KR20180033294A - Thermally enhanced glass and related systems and methods - Google Patents

Abstract

The present invention relates to a process and a system for manufacturing such reinforced glass or glass-ceramic sheets or articles, as well as reinforced glass or glass-ceramic sheets or articles. The process includes cooling the glass sheet by non-contact thermal conductivity sufficient to compress the surface of the sheet and to fix the center tension. As a result, the process produces a thermally enhanced glass sheet.

Description

Thermally enhanced glass and related systems and methods

This application claims priority under 35 USC §119 to U.S. Provisional Patent Application No. 62 / 288,851, filed January 29, 2016, and also assigned to 35 U.S.C. U.S. Patent Application No. 14 / 814,232, filed July 30, 2015, U.S. Patent Application No. 14 / 814,181, filed July 30, 2015, filed July 30, 2015, U.S. Patent Application No. 14 / 814,274 filed on July 30, 2015, U.S. Patent Application No. 14 / 814,293 filed on July 30, 2015, U.S. Patent Application No. 14 / 814,303 filed on July 30, 2015, U.S. Patent Application No. 14 / 814,363 filed on March 30, U.S. Patent Application No. 14 / 814,319 filed on July 30, 2015, U.S. Patent Application No. 14 / 814,335 filed on July 30, 2015 , The entire contents of which are hereby incorporated by reference.

The present invention is related to U.S. Provisional Patent Application No. 62 / 031,856, filed July 31, 2014, U.S. Provisional Patent Application No. 62 / 074,838, filed November 4, 2014, U.S. Patent Application No. 14 / 814,181, filed July 30, 2015, July 30, 2015, and U.S. Patent Application Serial No. 60 / 031,856, filed July 30, 2015, U.S. Patent Application No. 14 / 814,274 filed on July 30, 2015, U.S. Patent Application No. 14 / 814,293 filed on July 30, 2015, U.S. Patent Application Serial Nos. 14 / 814,303, 2015 U.S. Patent Application No. 14 / 814,363, filed on July 30, 2007, U.S. Patent Application No. 14 / 814,319, filed July 30, 2015, U.S. Patent Application No. 14 / U.S. Provisional Patent Application No. 62 / 236,296, filed October 2, 2015, U.S. Provisional Patent Application No. 62 / 288,549, filed January 29, 2016, United States of America U.S. Provisional Patent Application No. 62 / 288,666, filed January 29, 2016, U.S. Provisional Patent Application No. 62 / 288,615 filed January 29, 2016, U.S. Patent Application No. 62 / 288,695 filed January 29, 2016, U.S. Provisional Patent Application No. 62 / 288,755 filed on May 29, which is hereby incorporated by reference.

[0001] This disclosure relates generally to thermally controlled (e.g., tempered, tempered, heated, etc.) glasses, and more particularly relates to thermally enhanced glass and thermally enhanced glass, ≪ / RTI >

In the thermal (or "physical) tempering of the glass sheet, the glass sheet is heated to an elevated temperature above the glass transition temperature of the glass, and then the surface of the sheet is cooled rapidly quot; quenching. ") The inner region is cooled more slowly because it is insulated due to the thickness of the glass and the significantly lower thermal conductivity. The differential cooling is the residual of the glass surface region, which balances the residual tensile stress of the central region of the glass Creates compressive stress.

The thermal strengthening of the glass is distinguished from the chemical strengthening of the glass, in which the surface compressive stress is caused by a change in the chemical composition of the glass in the area near the surface by a process such as ion diffusion. In some ion diffusion based processes, the outer portion of the glass is strengthened by exchanging larger ions for smaller ions near the glass surface to give compressive stress (also called negative tensile stress) at or near the surface . Compressive stress is believed to limit crack initiation and / or propagation.

Thermal strengthening of the glass is also distinguished from glass reinforced by a process in which the outer part of the glass is reinforced or arranged by combining the two types of glass. In this process, the layers of the glass composition having different coefficients of thermal expansion are bonded or laminated together at a high temperature. For example, sandwiched molten glass having a higher coefficient of thermal expansion (CTE) between the layers of molten glass with a lower coefficient of thermal expansion (CTE), such that when the glass is cooled, The layers are compressed to re-form compressive stresses on the surface to balance the positive tensile stresses. This surface compressive stress provides reinforcement.

Thermally enhanced glass has advantages over ungardened glass. Surface compression of reinforced glass provides greater resistance to fracture than unincorporated glass. The increase in strength is generally proportional to the amount of surface compressive stress. If the sheet has a significant level of thermal strengthening relative to its thickness, then the sheet will break and will split into smaller fragments than generally large or long pieces with sharp edges. "Dices ", as defined by glass, or by various established standards, destroyed by sufficiently small fragments, are known as safety glass, or" fully tempered "glass, or sometimes simply" tempered "glass .

Since the degree of consolidation depends on the temperature difference between the surface and the center of the glass sheet during quenching, the thinner glass requires a greater cooling rate to achieve the given stress. In addition, thinner glass generally requires higher surface compressive stresses and center tensile stresses to achieve dicing with smaller particles at breakdown. Thus, it has been extremely difficult, if not impossible, to achieve the desired level of tempering in glass having a thickness on the order of 3 mm or less.

The aspects of the present disclosure also relate to glass or glass-ceramics having a stress profile for reinforcing the outer portion of the glass generally. Glass and glass-ceramic products such as sheets of glass can be used for a wide range of applications. Embodiments of this field include but are not limited to applications such as windows, countertops, containers (e.g., food, chemistry), backplanes, fronts, cover glasses, etc. for display devices (e.g., , ≪ / RTI > or other uses.

This disclosure relates in part to highly enhanced thin glass sheets and articles and to methods, processes, and systems for achieving very high levels of thermal strengthening of glass sheets at thicknesses not previously achievable. In various embodiments, the processes and methods of the present disclosure are based on the use of conventional convective gas thermal strengthening processes without the need to contact the glass with liquid or solid heat sinks, transfer rates) and is believed to be superior to glass thickness limit. In such systems and processes, during quenching, the glass only contacts the gas. The disclosed systems and methods enable thermal strengthening, including in a glass sheet with a thickness as thin as at least 0.1 mm (in at least some contemplated embodiments), to "fully tempered" or dicing behavior; And in some embodiments, provides enhanced tempering of the thin glass with low roughness and high flatness resulting from lack of liquid or solid contact during quenching. In various embodiments, these advantageous glass sheet material properties are provided by systems and methods that have substantially lower quenching power requirements than conventional convective glass tempering systems.

One embodiment of the present disclosure relates to a process for thermally enhancing a glass material. The process includes providing a product formed from a glass material. The process includes heating the product above the glass transition temperature of the glass material. The process includes moving the heated product to a cooling station. The cooling station includes a heat sink having a heat sink surface facing the heated product and a gas gap separating the heat sink surface from the heated product such that the heat sink surface is not in contact with the heated product. The process includes cooling the heated product to a temperature below the glass transition temperature such that surface compressive stress and center tensile stress are produced in the product. The product is cooled by transferring heat energy from the heated product to the heat sink by conduction across the gap so that more than 20% of the heat energy leaving the heated product crosses the gap, Lt; / RTI >

Another embodiment of the present disclosure relates to a system for thermally strengthening a glass sheet. The system includes a heating station including a heating element for transferring heat to a glass sheet, and the glass sheet has a first major surface, a second major surface, and a second minor surface between the first and second major surfaces Lt; / RTI > The system includes a cooling station wherein the system includes opposing first and second heat sink surfaces and forms a channel therebetween, wherein the glass sheet is positioned within the channel during cooling. The system includes a gas bearing that delivers pressurized gas to the channel such that the glass sheet is supported in the channel without contacting the first and second heat sink surfaces and the gas bearing defines a gap region. Wherein the gas bearing delivers a gas to the channel such that the total mass flow rate of the gas into the channel is greater than zero and less than or equal to 2 k / gC _p per square meter of gap area, where k is an estimate in the thermal conduction direction G is the distance between the glass sheet and the heat sink surface, and Cp is the specific heat capacity of the gas in the channel.

Another embodiment of the present disclosure relates to an enhanced glass or glass-ceramic article. The article includes a first major surface, a second major surface opposite the first major surface, and an interior region located between the first and second major surfaces. The article comprises an average thickness of less than 2 mm between the first major surface and the second major surface. The product comprises at least 70% by weight silicon dioxide. The ionic content and chemical composition of at least a portion of both the first major surface and the second major surface are the same as the ionic content and chemical composition of at least a portion of the interior region. The first major surface and the second major surface are under compressive stress, the inner zone is under tensile stress, and the compressive stress exceeds 150 MPa. The surface roughness of the first main surface, is 0.2 to 1.5 nm R _a roughness.

Another embodiment of the present disclosure is directed to a process for thermally enhanced glass articles. The process includes heating the product of the glass material above the glass transition temperature of the glass material and supporting the heated product with a flow of pressurized gas. The process includes cooling the heated product within the cooling station, wherein the cooling station includes a heat sink having a heat sink surface facing the heated product and a gas gap separating the heat sink surface from the heated product. The heated product is supported in a gas gap with a flow of pressurized gas so that the heat sink surface is not in contact with the heated product. The heated product is cooled to a temperature below the glass transition temperature in the cooling station, resulting in a surface compressive stress in the product. The flow of pressurized gas is transferred to the gas gap at a flow rate of 50 slpm to 50,000 slpm per square meter of the surface area of the heated product.

Another embodiment of the present disclosure is directed to a system for a thermally enhanced glass sheet having a surface area. The system includes a heating station including a heating element for transferring heat to a glass sheet. The system includes first and second opposing heat sink surfaces and forms a channel therebetween, wherein the glass sheet is positioned within the channel during cooling. The system includes a gas bearing that delivers pressurized gas into the channel such that the glass sheet is supported within the channel. The gas bearing delivers pressurized gas to the channel at a flow rate of 50 slpm to 50,000 slpm per square meter of surface area of the glass sheet.

Another embodiment of the present disclosure relates to an enhanced glass article. The article includes a first major surface, a second major surface opposite the first major surface, and an inner region positioned between the first and second major surfaces. At least one of the first and second major surfaces has a relatively large surface area, i.e., at least 2500 mm < 2 >. Wherein at least one of the first and second major surfaces is under compressive stress and the internal region is under tensile stress and the compressive stress comprises a thermal tempering stress of at least 100 MPa and a catalytic tempering stress of less than 20% do.

Additional features and advantages will be set forth in the description which follows, and in part will be apparent to those skilled in the art from the following detailed description, or to practice the embodiments described herein, including the following detailed description, claims, It will be easily recognized.

It is to be understood that both the foregoing background and the following detailed description are exemplary only and are intended to provide an overview or framework for understanding the nature and features of the claims.

The accompanying drawings are included to provide further understanding and are incorporated in and constitute a part of this specification. The drawings are provided to illustrate one or more embodiments and to explain the principles and operation of the various embodiments in conjunction with the detailed description.

Figure 1 (prior art) is a graph of the blower power required for "complete tempering " with a function of glass thickness.
2 (prior art) is a graph of the blower power required for "complete tempering " according to a function of glass thickness for the previous process or machine O and for a new process or machine N.
Figure 3 (prior art) is a graph of the previous curve O and the new curve N of Figure 2 scaled and superimposed to match on the graph of Figure 1.
4 is a perspective view of a glass or glass-ceramic article or sheet according to an exemplary embodiment.
Figure 5 is a schematic partial cross-sectional view of the thermally enhanced glass sheet of Figure 4 in accordance with an exemplary embodiment.
6 is a graph depicting the estimated tensile stress versus thickness for a glass or glass-ceramic article according to an exemplary embodiment.
Figure 7 shows a portion of a broken glass or glass-ceramic article according to an exemplary embodiment.
Figure 8 is a plot of the fragmentation per square centimeter as a function of positive tensile stress from the experiment.
Figure 9 is a plot of the magnitude of the negative tensile stress at the surface as a function of the initial hot zone temperature from the experiment and represents a threshold for achieving dicing.
10 is a plot of a zero-dimensional surface virtual temperature parameter [theta] s for a virtual temperature obtained by one or more embodiments of the method and system of the present invention.
11 is a plot of the surface compressive stresses calculated by simulation for different glass compositions plotted against the proposed temperability parameter? For the various compositions shown.
12 and 13 are graphs of two parameters P ₁ and P ₂ as a function of the heat transfer coefficient h.
Fig. 14 is a graph of surface compression in MPa units of glass sheet as a function of sheet thickness t in millimeters, showing areas of newly initiated performance as one or more embodiments of the present systems and methods.
Figure 15 is a graph showing compressive stresses as a function of plotted thickness for selected exemplary embodiments of the tempered glass sheet of this disclosure.
16 is a flow chart illustrating some aspects of the method according to the present disclosure.
Figure 17 is a flow chart illustrating some aspects of yet another method according to this disclosure.
FIG. 18 is a cross-sectional view of an embodiment of the present invention, in contrast to the prior art, in which the method and system of the present disclosure enable operation, with regions R and points A, B, A ', and B' .
Figure 19 shows the area R and points A, B, A ', and B' of Figure 18 (although it is shown adjacent to (and positioned against) the reduced size copy of Figure 2 Expression.
Figure 20 (prior art) is a graph of the heat transfer coefficient required for tempering with a function of glass thickness.
21 is a schematic cross-sectional view of a glass sheet cooled by conduction by convection rather than by convection according to an exemplary embodiment;
22 is a schematic cross-sectional view of a conduction enhancing system according to an exemplary embodiment.
23 is a cutaway perspective view of another embodiment of a system similar to that of Fig. 22 according to an illustrative embodiment.
Figure 24 is a cutaway perspective view of an alternate embodiment of the inset feature of Figure 23 in accordance with an exemplary embodiment.
Figure 25 is a cutaway perspective view of yet another alternative embodiment of the insertion feature of Figure 23 in accordance with an exemplary embodiment.
Figure 26 is a flow chart illustrating some aspects of another method according to an exemplary embodiment.
27 is a perspective view of a building having a windshield according to an exemplary embodiment;
28 is a perspective view of a display on a cooking surface according to an exemplary embodiment;
29 is an exploded perspective view of a device including a glass or glass-ceramic article in accordance with an exemplary embodiment.
30 is a perspective view of a glass or glass-ceramic article or sheet according to an exemplary embodiment.
31 is a block diagram of a system including a glass forming or forming and melting system in-line in a thermal processing system according to an exemplary embodiment;
32 is a diagram schematically illustrating a glass ribbon to be thermally processed in a roll-to-roll system according to an exemplary embodiment;

Applicants have recognized the need for improvement in thermal processing of glass, both in the method and system for thermally strengthening glass and in the resulting thermally enhanced glass sheet itself. For example, although thinner, stronger optical-quality glass sheet materials and products containing such glass sheets are useful for many applications, including portable electronic devices, automotive glass, structural glass, and the like. Glass is very strong for compression, but relatively weak for surface tension. By providing compression at the surface of the sheet, which is balanced by tension at the center of the exposed surface, the useful strength of the glass sheet is dramatically increased. However, the traditional thermal strengthening of the glass is generally cheaper and faster than the optional strengthening methods (e.g. chemical strengthening, laminate-based strengthening), but the traditional thermal strengthening of the glass is thin glass Lt; / RTI > and less than < RTI ID = 0.0 > -3mm). ≪ / RTI > Conventional thermal glass strengthening methods are commonly thought to be limited to thicker glass sheets because the level of consolidation depends on the temperature difference created between the surface and the center of the glass sheet during quenching; It is difficult to achieve a sufficient temperature difference between the surface and the center of the thin glass sheet due to the relatively uniform cooling normally occurring throughout the thin glass sheet due to the limitations of the thermal conduction rate of the conventional tempering methods.

On the other hand, the strengthening of thin glass through ion exchange may be time-consuming and cumbersome, such as requiring chemical bathing of glass for an extended period of time. Direct lamination of different types of glass together may require a complex manufacturing process, such as involving a dual-isopipe fusion draw.

Accordingly, glass or glass-ceramic products having a stress profile that results in the strengthening of the glass for a variety of applications, such as windows, culverts, devices, etc., made by processes that are less resource-intensive and / or less cumbersome than conventional processes There is a need for In particular, the processes and systems discussed herein form a glass product having a stress profile that strengthens the outer portion of the glass, which ultimately alleviates cracking and damage while at the same time providing various other desirable glass qualities (e.g., Structure, surface quality, transmittance of visible light, flexibility, etc.), making it easy to use in various automotive glass applications.

The present disclosure provides improved methods and systems that utilize thermal strengthening to produce highly reinforced glass materials, and in particular, highly reinforced thin glass sheets. The method and system solve the various limitations of conventional glass-reinforced processes to achieve a thickness of less than about 3 mm, less than 2 mm, less than 1.5 mm, less than 1.0 mm, less than 0.5 mm, less than about 0.25 mm, and less than about 0.1 mm Lt; RTI ID = 0.0 > glass sheet < / RTI > In particular, Applicants have developed systems and methods that provide a very high rate of thermal conduction that creates a sufficiently large temperature difference between the surface and the center of the glass sheet to provide reinforcement or tempering even on very thin glass sheets.

An overview of conventional thermal tempering techniques and limitations

Conventional industrial processes for thermally strengthening glass require heating the glass sheet to a predetermined temperature in a radiant energy furnace or a convection heating furnace (or "combination mode" heating furnace using both techniques) ("Quenching") through conventional convection, blowing a large amount of ambient air along or against the glass surface. This gas cooling process is predominantly convective, whereby heat transfer is achieved by mass movement (collective movement) of the fluid through diffusion and entrainment as the gas carries heat from the hot glass sheet.

In conventional tempering processes, certain factors can limit the amount of consolidation that is usually considered to be possible in glass sheets, particularly thin glass sheets. There is a partial restriction, since the amount of compressive stress on the finished sheet is directly related to the magnitude of the temperature difference between the surface and the center of the sheet, achieved during quenching. However, the larger the temperature difference during quenching, the more likely the glass will be destroyed during quenching. For a given cooling rate, breakdown can be reduced by starting quenching at a higher initial glass temperature. In addition, higher starting temperatures typically allow the tempered glass sheet to achieve sufficient consolidation potential provided by high cooling rates. However, increasing the temperature of the sheet at the beginning of quenching also has its own potential drawbacks. For example, a high initial glass temperature can result in deformation of the excess sheet, while the sheet is further softened, again restricting the temperature difference that is practically achievable.

In conventional tempering processes, the sheet thickness also imposes significant restrictions on the temperature differences achievable during quenching. The thinner the sheet, the lower the temperature difference between the surface and the center for a given cooling rate during quenching. This is because the glass is thermally insulated from the surface and the glass thickness is thin. Thus, thermal strengthening of thin glass typically requires a higher cooling rate (as compared to thermal strengthening of thicker glass), and therefore, the removal of the faster heat from the outer surface of the glass is more likely to occur at the inner and outer portions of the glass sheet Lt; RTI ID = 0.0 > temperature < / RTI >

By way of example, FIG. 1 shows that there is sufficient ambient air to "fully temper" soda-lime glass ("SLG ") as a function of glass thickness in millimeters, based on industry- It represents the required power (in kilowatt per square meter of glass sheet area) by the air blower used to blow. The required power increases exponentially as the used glass becomes thinner. Thus, glass sheets of about 3 mm thickness were the thinnest fully thermally tempered commercial glass available for many years.

Moreover, the thinner the sheet, the greater the likelihood of deformation at a given ductility (i.e., given viscosity) of the glass. Thus, reducing the thickness directly reduces the achievable temperature difference, and because the risk of deformation of the sheet increases, to achieve the full benefit of higher cooling rates and to avoid glass breakage caused by higher cooling rates there is a tendency to reduce the chance of using a higher sheet temperature to prevent breakage. Thus, in a conventional convective gas glass tempering process, a higher cooling rate increases the air flow rate, reduces the distance of the air nozzle opening to the glass sheet surface, increases the temperature of the glass (at the start of cooling) And, optionally, reducing the temperature of the cooling air.

As a more recent example, the performance curve of Figure 2 (prior art) was disclosed using state of the art glass thermal strengthening equipment. This improved equipment replaces the rollers used to support the glass during heating with a system that continues to use conventional air injection convection processes to cool the glass, but at least utilizes air to support the glass during the last stage of heating . Without roller contact, the glass can be heated to a higher temperature (higher ductility / lower viscosity) before quenching, which, according to the report, allows the production of fully tempered glass at 2 mm thickness. As shown in Figure 2, the reported blower power required to strengthen the 2 mm thick sheet is higher than the higher temperature possible using air to support the glass (curve O) (Curve N)) to 1200 kW / m2 to 400 kW / m2.

Although it represents an advance to be able to produce a fully tempered 2 mm thick glass, the previous curve O and the new curve (FIG. 2) of FIG. 2 N is such that the improvement in performance achieved by the latest convection tempering process (shown in Figure 2) is relatively small and is merely an incremental change under the previous understanding of the energy demand in the convection enhancement of the glass sheet . In Figure 3, the previous curve O and the new curve N of Figure 2 are scaled to match the graph of Figure 1 (cut at the top at 240 kW / m < 2 > for easier viewing of the new curve N To the previous curve (O), which is discarded). From Fig. 3, it is clear that the technique indicated by curve N changes the performance curve of the convective gas quenching process only slightly, as the glass thickness is reduced from 3 mm to 2 mm. The high operating point (blower power of 400 kW / m < 2 > for 2 mm glass) shows a sharp increase in the power still needed to process thinner glass by this method. The sudden increase in airflow and hence the required power, as a matter of engineering practice and economics, is the result of a fully tempered Suggesting the difficulty of advancing below 2 mm thickness while producing glass. Additionally, the very high airflow required can also modify the shape of the thinner sheet. Thus, in order to reach complete tempering of glass with a thickness of less than 2 mm or to reach full tempering at 2 mm in glass with a lower coefficient of thermal expansion ("CTE ") than that of soda- , The Applicant has found that another tempering method / system is needed.

