration of two or more items, may be any one of the enumerated items, alone or in the enumerated items. It means that it can be used in any combination of two or more. For example, if the composition is described as containing components A, B and / or C, then the composition is A only, B only, C only, A and B combination, A and C combination, B and C. Or a combination of A, B and C can be included.

As used herein, terms indicating relationships such as first and second, above and below are used only to distinguish one entity or act from another, and between such entities or acts. It does not necessarily imply or require any actual such relationship or order.

Those skilled in the art and those who manufacture or use the disclosure will come up with modifications to the disclosure. Accordingly, the embodiments shown in the drawings and described above are for illustrative purposes only and are defined by the following claims as interpreted in accordance with the principles of patent law, including the doctrine of equivalents. It is understood that it is not intended to limit the scope of.

The term "about" as used herein is not accurate in quantity, size, formulation, parameters and other quantities and properties, and does not have to be accurate, but tolerances, conversion factors as required. , Rounding, measurement error, etc., and may be approximate and / or may be greater or lesser than that, reflecting other factors known to those skilled in the art. When the term "about" is used in the description of range values or endpoints, the present disclosure should be understood to include the particular values or endpoints referred to. Regardless of whether the numbers or endpoints in the range of the specification contain "about", the numbers or endpoints in the range are either modified by "about" and not modified by "about". It is intended to include one embodiment. Moreover, it will be understood that the endpoints of each range have both meanings in relation to the other endpoints and independently of the other endpoints.

As used herein, the terms "substantial", "substantially" and their variants are intended to refer to the features described being equal to or approximately equal to a value or description. For example, a "substantially flat" surface is intended to mean a surface that is flat or nearly flat. Furthermore, "substantially" is intended to indicate that the two values are equal or nearly equal. In some embodiments, "substantially" may indicate a value within about 10% of each other, eg, within about 5% of each other or within about 2% of each other.

Orientation terms used herein, such as top, bottom, right, left, front, back, top, bottom, refer only to the figures depicted and are meant to mean absolute directions. Is not intended.

The terms "the", "a" or "an" as used herein mean "at least one" and are limited to "only one" unless expressly indicated otherwise. Should not be done. Thus, for example, a reference to "a component" includes an embodiment having two or more such components, unless the context clearly indicates otherwise.

As used herein, the terms "upper liquid phase viscosity" and "upper liquid phase temperature" are used in the articles and methods of the present disclosure at the time the glass forms a crystalline, homogeneous melt. Refers to the respective viscosities and temperatures of. In addition, the terms "upper limit liquidus viscosity" and "liquidus viscosity" are used interchangeably herein, and the terms "upper limit liquidus temperature" and "liquidus temperature" are also interchangeable herein. Used for.

Similarly, the terms "lower limit liquid phase viscosity" and "lower limit liquid phase temperature" as used herein are used in the articles and methods of the present disclosure at a time when one or more crystalline phases of glass can be facilitated to grow. Refers to the respective viscosity and temperature of the glass used.

As used herein, the "devitrification zone" of glass used in the articles and methods of the present disclosure exceeds the temperature range given by the upper limit liquid phase temperature to the lower limit liquid phase temperature, eg, glass exceeds 0.01 μm / min. It is a temperature range in which crystal growth of one or more crystal phases is carried out.

As used herein, the "average viscosity" of the glass used in the articles and methods of the present disclosure is sufficient to confirm the average viscosity value according to the analytical and measuring methods understood by those skilled in the art of the present disclosure. Refers to the viscosity of the glass, glass ribbon, glass sheet or other article of the present disclosure as measured during the steps (eg, stretching) of the process or method referred to over the area and time of the article.

As used herein, the term "continuous" is configured to form glass sheets, ribbons and other articles without the need for intermediate and / or post-cooling heat treatments such as annealing or re-stretching. Refers to the methods and processes of the present disclosure made. In other words, the processes and methods of the present disclosure are configured to form glass sheets, glass ribbons and other articles that are not cut or cut prior to the stretching step.

As used herein, "maximum crystal growth rate" is the maximum of any crystal phase of glass used in the articles and methods of the present disclosure, eg, in μm / min, within a reference temperature or reference temperature range. Refers to the growth rate. Similarly, as used herein, "crystal growth rate" is in reference temperature or within the reference temperature range, eg, in units of μm / min, for any crystal phase of glass used in the articles and methods of the present disclosure. Refers to the growth rate of.

As used herein, the "thickness variation" of glass wafers, glass ribbons, glass sheets or other articles of the present disclosure is by mechanical contact calipers or micrometer, or articles with a thickness of 1 mm or more. Is measured by a non-contact laser gauge by determining the minimum and maximum thickness difference of a glass wafer, glass ribbon, glass sheet or other article.

As used herein, the "warp" of a glass wafer, glass ribbon, glass sheet or other article of the present disclosure is measured by subtracting the average thickness of the article from the distance between two planes containing the article. NS. For glass ribbons, glass sheets and other glass articles of the present disclosure in substantially rectangular shape, warpage is measured according to principles understood by those skilled in the art of the present disclosure. Specifically, warpage is assessed from a square measurement area of length defined by the quality area between the beads of the article, subtracted 5 mm from the inner edge of each bead. Similarly, for glass wafers of the present disclosure having a substantially circular disc-like shape, warpage is measured according to principles understood by those skilled in the art of the present disclosure. Specifically, warpage is evaluated from a circular measurement area with a radius defined by subtracting 5 mm from the outer diameter of the wafer.

As used herein, the "critical cooling rate" of a glass, glass ribbon, glass sheet or other article of the present disclosure refers to a plurality of samples of a glass, glass sheet or other article thereof at a variety of selected cooling rates. Determined by melting to glass transition temperature. The sample is then cross-sectioned by standard cutting and polishing techniques, evaluated at 100x with a light microscope, and the presence of crystals on the bulk and its free surface (ie, the top surface, the bottom surface of the interface with the exposed surface and the crucible, etc.). Is confirmed. The critical cooling rate corresponds to the sample with the lowest cooling rate and no crystals on its surface and bulk.

Although drawings are generally referred to, in particular FIG. 1, the illustrations are intended to illustrate particular embodiments and are not intended to limit the disclosure to the scope of the claims attached thereto. Will be understood. The figures are not necessarily to scale, and certain features and indications of the figure may be exaggerated in scale or schematic form for clarity and brevity.

In the present disclosure, a method for producing a glass ribbon, more particularly a glass having a relatively low liquidus viscosity (eg <5 × 10 ⁵ pores (5 × 10 ⁴ Pa · s)) and / or a relatively high glass refractive index. A method of continuously producing glass ribbons for lenses and other optics from the composition is described. The glass ribbons produced by these methods have high dimensional stability and low warpage, and are produced with the same final dimensions as the desired final product. As a result, glass ribbons manufactured according to the methods of the present disclosure require limited post-treatment. As a result, the process methods of the present disclosure have significantly lower manufacturing costs as compared to conventional glass forming processes used in the manufacture of lenses from glass compositions with low liquidus viscosities. Further, the method of the present disclosure has a remarkably high utilization rate of the molten glass and a small amount of waste.

In particular, the methods of making glass ribbons of the present disclosure are continuous in the sense that they do not require post-manufacturing annealing or other post-manufacturing heat treatments. This method employs, for example, transporting cast glass through casters to cool it through a devitrification zone to a temperature higher than the ambient temperature (eg> 50 ° C.). After cooling the glass to a temperature higher than the ambient temperature, the method employs an additional stretching step with some reheating to the devitrification zone. The stretching step results in a final final product, such as a glass ribbon with a thickness dimension intended for high refractive index wafers, lenses or other optics. In addition, it is advantageous that the stretching step be performed for a limited time at a glass viscosity and temperature that minimizes devitrification or eliminates the possibility of devitrification. In addition, this method requires post-cooling (ie, after reaching ambient temperature) heat treatment, such as annealing or re-stretching, to obtain the final product, such as glass ribbons, wafers, lenses or other glass articles. It is especially advantageous in the sense that it does not. Equally advantageous, a plurality of aspects of the methods of the present disclosure allow a glass that does not require additional mechanical treatment, such as polishing or grinding, to satisfy warpage and / or thickness variation levels of the optics. Ribbons, wafers, lenses or other glass articles are obtained.

Here, referring to FIG. 1, a schematic view of a method 100 for manufacturing the glass ribbon 30b is shown. As shown in FIG. 1, the _{glass 30 is melted in a caster 20 having a width (W cast} ) 22 of about 200 mm to about 5 m and a thickness (t) 24 (see FIG. 2) of 1 mm or more. A method 100 for manufacturing a glass ribbon 30b is provided, which comprises a step 110 of pouring from the device 10 to form the cast glass 30a. Method 100 to produce a glass ribbon 30b further includes a step 120 of cooling in viscosity and 50 ° C. or more temperatures of at least 10 ⁸ poise cast glass 30a in the caster ^{20 (10 7 Pa · s)} . The method 100 for manufacturing the glass ribbon 30b also includes a step 130 of transporting the cast glass 30a from the caster 20. In addition, a method 100 for producing a glass ribbon 30b is 10 ⁷ poises cast glass 30a of ⁽¹⁰ 6 Pa · s) of less than average viscosity, the width of the cast glass 30a _{(W cast)} 22 having a width smaller than _{(W ribbon} ) 32 further comprises step 140 stretching to a final thickness of 24 (t). Further, the stretching step 140 comprises heating the cast glass 30a to the average viscosity of less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s). The method 100 for manufacturing the glass ribbon 30b further includes a step 150 of cooling the glass ribbon 30b to an ambient temperature.

With respect to step 110 of pouring the glass shown in FIG. 1, a suitable melting device 10 has a maximum dimension 12 which is the approximate width of the glass 30 as it exits the melting device 10 and flows into the casters 20. The glass 30 can be fed through the outlet element 4 having the. Depending on the viscosity of the glass 30 flowing from the melting device 10, the glass 30 can have a width approximately equal to or smaller than the maximum dimension 12 of the outlet element 4. According to some embodiments of the method 100 for manufacturing the glass ribbon 30b, the maximum dimension 12 of the outlet element 4 is less than or equal to _{the width (W cast) 22 of the caster 20.} In another embodiment, the maximum dimension 12 of the outlet element 4 is a composition of glass 30 having, for example, a relatively low upper liquid phase viscosity (eg, 5 poise (0.5 Pa · s) to 5000 poise (500 Pa · s)). Can be made larger than the width (W _{cast) 22 of the caster 20.} In particular, these glasses, when melted, can become a "neck" as they leave the outlet element 4 of the melting device 10 and have a width 22 that is smaller than the maximum dimension 12 of the exit element 4 of the melting device 10. It can flow into the caster 20.

Revisiting method 100 for manufacturing the glass ribbon 30b shown in FIG. 1, a plurality of embodiments of the melting apparatus 10 are of an overflow forming apparatus or orifice form in which the outlet element 4 functions to distribute the glass 30. Includes a melter with an outlet element 4. In the latter embodiment, the melting apparatus 10 can include a weir that allows the glass 30 to overflow and spread along the outlet element 4 in the form of an isopipe (eg, shown in FIGS. 3A and 3B). See overflow molding equipment with isopipes that are used). In such an embodiment, the glass 30 can extend to one or both sides of the isopipe. With respect to the former embodiment, the melting device 10 may include a melting device with an orifice that distributes the molten glass 30 as it leaves the melting device 10. Further, those skilled in the art of the present disclosure can configure another melting apparatus 10 suitable for use in the method 100 for manufacturing the glass ribbon 30b.