Although alternative thermal strengthening methods for current commercial convection gas enhancement have also been attempted, each has some drawbacks compared to convective gas enhancement. In particular, conventional selective thermal strengthening methods to achieve higher cooling rates typically require at least some liquid or solid contact with the glass surface, rather than just gas contact. This contact with the glass sheet can adversely affect the quality of the glass surface, the glass flatness, and / or the uniformity of the tempering process. These defects can sometimes be perceived by the human eye, especially in terms of reflected light. As will be described in more detail below, in at least some embodiments, the conductive thermal tempering system of the present disclosure reduces or eliminates such contact-related defects.

Liquid contact enhancement, in the form of dipping in a liquid bath or flowing liquid, but also in the form of injection, has been used to achieve a higher cooling rate than convective gas consolidation, but excessive thermal changes across the sheet during the cooling process . ≪ / RTI > In the immersion or immersion-type spray or liquid flow, a large thermal change can occur over a small area due to spontaneous convection in the liquid bath or liquid flow. In finer spraying, the effects of separate spray droplets and nozzle spray patterns also produce significant thermal changes. Excessive thermal changes tend to cause glass break during thermal strengthening by liquid contact, which can be mitigated by limiting the cooling rate, but limiting the cooling rate also lowers the resulting strength which can be achieved. Moreover, the necessary handling of the sheet (to position or hold the sheet in a liquid bath or liquid flow or liquid spray) also results in physical stresses and excessive thermal deformation from physical contact with the sheet, And limits the cooling rate and the resulting strength. Finally, some liquid cooling methods, such as oil immersion and high cooling rate quenching by various spray techniques, can change the glass surface during this cooling, and later removal of the glass material from the sheet surface to create a satisfactory finish .

Solid contact thermal strengthening involves contacting the cold solid surface with the surface of the hot glass. Excessive thermal changes, such as seen in liquid contact enhancement, such as liquid contact enhancement, can easily occur during the quenching process. Any incompleteness in the surface finish of the glass sheet, in the quenching surface, or in the consistency of the thickness of the sheet, results in incomplete contact across several zones of the sheet, and such incomplete contact may cause the glass to break And can also cause undesired birefringence if the sheet is durable. In addition, the contact of the hot glass sheet with the solid object may result in the formation of surface defects, such as chips, checks, cracks, scratches and the like. Achieving good physical contact across the entire surface of the glass sheet can also increase the difficulty as the size of the sheet increases. Physical contact with the solid surface can also mechanically stress the sheet during quenching, increasing the likelihood of breaking the sheet during processing. Moreover, excessive high speed temperature changes in initial contact can cause fracture during sheet processing, whereby contact cooling of thin glass substrates is not commercially feasible.

Summary of applicant's thermally enhanced glass and related conductive cooling processes and methods

This disclosure is based on the discovery that without generating various flaws that are common in conventional processes, for example, without damaging the surface of the glass, not inducing birefringence, without uneven reinforcement, and / Etc., and enhances effective, efficient, and even thermally enhanced thin glass sheets on a commercial scale without exceeding the conventional processes described above. Thin and thermally tempered / tempered glass sheets that have not previously been obtainable can be produced by one or more embodiments disclosed herein. The systems and processes disclosed herein achieve this by providing a very high heat transfer rate in a precise manner with good physical control and careful handling of the glass. In certain embodiments, the processes and systems discussed herein provide a cooling / quenching section that ensures that the Applicants result in a higher thermal enrichment level, in view of the processing of thin glass sheets at higher relative temperatures at the beginning of cooling. A gas bearing of a small-gap is utilized. As described below, this small-gap gas bearing cooling / quenching section achieves a very high heat transfer rate through conductive heat transfer to the heat sink (s) across the gap, rather than using high air flow based convection cooling do. This high-speed, conductive heat transfer is accomplished by supporting the glass on the gas bearing in the gap, without contacting the glass with liquid or solid material. As disclosed below, Applicants have also found, in at least some embodiments, that the processes and systems discussed herein form thermally enhanced glass, specifically thermally enhanced thin glass, with one or more unique properties .

Some embodiments of the glass sheet treated by the method and / or system according to the present disclosure have a higher level of permanently thermally induced stress than previously known. Although not wishing to be bound by theory, it is believed that the achieved level of thermally induced stress can be obtained for a variety of reasons. Here, the high uniformity of heat transfer in the detailed process reduces or eliminates physical and unwanted thermal stresses in the glass, allowing the glass sheet to be tempered at a higher heat transfer rate without breaking. Moreover, the method can be performed at lower glass sheet viscosity (higher initial temperature at the beginning of quenching) while still preserving the desired glass flatness and shape, which provides a much larger change in temperature in the cooling process , Thereby increasing the level of heat strengthening achieved.

Thermally Tempered Glass Sheet

As discussed above, Applicants have developed a system and process for forming thermally enhanced glass sheets, particularly thin glass sheets, and as discussed in this section, thermally enhanced, The thin glass sheet has one or more unique characteristics and / or combinations of properties that could not previously be achieved through conventional thermal or other strengthening methods.

Thermally Tempered Glass Sheet Structure and Dimensions

Referring to Figures 4 and 5, a thermally enhanced glass sheet having a high surface compressive stress and / or a high center tension is shown in accordance with an exemplary embodiment. FIG. 4 shows a perspective view of a thermally enhanced glass or glass-ceramic article or sheet 500, and FIG. 5 is a schematic partial cross-sectional view of a thermally enhanced glass sheet 500 according to one or more embodiments.

4, the reinforced glass or glass-ceramic article 500 (e.g., sheet, beam, plate) includes a first major surface 510, a second major surface 520 A dotted line to the back side of the sheet 500, which may be translucent as shown, and a body 522 extending therebetween. The second major surface 520 is on the opposing surface of the body 522 from the first major surface 510 such that the thickness t of the reinforced glass or glass-ceramic sheet 500 is greater than the thickness of the first and second Is defined as the distance between the major surfaces (510, 520), wherein the thickness (t) is also a measure of the depth. The width w of the reinforced glass or glass-ceramic sheet 500 is defined as the first dimension of one of the first or second major surfaces 510, 520 that is perpendicular to the thickness t. The length l of the reinforced glass or glass-ceramic sheet 500 is determined as a second dimension of one of the first or second major surfaces 510, 520 that is perpendicular to both the thickness t and the width w Is defined.

In an exemplary embodiment, the thickness t of the glass sheet 500 is less than the length l of the glass sheet 500. In another exemplary embodiment, the thickness t of the glass sheet 500 is less than the width w of the glass sheet 500. In another exemplary embodiment, the thickness t of the glass sheet 500 is less than both the length l and the width w of the glass sheet 500. As shown in FIG. 5, the glass sheet 500 includes first and second regions (not shown) that are balanced by a region 550 of the thermally induced permanent tensile stress at the center portion of the sheet Further having regions 530, 540 of thermally induced compressive stress that are permanent at and / or near surfaces 510, 520.

The method and system may be used to form a reinforced glass sheet having a wide range of thicknesses. In various embodiments, the thickness t of the glass sheet 500 is in the range of 0.2 mm, 0.28 mm, 0.4 mm, 0.5 mm, 0.55 mm, 0.7 mm, 1 mm, 1.1 mm, 1.5 mm, 1.8 mm, 2 mm and 3.2 mm, in the range of 0.1 mm to 5.7 or 6.0 mm. Specific embodiments contemplated are those having a thickness of from 0.1 to 20 mm, from 0.1 to 16 mm, from 0.1 to 12 mm, from 0.1 to 8 mm, from 0.1 to 6 mm, from 0.1 to 4 mm, from 0.1 to 3 mm, from 0.1 to 2 mm, Thermally enhanced glass sheet 500 having a thickness t in the range of 0.1 mm to 1 mm, 0.1 to 0.7 mm, 0.1 to 0.5 mm, and 0.1 to 0.3 mm.

In some embodiments, a glass sheet 3 mm or less in thickness is used. In some embodiments, the glass thickness is less than or equal to about 8 mm, less than or equal to about 6 mm, less than or equal to about 3 mm, less than or equal to about 2.5 mm, less than or equal to about 2 mm, less than or equal to about 1.8 mm, Less than about 1.4 mm, less than about 1.2 mm, less than about 1 mm, less than about 0.8 mm, less than about 0.7 mm, less than about 0.6 mm, less than about 0.5 mm, less than about 0.4 mm, less than about 0.3 mm or less than about 0.28 mm.

In some embodiments, thermally enhanced glass sheets have high aspect ratios - that is, the ratio of length to width to width is large. Because the thermal tempering process discussed herein does not rely on high pressure or large volumes of air, various glass sheet properties, such as surface roughness and flatness, are maintained after being tempered using the gas bearings and high heat transfer rate systems discussed herein . Similarly, the thermal tempering process discussed herein is advantageous in that a high aspect ratio glass sheet (i.e., a glass sheet having a high ratio of width to thickness, or a high ratio of width to thickness, or both) And to be thermally strengthened. Specifically, a sheet having a length to thickness of at least about 10: 1, at least 20: 1, and up to 1000: 1 and over and / or a width to thickness ratio ("aspect ratio") can be enhanced. In contemplated embodiments, sheets having an aspect ratio of at least 200: 1, at least 500: 1, at least 1000: 1, at least 2000: 1, at least 4000:

According to an exemplary embodiment, the length l of the reinforced glass or glass-ceramic sheet 500 is at least twice the width w, at least five times the width w, and / (W) or more, such as 50 times or less. In some of these embodiments, the width w of the reinforced glass or glass-ceramic sheet 500 is at least two times the thickness t, at least five times the thickness t, and / (T) or more, such as 50 times or less.

In some embodiments, for example, the length l of the glass or glass-ceramic sheet 500 is at least 3 cm, at least 5 cm, At least 1 cm, such as at least 7.5 cm, at least 20 cm, at least 50 cm, and / or no more than 50 m, such as no more than 10 m, no more than 7.5 m, no more than 5 m. In some such embodiments, the width w of the glass or glass-ceramic sheet 500 is at least 1 cm, such as at least 3 cm, at least 5 cm, at least 7.5 cm, at least 20 cm, at least 50 cm, and / Or 10 m or less, 7.5 m or less, 5 m or less, and 50 m or less. Referring to Figure 4, glass or glass-ceramics may have a thickness of less than 2.5 cm, less than 1 cm, less than 5 mm, less than 2.5 mm, less than 2 mm, less than 1.7 mm, less than 1.5 mm, less than 1.2 mm, In embodiments, it is in the form of a sheet 500 having a thickness t less than 5 cm, such as less than or equal to 1 mm, such as less than or equal to 0.8 mm; And / or the thickness t is at least 10 占 퐉, such as at least 50 占 퐉, at least 100 占 퐉, at least 300 占 퐉.

In other contemplated embodiments, the glass or glass-ceramic article may have a size different from that disclosed herein. In a considered embodiment, the length l, the width w and / or the thickness t of the glass or glass-ceramic article may vary, as in the case of a more complex geometric structure And the dimensions disclosed herein apply at least to the perspective of a corresponding glass or glass-ceramic article having the above-mentioned definition of length (l), width (w), and thickness (t) with respect to each other.

In some embodiments, at least one of the first or second surfaces 510, 520 of the glass sheet 500 has a relatively large surface area. In various embodiments, the first and / or second surface 510, 520 is at least 900 mm 2, at least 2500 mm 2, at least 5000 mm 2, at least 100 cm 2, at least 900 cm 2, at least 250 cm 2, An area of 100 mm 2 and / or an area of 2500 m 2 such as 100 m 2 or less, 5000 cm 2 or less, 2500 cm 2 or less, 1000 cm 2 or less, 500 cm 2 or less, or 100 cm 2 or less. As such, the glass or glass-ceramic sheet 500 may have a thickness, surface quality, and / or strain homogeneity, as discussed herein, other than the methods and systems disclosed herein, It can have a relatively large surface area, which can be difficult or impossible. Moreover, with the exception of the method and system disclosed herein, it is difficult to achieve a stress profile, particularly a negative tensile stress portion (see FIG. 6) of the stress profile, without relying on ion-exchange or changing the type of glass It may not be possible.

Thermally Strengthened Glass Sheet Compression and Tensile Stress

As described above, the thermally-enhanced sheet discussed herein can have a very high surface compressive stress, for example, in regions 530 and 540 shown in Figure 5, in region 550 shown in Figure 5, Tensile stress, and / or a unique stress profile (see FIG. 6). This is particularly important in light of the thin thickness of the glass sheet 500 and / or other unique physical properties (e.g., very low roughness, high degree of flatness, various optical properties, virtual temperature characteristics, etc.) It is true.

The compressive stresses of the glass formed by the processes and systems disclosed herein (e.g., in regions 530, 540 shown in Figure 5) may vary depending on the function of the thickness t of the glass. At least 100 MPa, at least 150 MPa, at least 200 MPa, at least 250 MPa, at least 300 MPa, at least 350 MPa, at least 200 MPa, at least 300 MPa, at least 300 MPa, at least 350 MPa, MPa, at least 400 MPa, and / or 1 GPa or less (for example, surface compressive stress). In a contemplated embodiment, a glass having a thickness of less than or equal to 2 mm may be at least 80 MPa, at least 100 MPa, at least 150 MPa, at least 175 MPa, at least 200 MPa, at least 250 MPa, at least 300 MPa, at least 350 MPa, , And / or a compressive stress of 1 GPa or less. In a contemplated embodiment, a glass having a thickness of less than or equal to 1.5 mm may be at least 80 MPa, at least 100 MPa, at least 150 MPa, at least 175 MPa, at least 200 MPa, at least 250 MPa, at least 300 MPa, at least 350 MPa, and / Or a compressive stress of 1 GPa or less. In a contemplated embodiment, a glass having a thickness of less than or equal to 1 mm may be at least 80 MPa, at least 100 MPa, at least 150 MPa, at least 175 MPa, at least 200 MPa, at least 250 MPa, at least 300 MPa, and / Compressive stress. In a contemplated embodiment, a glass having a thickness of less than or equal to 0.5 mm may be at least 50 MPa, at least 80 MPa, at least 100 MPa, at least 150 MPa, at least 175 MPa, at least 200 MPa, at least 250 MPa, and / Compressive stress.

In some embodiments, the thermally induced central tensile (e.g., region 550 shown in FIG. 5) in the glass formed by the processes and systems disclosed herein is greater than 40 MPa, greater than 50 MPa, greater than 75 MPa, It may exceed 100 MPa. In other embodiments, the thermally induced center tension may be less than 300 MPa, or less than 400 MPa. In some embodiments, the thermally induced center tension can be from about 50 MPa to about 300 MPa, from about 60 MPa to about 200 MPa, from about 70 MPa to about 150 MPa, or from about 80 MPa to about 140 MPa. In some embodiments, the thermally enhanced glass sheet has a high degree of thinness, i. E. Since a very high heat transfer rate can be applied through the systems and methods disclosed herein, a significant thermal effect, for example a center tension of at least 10 MPa or even at least 20 MPa, can be produced in a sheet of SLG less than 0.3 mm thick have. In fact, a sheet that is as thin as at least 0.1 mm, which is a very thin sheet, can be thermally enhanced. The specific level of thermal stress achieved and attainable, which is considered according to the thickness and the function of the other variables, is described in more detail herein.

6, at room temperature and standard atmospheric pressure of 25 ° C, the conceptual stress profile 560 of the reinforced glass or glass-ceramic sheet 500 of FIG. 4 shows the glass or glass- The inner portion 550 of the ceramic sheet 500 and the portion of the reinforced glass or glass-ceramic sheet 500 outside and adjacent to the inner portion 550 under negative tensile stress (e.g., positive compressive stress) (530, 540). Applicants believe that negative tensile stress limits the initiation and / or propagation of cracks through it, thereby at least partially strengthening the reinforced glass or glass-ceramic sheet 500.

Considering the relatively large surface area and / or the thin thickness of the reinforced glass or glass-ceramic sheet 500 as disclosed herein, which is believed to be unique to the techniques of the present invention, tensile stresses in the stress profile 560 Between the positive tensile stress of portion 550 and the negative tensile stress of portions 530 and 540 that are external and adjacent to the internal portion 550. Such a sharp transition can be achieved with a thickness of 1 mm, such as a distance of 500 [mu] m, 250 [mu] m, or 100 [mu] m (which is a distance used to quantify the rate of change and not necessarily a dimension of the product geometry, 100 MPa, 200 MPa, 250, which is the difference in the magnitude of the stress divided by the distance of the thickness at which the change takes place (e.g., the difference in the peak values of positive and negative tensile stress + (I.e., slope), which can be expressed as a tensile stress (MPa, 300 MPa, 400 MPa). In some of these embodiments, the rate of change in tensile stress does not exceed 7000 MPa divided by 1 mm, such as not exceeding 5000 MPa divided by 1 mm. In a considered embodiment, the difference in the peak values of positive and negative tensile stresses is at least 100 MPa, at least 150 MPa, at least 200 MPa, at least 250 MPa, at least 300 MPa, at least 400 MPa, at least 500 MPa, 50 MPa and / or 50 GPa. In a contemplated embodiment, the glass or glass-ceramic sheet 500 is at least 100 MPa, at least 150 MPa, at least 200 MPa, at least 250 MPa, at least 300 MPa, at least 400 MPa, at least 500 MPa, And has a peak negative tensile stress of 50 MPa. The steep tensile curve transformation generated by the systems and methods discussed herein can achieve a higher magnitude of negative tensile stress at the surface of the glass sheet for a given thickness and / or can be achieved, for example, by dicing as described herein It is believed to be an indicator of the ability to produce thinner glass products with higher negative tensile stresses, such as achieving the possibility of fragmentation of the glass. Conventional thermal tempering approaches may not be able to achieve this steep tensile stress curve.

According to an exemplary embodiment, the high rate of change in tensile stress is at least 5% of the thickness of the glass sheet 500, at least 10% of the thickness, at least 15% of the thickness, or at least 25% 2% of the thickness-wise stretch of the stress profile (560). In the considered embodiment, the reinforcement is such that the thickness-direction stretch with a high rate of change of tensile stress is less than the center of the core at a depth from 20% to 80%, for example, thickness from the first surface, Ceramic sheet 500 so as to allow the glass sheet to be heated.

In at least some contemplated embodiments, the reinforced glass or glass-ceramic article includes changes in its composition in terms of ion content, conceptually indicated by dashed line 562 in FIG. More particularly, in this embodiment, the composition of the reinforced glass or glass-ceramic article 500 includes implanted ions that affect the stress profile 560. [ In some such embodiments, the exchanged or implanted ions may be doped with a dopant such as doped or doped amorphous silicon, doped with a dopant, But does not extend completely through portions 530,540.

Thus, the curve of the tensile stress profile 560 with an ion exchange strength increase rate includes discontinuities or abrupt changes 564 in different directions, either at the tangent of the curve, discontinuously or abruptly at 564. The abrupt change 564 is located in portions 530, 540 under negative tensile stress such that the tensile stress is negative in the plane immediately adjacent to the discontinuity or sudden change 564. Discontinuous or abrupt changes 564 may correspond to depths of other ionic content, but in some such embodiments, under negative tensile stress, other portions of portions 530, 540 are still under positive tensile stress Has the same composition in terms of ion content and portion 550.

In certain embodiments where the reinforced glass or glass-ceramic sheet 500 is thermally tempered and increased in ion-exchange strength (e.g., as shown by discontinuity 564 in the stress profile shown in FIG. 6) The relative amount of negative tensile stress produced or caused by exchange is relatively low due to the high level of negative tensile strength generated by the thermal tempering process described herein. For example, in these embodiments, the reinforced glass or glass-ceramic sheet 500 is thermally tempered as discussed herein and then further thermally tempered such that the reinforced glass or glass-ceramic sheet 500 Ion exchange. In this embodiment, the increase in negative tensile stresses located at the surfaces 510, 520 created or caused by ion exchange enhancement is less than 20%, in particular less than 10%, of the negative tensile stresses produced or caused by thermal tempering. For example, in certain embodiments, the reinforced glass or glass-ceramic sheet 500 may have a total negative tensile stress at the surface 510, 520 of up to 240 MPa and, more particularly, up to 220 MPa, And has a thermally enhanced negative tensile stress located at the increased or increased surface 510, 520 with exchange strength. As will be appreciated, in embodiments in which thermal tempering is increased in chemical strength, the tempered glass article on at least one of the first and second major surfaces has a composition located at least in part of the interior portion in terms of ion content and chemical composition Different, under tensile stress, at least some compressive stress (e.g. in a relatively thin zone adjacent to the main surface) depends on the composition of the reinforced glass product.

In other words, for at least some reinforced glass or glass-ceramic articles 500, the reinforced glass, which is under negative tensile stress, with and without ion-exchange or injection, Or at least a portion of the portions 530, 540 of the glass-ceramic sheet 500 is the same as the composition of at least a portion of the interior portion 550 under a positive tensile stress. In this embodiment, at least a portion of the negative tensile stress of the stress profile is independent of the change in the composition of the reinforced glass or glass-ceramic sheet 500 (e.g., ion composition). Such a structure can provide sufficient strength without chemical tempering and / or with less chemical tempering to simplify the composition of the glass or glass-ceramic sheet 500 that has been reinforced to at least to some extent. Moreover, such a structure can reduce stress concentrations in glass or glass-ceramic sheets 500 that have been reinforced due to discontinuities / variations in the composition, thereby reducing possible delamination and / or cracking changes in composition discontinuities .

 In certain embodiments, the reinforced glass or glass-ceramic article 500 comprises at least some sections or portions that are thermally tempered and not chemically strengthened (such as ion exchange enhancement). In some such embodiments, the chemical composition (e.g., ionic composition) of at least a portion of portions 530, 540 under negative tension and the chemical composition of at least a portion of surfaces 510, Is the same as the chemical composition of at least a part of. In certain embodiments, the chemical composition (e.g., ionic composition) of all portions 530, 540 and the chemical composition of all surfaces 510, 520 under negative tensile stress is determined by the chemical composition of internal portion 550 same. In some of these embodiments, the chemical composition of the reinforced glass or glass-ceramic article 500 is practically constant over the thickness t measured at least at some cross-sectional thickness locations. In this embodiment, the stress profile of the reinforced glass or glass-ceramic sheet 500 is a thermally tempered stress profile, which is the compressive stress (e. G., Negative tensile stress) and positive tensile stress For example, the various levels of the center tensile stress) are generated only through thermal tempering.