In a plurality of embodiments of the method 100 for producing the glass ribbon 30b shown in FIG. 1, the glass 30 is a borosilicate glass, an aluminhosilicate glass, an aluminosilicate glass, a fluorosilicate glass, a phosphoric acid. It is obtained from a glass composition comprising salt glass, fluorophosphate glass, sulfophosphate glass, germanate glass, vanadate glass, borate glass and phosphate glass. According to one embodiment, the glass 30 is obtained from any glass composition that exhibits suitable optical properties for lenses and optical components (eg, transmittance, refractive index, coefficient of thermal expansion, etc.). According to one embodiment, the glass 30 is the following glass composition (referred to herein as “glass A”), ie 40.2 mol% SiO ₂ , 2.4 mol% B ₂ O ₃ 11.3 mol% Li ₂ O, 22.9 mol% CaO, 5.4 mol% La ₂ O ₃ , 3.8 mol% ZrO ₂ , 4.8 mol% Nb ₂ O ₅ and Obtained from 9.3 mol% of TiO _2. According to another embodiment, the glass 30 is the following glass composition (referred to herein as “glass B”), ie 42.7 mol% SiO ₂ , 3.9 mol% B ₂ O. ₃ , 4.7 mol% BaO, 26.6 mol% CaO, 4.5 mol% La ₂ O ₃ , 2.2 mol% ZrO ₂ , 6.1 mol% Nb ₂ O ₅ and 9 Obtained from .3 mol% of TiO _2.

In some embodiments of the method 100 for producing the glass ribbon 30b shown in FIG. 1, the glass 30 has an upper liquid phase viscosity of less than ^{5 × 10 5} poise (5 × 10 ^{4 Pa · s).} According to some embodiments, the glass 30 is ^{less than 5 × 10 5} poise (5 × 10 ⁴ Pa · s), less than 1 × 10 ⁵ poise (1 × 10 ⁴ Pa · s), 5 × 10 ⁴ poise. Less than (5 × 10 ³ Pa · s), less than 1 × 10 ⁴ Poise (1 × 10 ³ Pa · s), less than 5 × 10 ³ Poise (5 × 10 ² Pa · s), 1 × 10 ³ Poise (1) ^{Less than x10 2} Pa · s), 5 x 10 ² Poise (50 Pa · s), less than 100 Poise (10 Pa · s), less than 50 Poise (5 Pa · s), less than 40 Poise (4 Pa · s), 30 Poise It may consist of a composition showing an upper limit liquid phase viscosity of less than (3 Pa · s), less than 20 poises (2 Pa · s), less than 10 poises (1 Pa · s) and all upper upper liquid phase viscosities between these levels. can. According to some embodiments of the method, the upper limit liquid phase viscosity of the glass 30 in step 110 is in the range of about 5 poises (0.5 Pa · s) to about 50,000 poise (5000 Pa · s). Further, in a particular embodiment of Method 100, the glass 30 is obtained from a glass composition having a refractive index of about 1.5 to about 2.1. In some embodiments, the glass 30 has a refractive index of about 1.6 to about 2.0, about 1.65 to about 1.9, about 1.7 to about 1.85 and all between these levels. It is obtained from a glass composition having a refractive index value of.

With reference to the pouring step 110 of the method 100 for manufacturing the glass ribbon 30b shown in FIG. 1, this step can be performed so that the glass 30 flows at a temperature of 1000 ° C. or higher. The glass 30 has about 1000 ° C. to about 1500 ° C., about 1000 ° C. to about 1400 ° C., about 1000 ° C. to about 1300 ° C., about 1000 ° C. to about 1250 ° C., about 1000 ° C. to about 1200 ° C., and about 1000 ° C. to about 1150. It can be fluidized at ° C. and at temperatures of all values between these levels. The pouring step 110 can be performed so that the glass 30 has a viscosity of less than ^{5 × 10 4} poise (5 × 10 ^{3 Pa · s) as it flows from the melting apparatus 10.} In some embodiments, the glass 30 exiting the outlet element 4 of the melting apparatus 10 and flowing into the caster 20 is ^{less than 5 × 10 4} poises (5 × 10 ³ Pa · s) and 1 × 10 ⁴ poises (5 × 10 3 Pa · s). Less than 1 x 10 ³ Pa · s) 5 x 10 Less than ³ Poise (5 x 10 ² Pa · s) 1 x 10 Less than ³ Poise (1 x 10 ² Pa · s) 5 x 10 ² Poise (50 Pa · s) Less than s), less than 100 poises (10 Pa · s), less than 50 poises (5 Pa · s), less than 40 poises (4 Pa · s), less than 30 poises (3 Pa · s), less than 20 poises (2 Pa · s), 10 It has a viscosity of less than Poise (1 Pa · s) and all viscosities between these levels. According to some embodiments of Method 100, the glass 30 as it exits the melting apparatus 10 is about 10 Poises (1 Pa · s) to about 1000 Poises (100 Pa · s) or about 10 Poises during step 110. It has a viscosity in the range of (1 Pa · s) to about 50,000 poise (5,000 Pa · s).

Revisiting step 110 of method 100 for manufacturing the glass ribbon 30b shown in FIG. 1, this step has a width (W _cast ) 22 of about 200 mm to about 5 meters (m) and a thickness of 1 mm to about 500 mm. The cast glass 30a is formed by pouring the glass 30 into the caster 20 having the (t) 24 (see FIG. 2). In some embodiments, the width (W _cast ) 22 of the caster 20 is about 200 mm to about 5 meters (m), about 250 mm to about 5 m, about 300 mm to about 5 m, about 350 mm to about 5 m, about 400 mm to about 400 mm. 5 m, about 450 mm to about 5 m, about 500 mm to about 5 m and all width values between these levels. According to some embodiments, the width (W _cast ) 22 of the casters 20 is about 200 mm to about 5 m, about 200 mm to about 4 m, about 200 mm to about 3 m, about 200 mm to about 2 m, about 200 mm to about 1 m, Values of about 200 mm to about 0.9 m, about 200 mm to about 0.8 m, about 200 mm to about 0.7 m, about 200 mm to about 0.6 m, about 200 mm to about 0.5 m and all widths between these levels. Is. Further, in some embodiments, the thickness (t) 24 of the caster 20 (see FIG. 2) is about 1 mm or more, about 2 mm or more, about 3 mm or more, about 4 mm or more, about 5 mm or more, about 7 mm or more. Any of about 8 mm or more, about 9 mm or more, about 10 mm or more, about 15 mm or more, about 20 mm or more, about 25 mm or more, about 30 mm or more, about 35 mm or more, about 40 mm or more, about 45 mm or more, about 50 mm or more, or about 500 mm. The thickness.

Referring now to step 120 of method 100 to produce a glass ribbon 30b shown in FIG. 1, the viscosity of this step is at least 10 ⁸ poise cast glass 30a in the caster 20 ⁽¹⁰ 7 Pa · s) And for cooling to a temperature of 50 ° C. or higher. Therefore, as understood by those skilled in the art of the present disclosure, for example, when the cast glass 30a is conveyed by the traction device 40 in the direction of the arrow shown in FIG. 1, the caster 20 pulls the cast glass 30a 50. The casters 20 may be of various constructions of various materials, eg, with or without additional cooling capacity, provided that the glass 30 can be cooled through a devitrification zone for cooling to a temperature above ° C. can. In step 120 of cooling the cast glass 30a, the maximum growth rate of any crystal phase is less than 10 μm / min from the upper liquid phase viscosity of the glass 30a to the lower liquid phase viscosity (also referred to herein as the “devitrification zone”). Can be done as is. In some embodiments, step 120 of cooling the cast glass 30a has a maximum growth rate of any crystal phase of the glass 30 passing through the devitrification zone of less than 10 μm / min, less than 9 μm / min, 8 μm / min, 7 μm. Less than / min, less than 6 μm / min, less than 5 μm / min, less than 4 μm / min, less than 3 μm / min, less than 2 μm / min, less than 1 μm / min, less than 0.5 μm / min, less than 0.1 μm / min, 0 It is done to be less than 0.01 μm / min and all growth rates below and / or between these rates. In particular, the maximum crystal growth rate (Vmax) of the compositions of glass A and glass B is about 6 to 7 μm / min at 1030 ° C. and about 2 to 3 μm / min at 1050 ° C., respectively. Therefore, in a plurality of aspects of the method 100, the cooling step 120 is such that the crystal growth rate of the glass 30 when manufactured from the composition of glass A or glass B is smaller than these maximum crystal growth rate (Vmax) values. Including doing.

According to another aspect of the method 100 for producing the glass ribbon 30b shown in FIG. 1, the cooling step 120 cools the cast glass 30a to a critical cooling rate of the cast glass 30a or a higher temperature (ie, 50 ° C.). Can be done to cool to (above). As used herein, a "critical cooling rate" is determined by melting a plurality of samples of a given glass composition to its glass transition temperature at a variety of selected cooling rates. The sample is then cross-sectioned by standard cutting and polishing techniques, evaluated at 100x by light microscopy, and the presence of crystals on the bulk and its free surface (ie, the top surface, the bottom surface of the interface with the exposed surface and the crucible, etc.). Is confirmed. The critical cooling rate corresponds to the sample with the lowest cooling rate and no crystals on its surface and bulk.

According to one embodiment, the traction device 40 is one or more for controlling the speed of the cast glass 30a as the cast glass 30a passes through the casters 20 during the cooling step 120 and the transport step 130, respectively. Including rollers. Advantageously, the cooling step 120 is continuous with the method 100, taking into account the additional heating that takes place so that the cast glass 30a does not fall below 50 ° C. and is performed between the subsequent transport steps 130 and the stretching step 140, respectively. It is done to ensure that the sex is maintained. In some embodiments, the cast glass 30a remains in the cast glass 30a after the cooling step 120 in order to reheat the cast glass 30a from its core towards its surface during each subsequent transport step 130 and stretching step 140, respectively. Thermal energy is used.

In some embodiments of method 100 shown in FIG. 1, the temperature during the cooling step 120 is 50 ° C. or higher, 100 ° C. or higher, 150 ° C. or higher, 200 ° C. or higher, 250 ° C. or higher, 300 ° C. or higher, 350. All temperature values between ° C. and above, 400 ° C. and above, 450 ° C. and above, 500 ° C. and above, and these lower threshold levels. In an embodiment of Method 100, the cooling step 120 comprises cooling the cast glass 30a in the caster 20 to a temperature below 800 ° C. and above 50 ° C. According to embodiments of Method 100, steps 110-140 of pouring, cooling, pulling and stretching are such that the cast glass 30a is at a temperature below 50 ° C. to ensure that Method 100 can be carried out continuously, for example. It is done so that it does not reach. According to some embodiments of the method 100, the step of cooling 120, cast glass 30a in the caster 20 is at least 10 ⁸ poises ⁽¹⁰ 7 Pa · s), at least 5 × 10 ⁸ poise (5 × ¹⁰ 7 Pa S), at least 10 ⁹ Poise (10 ⁸ Pa · s), at least 5 × 10 ⁹ Poise (5 × 10 ⁸ Pa · s), at least 10 ¹⁰ Poise (10 ⁹ Pa · s), at least 5 × 10 ¹⁰ Poise The viscosity is (5 × 10 ⁹ Pa · s) or higher. In some embodiments of the method 100 to produce a glass ribbon 30b, the cooling step 120 is maintained at a viscosity temperature cast glass 30a is about 650 ° C. ~ about 750 ° C. and at least 10 ⁹ poises ⁽¹⁰ 8 Pa · s) It is done so that.

With reference to the method 100 for manufacturing the glass ribbon 30b shown in FIG. 1, this method further includes a transport step 130 for transporting the cast glass 30a from the casters 20. The transport mode of step 130 can be partially performed by the action of the traction device 40. Specifically, the cast glass 30a is moved by the traction device 40 from the end of the caster 20 toward the optional bank of the heater 50 and the edge roller 60 during step 130, or is conveyed in another form. NS. According to a plurality of embodiments of the method 100, the transfer step 130 can be performed so as to control the speed of the cast glass 30a so that, for example, the flow rate of the cast glass 30a fluctuates by only 1% or less.