Thermally Tempered Glass Sheet Break Performance

If sufficient energy is stored in the region 550 of tensile stress, the glass will fracture like a safety glass or "die" if fully damaged. As used herein, a glass sheet is considered a die when the area of the glass sheet 25 cm < 2 > is broken into more than 40 pieces. In some embodiments, the dicing is used as a qualitative measurement indicating that the glass sheet is "fully tempered" (i.e., thicker glass of 2 mm or more, wherein the glass sheet has a compressive stress of at least 65 MPa or at least 67 MPa of edge compression). In various embodiments, the glass sheet 500 has sufficient tensile stress in the region 550 of tensile stress such that the glass sheet 500 with an area of 25 cm 2 is broken into more than 40 pieces.

7, a glass or glass-ceramic article 610 having properties as described herein for a glass or glass-ceramic sheet, such as a sheet 500, may be formed, for example, by a pointed punch or other Are broken using a tool and / or generally in accordance with American National Standards Institute (ANSI) Z97.1 (impact test) and ASTM 1048 standard. According to an exemplary embodiment, the glass or glass-ceramic article 610 is reinforced to the extent that dicing occurs at break, forming a plurality of small granular masses 616 (e.g., debris, pieces) . In some embodiments, the glass or glass-ceramic article 610 is a glass or glass-ceramic article 610 in a fragmentation test, wherein the impact is applied to the hammer or punch to initiate cracking of the glass into granular pieces. Has a thermally-induced stress sufficient to produce a plurality of granular masses (616) of at least 40 in an area of 50 mm x 50 mm. A standard office tack 612, having a metal pin length 614 of about 1 cm, is shown for reference.

According to various contemplated embodiments, in spite of the thin thickness of the reinforced glass or glass-ceramic article 610, the stress profile (generally, Fig. 6) 610) having an area for the first or second surface of less than 90 mm 2, such as less than 50 mm 2, such as less than 20 mm 2, such as less than 10 mm 2, such as less than 5 mm ² , and / Ceramic product 610 so as to be shattered by the granular mass 616 of the glass-ceramic article 610. In some such embodiments, the fragmentation potential of the reinforced glass or glass-ceramic article 610 is such that at least 20% of the granular mass 616 (e.g., , At least 50%, at least 70%, at least 95%) of at least one of the above-mentioned amounts of the first or second surface.

In some embodiments, reinforced glass or glass, such as glass or ceramic, may be used, at least in part due to the particularly thin geometry of the glass or glass-ceramic article 610, which may be produced with tensile stress as disclosed herein using the techniques of the present invention The fragmentation potential of the ceramic product 610 is such that at break the reinforced glass or glass-ceramic article 610 is less than 50 mm ³ , such as less than 40 mm ^3, less than 30 mm ³ , for example less than 25 mm ³ And / or with a volume of at least 50 mu m < ^{3 &} gt ;, in particular a low-volume granular mass.

In some embodiments, the reinforced glass or glass-ceramic article 610, which is at least partially due to the particularly large area of the glass or glass-ceramic article 610 that can be produced with tensile stress as disclosed herein using the techniques of the present invention, The fragmentation potential of the ceramic product 610 is such that at breakage the reinforced glass or glass-ceramic article 610 is divided into at least 100 granular masses 616 of at least 50 占 퐉 ³ in volume, At least 200, at least 400, at least 1000, at least 4000 granular masses (616) of at least 50 占 퐉 ³ .

Referring now to Figures 8 and 9, experiments were conducted to determine the amount of silicon dioxide, at least 70 wt.% Silicon dioxide, and / or at least 10 wt.% Sodium oxide, and / or at least 7 wt.% Calcium oxide, And a reinforced 1.1 mm thick glass sheet using the equipment and process disclosed herein. As shown in FIG. 8, the number of granular masses 616 per square centimeter of glass is found to be generally related to the magnitude of the positive tensile stress at the center of each glass or glass-ceramic article 610 lost. 9, the fragmentation potential of each glass or glass-ceramic article 610 is also determined by the size and gap of the gap between the glass sheet surface and the heat sink / gas bearing during quenching, (H) calculated in cal / cm 2 s 占 폚 unit (SI unit is watt / m 2 K) effectively applied to the glass surface during quenching based on the thermal conductivity, and a high temperature zone (for example, , Fig. 22 and Fig. 23).

Thermally Tempered Glass Sheet Virtual Temperature

In various embodiments, the thermally enhanced glass sheet (e.g., glass sheet 500) formed by the systems and methods discussed herein has a high virtual temperature. In various embodiments, the high virtual temperature of the automotive glass material discussed herein will be understood to relate to a high level of tempering, high center tensile stress and / or high compressive surface stress of the glass sheet 500. Virtual surface temperature can be determined by differential scanning calorimetry, Brill ruin minutes gwangbeop any suitable method, including a (Brillouin spectroscopy), or Raman spectroscopy.

According to an exemplary embodiment, the glass or glass-ceramic sheet 500 can be made to have a thickness of at least 500 캜, such as at least 600 캜, or even at least 700 캜, in some embodiments, such as in the case of soda- Ceramic sheet, such as at or near the first and / or second surface 510, 520 having a fictive temperature. According to an exemplary embodiment, the glass or glass-ceramic sheet 500 may have a thickness of, for example, at least 10 占 폚, at least 30 占 폚, at least 50 占 폚, at least 70 占 폚, or even at least 100 占 폚 And a portion of the glass or glass-ceramic sheet, such as at or near the first and / or second surface 510, 520, having a particularly high virtual temperature compared to the annealed glass of the same chemical composition. High virtual temperatures can be achieved by the presently discussed inventive techniques, at least in part, due to the rapid transition from a hot zone to a cooling zone in a fortification system (e.g., see Figs. 21, 22, and 23). The inventors believe that high virtual temperatures can correspond to or be associated with increased damage resistance of the glass.

In some methods of determining the surface virtual temperature, it may be necessary to destroy the glass to mitigate the "tempering stress" induced by the heat-hardening process to measure the imaginary temperature with reasonable accuracy. The characteristic structure bands measured by Raman spectroscopy are well known to shift in a controlled manner for both the virtual temperature and the stress applied in the silicate glass. Such a shift can be used to non-destructively measure the fictitious temperature of the thermally enhanced glass sheet when the tempering stress is known.

Generally, with reference to FIG. 10, the determination of a virtual temperature for some representative glassware is shown. The stress effect on the Raman spectrum of silica glass is described in DR Tallant, TA Michalske, and WL Smith, "The effects of tensile stress on the Raman spectrum of silica glass, J. Non-Cryst. Solids , 106 380-383 (1988). A commercial advantage of 65 wt.% Or more of silica has substantially the same reaction. In the case of biaxial stress states, such as those observed in tempered glass, where the reported stress response is for uniaxial stresses, σ _xx = σ _yy , the peaks are twice as predicted by uniaxial stress Can be expected to be shifted. Soda-peak near 1090cm ^-1 in lime glass and glass 2 is, 1050cm ^-1 corresponds to the peak observed in the silica glass. The effect of the stress on the 1050 cm ^{- 1} peak in silica and the corresponding peak in SLG and other silicate glasses is determined by a function of the stress? In units of MPa, by the formula a)? (Cm ^-1 ) = 1054.93-0.00232? , ≪ / RTI >

A calibration curve of the Raman band position with a function of the virtual temperature for SLG and another glass, Glass 2, is generated. The glass sample is heat-treated for various times, 2-3 times longer than the structural relaxation time calculated by? = 10 *? / G, where? Is the viscosity and G is the shear modulus. After the heat-treatment, the glass is quenched in water to cool the imaginary temperature at the heat-treating temperature. The glass surface is then, in the micro,, 1-2 ㎛ spot size and 50x magnification using a 442nm laser, a 10-30 second exposure time, and 100% power over a range of 200-1800cm ^-1 Raman (micro Raman) . The position of the peak at 1000-1200 cm ^-1 , in this case, was fitted using Renishaw WiRE version 4.1, computer software. The good fit of the 1090 cm ^-1 Raman peak measured at the SLG to the air side according to a function of the imaginary temperature T _f (° C) is given by the equation b) ω (cm ^-1 ) = 1110.66 - 0.0282 · T _f . For glass 2, an excellent fit is given by the equation c) ω (cm ^-1 ) = 1102.00 - 0.0231 · T _f .

It is possible to express the virtual temperature of the glass according to the function of the Raman peak position measured with the correction factor due to the surface compressive stress, using the relation set in equation (a), (b) and (c). A compressive stress of 100 MPa, σ _c , shifts the Raman band position, such as approximately 15 to 20 ° C reduction at the imaginary temperature. The following Equation (1) can be applied to the SLG:

[Equation 1]

The formula applicable to glass 2 is: < RTI ID = 0.0 >

&Quot; (2) "

These equations, ω is the frequency peak (wavenumber) measured for the peak near 1090cm ^-1, σ _c is a surface compressive stress measured by any suitable technique, a virtual temperature stress as ℃ unit - the corrected measured Lt; / RTI > As a demonstration of the increased abrasion resistance associated with the determined fictitious temperature, four glass sheet samples are prepared, two 6 mm soda-lime glass (SLG) sheets having a surface compressive stress (CS) of about 70 and 110 MPa, By the tempering method, and the two 1.1 mm SLG sheets are prepared by the method and system disclosed herein at approximately the same level of CS. Two additional sheets, one of each thickness, are used as a control. The surface of each test sheet is subjected to standard Vickers indentation. During each 15 seconds, and is applied becomes different levels of power, after waiting for 24 hours, the press is that each investigation. As shown in Table 1, a 50% crack threshold (defined as the load at which two of the four points of the indenter that tend to start cracking are represented by the average number of cracks) is determined for each sample.

Table 1 shows that the Vickers crack initiation threshold for the SLG machined by conventional convective gas tempering (as reflected in the 6 mm sheet) is essentially the same as for the annealed or guided-as-SLG sheet, (N) from about 1 to 2 Newtons (N). (T _fs or T f _surface ) of ~ 25 to 35 ° C compared to the glass transition temperature (η = 10 ^12-13.3 Poise defined for ^traditional SLG, T _g = 550 ° C for SLG) provided by conventional tempering It is related to a relatively moderate rise. In contrast, by the tempering with the present method and system, the Vickers crack initiation threshold is improved beyond 10 N, which is a 10-fold increase over the Vickers damage tolerance imparted by conventional tempering. In the specified glass, T _fs - T _g is in the range of at least 50 ° C, or at least 75 ° C, or at least 90 ° C, or approximately 75 ° C to 100 ° C. Even in embodiments involving a low level of thermal strengthening, the incorporated glass can still provide increased resistance at the same level as, for example, 5N. In certain contemplated embodiments, a crack threshold of 50% after the 15 second Vickers crack initiation test may be 5N, 10N, 20N, or 30N or higher.

Table 1 Sample Thickness (mm) CS (MPa) Surface T _f (° C) Crack Threshold (N) Control 1.1 Annealing T _g (550) 0 - 1 Control 6 Annealing T _g (550) 0 - 1 Thin low strength 1.1 -72 626 10 - 20 Thick low strength 6 -66 575 1 - 2 Thin Medium Strength 1.1 -106 642 10 - 20 Thick Medium Strength 6 -114 586 1 - 2

The following non-dimensional virtual temperature parameter [theta] can be used to compare the relative performance of the thermal strengthening process in terms of the generated virtual temperature. In this case, considering the surface virtual temperature &thetas; s, the following equation (3)

&Quot; (3) "

θ s = ( T _fs - T _anneal ) / ( T _soft - T _anneal )

Where T _fs is the surface virtual temperature, T _{anneal (} η = 10 ^13.2 Poise viscosity glass temperature) is the annealing point and T _{soft (} η = 10 ^7.6 Poise viscosity glass temperature) is the glass sheet softening point to be. 10 is a plot of? S versus surface virtual temperature measured according to a function of heat transfer rate (h) applied during thermal strengthening to two different glasses. As shown in Fig. 10, the results for the two different glasses are superimposed very close to each other. This means that the parameter [theta] provides a means for comparing the virtual temperatures of other glasses directly compared with the heat transfer rate (h) required to produce the glass. The vertical extent of the result at each h corresponds to a change in the value of T ₀ , which is the initial temperature at the beginning of the quenching. In an embodiment, the parameter θ s is from about 0.2 to about 0.9, or from 0.21 to 0.09, alternatively from 0.22 to 0.09, alternatively from 0.23 to 0.09, alternatively from 0.24 to 0.09, alternatively from 0.25 to 0.09, alternatively from 0.30, Or 0.09, or 0.40 to 0.09, or 0.5 to 0.9, or 0.51 to 0.9, or 0.52 to 0.9, or 0.53 to 0.9, or 0.54 to 0.9, or 0.54 to 0.9, or 0.55 to 0.9, or 0.6 to 0.9, 0.65 to 0.9.

Thermally Tempered  Glass sheet Tempering  Possibility parameter

In various embodiments, the thermally enhanced glass sheet (e.g., glass sheet 500) formed in the systems and methods discussed herein has a high temperability and / or heat transfer value. The "specific thermal stress" of the glass is given by

&Quot; (4) "

Where α is the glass (low temperature linear) CTE, E is the modulus of elasticity of the glass material, and μ is the Poisson's ratio of the glass material. These values are used to indicate the level of stress produced within a given glass composition when subjected to a temperature gradient. It can also be used thermally as a canter of "temperability ". At high heat transfer rates (for example, above about 800 W / m2K), however, the high temperature or "liquidus" CTE of the glass begins to affect the tempering performance. Therefore, under these conditions, the tempering likely parameter Ψ is based on an approximation of the integral of the CTE value that changes across the curve for viscosity were found to yonghan oil as shown in Equation 5:

&Quot; (5) "

Here, α ^S _CTE Is a (equal to the average coefficient of linear expansion of 0-300 ℃ for glass), low-temperature linear CTE, which is expressed by 1 / ℃ (℃ ^-1), α ^L _CTE is expressed in 1 / ℃ (℃ ^-1) (The same as the high temperature linear CTE (the high temperature plateau value observed to occur anywhere between the glass transition and the softening point), and E is the (non-dimensional) parameter Is a modulus of elasticity of glass, expressed in GPa (not MPa), which allows the value of Ψ, and T _strain is the _strain point of glass, expressed in degrees Celsius (η = 10 ^14.7 Poise viscosity) Temperature, and T _soft is the softening point of the glass, expressed in degrees Celsius (the temperature of the glass at a viscosity of? = 10 ^7.6 Poise).

The thermal strengthening process and the resulting surface compressive stresses are modeled for glass with properties that vary to determine the tempering parameter, [Psi]. The glass is modeled at the same starting point viscosity of 10 ^8.2 Poise and a varying heat transfer coefficient. The properties of the various glasses are shown in Table 2, together with the temperature for each glass at 10 ^8.2 Poise and the calculated values of the temperability parameter Ψ for each.

Glass Modulus CTE And CTE 10 ^8.2 Poise ° C Softening point ℃ Strain point ℃ Ψ SLG 72 8.8 27.61 705 728 507 0.76 2 73.3 8.53 20.49 813 837 553 0.77 3 65.5 8.26 26 821 862 549 0.83 4 65 8.69 20.2 864 912 608 0.74 5 63.9 10.61 22 849 884 557 0.84 6 58.26 3.5 20.2 842 876 557 0.49 7 73.6 3.6 13.3 929 963 708 0.44 8 81.1 3.86 12.13 968 995 749 0.48

The results in Table 2 show that [Psi] is proportional to the thermal strengthening performance of the glass. This correlation is further shown in FIG. 11, which provides a concrete embodiment for a glass sheet thickness of only 1 mm and a high heat transfer coefficient (heat transfer coefficient of 2093 W / m 2 K (0.05 cal / s. . As can be seen in the figure, the change in the resulting compressive stress of the seven different glasses is highly correlated with the change in the proposed temperability parameter Ψ.

Relationship between thermally tempered glass sheet heat transfer coefficient and surface compressive stress and center tensile stress

In other respects, for any given glass, the surface compressive stress (in MPa units, _CS ) versus the thickness (t, mm) at any given value of the heat transfer coefficient h (expressed in cal / Units) can be fitted in a hyperbola (for a range of 0 to 6 mm), where P ₁ and P ₂ are functions of h as follows:

&Quot; (6) "

Alternatively, as a replacement for Ψ, the curve of the compressive stress σ _cs (Glass, h, t) is given by:

&Quot; (7) "

Here, in the equation (6) or (7), the constants P ₁ and P ₂ are successive functions of the heat transfer value, h, given by the following equations (8) and

&Quot; (8) "

And

&Quot; (9) "

The constants P ₁ and P ₂ are plotted according to the function of h in FIGS. 12 and 13, respectively. Thus, for a given h and the corresponding P ₂ , using the value of P ₁ , the surface compressive stress (CS) that can be obtained at h, depending on the function of thickness t, for the same h in Equation 6 or 7, ) Is specified.

In some embodiments, a similar equation can be obtained by simply dividing the predicted compressive stresses under the same conduction into 2, in particular, at a thickness of 6 mm or less, and at a heat transfer coefficient, such as 800 W / Can be used to predict the center tension (CT). Thus, the expected center tension can be given as: < RTI ID = 0.0 >

&Quot; (10) "

Here, P 1 _CT and P 2 _CT are given by the following equations (11) and (12):

&Quot; (11) "

And

&Quot; (12) "

In some embodiments, h and h _CT may have the same value for a given physical instance of thermal strengthening. However, in some embodiments, they may be variable, providing individual variables, and allowing for a change between them, to illustrate the case where a typical ratio of 2: 1 CS / CT is not maintained, a descriptive performance in the curves).

One or more embodiments of the presently disclosed processes and systems produce thermally enhanced SLG sheets at all of the heat transfer rate values (h and h _CT ) shown in Table 3.

The h and h _CT values < RTI ID = 0.0 > cal / s · ㎠ · ° C W / ㎡K cal / s · ㎠ · ° C W / ㎡K cal / s · ㎠ · ° C W / ㎡K 0.010 418.68 0.042 1758.456 0.070 2930.76 0.013 544.284 0.045 1884.06 0.071 2972.628 0.018 753.624 0.047 1967.796 0.078 3265.704 0.019 795.492 0.048 2009.664 0.080 3349.44 0.020 837.36 0.049 2051.532 0.081 3391.308 0.021 879.228 0.050 2093.4 0.082 3433.176 0.022 921.096 0.051 2135.268 0.095 3977.46 0.023 962.964 0.052 2177.136 0.096 4019.328 0.027 1130.436 0.053 2219.004 0.102 4270.536 0.028 1172.304 0.054 2260.872 0.104 4354.272 0.029 1214.172 0.055 2302.74 0.105 4396.14 0.030 1256.04 0.060 2512.08 0.127 5317.236 0.031 1297.908 0.061 2553.948 0.144 6028.992 0.033 1381.644 0.062 2595.816 0.148 6196.464 0.034 1423.512 0.063 2637.684 0.149 6238.332 0.038 1590.984 0.065 2721.42 0.184 7703.712 0.040 1674.72 0.067 2805.156 0.041 1716.588 0.069 2888.892

In some embodiments, the heat transfer coefficient values ( h and h _CT ) may be from about 0.024 to about 0.15, from about 0.026 to about 0.10, or from about 0.026 to about 0.075 cal / s 占 · m 占 폚.

Figure 14 is a graph of C (h, t) · Ψ (SLG) versus the value of selected h according to Equation 6-9 with Ψ (SLG) corresponding to the value of Ψ for SLG in Table 2 Shows the newly opened performance space in units of MPa of the surface compression of the glass sheet according to a function of thickness (t) (mm). Trace labeled (GC) is assumed to be such that the heat transfer coefficient at this level can be used in the process at about 704 캜, which is a temperature above the glass viscosity of 10 ^8.2 Poises or the capability of a convective gas process. The maximum stress for the thickness of the SLG sheet, which can be achieved by gas convection tempering, at 0.03 cal / s 占 · m 占 폚 or 1250 W / m2K from cal / s 占 · m 占 폚 (or 840 W / Represents the expected range.

Examples of the highest reported sheet CS values based on gas convection tempering processes are represented by triangular markers labeled with a gas in the legend. The value 601 represents the commercial product performance of the commercial equipment, while the value 602 is based on the oral report at the Glass Processing Society. The trace label (LC) is given by the heat transfer coefficient h of 0.0625 cal / s 占 ㎠ m2 占 폚 (or about 2600 W / m2K), assuming also the process at an initial heated glass viscosity of about 10 ^8.2 Poise or about 704 占Shows the curve of the maximum stress with respect to the thickness of the SLG sheet which is expected to be achievable by liquid contact tempering. An example of the highest reported sheet CS value based on a liquid contact tempering process is represented by a circular marker labeled as liquid in the legend. The higher of the two values at a thickness of 2 mm is based on the report of tempering of the borosilicate glass sheet, and the achieved stress is plotted as (S _SLG ) / (Ψ _borosilicate ) for the scaled direct comparison Lt; / RTI >

The trace mark 704 may be used in one or more of the methods and systems disclosed herein at an initial temperature of 704 占 폚 at a heat transfer rate of 0.20 cal / s 占 ㎠ m 占 폚 (or about 8370 W / ≪ / RTI > The level of stress on the glass sheet achievable in this manner represents an improvement of almost the same category above the liquid tempering strength level, as liquid tempering represents more than state of the art gas convection tempering. However, the trace mark 704 is not an upper limit - the embodiment is more than this value because of good control of the shape and flatness achievable in the gas-bearing thermal strengthening of the small-gap at even higher temperatures (low viscosity of the glass) Lt; / RTI > The trace label 730 is achieved by a heat transfer rate of 0.20 cal / s 占 ㎠ m 占 폚 (or about 8370 W / m2K) at a starting temperature for the SLG sheet of 730 占 폚, which is very close to or above the softening point of the glass ≪ / RTI > Significant improvements in compressive stresses, and thus in glass sheet strength, are due to the combination of the use of as high a starting temperature as possible, especially by a high heat transfer rate and good handling and control of sheet flatness and shape in tight gas bearings And the improvement is particularly pronounced at thicknesses of less than 2 mm.

Figure 15 is a plot of the thermal conductivity of a glass sheet plotted against a selected embodiment of an enhanced glass sheet produced by one or more embodiments of the present disclosure at 2 mm or less but showing an extreme combination of thermal enhancement levels and cuts possible by this disclosure Figure 14 shows the trace of Figure 14 described above with compressive stresses as a function of thickness.

Low surface roughness and high Flatness  Thermally-tempered glass sheet

In various embodiments, the thermally enhanced glass sheet disclosed herein, such as sheet 500, has both a high thermal stress and a low, surface-to-surface roughness. The processes and methods disclosed herein can thermally enhance the sheet of glass without increasing the surface roughness of the formed-in-surface. For example, an incoming float glass air-side surface and an inflow-fusion-formed glass surface are characterized by atomic force microscopy (AFM) before and after the process. The R _a surface roughness is less than 1 nm (0.6-0.7 nm) for the inflowing 1.1 mm soda-lime float glass and the R _a surface roughness is not increased by thermal strengthening according to the present process. Similarly, an R _a surface roughness of 0.3 nm or less (0.2-0.3) for a 1.1 mm sheet of fusion-formed glass is maintained by thermal strengthening according to the present disclosure. Thus, the thermally enhanced glass sheet can have a thickness in the range of R _a roughness, such as 0.2 to 1.5 nm, 0.2 to 0.7 nm, 0.2 to 0.4 nm, or even 0.2 to 0.3 nm, for an area of at least 10 x 10 μm And has at least a surface roughness with respect to the first surface. The surface roughness can be measured in an exemplary embodiment, for an area of 10 x 10 mu m, or in some embodiments for an area of 15 x 15 mu m.

In some contemplated embodiments, the thermally enhanced glass sheet disclosed herein has both a high thermal stress and a low, formed-like (e. G., Unpolished) surface roughness and / or a coated surface. The processes and methods disclosed herein can be applied to various types of glass substrates without increasing the surface roughness of the smoothly formed-in-conveyor or guided-boulevard surfaces of the glass sheet, and without damaging sensitive low-E or anti- The sheet can be thermally strengthened. The inflow float glass air-side surface, and the inflow-fusion-formed glass surface, can be characterized by atomic force microscopy (AFM) before and after the process. The R _a surface roughness is less than 1 nm (such as 0.6 to 0.7 nm) for influx on the air side of a 1.1 mm soda-lime float glass and is not increased by the thermal strengthening according to this disclosure. R _a surface roughness is 0.3 nm or less (such as 0.2 to 0.3 nm) for the influx on a 1.1 mm sheet of fusion-formed glass, and likewise, is not increased by the thermal strengthening according to the present disclosure. Thus, in a contemplated embodiment, a thermally enhanced glass sheet according to the present disclosure has an R _a roughness of at least 0.2 nm and / or 1.5 nm or less, such as 0.7 nm or less, such as 0.4 nm or less, or even 0.3 having a surface roughness on the first surface in the range of R _a roughness of less than or equal to nm, or having a thermally enhanced sheet having a coating on a sheet of the type that can be applied prior to the tempering, Coatings and combinations of these low roughness values obtained from the present process used with the sheet. In certain embodiments, the thermally enhanced glass sheet according to the present disclosure has the low surface roughness mentioned in both the first and second major surfaces (e.g., surfaces 510 and 520 shown in FIG. 5) In such embodiments, the first and second major surfaces are un-polished surfaces having the low surface roughness described above. Such protection of the surface quality and / or surface coating (s) may require pre-use of convective gas tempering or perhaps a low heat transfer liquid tempering process that produces a limited thermal strengthening effect over the entire range available with the present process and method The applicant of the present invention understands that,

In yet another embodiment, the thermally enhanced glass sheet described herein has a high flatness. In various embodiments, the reinforcing system discussed herein utilizes a controlled gas bearing to support the glass material during transfer and heating, and in some embodiments, helps to control and / or improve the flatness of the glass sheet , Resulting in a higher flatness than previously obtained, especially for thin and / or highly reinforced glass sheets. For example, a sheet of at least 0.6 mm can be reinforced with improved post-enhancement flatness. The flatness of the thermally enhanced glass sheet embodied herein may be determined by measuring a total indicator run-out (TIR) of less than or equal to 100 microns along any 50 mm length along one of the first or second surfaces, Less than 300 占 퐉 TIR within 50 mm length on one, or 70 占 퐉 TIR or less within 50 mm length on one of the first or second surfaces. In an exemplary embodiment, the flatness is measured along any 50 mm or less profile of the glass sheet. In a contemplated embodiment, the sheet having the thickness disclosed herein has a flatness of 200 占 퐉 TIR or less, e.g., a flatness of 100 占 퐉 TIR or less, a flatness of 70 占 퐉 TIR or less, And a flatness of 50 mu m TIR or less.

According to a contemplated embodiment, the reinforced glass or glass-ceramic article discussed herein (e. G., The first and second surfaces 510 and 520 of the reinforced glass or glass-ceramic sheet 500 in Fig. 4) Degree dimensional conformity such that the thickness t thereof does not vary by not more than 5 占 퐉 and not more than 2 占 퐉 by 50 占 퐉 or less such as 10 占 퐉 or less along a 1 cm longitudinal stretch of the body 522. [ This dimensional correspondence can be determined by solid quenching due to actual considerations, such as cold plate alignment and / or surface irregularities that can distort the dimensions, such that a given thickness, area, and / Can not be achieved for the magnitude of the stress.

According to a contemplated embodiment, the reinforced glass or glass-ceramic article discussed herein is characterized in that a 1 cm longitudinal profile is thereby formed within a straight line of 50 m, such as within 20 m, 10 m, 5 m, 2 m, To stay; And / or the 1 cm width direction profile is thus set so as to remain within a straight line of 50 m, such as within 20 m, 10 m, 5 m, 2 m, (E. G., Reinforced glass in FIG. 4 or first and second surfaces 510 and 520 of glass-ceramic sheet 500). Such high flatness can be achieved by liquid quenching due to substantial considerations such as warping or bending of the glass reinforced in these processes due to liquid convection and associated forces, Can not be achieved for a given thickness, area, and / or magnitude of negative tensile stress.

Thermally enhanced glass sheet CTE

Another aspect includes thermally enhanced low thermal expansion coefficient (CTE) glass sheets. As described above (see Equations 7 and 10), the thermal strengthening effect is highly dependent on the CTE of the glass in which the glass sheet is contained. However, the thermal strengthening of low CTE glass can provide enhanced glass compositions with favorable properties, such as, for example, increased chemical resistance, or excellent compatibility with electronic devices due to low alkali content. A glass sheet having CTEs of 65, 60, 55, 50, 45, 40, and even 35 x 10 ^-6 캜 ^-1 or less has a fracture pattern at a thickness of 4 mm or less, 3.5 mm or less, 3 mm or less, ("Dicing"). A glass having a CTE value of 40 x 10 < ^-6 > C ¹ or less can be strengthened using the process described herein. This low CTE automotive glass enhanced by the systems and methods discussed herein can have a surface compression similar to a SLG sheet reinforced by conventional commercial (gas convection) processes at the same thickness. In some embodiments, the compressive stress of the low CTE automotive glass is less than 1 cm, less than 5 mm, less than 3 mm, less than 2 mm, less than 1.5 mm, less than 1 mm, less than 0.75 mm, less than 0.5 mm, less than 0.3 mm, At least 100 MPa, at least 125 MPa, at least 150 MPa, at least 200 MPa, at least 250 MPa, at least 300 MPa, or at least 400 MPa for a glass sheet having a thickness of 0.2 mm or less, or 0.1 mm or less can do.

Glass sheets formed in accordance with the present disclosure have a number of applications, for example, in electrodevices, electronic displays, in laminates, such as glass-interlayer-glass laminates used in automotive glass sidelights. Stronger and thinner laminates can be produced, resulting in reduced weight and cost, and greater fuel efficiency. Preferably, the thermally enhanced thin sheet can be bended at low temperatures and laminated to the formed thick glass, providing an easy and reliable manufacturing process that does not require any high temperature molding of the thin sheet.

The alpha of the thermally tempered glass sheet

The following Table 4 summarizes the results obtained by the method of the present disclosure (indicated in the table as the "source of the method") and the figure of merit, that is, the approximate measurement of the coefficient of heat exchange obtained in the tempering process, (Alpha). Alpha is given by: < RTI ID = 0.0 >

&Quot; (13) "

Where CS is the physical compression stress (MPa), t is the thickness in millimeters, CTE is the coefficient of thermal expansion in units of C ^-1 , E is the elastic modulus of the glass in MPa, and alpha is in units of C / mm do.

Sample 1 and Sample 3 are repeatable values obtained from the disclosed process, Sample 1 uses air as the gas in the process and Sample 3 uses helium. Sample 2 exhibits a "champion" value using air in the process, i.e. it can not be repeated reliably to date. The glass samples (Samples 1-3) processed by the process of this disclosure all exceed alpha 117 C / mm. The present inventors believe that the slope of alpha according to thickness can have a lower inherent tendency depending on the lower glass thickness. The glass disclosed herein, in some embodiments, has alpha above 20t + 77, where t (mm) is the thickness of the glass.

Thermal strengthening systems and processes

In various embodiments, the process for strengthening a glass sheet may include at least a portion of a glass sheet, such as a glass sheet 500, to produce a reinforced glass sheet having at least one of the characteristics discussed herein, Lt; RTI ID = 0.0 > cooling / quenching zone. ≪ / RTI > In various embodiments, the glass sheet is at least partially supported by the flow or pressure of the gas delivered to the gap between the surface of the glass sheet and the at least one heat sink. In general, the temperature of the glass sheet is above the transition temperature of the glass when the sheet is moved into the cooling zone, and, in various embodiments, the glass sheet is cooled in the cooling zone by thermal conduction rather than convection. Conduction is the process of heat transfer through which energy is transferred through interaction between adjacent molecules, and convection occurs when a heated fluid is moved away from a heat source and replaced by a cooler fluid, , Air, helium, etc.) is the process of heat transfer through which energy is transferred. Thus, the present system is significantly different from conventional convection-based glass tempering / tempering systems where the main mode of heat transfer during cooling of the glass sheet is convection.

In some embodiments, the entire process for strengthening the glass sheet comprises heating the glass sheet in the high temperature zone and then cooling the glass sheet in the cooling zone. The glass sheet has a transition temperature at which the viscosity of the glass is a temperature having a value of eta = 10 ¹² - 10 ^13.3 Poise. The glass is heated sufficiently to raise the glass sheet above the transition temperature, and then transferred to the cooling zone. Alternatively, the glass can be converted from a high temperature zone to a cooling zone through a transition zone. In the cooling zone, the surface of the glass sheet is positioned adjacent to the heat sink, one on each side of the glass sheet, with a gap between one of the glass surfaces and the opposing surface of the heat sink, respectively. The gas is conducted to the gap through the plurality of holes in the heat sink, and in some embodiments, the thus delivered gas forms an air bearing that supports the glass between the heat sinks so that the glass surface does not contact the heat sink . Within the cooling zone, the glass sheet is cooled by conduction, rather than convection, and thermally induced surface compression of the sheet providing increased strength as discussed herein and sufficient And cooled. In various embodiments, the main cooling through conduction is achieved by having a very small gap size in the cooling zone such that the glass sheet does not touch but close to the opposing surface of the heat sink.

The apparatus for enabling the disclosed process may provide a tempered glass sheet including a heating zone for heating the glass sheet to a temperature above the transition temperature and a cooling zone for cooling the heated glass sheet. The apparatus may include a selective transition zone between the heating zone and the cooling zone. The cooling zone may include a heat sink having a pair of opposing surfaces defining a gap in which the heated glass sheet is received. The cooling zone may include a pair of gas bearings disposed on opposing sides of the gap that serve to support the glass sheet in the gap. The gap can be configured to cool the glass sheet heated by conduction rather than convection. In some embodiments, the gas bearing may include a plurality of apertures for delivering gas to the gap, and the gas bearing surface may be a heat sink, which is capable of conducting heat from the heated glass sheet by conduction, .

The tempering process and apparatus disclosed herein (see Figs. 21-25 in general) can be applied to a glass or glass-ceramic article (see Figs. 4-7 and 27-30, generally) by unique type of thermal tempering Enables enhancement. The process enables a steep slope near the surface of a steep, tensile stress versus thickness / depth curve (see Fig. 6 in general), particularly a glass or glass-ceramic article, which can be strengthened by ion- And allows for the strengthening of glass or glass-ceramic products with a particularly high negative tensile stress for a given thickness near the surface of each product. However, in some embodiments, the thermal tempering process disclosed herein can be increased by ion exchange or applied to glass-to-glass lamination. The thermal tempering process disclosed herein may be too large to be enforced through conventional thermal tempering methods, such as alignment limitations of contact quenching equipment, cooling rate limitations of conventional convective systems, and / or torsional damage associated with liquid quenching tempering Particularly high levels of strength in large-area products (e. G., Sheets). The process disclosed herein can be used for a variety of purposes, for example, due to the cooling rate limitations of conventional convection tempering and / or contact forces associated with solid or liquid quenching and sensitivity to fracture or fracture of thin glass or glass- , Which uniquely enables a high level of reinforcement, especially in thin sheets, which can be too thin to strengthen through conventional tempering methods. However, in other contemplated embodiments, glass or glass-ceramic articles as disclosed herein can be made with at least some solid or liquid quenching, such as in combination with the unique tempering process disclosed herein.

One embodiment of the method according to the present disclosure is illustrated in the flow chart of Fig. The method or process (100) includes providing (140) a glass sheet at a temperature above the transition temperature of the glass sheet. The method or process 100 also includes supporting 160 the glass sheet at least partially (via gas flow and pressure) by gas. Step 160 may be performed while the glass sheet is supported by a gas, such as by 1) conduction through the gas to heat sink rather than convection, and 2) thermally-induced surface compressive stress and thermal - cooling the sheet to sufficiently generate or fix the induced central tensile stress.

According to a variation of the embodiment of FIG. 16, illustrated in the flowchart of FIG. 17 by method 100 ', the method may include the step 110 of sufficiently heating the glass sheet so that the sheet is above the transition temperature of the glass have. As a prelude to, or as part of, the cooling step 160, the method 100 'includes, at step 120, first and second heat sink surfaces, each having a hole, (Either as a single piece or as an individual piece) having a heat sink (not shown). In step 130A, the method includes positioning a first sheet surface opposite the first heat sink surface across the first gap, and, in step 130B, passing the second gap across the second heat sink surface And positioning the facing second sheet surface. The heat sink surface may include holes, and / or may be porous. The method 100'includes, at step 160, to sufficiently strengthen the glass (e.g., to sufficiently generate or fix the thermally-induced surface compressive stress and the thermally-induced central tensile stress in the sheet) ), Cooling the sheet by conduction through the gas to each heat sink surface rather than by convection. Step 160 may also include the step of transferring the gas to the first and second gaps through a hole or porous heat sink, and in some such embodiments, the gas may be heated To form an air bearing. In some embodiments, the gas is only passed through a hole in the heat sink or only through pores or pores and holes in the porous heat sink.

These and other related methods of the present disclosure are contrary to the current dominant technology of gas-convection-cooling using conduction as a fundamental mode of cooling, instead of convection. Instead of a solid-to-gas (glass-to-air) heat exchange, the method disclosed herein can be used to both initiate and complete cooling to create thermal strengthening (e.g., without physical contact between the glass surface and the heat sink Solid-to-solid (glass-to-heat-sink) heat exchange mediated across a small gap by a small amount of gas. Conduction, which is directly across the gap, through the gas and through the heat sink, is the main mode of cooling, although some convection is a small gap and gas (e.g., air bearing gas) is present along the flow. The inventors have found that the dominance of conduction heat transfer increases the heat transfer rate as compared to a convection-dominant cooling process.

Because the solid-to-solid conduction (even across the gap) allows for faster heat flow than convection, the required cooling rate increase for thinner glass sheets is not related to gas velocity and volume. According to various embodiments, in order to control the stiffness of the gas cushion in the gap, without constraints normally imposed by the gas flow and gap size in the convection system, To optimize heat conduction, to maintain sheet flatness and / or shape during thermal strengthening, and / or to balance between easy handling and high cooling rate of the sheet, And gap size may be selected, controlled, or optimized for other purposes. For example, in some embodiments, because cooling is not through convection, helium becomes an economically viable alternative to air in the system of this disclosure because of the very low gas flow rate that supports the gas bearing, and In these embodiments, helium provides about five times the thermal conductivity of air. Even helium with a price expected to be several times that currently available becomes an economically feasible alternative at low flow rates of the present disclosure.

Moreover, since the system of the present disclosure reduces the volume of air flowing relative to the glass sheet during cooling (as compared to a convection system), the systems and methods discussed herein provide a high velocity, high volume air flow required for conventional convection- ≪ / RTI > reduces the potential risk of deformation of the high temperature thin sheet of glass normally caused by the glass. This also allows a softer, hot glass sheet to be handled without distortion or with minimal distortion, further improving the achievable degree of reinforcement. Removal of the high air flow rate can also be used to transfer the sheet to a quenching chamber (which moves inversely to the high air flow) and to allow high-flow, cool air to enter and cool adjacent portions of the heating furnace used to heat the sheet It helps alleviate problems that are often seen.

Moreover, the use of conduction through the gas can alleviate contact damage, distortion, deformation, etc., associated with conventional liquid contact or solid contact quenching tempering. The use of gas as an intermediate conductor preserves the surface quality of the processed product by avoiding solid-to-solid contact. Mediating high conduction velocity through the gas also avoids liquid contact. Some types of liquid quenching can introduce unwanted distortion, spatial deformation in tempering, and contamination of the glass surface. These embodiments provide intrinsically non-contact (but not gas), but very high-speed cooling. In other embodiments, as discussed above, solid-liquid or liquid-contact may be included.

Power consumption of thermal tempering system / process

Another advantage of avoiding high air flow is in the power and energy savings achieved using solid-gas-solid conduction as the main glass cooling mechanism. Points A and B in Figures 18 and 19 represent the highest estimate of the peak power use of the air bearing per glass sheet square meter, by compressed air supply in a relatively high flow. The actual minimum peak power usage of the compressed air may be as small as 1/16 of the indicated value. Points A and B do not include active cooling of the heat sink, but may be included in some embodiments, particularly when the machine is continuous, semi-continuous or high frequency operation.

Referring to Figures 18 and 19, points A 'and B' indicate that the thermal load equivalent of 300 deg. C drop at the glass sheet temperature is 2.1 seconds for point A 'and 1 second for point B' (Or electricity) efficiency ratio of 7.5 to 1 within a time limit within a predetermined time period, for example, at a point A and B, when active cooling of the heat sink surface is considered, It represents the conservatively predicted peak power level for the operation of the air bearing. (These points correspond substantially to the glass sheets actually tempered in the apparatus disclosed herein.)

Although the four points in the area R of Figures 18 and 19 illustrate the significance of the improvements that can be achieved by the method and system of the present disclosure (at least to some extent), the maximum benefit is significant in the Figures It should be noted that there is a possibility of being underestimated. For example, the peak power of an air blower, such as that shown by curve N, can not be effectively turned on and off, and if a large fan (with a reduced load) Lt; RTI ID = 0.0 > airways < / RTI > The peak power demand of a fluid cooling system, such as chilled water plants, represented by points A 'and B' as an embodiment that can be easily achieved in accordance with the present disclosure, can generally be supplied much more efficiently, and The effective peak power is much lower, so that only A 'and B' can be accessed as full continuous operation is approached. Thus, the difference in total energy demand tends to be greater than the difference in peak power demand shown in the figure. In some embodiments, the process described herein may be used to heat a glass sheet of 2 mm or less in thickness to 120 KW / Less than 100 KW / ㎡ And a peak power of less than 80 KW / m < 2 >.

Heat transfer from a thin sheet of glass during thermal tempering

Generally, the heat transfer from a thin glass sheet in the system and process of the present disclosure includes a conduction component, a convection component, and a radiation component. The thermal tempering system of the present disclosure, as detailed and discussed herein in detail, utilizes conductive heat transfer as the main mechanism for quantifying thin glass sheets to provide thin glass tempering.

The following is the applicant's understanding of the basic theory. A sufficiently high cooling rate for a thin glass sheet (e.g., 2 mm or less) can actually be achieved by conduction through a gas such as air - and if so, whether this speed can be achieved at the actual gap size It is natural for a person skilled in the art of glass tempering to question whether the conduction effect is usually too small to be ignored for analysis of convection and radiation.

The amount of heat conduction in the conditions specified in the process using the system disclosed herein can be determined through: First, in the context of thermal strengthening by conduction as in this disclosure, the thermal conductivity of the gas in the gap must be evaluated in the direction of conduction along the thermal gradient. At or near the surface of the sheet to be cooled, the hot air has a thermal conductivity sufficiently higher than the lower temperature air, such as air at or near room temperature, at or near the surface of the heat sink ((dry) The nominal thermal conductivity of room temperature air (25 캜) is approximately 0.026 W / m K). An approximation is used that assumes that the air across the entire gap is at the average temperature of the two opposing surfaces at the beginning of the cooling. At the beginning of cooling, the glass sheet may be at a temperature of, for example, 670 캜, while the heat sink surface may start at, for example, 30 캜. Thus, assuming that the sheet is reasonably finished with a high surface and thickness consistency, the average temperature of the air in the gap will be 350 DEG C, where the dry air will flow through the gaps in the system of this disclosure, Of about 0.047 W / m 占 충분히, which is sufficiently high to conduct large amounts of thermal energy through the size of the substrate and at least 75% higher than its thermal conductivity at room temperature.

The heat transfer coefficient Q _cond of the conduction component through the gap _g of the gap with the area A _g in all directions perpendicular to the direction of the gap distance g is given by the following equation: 14: < RTI ID = 0.0 >

&Quot; (14) "

Where T _s is the temperature of the glass surface and T _HS is the temperature of the heat sink surface (in other embodiments, the temperature of the heat source, in other embodiments), k is the thermal conductivity of the material Surface). It will be necessary to integrate the thermal conductivity of the gas along the direction of the conduction heat flow (or vice versa), since the thermal conductivity of the gas varies with temperature to obtain a value of k strictly as described above, As a good approximation, k can be taken as the value of k for gas in the gap when it is the average of the temperatures of the two surfaces ( T _S and T _HS ).