Method 100 to produce a glass ribbon 30b, the step 140 of drawing average viscosity lower than the viscosity of the cast glass 30a in the conveying step 130, the cast glass 30a with average viscosity lower than, for example, 10 ⁷ poises ⁽¹⁰ 6 Pa · s) Also includes. Step 140 also includes heating the cast glass 30a to the average viscosity of less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s), for example, using optional bank of heaters 50. Heater 50, if present, resistive heating elements, induction heating element, such as an infrared heating element and that the present disclosure of the other will be understood by those skilled in the art of the cast glass 30a 10 ⁷ poises (10 6 ^Pa · s ) Can include, but is not limited to, any variety of structures and components for heating to an average viscosity of less than. In some embodiments, aspects of step 140 comprises heating the cast glass 30a to the average viscosity of less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s) do not provide additional thermal energy to cast glass 30a. For example, the stretching step 140 may be performed as the core of the cast glass 30a to heat the surface of the cast glass 30a on an average viscosity of at least partially less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s).

Further, the cast glass 30a has a final thickness (t) 34 having a width 32 ( _ribbon ) of the caster 20 having a width 22 (W _cast ) or less and a thickness (t) 24 or less of the cast glass 30a. A stretching step 140 of stretching the cast glass 30a is performed in order to stretch the glass ribbon 30b (see also FIG. 2). In some embodiments, the glass ribbon 30b of width _{32 (W ribbon)} is about 10mm~ about 5 mm, about 20mm~ about 5 mm, about 30mm~ about 5 mm, about 40mm~ about 5 mm, about 50mm~ about 5 mm, about 100mm ~ About 5 mm, about 200 mm to about 5 mm, about 250 mm to about 5 mm, about 300 mm to about 5 mm, about 350 mm to about 5 mm, about 400 mm to about 5 mm and all width values between these levels. The aspect of step 140 for stretching the cast glass 30a to the ribbon 30b can be partially performed by the action of the edge roller 60 shown in FIG.

According to some embodiments of the method 100 for producing the glass ribbon 30b, the stretching step 140 takes less than 30 minutes with respect to the cast glass 30a (ie, steps 120 for cooling the cast glass 30a and the cast glass 30a). After step 130 for transporting (before subsequent step 150 for cooling the glass ribbon 30b to ambient temperature). It should be understood that according to Method 100, the cast glass 30a is at a temperature of about 50 ° C. or higher during each of steps 110-140. In some embodiments, the stretching step 140 maintains a time of at least 30 seconds, 30 minutes or less, 25 minutes or less, 20 minutes or less, 15 minutes or less, 10 minutes or less, 5 minutes or less, and their upper limits. It can be done for all time below the threshold. As mentioned above, a plurality of aspects of the method 100 for producing the glass ribbon 30b are such that the cast glass 30a is maintained at a viscosity sufficiently low to affect the stretching mode of this step, that is, the cast glass 30a. The temperature and / or time in the stretching step 140 to ensure that the cast glass 30a hardly crystallizes at all or little while converting to a glass ribbon 30b having a width 32 smaller than the width 22 of the cast glass 30a. It is done to be advantageously minimized.

According to some embodiments of the method 100 to produce a glass ribbon 30b shown in FIG. 1, the transport steps 130 and stretching step 140, cast glass 30a is less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s) Less than 5, × 10 ⁶ Poise (5 × 10 ⁵ Pa · s), less than 10 ⁶ Poise (10 ⁵ Pa · s), less than 5 × 10 ⁵ Poise (5 × 10 ⁴ Pa · s), 10 ⁵ Poise (10) ^{Less than 4} Pa · s), 5 × 10 ⁴ Poise (5 × 10 ³ Pa · s), while 10 ⁴ Poise (10 ³ Pa · s) or more, average viscosity and all averages between these levels It is done so that the viscosity is maintained. The method in some embodiments of 100, an average viscosity of cast glass 30a is 10 ⁶ poise at a temperature of 750 ° C. to 900 ° C. during the transport steps 130 and stretching steps ^{140 (10 5 Pa · s)} ~10 4 It is maintained at a poise ⁽¹⁰ 3 Pa · s).

Referring again to method 100 for manufacturing the glass ribbon 30b shown in FIG. 1, the final cooling step 150 of the method may include cooling the glass ribbon 30b to ambient temperature. As mentioned above, a plurality of embodiments of the method 100 are carried out so that the glass 30 and the cast glass 30a are maintained at a temperature of 50 ° C. or higher during steps 110-140, so that the method 100 is continuous. Can be reliably implemented. According to some embodiments of Method 100, steps 110-140 are 50 ° C. or higher, 75 ° C. or higher, 100 ° C. or higher, 150 ° C. or higher, 200 ° C. or higher, 250 ° C. or higher, 300 ° C. or higher, and their lower limit temperatures. It is done at temperatures of all lower temperature thresholds in between. Further, step 150 for cooling the glass ribbon 30b can be performed with or without external cooling, as will be appreciated by those skilled in the art of the present disclosure. Further, in some aspects of Method 100, the edge roller 60 may include a cooling capacity for performing some or all of the cooling in the cooling step 150.