(14) is reconstructed as a unit of heat transfer coefficient (unit of heat flow power per square meter per Kelvin temperature) is given by Equation (15): " (15) "

&Quot; (15) "

Thus, the effective heat transfer coefficient for conduction across the gap is the thermal conductivity (in W / mK) of the medium (in this case air) at a gap divided by the length of the gap in meters, Provides a value of Watt per square meter. Table 5 shows the heat transfer coefficient (k / g) due to sole conduction for air and helium filling gaps of gap sizes from 10 mu m to 200 mu m in each 10 mu m step.

Figure 20 (prior art) shows that, under certain hypothetical conditions, an industry about 35 years ago (with a baseline at 2 mm added) indicating the heat transfer coefficient needed to fully temper the sheet of glass, as a function of thickness in mm, Standard curve. As can be seen from a comparison of Fig. 20 and Table 5, a gap filled with air of approximately 40 占 퐉 can enable complete tempering of 2 mm thick glass by conduction. While somewhat smaller gaps of slightly less than 40 micrometers, planar porous air bearings in conveyor applications can be reliably operated with a gap typically as small as 20 micrometers. Thus, 37 micrometers can be achieved for the air gap supplied by the pores at the heat sink surface. When helium (or hydrogen having a similar thermal conductivity) is used as the gas, a gap of about 200 mu m can be used to completely temper the 2 mm thick glass. The use of helium or hydrogen as the gas allows about a five times larger gap size for the same heat transfer coefficient. In other words, the use of hydrogen or helium as a gaseous gas in the gap increases the heat transfer coefficient to allow quenching about 5 times at the same gap size. Thus, even if air is used, the spacing is not practical and, in the case of highly conductive gas, the gap spacing can be relatively easily achieved even with a sheet thickness of less than 2 millimeters.

In addition to cooling via conduction by convection rather than convection, another embodiment includes heating (or heating and / or cooling) through a gas by conduction rather than convection. For a relative contribution of conduction and convection, whether for heating or cooling, the heat transfer coefficient ( Q _conv ) of the convection component across the gap (or gaps) can be given as:

&Quot; (16) "

은 가스의 질량 유속이며, Cp는 가스의 비열용량이고, Ti는 가스가 갭으로 흐를 때 가스의 유입 온도이며, 및 e는 갭에서 흐르는 가스, 시트 표면 및 히트 싱크/열원의 표면 (갭의 "벽들") 사이에서 열교환의 유효성 (effectiveness)이다. e의 값은 (0의 표면-대-가스 열교환을 나타내는) 0으로부터 (가스가 표면 온도에 완전한 도달을 나타내는) 1로 변한다. e의 값은, 예를 들어, e-NTU 방법을 사용하여 열전달의 기술분야의 당업자에 의해 계산될 수 있다. here,

Ti is the inlet temperature of the gas when the gas flows into the gap, and e is the temperature of the gas flowing in the gap, the surface of the sheet and the surface of the heat sink / heat source (the " Walls "). ≪ / RTI > The value of e changes from 0 (indicating zero surface-to-gas heat exchange) to 1 (gas indicates complete attainment of surface temperature). The value of e can be calculated by one of ordinary skill in the art of heat transfer, for example, using the e-NTU method.

Typically, however, if the gap between the surface of the sheet and the surface of the heat sink / heat source is small, the value of e will be approximately equal to one before the gas leaves the gap, On the whole, it means that the gas is almost completely heated. Assuming that e = 1 (slightly overestimated convective heat transfer rate) and the gas is fed into the gap through the surface of the heat sink / heat source, the initial temperature of the gas in the gap is equal to the temperature of the surface of the heat sink / ( T _i = T _HS ). The heat transfer rate due to convection can then be simplified as: < RTI ID = 0.0 >

&Quot; (17) "

At temperatures typically useful for heat strengthening or heat treating glass and similar materials, the radiative heat transfer from the sheet during processing is relatively small. (E.g., the sheet 200 shown in FIG. 21) in the region of the gap (e.g., the gap 204a, 204b shown in FIG. 21) (Assuming that the amount of radiation from the heat source is not too high), then only the following equation 18 is required:

&Quot; (18) "

Combining Equation (18) with Equations (14) and (17) gives the condition of Equation (19): <

&Quot; (19) "

은 갭 구역의 제곱미터 당 2kA _g / gC _p , 또는 2k/ gC _p 미만이어야 한다. 하나의 구체 예에서,

< B· (2kA _g / gC _p ), 여기서 B는 전도 냉각에 대한 대류 냉각의 비이다. 여기에 사용된 바와 같이, B는 1보다 작고 0보다 큰 양의 정수이며, 구체적으로 2/3 이하, 또는 심지어 4/5 또는 9/10 이하의 값을 갖는다. 일반적으로, 유리 시트 (예를 들어, 히트 싱크 표면에 대한 도 21에 나타낸 시트 (200)) (예를 들어, 도 21에 나타낸, 히트 싱크 표면 (201b, 202b))의 위치 또는 열교환 표면 자체의 위치를 제어하는데 가스 유동을 사용할 필요성에 맞게,

은 가능한 낮게 유지되어야 한다. 전도 냉각에 대한 대류 냉각의 비는 1 미만 내지 1x10^-8의 값일 수 있다. 몇몇 구체 예에서, B는 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.1, 5x10^-2, 1x10^-2, 5x10^-3, 1x10^-3, 5x10^-4, 1x10^-4, 5x10^-5, 1x10^-5, 5x10^-6, 1x10^-6, 5x10^-7, 1x10^-7, 5x10^-8, 또는 1x10^-8 미만이다. 몇몇 구체 예에서,

은 히트 싱크 표면에 대해 시트 위치를 제어하고 지지하기 위해 가스 유동을 이용할 필요성에 맞게, 최소화된다. 다른 구체 예에서,

은 시트에 대해, 열교환 표면 그 자체의 위치를 제어하기 위해 선택되어야 한다. Equation 19 will essentially guarantee that, in the region of the gap in question, the sheet is cooled (or heated) primarily by conduction when held. Therefore, the gas mass flow rate

Is ₂ kA _g / gC _p , or 2 k / g C _p . In one embodiment,

&Lt; B (2 kA _g / gC _p ), where B is the ratio of convection cooling to conduction cooling. As used herein, B is a positive integer less than 1 and greater than 0, specifically less than or equal to 2/3, or even less than or equal to 4/5 or 9/10. Generally, the position of the glass sheet (e.g., the sheet 200 shown in FIG. 21 relative to the heat sink surface) (e.g., heat sink surfaces 201b, 202b shown in FIG. 21) Depending on the need to use a gas flow to control the position,

Should be kept as low as possible. The ratio of convection cooling for conduction cooling may be a value of less than 1 to 1 x 10 &lt;&quot; ⁸ &gt;. In some embodiments, B is 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.1, 5x10 -2, 1x10 -2, 5x10 -3, 1x10 -3, 5x10 -4, 1x10 -4, 5x10 -5, 1x10 ^-5, 5x10 ^-6, 1x10 ^-6, a ^{5x10 -7, 1x10 -7, 5x10 -8} , or less than 1x10 ^-8. In some embodiments,

Is minimized to meet the need to utilize the gas flow to control and support the seat position relative to the heat sink surface. In another embodiment,

For the sheet, should be selected to control the position of the heat exchange surface itself.

)은, 종래의 대류-기반 템퍼링 시스템과 비교하여 실질적으로 더 낮다. 이러한 실질적으로 더 낮은 가스 유속은, 여기서 논의된 바와 같이, 전도성 시스템이 실질적으로 감소된 전력 사용으로 작동되는 것을 가능하게 한다. 더욱이, 적어도 몇몇 구체 예에서, 감소된 가스 유속은 또한 종래의 대류 냉각 시스템과 비교하여 실질적으로 더 조용한 냉각 시스템을 결과한다. 이러한 구체 예에서, 소음의 감소는 청각 손상의 잠재성을 감소시키고 및 심지어 작업자가 청각 보호를 사용할 필요성을 감소시키거나 제거하여, 작업자 안전을 증가시킬 수 있다. 몇몇 구체 예에서,이러한 낮은 가스 유속 장점은 전도성-기반 냉각 시스템 내에서 실현되어, 여기에 논의된 결과적으로 개선된 템퍼링과 유리 특징 및 높은 냉각 속도를 가능하게 한다. In various embodiments, the mass flow rate of the gas in the conductive-based cooling system of the present disclosure

) Is substantially lower compared to conventional convection-based tempering systems. This substantially lower gas flow rate enables the conductive system to be operated with substantially reduced power usage, as discussed herein. Moreover, in at least some embodiments, the reduced gas flow rate also results in a cooling system that is substantially quieter as compared to conventional convection cooling systems. In this embodiment, the reduction in noise can reduce the potential for hearing damage and even reduce or eliminate the need for the operator to use hearing protection, thereby increasing operator safety. In some embodiments, this low gas flow rate advantage is realized within a conductive-based cooling system, resulting in improved tempering and glass characteristics and high cooling rates as discussed herein.

In certain embodiments, the total gas flow rate in the air bearing channel of the conductive-based cooling system is low (i.e., the gas is not delivered in convective cooling) and, in some embodiments, Flow rate. In certain embodiments, the gas flow rate in the air bearing channel (e.g., all surfaces of the glass product) is from 50 standard liters per minute (slpm) to 50,000 slpm per square meter of glass surface area, Lt; RTI ID = 0.0 &gt; slpm &lt; / RTI &gt; In some of these embodiments, the gap length g is 10 占 퐉 or more and 500 占 퐉 or less, particularly 25 占 퐉 or more and 300 占 퐉 or less. In certain embodiments, the gas may be air, helium, or other suitable gas. Compared to at least some convection-based tempering systems, Applicants believe that the air flow rate embodied in the system of this disclosure is typically less than at least 20% gas flow rate in at least some convection-based tempering systems, typically at least 0.1 % Gas flow rate.

For example, to further illustrate the low gas flow rates to be used in the conductive-based cooling systems discussed herein, Applicants have tested cooling systems that use air, such as gas bearing gas, helium, various gap lengths, and various air flow rates . The Applicant cools the glass sheet using air as the bearing gas with a gap length of 38 mu m at an air flow rate of 3600 and 12,000 slpm per square meter of glass surface area to provide conductive heat transfer with total heat transfer rates of 95% and 92% Respectively. Applicants use air as a bearing gas with a gap length of 250 mu m at an air flow rate of 3600 to 12,000 slpm per square meter of glass surface area to cool the glass sheet to provide a conductive heat transfer with a total heat transfer rate of 76% Respectively.

The Applicant cools the glass sheet using helium as a bearing gas having a gap length of 38 μm at a helium flow rate of 3600 and 12,000 slpm per square meter of glass surface area, and has conductive heat transfer with a total heat transfer rate of 99% and 98%, respectively . The Applicant cools the glass sheet using helium as a bearing gas with a gap length of 250 microns at a helium flow rate of 3600 and 12,000 slpm per square meter of glass surface area, resulting in a total heat transfer rate of 94% and 90% Respectively.

In the contemplated embodiment, the Applicant has found that the conductive cooling zones discussed herein using air as the bearing gas with a gap length of 25 microns at an air flow rate of 100 and 28,700 slpm per square meter of glass surface are 98% and 91 % Of the total heat conductivity. In another contemplated embodiment, the Applicant has found that the conductive cooling zones discussed herein using air as the bearing gas with a gap length of 300 microns at air flow rates of 100 and 28,700 slpm per square meter of glass surface area, It is determined that conductive heat transfer is achieved with a total thermal conductivity of 44%.

In another contemplated embodiment, applicants have found that the conductive cooling zones discussed herein using helium as a bearing gas with a gap length of 25 [mu] m at a helium flow rate of 100 and 10,000 slpm per square meter of glass surface area, It is determined that conductive heat transfer is achieved with a total thermal conductivity of 99%. In another contemplated embodiment, applicants have found that the conductive cooling zones discussed herein using helium as a bearing gas having a gap length of 300 microns at a helium flow rate of 100 and 10,000 slpm per square meter of glass surface area, It is determined that conductive heat transfer is achieved with a total thermal conductivity of 89%. In certain embodiments, the conductive heat transfer rate discussed herein is based on a glass material having a Tg of 680 캜.

)으로 제공된다. 이러한 구체 예에서,

은 0보다 크고 (2k₁A_g1)/ (g₁C_p1)보다 작다. 더욱이, 제2 가스는 열 용량 (C_p2) 및 열 전도도 (k₂)를 가지며, 제2 유동은 질량 유속 (

)으로 제공된다. 이러한 구체 예에서,

는 0보다 크고 (2k₂A_g2)/ (g₂C_p2)보다 작다. 이러한 구체 예에서, 제1 및 제2 유동은 유리 시트가 히트 싱크 표면에 접촉함 없이 지지되도록 유리 시트와 접촉한다. 이러한 방식으로, 시트는 시트의 중심 장력 및 표면 압축 응력을 생성하는 방식으로, 대류보다 전도에 의해 많이 냉각된다. As will be appreciated, in embodiments in which sheets of glass material are supported on air bearings between opposing heatsink surfaces, conductive heat transfer will occur from both sides of the glass sheet to both heat sink surfaces. Thus, in this embodiment, the glass sheet has first and second sheet surfaces, and the cooling of the glass sheet is performed such that the first gap is between the first sheet surface and the first heat sink surface, (E.g., the lower surface of the glass sheet) adjacent the first heat sink surface (e.g., the surface of the lower heat sink) so that the second gap is positioned between the second sheet surface and the second heat sink surface By positioning the second sheet surface (e.g., the upper surface of the glass sheet) adjacent to the second heat sink surface (e.g., the surface of the upper heat sink). In this embodiment, thermal conduction is allowed to occur from the first sheet surface to the first heat sink surface and from the second sheet surface to the second heat sink surface. In these embodiments, the first gap has an area of the first gap length, and A _g1 over the first gap g _1, the second gap to the second gap in the longitudinal and A _g2 over the second gap g ₂ . In this embodiment, a first flow of the first gas to the first gap is provided and a second flow of the second gas to the second gap is provided. As will be appreciated, similar to the discussion above, the first gas has a heat capacity (C _p1 ) and a thermal conductivity (k ₁ ), the first flow is the mass flow rate

). In this embodiment,

Is greater than zero and less than (2k ₁ A _g1 ) / (g ₁ C _p1 ). Further, the second gas has a heat capacity (C _p2 ) and a thermal conductivity (k ₂ ), and the second flow has a mass flow rate

). In this embodiment,

Is greater than 0 (2k ₂ A _g2) / less than (g ₂ C _p2). In this embodiment, the first and second flows contact the glass sheet such that the glass sheet is supported without contacting the heat sink surface. In this way, the sheet is much more cooled by conduction than by convection, in a manner that produces the center tension and surface compressive stress of the sheet.

Glass reinforced systems including high conductivity cooling zones

Referring to Figure 21, there is shown a schematic cross-section of a high-conductivity glass cooling / quenching station and a glass sheet that is much more cooled by conduction than convection. High temperature glass The sheet 200 includes first and second surfaces 201b and 202b respectively facing first and second surfaces 201b and 202b of respective first and second heat sinks 201a and 202a across gaps 204a and 204b, And second (main) surfaces 200a and 200b. Gas 230 is supplied through first and second surfaces 201b and 202b as indicated by arrows to provide gaps 204a and 204b and to direct the glass sheet to the center of heat sinks 201a and 202a, It helps to place them between the heat sinks. Air or other gas may pass the edges of heat sinks 201a, 202a as indicated by arrow 240. In accordance with the discussion herein, by selecting the size of the gaps 204a, 204b and the flow rate of the gas and gas 230, the glass sheet 200 will be much more cooled by conduction than convection. In certain embodiments, the glass sheet 200 is greater than 20%, greater than 30%, greater than 40%, specifically greater than 50%, and more specifically greater than 80% exiting the heated product, such as a glass sheet 200, Is cooled by heat sinks 201a and 202a such that excess thermal energy is received by heat sinks 201a and 202a across gaps such as gaps 204a and 204b.

In some embodiments, the gaps 204a, 204b are configured to have a sufficient thickness or distance across the gap such that the heated glass sheet is much more cooled by conduction than convection. As will be appreciated, the size of the gaps 204a, 204b is generally the distance between the major glass surface and the opposing heat sink surface.

In some embodiments, the gaps 204a and 204b may be about 100 microns or greater (e.g., +/- 1%) (E.g., from about 100 microns to about 200 microns, from about 100 microns to about 190 microns, from about 100 microns to about 180 microns, from about 100 microns to about 170 microns, from about 100 microns to about 160 microns, from about 100 microns to about 150 um, from about 110 um to about 200 um, from about 120 um to about 200 um, from about 130 um to about 200 um, or from about 140 um to about 200 um). In other embodiments, gaps 204a and 204b may be about 100 microns or less (e.g., about 10 microns to about 100 microns, about 20 microns to about 100 microns, about 30 microns From about 10 microns to about 100 microns, from about 40 microns to about 100 microns, from about 10 microns to about 90 microns, from about 10 microns to about 80 microns, from about 10 microns to about 70 microns, from about 10 microns to about 60 microns, About 50 [mu] m).

The heat sinks 201a, 202a may be in solid or porous form. Suitable materials include, but are not limited to, aluminum, bronze, carbon or graphite, stainless steel, and the like. The heat sink dimensions can be designed to handle the size of the glass sheet and to be sufficient to efficiently and effectively transfer heat without significantly changing the heat sink temperature. In the case where heat sinks 201a and / or 202a are porous, they may still include additional holes or holes to flow the gas, or may use porous structures to provide flow, or both . In some embodiments, the heat sink further includes a passageway for allowing fluid flow to control the temperature of the heat sink, as described in more detail in Figures 23-25 and below.

Removing the prior art high gas flow rate may enable the use of very small holes or pores 206 on the heat sink surface, as shown in FIG. 21, to provide gas to the gap (s). In some embodiments, the apertures are less than 2 mm, less than 1.5 mm, less than 1 mm, less than 0.5 mm, less than 0.25 mm, or less than 200, 150, or 150 mm, as measured in the smallest direction (e.g., 100, 50, 30, 20, or 10 탆 or less. In some embodiments, the pores are from about 10 microns to about 1 millimeter, from about 20 microns to about 1 millimeter, or from about 50 microns to about 1 millimeter (e.g., +/- 1%).

The spacing between adjacent holes 206 may be from about 10 microns to about 3 mm, from about 20 microns to about 2 mm, or from about 50 microns to about 1 mm . The small holes or pores can serve as individual flow restrictors to provide a high performance, high-performance, high-performance, high- - Provides bearing-type kinetics and enables high homogeneity of the thermal strengthening effect to avoid or reduce stress birefringence. Moreover, since very small pores or holes can be used, the relative amount of solids at the surface of the heat sink facing the sheet surface across the gap (s) can be maximized, thereby increasing conductive heat flow.

According to various embodiments, since the heat sinks 201a and 202a act as both the gas bearing that supports the hot glass sheet 200 and the heat sink that actually cools the hot glass sheet 200, Are configured to perform these dual roles. In certain embodiments, the heat sinks 201a, 202a are configured to receive heat through conduction from the hot glass sheet 200 while at the same time having sufficient thermal mass to sufficiently deliver the gas supporting the hot glass sheet 200 do.

In some such embodiments, the amount of heat sinks 201a, 202a occupied by holes 206 is relatively small to increase or maximize the amount of material present in the heat sinks 201a, 202a to accommodate the heat. In certain embodiments, the holes 206 occupy less than 10%, specifically less than 5%, specifically less than 2%, and more specifically less than 1% of the surface area of the heat sink surfaces 201b, 202b. Applicants use 1.1% and 0.5% of the surface area of the heat sink surfaces 201b, 202b occupied by the holes 206 as a heat sink for conductive cooling in certain exemplary test systems. In certain embodiments in which the heat sinks 201a and 202a are formed of a porous material (e.g., porous graphite or porous aluminum), the surface area of the surfaces 201b and 202b, which pores are so small that they can be used for thermal conduction Lt; / RTI &gt; is essentially 100%. Applicants have found that the ratio of surfaces 201b, 202b that can be used for thermal conduction to the present system is actually high compared to at least some conventional air bearing designs.

According to various embodiments, the use of such apertures 206 as a unique path to provide gas to the gaps 204a, 204b and the use of apertures 206 that lie in a direction near the vertical lines of the heat sink surfaces 201b, Is optimized for air bearing type dynamics and by gas flow from a heat source other than through a larger aperture or through the heat sink surface (s) 201b, 202b adjacent the sheet 200, or And is not damaged by other excessive lateral flow. In other embodiments, the gas may be provided to the gaps 204a, 204b through other heat sources, such as in addition to the apertures 206 or pores. Accordingly, the teachings of the present disclosure enable power and energy savings by using low gas flow and solid-gas-solid conduction, for example, with respect to conventional convective tempering processes.

22-25 illustrate an exemplary embodiment of a glass fortification system 300 in accordance with the present disclosure. 22 shows a schematic cross-sectional view of a system 300 in which a glass sheet can be cooled by thermal conduction into a conductive heat sink from a glass sheet through a gas. The apparatus includes a high temperature zone (310), a cooling zone (330) and a transition gas bearing (320). The transition gas bearing 320 may move or move the glass product 400a from the hot zone 310 to the cooling zone 330 so that there is no contact or substantially no contact between the glass and the bearing, Guide. The high temperature zones 310 have gas bearings 312 that are each fed from a hot zone plenum 318 and the bearings 312 serve to heat the hot zone gas bearings 312 to the desired start process temperature And a cartridge heater 314 inserted into the hole through the bearing 312, The glass sheet (hot zone) 400a is maintained between the hot zone gas bearings 312 for a period long enough to have the desired pre-cooling temperature (e.g., above the transition temperature).

In some embodiments, heating the sheet in the high temperature zone can be largely accomplished by conduction of heat from the heat sink through a thin gas barrier. The conductive heating process used in the high temperature zone may be similar to the cooling process described herein, but may be reversed (e.g., pushing heat into the glass sheet).