Further referring to the method 100 for producing the glass ribbon 30b shown in FIG. 1, a plurality of embodiments of the method 100 are carried out so that the glass ribbon 30b has a thickness variation of less than 200 μm. According to some embodiments, the glass ribbon 30b is less than 200 μm, less than 150 μm, less than 100 μm, less than 75 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, less than 10 μm, less than 5 μm, less than 4 μm, less than 3 μm, It can have thickness variations of less than 2 μm, less than 1 μm, less than 0.5 μm and all thickness variation levels between these levels. From a practical point of view, the glass ribbon 30b manufactured according to Method 100 can have a thickness variation of only 0.01 μm. In some embodiments of Method 100, the glass ribbon 30b produced by Method 100 has a warp of less than 500 μm. According to some embodiments, the glass ribbon 30b produced by Method 100 is less than 500 μm, less than 400 μm, less than 300 μm, less than 200 μm, less than 150 μm, less than 100 μm, less than 50 μm, less than 40 μm, less than 30 μm, less than 20 μm, It has warpage values of less than 10 μm, less than 5 μm, less than 0.1 μm, more than 0.05 μm and all warpage values between these levels. From a practical point of view, the glass ribbon 30b manufactured according to Method 100 can have a warp of only 0.01 μm. In addition, some embodiments of Method 100 are performed such that the glass ribbon 30b has a surface roughness (Ra) of less than 5 μm (measured prior to any post-treatment). According to some embodiments, the glass ribbon 30b produced by Method 100 is less than 5 μm, less than 4 μm, less than 3 μm, less than 3 μm, less than 2 μm, less than 1 μm, less than 0.75 μm, less than 0.5 μm, 0. It has surface roughness values (Ra) of less than 25 μm, less than 0.1 μm, less than 50 nm, only 10 nm and all surface roughness values between these levels. According to one embodiment, the glass ribbon 30b produced by Method 100 is less than 1 μm, less than 0.9 μm, less than 0.8 μm, less than 0.7 μm, less than 0.6 μm, less than 0.5 μm, less than 0.4 μm. Surface roughness (Ra) of less than 0.3 μm, less than 0.2 μm, less than 0.1 μm, less than 90 nm, less than 80 nm, less than 70 nm, less than 60 nm, less than 50 nm, less than 40 nm, less than 30 nm, less than 20 nm, only 10 nm. It has all surface roughness values between these levels.

Here, with reference to FIG. 2, a schematic view of an apparatus that can be used according to the method 100 (see FIG. 1) for manufacturing the glass ribbon 30b according to the present disclosure is provided. Specifically, FIG. 2 shows, among other features, a melting device 10a with an orifice 4a, casters 20 and heater 50. In all other respects, the device shown in FIG. 2 is equal to or substantially similar to the device shown in FIG. 1 for use in method 100 for making the glass ribbon 30b ( See FIG. 1 and the description above). Thus, similarly numbered elements in FIG. 2 have the same or substantially similar function and structure as those shown in FIG. Further, according to an embodiment of method 100 (see FIG. 1), the pouring step 110 is from an orifice 4a to a glass 30 of a melting apparatus 10a (see FIG. 2) having a maximum dimension of less than 5 meters (m). It can be done by pouring. The maximum dimension 12 of the orifice 4a _{can be the width (W cast} ) 22 or less of the caster 20. Further, the width 14 of the orifice 4a is about 1 mm or more, about 2 mm or more, about 3 mm or more, about 4 mm or more, about 5 mm or more, about 7 mm or more, about 8 mm or more, about 9 mm or more, about 10 mm or more, about 15 mm or more, about. It can have any width of 20 mm or more, about 25 mm or more, about 30 mm or more, about 35 mm or more, about 40 mm or more, about 45 mm or more, about 50 mm or more, or about 500 mm.

Referring again to FIG. 2, depending on the viscosity of the glass 30 flowing from the melting apparatus 10a during the pouring step 110 (see FIG. 1), the glass 30 is approximately equal to or greater than the maximum dimension 12 of the orifice 4a. It can have a small width. Therefore, the maximum dimension 12 of the orifice 4a can be set to _{the width (W cast) 22 or less of the caster 20.} In another embodiment, the maximum dimension 12 of the orifice 4a is, for example, for a composition of glass 30 having a relatively low upper limit liquid phase viscosity (eg, 5 poise (0.5 Pa · s) to 50,000 poise (5000 Pa · s)). , Can be larger than the width (W _{cast) 22 of the caster 20.} In particular, these glasses, when melted, can become a "neck" as they leave the orifice 4a of the melting device 10a, and the caster 20 has a width 22 that is smaller than the maximum dimension 12 of the orifice 4a of the melting device 10a. Can flow into.

As also shown in FIG. 2, the glass ribbon 30b has _{an outer diameter in the range from substantially the same as the width 32 (Wribbon} ) of the glass ribbon 30b to about 50% of the width 32 of the glass ribbon 30b. It can be cut into the wafer 36 to have. In a plurality of embodiments, the step of cutting the wafer 36 from the glass ribbon 30b can be performed after the cooling step 150 of method 100 shown in FIG. 1 outlined above. The wafer 36 shown in the exemplary form in FIG. 2 is in the form of an optical disc. However, the wafer 36 can take any variety of shapes, such as, but not limited to, squares, rectangles, circles, ellipses, and the like. According to some embodiments, the wafer 36 can have a thickness of 34 (t) of about 2 mm or less and a maximum dimension of about 100 mm to about 500 mm (eg, diameter, width or other maximum dimension). In some embodiments, the wafer 36 has a thickness of 34 (t) of about 1 mm or less and a maximum dimension of 150 mm to about 300 mm. The wafer 36 can also have a thickness in the range of about 1 mm to about 50 mm or about 1 mm to about 25 mm. Wafer 36 can also have maximum dimensions in the range of about 25 mm to about 300 mm, about 50 mm to about 250 mm, about 50 mm to about 200 mm or about 100 mm to about 200 mm. Advantageously, the wafer 36 formed according to method 100 has the same thickness variation level, surface roughness and / or warpage level as outlined above in connection with the glass ribbon 30b, without additional surface polishing. Can be shown. In some embodiments, wafers 36 can be ground and polished to some extent in their outer diameter to obtain the final dimensions of the final product, eg, a lens for optical applications.

Here, referring to FIGS. 3A and 3B, an overflow melting apparatus 10b provided with an isopipe 8 for pouring the glass 30 used in the method 100 for manufacturing the glass ribbon 30b (see FIG. 1) according to one embodiment. A schematic is shown. In particular, the overflow melting device 10b can be used during the step 110 of pouring the glass 30. According to one embodiment, the glass 30 can be melted according to the melting mode of Method 100 and flow from the container 6 into the isopipe 8. Vessel 6 contains any of a variety of heating elements understood by those skilled in the art of the present disclosure regarding melting of glass. When the glass 30 overflows from a weir or a similar aspect of the isopipe 8, it flows over the isopipe 8 into the caster 20 (not shown). As shown in the exemplary embodiments of FIGS. 3A and 3B, the overflow melting device 10b can include a weir inside the isopipe 8, which allows the glass 30 to overflow and outside the isopipe 8. Can spread along the surface. In such an embodiment, the glass 30 can extend to a width of 4b on one or both sides of the isopipe 8. As shown in FIGS. 3A and 3B, the isopipe 8 has one side angled by an angle of 9 from the vertical. Typically, the angle 9 is about 0 ° to 30 °, preferably 0 ° to 20 °. According to one embodiment of the method 100 for manufacturing the glass ribbon 30b (see FIG. 1), the overflow melting apparatus 10b has a width 4b of less than 5 m, which is less than or equal to _{the width 22 (W cast) of the caster 20.} be.