In some embodiments, the gap 316 between the hot zone gas bearing 312 and the glass sheet 400a may be relatively large, on the order of 0.05 "(1.27 mm) to 0.125" (3.175 mm) or more, Because the sheet 400a can be heated relatively slowly and thermal radiation from the hot gas bearing 312 into the glass sheet 400a is suitable for this purpose. In other embodiments, the high temperature zone gap size may be as small as 150 microns per side or 500 microns per side. In some embodiments, smaller gaps may be advantageous because they enable the bearings to have a better "stiffness ", i.e., the ability to center the glass and flatten it while the glass is in the softened state Because. In some embodiments, the process can re-form the glass sheet-flatten them-in an initial heating step, for example, through the pressure supplied by the gas bearing 312. In some embodiments, the upper and lower high temperature zone bearings may be on the actuator to change the gap width in a continuous manner or, alternatively, allow the glass to enter the high temperature zone at a large gap, Lt; / RTI &gt; compresses the gap to flatten the car glass for a period of time that is still soft.

In a particular embodiment having a high temperature zone 310 configured to actually heat the glass sheet 400a through conduction, the total gas flow rate in the gap 316 of the conductive-based high temperature zone 310 system is low, In the example, the gas flow rate can be minimized to support the glass product in the hot zone 310. In some such embodiments, the gas flow rate at the gap 316 (e.g., both surfaces of the glass sheet 400a) is between 50 slpm and 50,000 slpm per square meter of glass surface area, and in particular between 100 slpm and 100 slpm per square meter of glass surface area 30,000 slpm. In some of these embodiments, the gap length g is greater than or equal to 50 microns and less than or equal to 1000 microns, and more specifically, less than or equal to 700 microns. In certain embodiments, the gas may be air, helium, or other suitable gas. In certain embodiments, the gas delivered to the hot zone 310 comprises water vapor, and in this embodiment the use of water vapor potentially enhances the low surface viscosity of the hot glass surface, resulting in crack healing do.

In the embodiment to be contemplated, the Applicant has found that a conductive heating zone &lt; RTI ID = 0.0 &gt; 310 &lt; / RTI &gt; such as the high temperature zone 310 discussed herein using air as the bearing gas, with a gap length of 75 microns at an air flow rate of 100 and 28,700 slpm per square meter of glass surface area, Are individually determined to be conductive heat transfer with a total heat transfer rate of 98% and 91%. In other contemplated embodiments, the Applicant has found that conductive heating (e.g., high temperature zone 310 discussed herein) using air as the bearing gas with a gap length of 700 microns at an air flow rate of 100 and 28,700 slpm per square meter of glass surface area, It is determined that the zones are conducting heat conduction at a total heat transfer rate of 74% and 27%, respectively.

In other contemplated embodiments, the Applicant has found that conductive heating with a gap length of 75 microns at a helium flow rate of 100 and 10,000 slpm per square meter of glass surface area and using the helium as the bearing gas, The zones are individually determined to be conductive heat transfer with a total heat transfer rate of 96% and 89%. In other contemplated embodiments, the Applicant has found that conductive heating with a gap length of 700 microns at a helium flow rate of 100 and 10,000 slpm per square meter of glass surface area and using the helium as the bearing gas, It is determined that the zones will conductively conduct heat individually at a total heat transfer rate of 74% and 46%. In certain embodiments, the conductive heat transfer rate discussed herein is based on a glass material having a Tg of 680 캜.

In this embodiment in which the high temperature zone gas bearing 312 heats the glass sheet 400a through thermal conduction from the gas bearing 312 to the glass sheet 400a, the gas bearing 312 supports the glass sheet 400a And to promote thermal conductivity. In certain embodiments, the gas bearing 312 may be heated to a temperature sufficient to transfer heat through the heat conduction to the glass sheet 400a in the hot zone gas bearing 312 and at the same time to deliver sufficient gas to support the glass sheet 400a Mass. In some such embodiments, the amount of gas bearing 312 occupied by the gas delivered to the bore is relatively small, thereby increasing or maximizing the amount of material present in the hot gas bearing 312 for transferring heat. In certain embodiments, the holes 206 occupy less than 10%, specifically less than 5%, specifically less than 2%, and more specifically less than 1% of the surface area of the heat sink surfaces 201b, 202b. In certain embodiments, the hot zone gas bearing holes occupy less than 10%, specifically less than 5%, and more specifically less than 4% of the surface area of opposing bearing surface bearings. In a particular exemplary test system, Applicants use 3.7% and 0.8% of the surface area of conflicting bearing surface bearings 312 occupied by gas delivery holes as the hot zone gas bearings 312. In other embodiments, the hot zone gas bearing 312 may be formed of a porous material (e.g., porous graphite or porous aluminum) rather than having a separate gas delivery hole. In this embodiment, the pores are so small that the surface area of the opposing surface of the hot zone gas bearing 312 that can be used for thermal conduction to the glass sheet 400a is essentially 100%.

The process temperature depends on a number of factors including the glass composition, glass thickness, glass properties (such as CTE), and the desired level of enhancement. In general, the starting process temperature may be any value between the glass transition temperature and the Littleton softening point, or even higher in some embodiments. In the case of SLG, for example, the system 300 heats the glass sheet 400a to a temperature of about 640 to about 730 [deg.] C or about 690 to about 730 [deg.] C. In some embodiments, the system 300 may have a temperature of about 620 to about 800 ° C, about 640 to about 770 ° C, about 660 to about 750 ° C, about 680 to about 750 ° C, about 690 to about 750 ° C, The glass sheet 400a is heated to a temperature of about 740 占 폚, or about 690 占 폚 to about 730 占 폚.

The glass sheet 400a is heated to its desired starting process temperature (e.g., above the auto glass transition temperature) and then moved from the hot zone 310 to the cooling zone 330 using any suitable means . In some embodiments, moving the glass sheet 400a from the high temperature zone 310 to the cooling zone 330 can be accomplished by, for example, (1) tilting the entire assembly to allow gravity acting on the glass sheet to cool (2) shutting off the gas flow from the leftmost outlet of the hot zone 310 (in this embodiment, the side is enclosed) so that all the gas from all the gas bearings flows from the rightmost outlet of the cooling zone (3) by a combination of the above items (1) and (2), so that a fluid force is applied to the glass sheet (400a) and then moved to the cooling zone (330).

The transition gas bearing 320 may be gas fed by the transition bearing plenum 328. The solid material thickness behind the surface of the transition gas bearing 320 may be thin, low thermal mass, and / or low thermal conductivity, allowing reduced thermal conduction from the hot zone 310 to the cooling zone 330. The transition gas bearing 320 may serve as a thermal break or transition between the two zones 310 and 330 and may extend from a larger gap 316 in the high temperature zone to a small gap 336 in the cooling zone 330 It can play a role of switching downward. Moreover, the low thermal mass and / or low thermal conductivity of the conversion gas bearing 320 restricts the amount of heat transfer and hence the cooling experienced by the glass sheet 400a while passing through the transition gas bearing 320. [

Once the glass sheet (cooling zone) 400b has been moved into the cooling zone 330 and channel 330a, the escape from the right outlet is stopped by a mechanical stop indicated by the stop gate 341 or any other suitable shut- do. Once the glass sheet 400b has been sufficiently cooled and the center passes through a glass transition (for example, for a 1 mm thick SLG of about 490 DEG C or less, corresponding to about 325 DEG C on the surface in this embodiment) The stop gate 341 may be moved to unblock the cooling zone channel 330a and then the glass sheet 400b may be removed from the system 300. [ If desired, the glass sheet 400b may be left in the cooling zone 330 somewhere near room temperature before being removed.

As described above, in the high temperature zone 310, the glass sheet 400 is heated to a temperature higher than the glass transition temperature of the glass sheet. 22, the cooling zone 330 receives the heated glass sheet 400b through the opening 330b, conveys the glass sheet 400b, and cools the glass sheet 400b in the cooling zone Channel 330a. In one or more embodiments, the channel 330a includes a gas bearing, a roller wheel, a conveyor belt, or a transport system that may include other means for physically transporting the glass sheet through the cooling zone. 22, the cooling zone 330 includes a high temperature zone plenum 318 and a gas bearing 332 supplied to the plenum 338 separated from the diverting plenum 328.

As shown in FIG. 22, the cooling zone 330 includes one or more heat sinks 331 disposed adjacent the channel 330a. When two heat sinks are used, such a heat sink may be placed on the opposite side of the mutually facing channel 330a across the channel gap 330a. In some embodiments, the heat sink includes a plurality of holes 331a that form some of the gas bearings 332, and the surface of the low temperature gas bearing 332 of the cooling zone 330 is formed as two heat sink surfaces It plays a role. Due to the low air flow rate in the channel 330a and the small size of the channel gap 330a the glass sheet 400b is prevented from touching the surface of the heat sink 400b from the glass sheet across the gap, And is cooled mainly in the cooling zone 330 by conduction of heat into the heat sink 331.

In some embodiments, the heat sink and / or its surface may be segmented. As described above, in some embodiments, the heat sink may be a porous, in these embodiments, the hole where the gas-bearing 332, the gas delivery is the porosity of the porous heat sink. The plurality of holes 332b, the gas source, and the channel gap 330a may be in fluid communication. In some embodiments, the gas flows through hole 331a to form a gas cushion, layer or bearing in channel gap 330a. Some embodiments of the gas cushion prevent the glass sheet 400b from contacting the surface of the heat sink 331. The gas also serves as a gas in which the glass sheet 400b is cooled more by conduction than by convection.

Since cooling is essentially caused by thermal conduction between solids across the gap, problems that do not exist in convective-dominant cooling may need to be resolved. For example, in the case of large and thin sheet tempering, the sheet may (1) be introduced quickly into the cooling zone, optionally at a faster rate than conventionally used in convection-based quenching, and / or (2) Is heated and cooled one after the other with a small space therebetween, and the heat sink is actively cooled to reach thermal equilibrium so that the front and trailing edges of the large sheet are similar And operates in quasi-continuous mode with thermal history.

In some embodiments, the gas flowing through hole 331a cools the heat sink. In some embodiments, the gas flowing through the holes facilitates thermal conduction from the glass across the gap into the heat sink and also cools the heat sink 331. In some instances, a separate gas or fluid may be used to cool the heat sink 331. For example, the heat sink 331 may include a passageway 334 that allows cooling fluid to flow to cool the heat sink 331, as described in more detail with respect to FIG. The passageway 334 may be enclosed.

If two heat sinks are used (i.e., the first heat sink and the second heat sink), one or more gas sources may be used to provide gas to the channel gap 330a. The gas source may comprise the same gas or another gas. The channel gap 330a may thus comprise a gas, a mixture of gases of different gas sources, or the same gas source. Exemplary gases include air, nitrogen, carbon dioxide, helium or other inert gases, hydrogen, and various combinations thereof. In an exemplary embodiment, the gas delivered to the channel gap 330a is water vapor. The gas can be described by its thermal conductivity when it enters the channel 330a just before it begins to conductively cool the glass sheet 400b. In some instances, the gas may be at least about 0.02 W / (m · K), at least about 0.03 W / (m · K), at least about 0.035 W / At least about 0.04 W / (mK), at least about 0.045 W / (mK), at least about 0.05 W / (mK) At least about 0.07 W / (mK), at least about 0.08 W / (mK), at least about 0.09 W / (mK), at least about 0.1 W / / (m · K) or more, or about 0.2 W / (m · K) or more).

The processes and systems described herein permit a high heat transfer rate, which, as discussed above, allows a degree of strengthening by temperature difference to be formed even in very thin glass sheets. By using air as a gas with a gap between the glass sheet and the heat sink, the high heat transfer rate is only possible by conduction to 350, 450, 550, 650, 750, 1000 and 1200 kW / m2 or higher. Using helium or hydrogen, a heat transfer rate of 5000 kW / m 2 or more can be achieved. In another embodiment, the liquid material may be delivered to the channel gap 330a instead of the gas. In some such embodiments, the liquid to be delivered is not phase-changed or decomposed at the highest temperature of the process, such as, for example, molten salt, molten metal, and the like.

The heat sink 331 of one or more embodiments can be fixed or moved to change the thickness of the channel gap 330a. The thickness of the glass sheet 400b is greater than the thickness of the channel gap 300a defined as the distance between the opposing surfaces of the heat sink 331 (e.g., the top and bottom surfaces of the heat sink 331 in the arrangement of FIG. 22) And may range from about 0.4 times thickness to about 0.6 times thickness. In some instances, the channel gap is configured to have a sufficient thickness such that the heated glass sheet is much cooled by conduction than convection.

In some embodiments, the channel gap is defined as the distance between the major surface of the glass sheet 400b and the heat sink surface (e.g., the distance between the major surface of the glass sheet 400b and the surface of the heat sink 400b when the glass sheet 400b is transported through the channel 330a, For example, the gap size discussed above may be less than about 100 占 퐉 (about 100 占 퐉 to about 200 占 퐉, about 100 占 퐉 to about 190 占 퐉, about 100 占 퐉 to about 180 占 퐉, From about 100 microns to about 200 microns, from about 130 microns to about 200 microns, or from about 140 microns to about 170 microns, from about 100 microns to about 160 microns, from about 100 microns to about 150 microns, from about 110 microns to about 200 microns, Mu m to about 200 mu m). In some embodiments, the channel gap is approximately equal to the distance (gap or gaps 336) between the glass sheet and the heat sink surface when the glass sheet 400b is transported through the channel, (E.g., from about 10 microns to about 100 microns, from about 20 microns to about 100 microns, from about 30 microns to about 100 microns, from about 40 microns to about 100 microns, from about 10 microns to about 90 microns, from about 10 microns to about 100 microns, From about 10 microns to about 80 microns, from about 10 microns to about 70 microns, from about 10 microns to about 60 microns, or from about 10 microns to about 50 microns). The overall thickness of the channel gap 330a depends on the thickness of the glass sheet 400b, but it can be generally characterized by the thickness of the glass sheet, or twice the distance between the heat sink surface and the glass sheet. In some embodiments, the distance or gap 336 between the glass sheet and the heat sink may not be the same. In this embodiment, the overall thickness of the channel gap 330a may be characterized by the thickness of the glass sheet plus the sum of the distance between the glass sheet and each heat sink surface.

In some instances, the overall thickness of the channel gap may be less than about 2500 占 퐉 (e.g., from about 120 占 퐉 to about 2500 占 퐉, from about 150 占 퐉 to about 2500 占 퐉, from about 200 占 퐉 to about From about 300 microns to about 2500 microns, from about 300 microns to about 2500 microns, from about 400 microns to about 2500 microns, from about 500 microns to about 2500 microns, from about 600 microns to about 2500 microns, from about 700 microns to about 2500 microns, From about 1000 microns to about 2500 microns, from about 120 microns to about 2250 microns, from about 120 microns to about 2000 microns, from about 120 microns to about 1800 microns, from about 120 microns to about 1600 microns, from about 1200 microns to about 1600 microns From about 120 μm to about 1500 μm, from about 120 μm to about 1400 μm, from about 120 μm to about 1300 μm, from about 120 μm to about 1200 μm, or from about 120 μm to about 1000 μm). In some instances, the total thickness of the channel gap may be greater than or equal to about 2500 microns (e.g., from about 2500 microns to about 10,000 microns, from about 2500 microns to about 9,000 microns, from about 2500 microns to about 8,000 microns, from about 2500 microns to about 7,000 microns From about 2500 microns to about 10,000 microns, from about 2500 microns to about 10,000 microns, from about 2500 microns to about 10,000 microns, from about 2500 microns to about 5,000 microns, from about 2500 microns to about 4,000 microns, from about 2750 microns to about 10,000 microns, From about 4000 microns to about 10,000 microns, from about 4500 microns to about 10,000 microns, or from about 5000 microns to about 10,000 microns).

The hole 331a in the heat sink 331 may be positioned perpendicular to the heat sink surface or may be about 20 degrees or less from perpendicular to the heat sink surface such as about 15 degrees About 10 degrees or less, or about 5 degrees or less.

In some embodiments, the material behind the surface of the heat sink (cooling bearing 332) may be any material that has a high heat transfer rate, including metals (e.g., stainless steel, copper, aluminum), ceramics, carbon, It may be a suitable material. Such a material may be relatively thick compared to the material behind the surface of the transition bearing 320, as shown in Fig. 22, so that the heat sink can easily accommodate a relatively large amount of thermal energy. In an exemplary embodiment, the material of the heat sink 331 is stainless steel.

Figure 23 is an exploded perspective view of an apparatus similar to that of Figure 22, even though the left and right are inverted. The apparatus additionally includes a load / unload gas bearing 342 on which the glass sheet 400c is placed, A load / unload zone 340, and then a cooling zone 330 of the system 300. 23 also uses a tight channel gap (not shown in the drawing) in the high temperature zone 310, the transition bearing 320, and the cooling zone 330.

23 shows an alternative embodiment of the cooling zone gas bearing 332a in which the gas bearing 322a is actively cooled by the coolant channel 334 between the gas bearing supply holes 333, The supply hole supplies a hole to the surface of the bearing 322a. The cooling channel 334 is defined between the heat sink segments 333b and the heat sink segments are assembled together to form a surface facing the heat sink 331 and the glass sheet 400b.

The cooling channel 334 may be located in close proximity to the surface of the heat sink 331 with the solid material of the gas bearing 332 wherein the nearest surface of the heat sink / gas bearing surface and coolant channel 334 The area of the solid bearing material between the edges has the same width as the nearest surface edge of the coolant channel 334. Thus, in some embodiments, there is no reduced cross-sectional area in the solid material of the heat sink 331 / gas bearing 332a between the coolant channel 334 and the surface facing the glass 400b. This differs from conventional convection gas cooling equipment because a high gas flow rate allows a substantial space to be provided in the middle of the gas nozzle array to escape the gas flow. When active cooling is used, the heat sink 331 / gas bearing 332a has a reduced cross-sectional area in the solid material of the gas nozzle design, relative to the solid material closest to the glass surface. The reduced cross-sectional area is typically positioned between the active cooling fluid and the glass sheet during processing to provide a high-volume path for a large amount of heated gas returning from the sheet.

Fig. 24 still shows another alternative embodiment of the cooling zone gas bearing 332 as in the illustration of Fig. In this embodiment, the coolant channel 334 includes a gas bearing supply member 335 that includes a gas bearing supply hole 333 and a gas bearing surface 332 that provides a glass sheet 400b that faces the surface of the gas bearing 332. [ Member 337a. 25 has a structure similar to that of the embodiment of Fig. 24, but a porous member 339 is provided between the bearing plate member 337b and the glass sheet 400b, so that the porous member 339 forms a surface facing the glass sheet 400b. Lt; RTI ID = 0.0 &gt; 332c &lt; / RTI &gt;

In various embodiments, the glass strengthening processes and systems described herein with respect to Figures 16-26 may be used with any combination of features, features, dimensions, physical properties, etc. of any of the glass product embodiments discussed herein Ceramic, glass, or glass-ceramic article (e.g., glass sheet 500).

Glass sheets that have undergone the thermal strengthening process described herein can be further processed by ion exchange to further enhance their strength. In some of these contemplated embodiments, the ion-exchange of the surface of the thermally enhanced glass as described herein is at least 20 MPa, such as at least 50 MPa, such as at least 70 MPa, such as at least 80 MPa, such as at least 100 MPa, Such as at least 150 MPa, such as at least 200 MPa, such as at least 300 MPa, such as at least 400 MPa, such as at least 500 MPa, such as at least 600 MPa and / or 1 GPa.

Systems and processes for thermally controlling and / or heating glass sheets

In addition to thermal strengthening of thin glass sheets, the processes and systems described herein may also be used in additional thermal conditioning processes. Although cooling is specifically discussed herein, systems and processes can be used to transfer heat into a glass sheet through a conductive method. Accordingly, there is an additional embodiment of the process of the present disclosure, including heating through gas by conduction more than convection. This process or method 700 is illustrated in the flow chart of Fig.

The method 700 includes two main steps. The first step (step 710) Providing a product, such as a glass sheet, having at least one surface. The second step (step 720) includes heating or cooling, including a portion of the surface of the article, the entire surface of the article, and the entire surface. Step 720 is performed much more by conduction than convection through a gas or heat source, such as a heat source or a heat sink source, as shown in lower portion 720a, and a lower portion 720a, And the conduction of cooling / heating in step 720 is performed sufficiently to achieve a thermal control of at least 450 kW per square meter of area of the sub-part 720b , With a high heat transfer rate.

For example, a product can be controlled much more thermally by conduction than convection, i.e., heated or cooled, by cooling or heating up to a portion of the product's surface, the entire surface of the product , The conduction is mediated through a gas, not through a solid-to-solid contact from a heat sink or heat source or from a heat sink or a heat source, and sufficiently completes the thermal environment of the product or part of the product surface, Heating or cooling is performed for at least several hours at a rate of at least 250, 450, 550, 650, 750, 800, 900, 1000, 1100, 1200, 1500, 2000, 3000, 4000 or even 5000 kW or more per square meter.

In addition to tempering, the high thermal power transfer rates provided by the systems and methods discussed herein can be achieved by any type of heating, including heating and cooling during tempering, edge strengthening of glass, firing or sintering of ceramics, / RTI &gt; thermal process or environment. Additionally, since heat is primarily extracted or conducted by conduction, it preserves surface smoothness and quality while providing tight control over thermal history and heat distribution in the treated product. Thus, still from another aspect of the present disclosure, strict control over thermal history and heat distribution in treated products is provided, since surface smoothness and quality are preserved, although heat is primarily extracted or conducted by conduction. Thus, by using the system and method of the present disclosure, by changing the gap, changing the heat sink / heat source material, changing the heat sink / heat source temperature, and changing the gas mixture, It will then be possible to intentionally change the stress profile from the reinforcement process - and both of these may be changed by the position along the path of the sheet or along the path of the sheet as the sheet moves, or potentially by position But can vary over time (for most parameters).

Tempered glass sheet device , Products and structures

The reinforced glass or glass-ceramic products and sheets discussed herein have broad applications in a wide variety of products, devices, products, structures, and the like.

27, a structure 1010 such as a building, house, vehicle, etc. includes a glass or glass-ceramic article 1012 in the form of a window, a portion of a wall (e.g., a surface), a partition, do. In a contemplated embodiment, a glass or glass-ceramic article 1012 can be a glass or glass-ceramic article 1012, such as a glass or glass-ceramic article 1012, as disclosed herein, having a surface on its surface that is balanced by positive tensile stress To have a negative tensile stress at or near &lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt; Furthermore, the glass or glass-ceramic article 1012 may be present in an outdoor environment with a relatively high silicon dioxide content, such as at least 70 wt.% Silicon dioxide, such as at least 75 wt.% Silicon dioxide. , It may have chemical and / or corrosion resistant compositions.

According to an exemplary embodiment, the glass or glass-ceramic article 1012 has a major surface at right angles to its thickness (see general sheet 500 as shown in Fig. 4), in this case the major surface (E.g., at least 5 cm 2, at least 9 cm 2, at least 15 cm 2, at least 50 cm 2, at least 50 cm 2, at least 50 cm 2, At least 250 cm &lt; 2 &gt;). In the considered embodiment, the total light transmittance through the glass or glass-ceramic article 1012 is less than the thickness t, such as less than 5 cm, 3 cm &lt; RTI ID = 0.0 &gt; Less than 2 cm, less than 1.75 cm, less than 1.5 cm, less than 1 cm, less than 5 mm, less than 3 mm, less than 2 mm, less than 1.75 mm, less than 1.5 mm, less than 1 mm, less than 0.8 mm, At least about 50% (e.g., at least about 65%) from a wavelength of about 300 nm to about 800 nm, such as less than 0.5 mm, less than 0.4 mm, less than 0.2 mm, and / or at least 10 micrometers, %, At least 75%).

The thin thickness of the glass or glass-ceramic article 1012 is advantageous compared to conventional products because the high level of strength of the glass or glass-ceramic article 1012 is provided by the inventive process disclosed herein, Ceramic, or other applications. &Lt; RTI ID = 0.0 &gt; [0042] &lt; / RTI &gt; The thin glass or glass-ceramic article 1012 may be particularly useful for architectural, automotive, or other applications, since the glass or glass-ceramic article 1012 may be lighter than these conventional articles, Thereby reducing the weight of the entire structure. In the case of automobiles, higher fuel efficiency can be achieved. In the case of buildings, it can result in a more robust or less resource-intensive structure. In other contemplated embodiments, the glass or glass-ceramic article disclosed herein can have a smaller size, a thicker thickness of area, can transmit less light, and / Lt; RTI ID = 0.0 &gt; 30 &lt; / RTI &gt;

28, surface 1110 may be formed by any combination of stress profiles, structures, and / or physical properties discussed herein, which function as a part of the cooktop and / or display, and / , Glass or glass-ceramic product (1112). In some embodiments, the total transmittance through the glass or glass-ceramic article 1012 is at least about &lt; RTI ID = 0.0 &gt; about &lt; / RTI &gt; about infrared light wavelengths from about 800 nm to about 1500 nm so as to facilitate use of surface 1110, such as a cooktop. 30% (e.g., at least 50%). In some embodiments, the glass or glass-ceramic article 1112 has a thickness of about 10 x 10 ^-7 C- ¹ to about 140 x 10 ^-7 C- ¹ , about 20 x 10 ^-7 C- ¹ to about 120 x 10 ^-7 DEG C- ¹ , about 30 x ^10-7 DEG C- ¹ to about 100 x ^10-7 DEG C- ¹ , about 40 x ^10-7 DEG C- ¹ to about 100 x ^10-7 DEG ^C- It has ^-7 ℃ ^-1 to about 100 × 10 ^-7 ℃ ^-1, or coefficient of thermal expansion (CTE) of about 60 × 10 ^-7 ℃ ^-1 to about 120 × 10 ^-7 ℃ ^-1. In various embodiments, the process is ideally suited for glass compositions having medium to high CTE. Representative glasses that work well in the processes described herein include alkali aluminosilicates, such as Corning's® Gorilla® glass, boroaluminosilicate, and soda-lime glass. In some embodiments, the glass used is 40 × 10 ^-7 / ℃ excess, 50 × 10 ^-7 / ℃ excess, 60 × 10 ^-7 / ℃ excess, 70 × 10 ^-7 / ℃ excess, 80 × 10 ^-7 / [Deg.] C and greater than 90 x 10 &lt; ^-7 &gt; / [deg.] C. Some such CTEs may be particularly low for thermal tempering as disclosed herein, wherein the degree of negative tensile stress is 50 MPa or less and / or at least 10 MPa.

29, a device 1210 (e.g., a handheld computer, a tablet, a portable computer, a cell phone, a television, a display board, etc.) may have a stress profile, structure and / Ceramic article 1212, 1214, 1216, and / or an electrical component 1218 and a housing 1220, as described herein, and / or any combination thereof, . In contemplated embodiments, the housing 1220 can be or include a glass or glass-ceramic article as disclosed herein. In the contemplated embodiment, the substrate 1222 for the electronic component 1218 may be a glass or a glass-ceramic article as described herein.

In some embodiments, the glass or glass-ceramic article 1212, 1214 can function as a front and back substrate, and the glass or glass-ceramic article 1216 can function as a cover glass in the device 1210 . According to an exemplary embodiment, the glass or glass-ceramic article 1216 of the device 1210 is an alkali-aluminosilicate glass. Such a composition may strengthen the glass or glass-ceramic article 1216 by thermal tempering, as described herein, and may have a particularly high negative tensile stress (e. G., At least 200 MPa, at least 250 MPa). &Lt; / RTI &gt; In other embodiments, the glass or glass-ceramic article 1216 may comprise at least one of sodium carbonate, calcium oxide, calcium magnesium carbonate, silicon dioxide (e.g., at least 70 wt.%), Aluminum oxide, and / ; And the inventive process disclosed herein. The glass or glass-ceramic article 1216 may be particularly thin, or may have a structure, such as having any of the dimensions as disclosed herein.

Referring now to Figure 30, a glass or glass-ceramic article 1310, made according to the process disclosed herein and / or in any combination of stress profile, structure and / or physical properties as disclosed herein, Curvature and / or variable cross-sectional dimension (D). Such a product may have a thickness as disclosed herein either as an average of the dimensions D or as the maximum of the dimensions D. While the glass or glass-ceramic article 1310 is shown as a curved sheet, other forms, such as a more complex form, may be enhanced by the process disclosed herein. In a contemplated embodiment, the glass or glass-ceramic article 1310 can be used for an automotive window (e.g., sunroof etc.), as a lens, as a container, or for other applications. In one embodiment, the glass or glass-ceramic article 1310 is cut from the heat-enhanced sheet prior to cutting. In another embodiment, the glass or glass-ceramic article 1310 is cut from the sheet of glass material prior to heat treatment and the glass or glass-ceramic article 1310 is thermally enhanced as discussed herein after being cut .

In various embodiments, the glass material produced according to any of the combinations of stress profiles, structures and / or physical properties as disclosed herein, and / or according to the processes disclosed herein, Is useful for forming at least one sheet of glass-polymer-interlayer-glass laminate. Stronger and thinner laminates can be produced, resulting in weight and cost savings and increased fuel efficiency. Preferably, the thermally enhanced thin sheet can be laminated to a glass which has been formed by cold bending (see Fig. 32 in general) and thicker, so that an easy and reliable Thereby providing a manufacturing process.

Glass or glass-ceramic material for thermally enhanced glass sheets

The systems and methods discussed can be used for thermal control, strengthening, and / or tempering a wide range of glass or glass-ceramic materials.

The processes and systems described herein can generally be used in almost all glass compositions and, in some embodiments, glass laminates, glass ceramics, and / or ceramics. In various embodiments, the process can be used in a glass composition having a high CTE. In embodiments, the glass reinforced through the processes and systems discussed herein includes alkali aluminosilicates, such as Corning's® Gorilla® glass, SLG, no-soda or no-alkali glass, and the like. In some embodiments, enhanced by the processes and systems discussed herein are glass, 40 × 10 ^-7 / ℃ excess, 50 × 10 ^-7 / ℃ excess, 60 × 10 ^-7 / ℃ excess, 70 × 10 ^{- 7} / ℃, greater than 80 × 10 ^-7 / ℃ exceeded, and has a CTEs of 90 × 10 ^-7 / ℃ out.

In some applications and embodiments, glass reinforced through the processes and systems discussed herein (such as glass sheet 500) may have a composition configured for chemical durability. In some such embodiments, the composition comprises at least 70 wt.% Silicon dioxide, and / or at least 10 wt.% Sodium oxide, and / or at least 7 wt.% Calcium oxide. Conventional products of such compositions may and may not be chemically tempered to deep depths, but are not susceptible to a negative surface tensile stress of sufficient size for thin thicknesses, due to the fragility and physical strength of conventional processes It may be difficult to thermally temper by conventional processes. However, in the contemplated embodiment, the inventive process disclosed herein enables, with such a composition, a reinforced glass or glass-ceramic article or sheet, such as a glass sheet 500, At least 10% of the thickness of the reinforced glass or glass-ceramic sheet from at least one of the first and second surfaces (e. G., Surfaces 510 and 520 of glass sheet 500) Ceramic, at least 15% of the thickness, at least 18% of the thickness, or at least 20% of the thickness.

In some embodiments, reinforced glass or glass-ceramic sheets and articles, as discussed herein, have one or more coatings that are placed on the glass prior to thermal strengthening of the glass sheet. The process discussed herein can be used to produce an enhanced glass sheet with one or more coatings, and in some embodiments, the coating is placed on glass prior to thermal strengthening and is not affected by the thermal strengthening process. Special coatings that are advantageously retained on the glass sheet of this disclosure include low E coatings, reflective coatings, antireflective coatings, anti-fingerprint coatings, barrier filters, pyrolytic coatings, and the like.

According to an exemplary embodiment, the glass or glass-ceramic sheet or product discussed herein, for example products 1212 and 1214 of device 1210 shown in Fig. 29, is a boro-aluminosilicate glass. In some embodiments, the glass or glass-ceramic sheet or article discussed herein, e.g., products 1212, 1214 of device 1210 shown in Figure 29, is generally a no-alkali glass, And has a stress profile and structure as disclosed. Such compositions can reduce the degree of relaxation of the glass and facilitate bonding of the transistors to the glass. In some embodiments, the glass sheet / product discussed herein is a flexible glass sheet. In another embodiment, the glass sheet / article discussed herein comprises a laminate of two or more glass sheets.

In some contemplated embodiments, glass reinforced through the processes and systems discussed herein (such as glass sheet 500) includes an amorphous substrate, a crystalline substrate, or a combination thereof, such as a glass-ceramic substrate can do. Enhanced glass through the processes and systems discussed herein may include alkali aluminosilicate glass, alkali containing borosilicate glass, alkali aluminosporosilicate glass, or alkali aluminoborosilicate glass. In one or more embodiments, the glass reinforced through the processes and systems discussed herein (such as glass sheet 500) can have a molar percent (mol%), a molar ratio (mol%), SiO _{2 in the} range of about 40 to about 80 mol%, Al ₂ O _{3 in the} range of about 10 to about 30 mol%, B ₂ O _{3 in the} range of about 0 to about 10 mol% From 0 to about 20 mol.% R ₂ O, and / or from about 0 to about 15 mol.% RO. In some contemplated embodiments, the composition may include one or both of ZrO _{2 in the} range of about 0 to about 5 mol.% And P ₂ O ₅ in the range of about 0 to about 15 mol.%. In some contemplated embodiments, TiO ₂ may be present in from about 0 to about 2 mol.%.

In some contemplated embodiments, the compositions used in the reinforced glass or glass-ceramic sheets or articles discussed herein may comprise Na ₂ SO ₄ , NaCl, NaF, NaBr, K ₂ SO ₄ , KCl, KF, KBr, and And 0-2 mol.% Of at least one fining agent selected from the group comprising SnO ₂ . The glass composition according to one or more embodiments comprises from about 0 to about 2 mol.%, From about 0 to about 1 mol.%, From about 0.1 to about 2 mol.%, From about 0.1 to about 1 mol.%, And may further contain SnO ₂ in the range of about 2 mol.%. The glass compositions disclosed herein for the reinforced glass or glass-ceramic sheet 500 may, in some embodiments, be substantially free of As ₂ O ₃ and / or Sb ₂ O ₃ .

In contemplated embodiments, the reinforced glass or glass-ceramic sheet or article discussed herein may comprise an alkali aluminosilicate glass composition or an alkali aluminoborosilicate glass composition that is further reinforced through an ion exchange process. One representative glass composition comprises SiO ₂ , B ₂ O ₃ , and Na ₂ O, wherein (SiO ₂ + B ₂ O ₃ ) ≥ 66 mol.%, And / or Na ₂ O ≥ 9 mol.%. to be. In an embodiment, the glass composition comprises at least 6 wt.% Aluminum oxide. In another embodiment, the reinforced glass or glass-ceramic sheet or article discussed herein may comprise a glass composition having at least one alkaline earth oxide, such that the content of alkaline earth oxide is at least 5 wt.% . A suitable glass composition, in some embodiments, further comprises at least one of K ₂ O, MgO, and CaO. In certain embodiments, the automotive glass composition used in the reinforced glass or glass-ceramic sheet or article discussed herein comprises 61-75 mol.% SiO ₂ ; 7-15 mol% Al ₂ O ₃ ; 0-12 mol% B ₂ O ₃ ; 9-21 mol.% Na ₂ O; 0-4 mol% K ₂ O; 0-7 mol% MgO; And / or 0-3 mol.% CaO.

Another representative glass composition suitable for the reinforced glass or glass-ceramic sheet or article discussed here is: 60-70 mol.% SiO ₂ ; 6-14 mol% Al ₂ O ₃ ; 0-15 mol% B ₂ O ₃ ; 0-15 mol% Li ₂ O; 0-20 mol% Na ₂ O; 0-10 mol% K ₂ O; 0-8 mol% MgO; 0-10 mol% CaO; . 0-5 mol% ZrO _2; 0-1 mol% SnO ₂ ; . 0-1 mol% CeO _2; As ₂ O ₃ less than 50 ppm; And Sb ₂ O ₃ less than 50 ppm, wherein 12 mol.% (Li ₂ O + Na ₂ O + K ₂ O) 20 mol.% And / or 0 mol.% (MgO + CaO) ≤ 10 mol.%. Still another representative automotive glass composition suitable for the reinforced glass or glass-ceramic sheet or article discussed here is: 63.5-66.5 mol.% SiO ₂ ; 8-12 mol% Al ₂ O ₃ ; 0-3 mol% B ₂ O ₃ ; 0-5 mol% Li ₂ O; 8-18 mol.% Na ₂ O; 0-5 mol% K ₂ O; 1-7 mol% MgO; 0-2.5 mol% CaO; . 0-3 mol% ZrO _2; 0.05-0.25 mol.% SnO ₂ ; 0.05-0.5 mol.% CeO ₂ ; As ₂ O ₃ less than 50 ppm; And Sb ₂ O ₃ of less than 50 ppm, wherein 14 mol.% (Li ₂ O + Na ₂ O + K ₂ O) ≦ 18 mol.% And / or 2 mol.% (MgO + CaO) ≤ 7 mol.%.

In certain contemplated embodiments, an alkali aluminosilicate glass composition suitable for a glass or glass-ceramic sheet or article discussed herein may comprise alumina, at least one alkali metal, and in some embodiments, greater than 50 mol.% SiO _2, in other embodiments, at least 58 mol.% SiO _2, and in still other embodiments, comprises at least 60 mol.% SiO _2, where _{(Al 2 O 3 + B 2} O 3) / Σ modifier (i. e. , The sum of modifiers) is greater than 1, and in this case, The components are expressed in mol.% And the modifier is an alkali metal oxide. This glass composition comprises, in certain embodiments, from 58 to 72 mol.% SiO ₂ ; 9-17 mol% Al ₂ O ₃ ; 2-12 mol% B ₂ O ₃ ; 8-16 mol% Na ₂ O; And / or 0-4 mol.% K ₂ O, wherein the ratio of (Al ₂ O ₃ + B ₂ O ₃ ) / S modifier (ie sum of modifier) is greater than 1. In yet another embodiment, the reinforced glass or glass-ceramic sheet 500 comprises 64-68 mol.% SiO ₂ ; 12-16 mol% Na ₂ O; 8-12 mol% Al ₂ O ₃ ; 0-3 mol% B ₂ O ₃ ; 2-5 mol% K ₂ O; 4-6 mol% MgO; And 0-5 mol.% CaO, wherein 66 mol.% SiO ₂ + B ₂ O ₃ + CaO 69 mol.%; Na ₂ O + K ₂ O + B ₂ O ₃ + MgO + CaO + SrO> 10 mol.%; 5 mol% MgO + CaO + SrO 8 mol.%; (Na ₂ O + B ₂ O ₃ ) - Al ₂ O ₃ ≤ 2 mol.%; 2 mol% Na ₂ O - Al ₂ O ₃ ≤ 6 mol.%; And 4 mol.% (Na ₂ O + K ₂ O) - Al ₂ O ₃ ≤ 10 mol.%, Based on the total weight of the glass composition. In an alternative embodiment, the reinforced glass or glass-ceramic sheet or article discussed herein may comprise at least 2 mol.% Al ₂ O ₃ and / or ZrO ₂ , or at least 4 mol.% Al ₂ O ₃ and / It may include an alkali aluminosilicate glass composition comprising a ZrO _2.

In the considered embodiments, examples of suitable glass-ceramics for the reinforced glass or glass-ceramic sheet or product discussed herein include Li ₂ O-Al ₂ O ₃ -SiO ₂ systems (ie, LAS-systems) glass- Ceramics, MgO-Al ₂ O ₃ -SiO ₂ systems (ie, MAS-systems) glass-ceramics, and / or β-quartz solid solutions, β-spodumene ss, cordierite, and lithium disilicate Ceramics, including glass-ceramics. The reinforced glass or glass-ceramic sheet or article discussed herein may be characterized by the manner in which it is formed. For example, the reinforced glass or glass-ceramic sheet or article discussed herein may be used in a variety of applications including, but not limited to, float-forming (i.e., formed by a float process), down- And a down-drawing process such as a process or a slot-drawing process).

A float-formed reinforced glass or glass-ceramic sheet or article may be characterized by a smooth surface and a constant thickness and is prepared by suspending molten glass on a molten metal, typically a bed of tin. In an exemplary process, molten glass or glass-ceramics fed onto the surface of the molten tin layer forms a floating glass or glass-ceramic ribbon. As the glass or glass-ceramic ribbon flows along the tin bath, the temperature gradually increases until the glass-ceramic ribbon solidifies into a hard glass or glass-ceramic article which can be lifted up from the tin onto the roller Lower. Once removed from the bath, the glass or glass-ceramic article can be further cooled and annealed to reduce internal stress. If the glass or glass-ceramic article is a glass ceramic, the glass article formed by the float process may be subjected to a ceramicizing process in which one or more crystalline phases are generated.

The down-drawing process produces a glass or glass-ceramic article having a constant thickness that retains the surface as it was originally. Since the average flexural strength of a glass or glass-ceramic article is controlled by the amount and size of surface flaws, the original surface with minimal contact has a higher initial strength. If such a high strength glass or glass-ceramic article is then to be further strengthened (e.g., chemically), the resulting strength will be higher than the strength of the glass or glass-ceramic article having the wraps and polished surface . The down-drawn glass or glass-ceramic article can be drawn to a thickness of less than about 2 mm. In addition, down-drawn glass or glass-ceramic products have a very flat, smooth surface that can be used for their final application without costly glinding and polishing. If the glass or glass-ceramic article is a glass ceramic, the glass or glass-ceramic article formed by the down-drawing process may be subjected to a ceramicizing process in which one or more crystalline phases are generated.

The fusion drawing process uses, for example, a drawing tank equipped with a channel to receive the molten glass raw material. The channel has a top open weir along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten glass overflows the ware. By gravity, the molten glass flows under the outer surface of the drawing tank with two flowing glass films. The outer surface of the draw tank extends downwardly so that these surfaces join together at the edge under the draw tank. The two flowing glass films fuse together at this edge and form a single flowing glass product. The fusion drawing method offers the advantage that the outer surface of the resulting glass article does not cause contact with any part of the device since the two glass films flowing over the channel are fused together. Thus, the surface properties of the fusion drawn glass article are not affected by such contact. If the glass or glass-ceramic article is a glass ceramic, the glass or glass-ceramic article formed by the fusion process may be subjected to a ceramicizing process in which one or more crystalline phases are generated.

The slot drawing process differs from the fusion drawing method. In the slot drawing process, the molten raw glass is provided to the drawing tank. The bottom of the draw tank has an open slot with a nozzle extending the length of the slot. The molten glass flows through the slots / nozzles and is drawn down into the annealing area as a continuous glass product. If the glass or glass-ceramic article is a glass ceramic, the glass article formed by the slot-drawing process may be subjected to a ceramicizing process that produces one or more crystalline phases.

In some embodiments, the glass article is formed using a thin rolling process, such as described in U.S. Patent No. 8,713,972, U.S. Patent No. 9,003,835, U.S. Patent Publication No. 2015/0027169, and U.S. Patent Publication No. 2005/0099618 , The entire contents of which are incorporated herein by reference. More particularly, the glass or glass-ceramic article is produced by a process comprising the steps of feeding a vertical stream of molten glass, melting glass or glass-ceramic with a pair of forming rolls, maintained at a surface temperature above about &lt; Forming a supply stream of the ceramic to form a formed glass ribbon having a formed thickness and sizing the formed ribbon of glass with a pair of sizing rolls maintained at a surface temperature of about 400 DEG C or less, Creating a sized glass ribbon having a desired thickness and a desired thickness consistency that is less than a formed thickness. The apparatus used to form the glass ribbon comprises a glass supply device for supplying a feed stream of molten glass; To define a glass forming gap between forming rolls having a glass forming gap vertically positioned below the glass feeding device to receive a molten glass feed stream and to form a formed glass ribbon having a formed thickness between the forming rolls A pair of forming rolls spaced apart from one another and maintained at a surface temperature of at least about 500 DEG C to thin the feed stream of molten glass; To define a glass sizing gap between sizing rolls having a glass sizing gap vertically positioned below the forming roll to accommodate the formed glass ribbon, and to thin the formed glass ribbon, To produce a sized glass ribbon having a desired thickness and a desired thickness consistency. &Lt; RTI ID = 0.0 &gt; [0031] &lt; / RTI &gt;

In some instances, a thin rolling process may be used, wherein the viscosity of the glass does not allow the use of fusion or slot drawing methods. For example, thin rolls can be utilized to form glass or glass-ceramic articles when the automotive glass exhibits a liquidus viscosity of less than 100 kP. A glass or glass-ceramic article can be acid polished or otherwise treated to remove or reduce the effects of surface flaws.