Although exemplary embodiments and examples have been described for illustrative purposes, the aforementioned description is not intended in any way to limit the scope of the disclosure and attachment claims. Accordingly, modifications and modifications can be made to the embodiments and examples described above without substantially departing from the spirit and various principles of the present disclosure. All such amendments and changes are included within the scope of this disclosure and are intended herein to be protected by the following claims.

Hereinafter, preferred embodiments of the present invention will be described in terms of terms.

Embodiment 1
A method for manufacturing glass ribbons
In order to mold the cast glass, a _{step of pouring the glass into a caster having a width (W cast} ) of about 100 mm to about 5 m and a thickness (t) of about 1 mm to about 500 mm,
And cooling the cast glass in the caster to a viscosity of at least 10 ⁸ poises ⁽¹⁰ 7 Pa · s),
The step of transporting the cast glass from the caster and
The cast glass was heated to an average viscosity of less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s), and the cast _glass, comprising the step of stretching the glass ribbon having a width less than _{W cast (W ribbon),} A step of stretching the cast glass from the casters, followed by
Including the step of cooling the glass ribbon to ambient temperature.
The cast glass during the cooling, transporting and stretching steps is above about 50 ° C.
Method.

Embodiment 2
The method according to the first embodiment, wherein the pouring step includes a step of pouring the glass with a viscosity of about 50,000 poise (5,000 Pa · s) to about 10 poise (1 Pa · s).

Embodiment 3
The method according to embodiment 1 or 2, wherein the cast glass during the cooling, transporting and stretching steps is at about 200 ° C. or higher.

Embodiment 4
The step of cooling the cast glass, the cast glass in the caster is carried out as cooled to a viscosity of at least 10 ⁹ poises (10 8 ^Pa · s), any one of embodiments 1 to 3 The method described.

Embodiment 5
Step, the cast glass is made to be heated to an average viscosity of less than 10 ⁶ poise (10 5 ^Pa · s), any one method of claimed in Embodiment 1 to 4 to the drawing.

Embodiment 6
The method according to any one of embodiments 1 to 5, wherein the glass comprises ^{an upper limit liquid phase viscosity of less than 5 × 10 5} poise (5 × 10 ^{4 Pa · s).}

Embodiment 7
The glass includes borosilicate glass, aluminhosilicate glass, aluminosilicate glass, fluorosilicate glass, phosphate glass, fluorophosphate glass, sulfophosphate glass, germanate glass, and vanazine salt. The method according to any one of embodiments 1 to 6, comprising a composition selected from the group consisting of glass, borate glass and phosphate glass.

8th Embodiment
The pouring step includes a step of pouring the glass at a temperature of 1000 ° C. or higher, and a step of cooling the cast glass includes a step of cooling the cast glass in the caster to a temperature of 800 ° C. or lower and 50 ° C. or higher. , The method according to any one of embodiments 1 to 7.

Embodiment 9
The method according to any one of embodiments 1 to 8, wherein the width (W _cast ) is from about 400 mm to about 5 m and the thickness (t) is from about 5 mm to about 500 mm.

Embodiment 10
The method according to any one of embodiments 1 to 9, wherein the stretching step is performed on the cast glass for about 30 seconds to about 30 minutes after the step of cooling the cast glass.

Embodiment 11
Wherein the step of stretching, the cast glass core is performed so as to heat an average viscosity of at least partially less than 10 ⁷ poise (10 6 ^Pa · s) the surface of the cast glass, from the embodiment 1 to 10 The method according to any one of the above.

Embodiment 12
The method according to any one of embodiments 1 to 11, wherein the glass ribbon has a thickness variation of about 0.01 μm to about 50 μm.

Embodiment 13
The method according to any one of embodiments 1 to 12, wherein the glass ribbon has a warp of about 0.01 μm to about 100 μm.

Embodiment 14
The pouring step is performed by pouring glass through an orifice having a width of about 100 mm to about 5 m in a melting device, wherein the width of the orifice is less than or equal to the _{width (W cast) of the caster.} The method according to any one of 1 to 13.

Embodiment 15
The method according to embodiment 14, wherein the melting device is an overflow molding device.

Embodiment 16
Any of embodiments 1 to 15, wherein the maximum crystal growth rate of any crystal phase of the cast glass is from about 0.01 μm / min to about 10 μm / min during the steps of cooling, transporting and stretching the cast glass. Or one method described.

Embodiment 17
Any of embodiments 1 to 15, wherein the maximum crystal growth rate of any crystal phase of the cast glass is from about 0.01 μm / min to about 5 μm / min during the steps of cooling, transporting and stretching the cast glass. Or one method described.

Embodiment 18
The composition of the glass further comprises a crystal growth rate of any crystal phase of about 0.01 μm / min to less than 1 μm / min as measured from the upper limit liquid phase temperature to the lower limit liquid phase temperature of the cast glass. The method according to Form 7.

Embodiment 19
The method according to any one of embodiments 16 to 18, wherein the glass ribbon has a thickness variation of about 0.01 μm to about 50 μm.

20th embodiment
The method according to any one of embodiments 16 to 19, wherein the glass ribbon has a warp of about 0.01 μm to about 100 μm.

21st embodiment
The method according to any one of embodiments 16 to 20, wherein the step of cooling the cast glass is performed to cool the cast glass to a temperature equal to or higher than the critical cooling rate for the cast glass.