In contemplated embodiments, the glass or glass-ceramic sheet or article discussed herein has another composition along the side surface. On one side of the glass or glass-ceramic sheet 500, exemplary compositions are: 69-75 wt.% SiO ₂ , 0-1.5 wt.% Al ₂ O ₃ , 8-12 wt.% CaO, 0-0.1 wt % Cl, 0-500 ppm Fe, 0-500 ppm K, 0.0-4.5 wt.% MgO, 12-15 wt.% Na ₂ O, 0-0.5 wt.% SO ₃ , 0-0.5 wt. _{2, 0-0.1 wt.% SrO,} 0-0.1 wt.% TiO 2, 0-0.1 wt.% ZnO, and / or 0-0.1 wt.% ZrO ₂ a. Typical compositions include: 73.16 wt.% SiO ₂ , 0.076 wt.% Al ₂ O ₃ , 9.91 wt.% CaO, 0.014 wt.% Cl, 0.1 % Fe ₂ O ₃ , 0.029 wt.% K ₂ O, 2.792 wt.% MgO, 13.054 wt.% Na ₂ O, 0.174 wt.% SO ₃ , 0.001 wt.% SnO ₂ , 0.01 wt. 0.01 wt.% TiO ₂ , 0.002 wt.% ZnO, and / or 0.005 wt.% ZrO ₂ .

In other contemplated embodiments, the glass or glass-ceramic sheet or composition of the product discussed herein may comprise 55-85 wt.% SiO ₂ , 0-30 wt.% Al ₂ O ₃ , 0-20 wt.% B ₂ O ₃ , 0-25 wt.% Na ₂ O, 0-20 wt.% CaO, 0-20 wt.% K ₂ O, 0-15 wt.% MgO, 5-20 wt. 0.06 wt.% Fe ₂ O ₃ , and / or 0.0001-0.06 wt.% Cr ₂ O ₃ . In other contemplated embodiments, the glass or glass-ceramic sheet or composition of the product discussed herein may comprise 60-72 mol.% SiO ₂ , 3.4-8 mol.% Al ₂ O ₃ , 13-16 mol.% Na ₂ O, 0-1 mol% K ₂ O, 3.3-6 mol% MgO, 0-0.2 mol% TiO ₂ , 0.01-0.15 mol% Fe ₂ O ₃ , 6.5-9 mol% CaO, and / Or 0.02-0.4 mol.% SO ₃ .

Integrated glass forming system

As shown in Figure 31, in various embodiments, the glass heating and / or tempering discussed herein may operate in conjunction with various glass melt / forming systems. For example, the tempering systems and processes disclosed herein can be operated in-line with glass forming or glass melting and forming processes to produce thermally enhanced, thermally treated glass at a lower cost. For example, a glass sheet or glass continuous ribbon can be received by a gas bearing thermal processing system, shown as system 1000 directly in the forming or melting and forming process 1002, and the gas itself is still close to the glass transition temperature Or above the glass transition temperature. In various embodiments, the system 1000 may be any of the tempering systems discussed herein. In one embodiment, the system 1000 may be the system 300 discussed above. In another embodiment, the system 1000 may be a gas bearing cooling arrangement as shown in FIG. This in-line process can control energy savings and thermal history of glass. In various embodiments, the process 1002 may include processes such as a float glass process, a fusion drawing process, a slot drawing process, a rolling process, and the like. In addition, the system 1000 may be integrated into the forming process at any position, for example, before or after the sheet separating process.

32, the systems and processes disclosed herein may also be used in a roll-to-roll (or roll-to-other configuration) of glass ribbon. As shown in Figure 32, the system 1400 includes a glass ribbon 1402 that is fed through a gas bearing thermal processing system, such as the system 300, at a roll 1404, and after thermal processing, a thermally tempered glass ribbon (1402) is stored on the roll (1406). It is possible to further reduce the warp-sensitivity of the glass ribbon by performing a thermally enhanced in-line during a roll-to-roll (or roll-to-other configuration such as a roll-to-sheet) process. The heating and cooling processes discussed herein enable short-distance heat strengthening along the ribbon path, resulting in reduced manufacturing space requirements compared to other heat strengthening processes.

Example

Device Setup - As described above, the device includes three zones-a hot zone, a switch zone, and a cold zone or quenching zone. The gaps between the upper and lower thermal bearings (heat sinks) in the high temperature zone and the quenching zone are set at desired intervals. The gas flow rate in the high temperature zone, the switching zone, and the quenching zone is set to ensure centering of the glass material, sheet or part in the air-bearing. The high temperature zone is preheated to the desired T _O , which is the temperature at which the glass product will subsequently be quenched. To ensure uniform heating, the glassware is preheated in a separate example-heat apparatus, such as a batch furnace or a continuous furnace. Generally, the glass sheet is preheated for more than 5 minutes prior to loading into the high temperature zone. In the case of soda-lime glass, the heat is carried out at about 450 &lt; 0 &gt; C. Example - After the thermal step, the automotive glass product is loaded into a hot zone and allowed to equilibrate, where the equilibrium is that the glass is homogeneous with T _O. T ₀ can be determined by the desired level of tempering / tempering, but is generally maintained in the range between the softening point and the glass transition temperature. The time to equilibration depends at least on the thickness of the glass. For example, in the case of a glass sheet of about 1.1 mm or less, the equilibrium occurs within about 10 seconds. In the case of a 3 mm glass sheet, the equilibration takes place in about 10 to 30 seconds. In the case of a thick sheet of up to approximately 6 mm, the equilibration time can be approximately 60 seconds. Once the glass is equilibrated to T ₀ , the glass is quickly transported to the cooling or quenching zone through the transition zone on the air bearing. The glass product is rapidly quenched in the quenching zone to a temperature below the glass transition temperature, Tg. The glass sheet can be maintained in the quenching zone for any period of time of 1 second, 10 seconds, or several minutes or more, depending on the degree of desired quenching of the glass upon removal and / or the desired temperature. During removal, the glass is allowed to selectively cool before handling.

The following examples are summarized in Table 6.

Examples 1 - Soda-lime silicate glass plates (e.g., at least 70 wt.% Silicon dioxide, and / or at least 10 wt.% Sodium oxide, and / or at least 7 wt. glass including calcium), for 10 minutes to 450 ℃ before sending it to a high temperature zone which is maintained at T ₀ of 690 ℃ for 60 seconds - is open. After equilibrating to T ₀ , the glass plate is quickly transported to a quenching zone filled with helium, with a gap of 91 μm (where the gap is the distance between the surface of the glass sheet and the nearest heat sink), where 10 Lt; / RTI &gt; The resulting product has a surface compression of -312 MPa, a center tension of 127 MPa, and a flatness of 83 [mu] m.

Example 2 A 5.7 mm thick soda-lime silicate glass plate is pre-heated to 450 캜 for 10 minutes before being transferred to a high temperature zone maintained at a T ₀ of 690 캜 for 60 seconds. After equilibrating, the glass plate is quickly transported to the quenching zone, with a gap of 90 [mu] m, where it is held for 10 seconds. The resulting product has a surface compression of -317 MPa, a center tension of 133 MPa, and a flatness of 89.7 占 퐉.

Example 3 - 1.1 mm thick soda-lime silicate glass plate, for example for 10 minutes to 450 ℃ before sending it to a high temperature zone which is maintained at T ₀ of 700 ℃ for 10 seconds - is open. After equilibration, the glass plate is rapidly transported to a quenching zone filled with helium, with a gap of 56 [mu] m, where it is held for 10 seconds. The resulting product has a surface virtual temperature measured at 661 占 폚, a surface compression of -176 MPa, a center tension of 89 MPa, a flatness of 190 占 퐉, and a Vickers cracking threshold of 10-20 N.

Example 4 - 0.55 mm thickness of soda-lime silicate glass plate is, for example, for 10 minutes to 450 ℃ before sending it to a high temperature zone which is maintained at T ₀ of 720 ℃ for 10 seconds - is open. After equilibrating, the glass plate is quickly transported to a quenching zone with a gap of 25 [mu] m, where it is held for 10 seconds, resulting in an effective heat transfer rate of 0.184 cal / (cm &lt; 2 &gt; The resulting product has a surface compression of -176 MPa and a center tension of 63 MPa. The resulting reinforced product also has a flatness of about 168 μm (for the initial 710 ° C. temperature sample) and 125 μm (for the initial 720 ° C. temperature sample).

Example 5 - A 1.5 mm thick CORNING® GORILLA® glass plate is pre-heated to 550 ° C. for 10 minutes before being transferred to a high temperature zone maintained at a T ₀ of 790 ° C. for 30 seconds. After equilibrium is achieved, the glass plate is quickly transported to the quenching zone, with a gap of 226 m, where it is held for 10 seconds. The glass product has an improvement in flatness measured at 113 [mu] m before the process and at 58 [mu] m after the process.

Example 6 - soda of 0.7 mm thick-lime silicate glass plate is, for example, for 10 minutes to 450 ℃ before sending it to a high temperature zone which is maintained at T ₀ of 730 ℃ for 10 seconds - is open. After equilibration, the glass plate is rapidly transported to a quenching zone filled with helium, having a gap of 31 mu m, where it is held for 10 seconds, resulting in an effective heat transfer rate of 0.149 cal / (cm &lt; 2 &gt; do. The resulting product has a surface compression of -206 MPa, a center tension of 100 MPa, and a flatness of 82 mu m. Upon breakage, the glass sheet was observed with a "die" (using standard terminology for sheet dicing greater than 2 mm thickness - i.e., a 5 x 5 cm 2 glass sheet was broken into more than 40 pieces) It suggests.

Example 7 - 3.3 Borofloat-33 glass plate in mm thickness, for 10 minutes to 550 ℃ before sending it to a high temperature zone which is maintained at T ₀ of 800 ℃ for 30 seconds - is open. After equilibration, the glass plate is quickly transported to the quenching zone, with a gap of 119 [mu] m, where it is held for 10 seconds. The resultant product has a flatness of 120 탆. At some fracture, the glass sheet is observed with a "die" (standard term for sheet dicing greater than 2 mm thick - i.e., a 5 x 5 cm 2 glass sheet is broken into more than 40 pieces) Lt; / RTI &gt;

Example 8 - 3.2 mm thickness of soda-lime silicate glass plate, for example for 10 minutes to 450 ℃ before sending it to a high temperature zone which is maintained at T ₀ of 690 ℃ for 30 seconds - is open. After equilibrium is achieved, the glass plate is quickly transported to the quenching zone, with a gap of 84 [mu] m, where it is held for 10 seconds. The resulting product has a surface compression of -218 MPa, a center tension of 105 MPa, and a flatness of 84 탆.

Example 9 - A 0.3 mm thick soda-lime silicate glass plate is pre-heated to 450 占 폚 for 10 minutes before being transferred to a high temperature zone maintained at a T ₀ of 630 占 폚 for 10 seconds. After equilibrating, the glass plate is quickly transported to the quenching zone, with a gap of 159 [mu] m, where it is held for 10 seconds. The resulting product has observable membrane stresses with gray field polarimetry, suggesting that the glass has incorporated thermal stresses.

Example 10 - A 0.1 mm thick CORNING® GORILLA® glass plate is pre-heated to 550 ° C. for 10 minutes before being transferred to a hot zone maintained at T ₀ of 820 ° C. for 10 seconds. After equilibration, the glass plate is rapidly transported to the quenching zone, with a gap of 141 μm, where it is held for 10 seconds, resulting in an effective heat transfer rate of 0.033 cal / (cm 2 s · ° C). At fracture, the resulting product exhibits behavior consistent with residual stressed glass.

Example 11 - 1.1 mm thickness of soda-lime silicate glass plate, for example for 10 minutes to 450 ℃ before sending it to a high temperature zone which is maintained at T ₀ of 700 ℃ for 10 seconds - is open. After equilibrium is achieved, the glass plate is rapidly transported to the quenching zone, with a gap of 65 mu m, where it is held for 10 seconds, resulting in an effective heat transfer rate of 0.07 cal / (cm &lt; 2 &gt; The resulting product has a surface virtual temperature measured at 657 占 폚, a surface compression of -201 MPa, a center tension of 98 MPa, a flatness of 158 占 퐉, and a Vickers cracking threshold of 10-20 N.

Example 12 - A 1.1 mm thick CORNING® GORILLA® glass plate is preheated to 550 ° C. for 10 minutes, before being transferred to a high temperature zone maintained at T ₀ of 810 ° C. for 10 seconds. After equilibrating, the glass plate is quickly transported to a quenching zone with a gap of 86 占 퐉, where it is held for 10 seconds, resulting in an effective heat transfer rate of 0.058 cal / (cm2 占 퐏 占 폚). The resulting product has a surface virtual temperature measured at 711 占 폚, a surface compression of -201 MPa, a center tension of 67 MPa, and a Vickers crack threshold of 20-30 N.

Example 13 - A 1.1 mm thick CORNING® GORILLA® glass plate is pre-heated to 550 ° C. for 10 minutes before being transferred to a high temperature zone maintained at T ₀ of 800 ° C. for 10 seconds. After equilibrium is achieved, the glass plate is rapidly transported to a quenching zone with a gap of 91 mu m, where it is held for 10 seconds. The resulting product has a surface virtual temperature measured at 747 占 폚, a surface compression of -138 MPa, a center tension of 53 MPa, a flatness of 66 占 퐉, and a Vickers cracking threshold of 20-30 N.

Example Thickness (mm) Composition gap
(탆) T ₀ gas CS
(MPa) CT
(MPa) Flatmaster (탆) email
(° C) Vickers
(N) One 5.7 SLG 91 690 helium -312 127 83 - - 2 5.7 SLG 91 690 helium -317 133 90 - - 3 1.1 SLG 56 700 helium -176 89 190 661.3 10-20 4 0.55 SLG 25 720 helium -176 63 125 - - 5 1.5 GG 226 790 helium - - 113 I /
After 58 - - 6 0.7 SLG 31 730 helium -206 100 82 - - 7 3.3 Borofloat 33 119 800 helium - - 121 - - 8 3.2 SLG 84 690 helium -218 105 81 - - 9 0.3 SLG 159 630 helium - - - - - 10 0.1 GG 141 820 helium - - - - - 11 1.1 SLG 65 700 helium -201 98 158 657 10-20 12 1.1 GG 86 810 helium -201 67 - 711 20-30 13 1.1 GG 91 800 helium -138 53 66 747 20-30

Additional Examples - 5.7 mm thick glass sheets comprising at least 70 wt.% Silicon dioxide, and / or at least 10 wt.% Sodium oxide, and / or at least 7 wt.% Calcium oxide, And gaps 204a and 204b (FIG. 21) of about 90 micrometers. The glass is heated to an initial temperature of &lt; RTI ID = 0.0 &gt; 690 C &lt; / RTI &gt; The resulting reinforced product has a negative tensile stress of about 300 MPa at its surface and a tensile stress in the amount of about 121 MPa at its center. The resulting reinforced product also has a flatness of about 106.9 micrometers.

Additional Examples-In one experiment using the inventive techniques disclosed herein, at least 70 wt.% Silicon dioxide, and / or at least 10 wt.% Sodium oxide, and / or at least 7 wt.% Oxidation A 1.1 mm thick glass sheet containing calcium proceeds with helium gas and gaps 204a, 204b (Figure 21) of about 160 micrometers. The glass is heated to an initial temperature of &lt; RTI ID = 0.0 &gt; 680 C &lt; / RTI &gt; The resulting reinforced product has a negative tensile stress of about 112 MPa at its surface and a tensile stress of about 54 MPa in its center. Prior to consolidation, the glass sheet has a flatness of about 96 micrometers, but the resulting reinforced product has a flatness of about 90 micrometers. Thus, the tempering process also flattenes the reinforced glass or glass-ceramic article.

Other aspects and advantages will become apparent from a review of the entire specification and the appended claims.

As shown in the various exemplary embodiments, the construction and arrangement of glass or glass-ceramic sheets and laminate are merely exemplary. Although only a few embodiments have been described in detail in this description, many variations (e.g., variations in size, dimensions, structure, form, and ratio of the various elements) can be made without departing substantially from the novel teachings and advantages of the subject matter described herein , Parameter values, mounting arrangements, use of materials, color, orientation) are possible. Some elements shown as being integrally formed can be composed of a number of parts or elements and the position of the elements can be reversed or changed separately and the nature or number of the individual elements or positions can be changed or changed . The order or order of any process, logic algorithm, or method step may be varied or reordered according to an optional embodiment. Other alternatives, modifications, variations, and omissions without departing from the scope of the present invention may also occur in the design, operating state, and arrangement of the various exemplary embodiments.

Claims (20)

Heating a product of the glass material above a glass transition temperature of the glass material;
Supporting the heated product with a flow of pressurized gas; And
And cooling the heated product at a cooling station, wherein the cooling station includes a heat sink having a heat sink surface facing the heated product and a gas gap separating the heat sink surface from the heated product Wherein the heated product is supported in the gas gap with a flow of the pressurized gas,
The heated product is cooled in the cooling station to a temperature below the glass transition temperature so that a surface compressive stress is generated in the product,
Wherein the flow of pressurized gas is transferred to the gas gap at a flow rate of 50 slpm to 50,000 slpm per square meter of the surface area of the heated product. The method according to claim 1,
Wherein the flow rate of the pressurized gas is such that the heated product is cooled to transfer heat energy to the heat sink by conduction across the gas gap from the heated product to cool the heated product, Wherein the gas is passed across the gas gap and is received by the heat sink. The method according to claim 1,
Wherein the flow rate of the pressurized gas is such that the heated product is cooled by transferring thermal energy to the heat sink by conduction across the gas gap from the heated product to cool the heated product to 50% Wherein said gas gap is received by said heat sink across said gas gap. The method according to claim 1,
The gas gap having a small average length between the outer surface of the heated product and the surface of the heat sink such that the product transfers thermal energy from the heated product to the heat sink by conduction across the gas gap, Wherein at least 20% of the heat energy leaving the heated product is received in the heat sink across the gas gap, wherein the average length of the gas gap is at least 10 占 퐉 and not more than 500 占 퐉. The method of claim 4,
Wherein an average length of the gas gap is 25 占 퐉 or more and 300 占 퐉 or less. The method according to claim 1,
Wherein the pressurized gas is air and the flow rate of pressurized air is greater than or equal to 100 slpm and less than 30,000 slpm per square meter of surface area of the heated product. The method according to claim 1,
Wherein the pressurized gas is helium and the flow rate of pressurized helium is greater than 100 slpm and less than 10,000 slpm per square meter of surface area of the heated product. The method according to claim 1,
Wherein the product of the glass material is a glass ribbon and the glass ribbon is fed from the first reel to the cooling station and the product of the glass material is stored on the second reel after cooling. The method according to claim 1,
Wherein the product of the glass material is at least one of melting and forming in-line with the cooling station. The method according to claim 1,
Wherein the glass material is one of an annealed glass and a glass-ceramic. A heating station including a heating element for transferring heat to the glass sheet;
A cooling station including opposing first and second heat sink surfaces and forming a channel therebetween, wherein during cooling the glass sheet is located within the channel; And
And a gas bearing for delivering a pressurized gas such that the glass sheet is supported within the channel,
Wherein the gas bearing transfers the pressurized gas to the channel at a flow rate of 50 slpm to 50,000 slpm per square meter of the surface area of the glass sheet. The method of claim 11,
Wherein the gas bearing transmits the pressurized gas through a hole formed in the first and second heat sink surfaces, the hole having a total hole area, the total hole area being smaller than the total hole area of the first and second heat sink surfaces And less than 10% of the total surface area. The method of claim 11,
Wherein the gas bearing transmits the pressurized gas through a hole formed in the first and second heat sink surfaces, the hole having a total hole area, the total hole area being smaller than the total hole area of the first and second heat sink surfaces And less than 5% of the total surface area. The method of claim 11,
Wherein the gas bearing transmits the pressurized gas through a hole formed in the first and second heat sink surfaces, the hole having a total hole area, the total hole area being smaller than the total hole area of the first and second heat sink surfaces And less than 1% of the total surface area. The method of claim 11,
Wherein the heating station further comprises a heating station gas bearing forming a heating channel and delivering the pressurized gas to the heating channel such that the glass sheet is supported in the heating channel, To the heating channel at a flow rate of 50 slpm to 50,000 slpm per square meter of surface area of the glass sheet. 16. The method of claim 15,
The heating channel having an average length of at least 50 microns and no more than 1000 microns between the outer surface of the glass sheet and the heating station gas bearing. 16. The method of claim 15,
Wherein the heating station comprises at least one heating element that generates heat to be delivered to the channel of the heating station. A first major surface;
A second major surface opposite the first major surface; And
An inner region located between the first and second major surfaces,
At least one of the first and second surfaces has a relatively large surface area, i.e., at least 2500 mm &lt; 2 &gt;
Wherein at least one of the first major surface and the second major surface is under compressive stress and the inner region is under tensile stress,
Wherein the compressive stress comprises a thermal tempering stress of at least 100 MPa and a catalytic tempering stress of less than 20% of the thermal tempering stress. 19. The method of claim 18,
Wherein the compressive stress comprises a thermal tempering stress of at least 500 MPa and a catalytic tempering stress of less than 10% of the thermal tempering stress. 19. The method of claim 18,
Wherein the composition of said reinforced glass product under said compressive stress and located in at least a portion of said portions of said reinforced glass product exterior and adjacent to said interior region has a composition of tensile stress of said interior region under tensile stress in terms of ionic content and chemical composition Wherein at least some of the compressive stresses are independent of the changes in the composition of the reinforced glass product and wherein the composition of the reinforced glass product at least on one of the first and second major surfaces comprises an ion content Wherein at least some compressive stresses depend on the composition of the tempered glass product under the tensile stress, different from a composition located at least in part of the internal region in terms of chemical composition.

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