Embodiment 22
It's a glass article
Includes an unpolished glass ribbon with a thickness of about 1 mm to about 25 mm and a width of about 25 mm to about 200 mm.
The glass ribbon includes borosilicate glass, aluminhosilicate glass, aluminosilicate glass, fluorosilicate glass, phosphate glass, fluorophosphate glass, sulfophosphate glass, germanate glass, and vanadic acid. Contains a composition selected from the group consisting of salt glass, phosphate glass and borate glass.
The composition further comprises an upper liquid phase viscosity of less than 5 × 10 ⁵ poise (5 × 10 ^{4 Pa · s).}
Further, the glass ribbon can be cut into glass wafers having a thickness variation of about 0.01 μm to about 50 μm and a warp of about 0.01 μm to about 200 μm.
Glass goods.

23rd Embodiment
22. The glass article according to embodiment 22, wherein the glass ribbon has a refractive index of about 1.65 to about 1.90.

Embodiment 24
The glass article according to embodiment 22 or 23, wherein the glass ribbon can be cut into a glass wafer having a thickness variation of about 0.01 μm to about 0.5 μm and a warp of about 0.01 μm to about 10 μm.

25.
The glass article according to any one of embodiments 22 to 24, wherein the glass ribbon has a thickness variation of about 0.01 μm to about 50 μm and a warp of about 0.01 μm to about 200 μm.

Embodiment 26
It's a glass article
Includes unpolished glass wafers with a thickness of about 1 mm to about 25 mm and a width of about 100 mm to about 200 mm.
The glass wafer includes borosilicate glass, aluminhosilicate glass, aluminosilicate glass, fluorosilicate glass, phosphate glass, fluorophosphate glass, sulfophosphate glass, germanate glass, and vanadic acid. Contains a composition selected from the group consisting of salt glass, phosphate glass and borate glass.
The composition further comprises an upper liquid phase viscosity of less than 5 × 10 ⁵ poise (5 × 10 ^{4 Pa · s).}
Further, the glass wafer has a thickness variation of about 0.01 μm to about 50 μm and a warp of about 0.01 μm to about 200 μm.
Glass goods.

Embodiment 27
The glass article according to embodiment 26, wherein the glass wafer has a refractive index of about 1.65 to about 1.90.

28.
The glass article according to embodiment 26 or 27, wherein the glass wafer has a thickness variation of about 0.01 μm to about 0.5 μm and a warp of about 0.01 μm to about 10 μm.

Claims (10)

A method for manufacturing glass ribbons
In order to mold the cast glass, a _{step of pouring the glass into a caster having a width (W cast} ) of about 100 mm to about 5 m and a thickness (t) of about 1 mm to about 500 mm,
And cooling the cast glass in the caster to a viscosity of at least 10 ⁸ poises ⁽¹⁰ 7 Pa · s),
The step of transporting the cast glass from the caster and
The cast glass was heated to an average viscosity of less than 10 ⁷ poise ⁽¹⁰ 6 Pa · s), and the cast _glass, comprising the step of stretching the glass ribbon having a width less than _{W cast (W ribbon),} A step of stretching the cast glass from the casters, followed by
Including the step of cooling the glass ribbon to ambient temperature.
The cast glass during the cooling, transporting and stretching steps is above about 50 ° C.
Method. The pouring step includes pouring the glass with a viscosity of about 50,000 poise (5,000 Pa · s) to about 10 poise (1 Pa · s), and the step of cooling the cast glass is in the caster. the cast glass was carried out as cooled to a viscosity of at least 10 ⁹ poises ⁽¹⁰ 8 Pa · s), the step of stretching, the average viscosity of the cast glass is less than 10 ⁶ poise ⁽¹⁰ 5 Pa · s) The method according to claim 1, wherein the method is carried out so as to be heated to. The method of claim 1, wherein the cast glass during the cooling, transporting and stretching steps is at about 200 ° C. or higher. The method according to claim 1, wherein the stretching step is performed on the cast glass for about 30 seconds to about 30 minutes after the step of cooling the cast glass. Step, the cast glass core is performed so as to heat an average viscosity of at least partially less than 10 ⁷ poise (10 6 ^Pa · s) the surface of the cast glass The method of claim 1 wherein the stretching .. The pouring step is performed by pouring glass through an orifice having a width of about 100 mm to about 5 m in a melting device, wherein the width of the orifice is less than or equal to the _{width (W cast) of the caster.} The method described. Any of claims 1 to 6, wherein the maximum crystal growth rate of any crystal phase of the cast glass is from about 0.01 μm / min to about 10 μm / min during the steps of cooling, transporting and stretching the cast glass. Or the method described in item 1. The glass includes borosilicate glass, aluminhosilicate glass, aluminosilicate glass, fluorosilicate glass, phosphate glass, fluorophosphate glass, sulfophosphate glass, germanate glass, and vanazine salt. It contains a composition selected from the group consisting of glass, borate glass and phosphate glass, and the composition of the glass is about 0 when measured from the upper limit liquid phase temperature to the lower limit liquid phase temperature of the cast glass. The method according to any one of claims 1 to 6, further comprising a crystal growth rate of any crystal phase of 0.01 μm / min to less than 1 μm / min. The method according to any one of claims 1 to 8, wherein the glass ribbon has a thickness variation of about 0.01 μm to about 50 μm and a warp of about 0.01 μm to about 100 μm. It's a glass article
Includes an unpolished glass ribbon with a thickness of about 1 mm to about 25 mm and a width of about 25 mm to about 200 mm.
The glass ribbon includes borosilicate glass, aluminhosilicate glass, aluminosilicate glass, fluorosilicate glass, phosphate glass, fluorophosphate glass, sulfophosphate glass, germanate glass, and vanadic acid. Contains a composition selected from the group consisting of salt glass, phosphate glass and borate glass.
The composition further comprises an upper liquid phase viscosity of less than 5 × 10 ⁵ poise (5 × 10 ^{4 Pa · s).}
Further, the glass ribbon can be cut into glass wafers having a thickness variation of about 0.01 μm to about 50 μm and a warp of about 0.01 μm to about 200 μm.
Glass goods.

Images