JP2018529611A - Heat tempered automotive glass - Google Patents

Abstract

  Provided are a tempered automotive glass sheet or automotive glass laminate and a process and system for producing the reinforced automotive glass sheet or automotive laminate. This process comprises cooling the sheet by non-contact heat conduction for long enough to fix the surface compression and central tension of the glass sheet. The process provides a thermally reinforced automotive glass sheet and automotive laminate.

Description

priority

  This application is filed on U.S. Provisional Patent Application No. 62/236296 filed on October 2, 2015 and U.S. Provisional Patent Application Nos. 62/281971 and January 29, 2016 filed on Jan. 22, 2016. US patent application filed July 30, 2015, claiming the benefit of priority under 35 USC § 119 of US Provisional Patent Application No. 62 / 288,851 No. 14/814232 and U.S. Patent Application No. 14/814274 filed on July 30, 2015 and U.S. Patent Application Nos. 14/814293 filed on July 30, 2015 and Jul. 30, 2015. U.S. Patent Application Nos. 14/814232 and 14/814303 and 2015 filed July 30, 2015. U.S. Patent Application No. 14/814363 filed on July 30, and U.S. Patent Application No. 14/814319 filed on July 30, 2015, and U.S. Patent Application No. 14/814319 filed on July 30, 2015. No. 14/814335, which is a continuation-in-part application and claims the benefit of priority under 35 USC 35, 120, the contents of which are all relied upon and cited herein. Is done.

  The present disclosure relates generally to thermally tempered automotive glass sheets and articles (including monoliths and laminates), and in particular, to thin thermally reinforced automotive glass sheets and articles, and to such automotive glass sheets. It relates to related methods and systems for thermal enhancement.

  Side windows, windshields, rear windows, display panels (head-up displays, infotainment display panels, global positioning system panels, etc.) in vehicles or transportation applications including automobiles, all vehicles, locomotives, boats, ships, and aircraft Glass) can be used as rearview mirrors, headlight covers, taillight covers, door trims, seat backs, pillars, door panels, dashboards, center consoles, and sunroofs. Such glass is often referred to as “glazing” when used in windows or windshields for vehicle or transportation applications. Glass is used as a monolith (ie, as a single, often thick sheet of glass) or as a laminate (including multiple sheets of glass and an optional intermediate layer between the glass sheets) There is. The glass may be transparent, semi-transparent, translucent, or opaque. Common types of glass panes used in vehicle or automotive applications are transparent and lightly colored. The laminate structure has several advantages including low cost, sufficient impact resistance for automobiles and other applications, and lower fuel consumption for each vehicle.

  In applications where strength is important (such as the automotive applications described above), the strength of conventional glasses is improved by several methods including coating, thermal strengthening, mechanical strengthening and chemical strengthening (eg, by an ion exchange process). be able to. Thermal strengthening has the advantage of forming a thick compressive stress layer through the glass surface, which is conventionally used for such applications with thick glass sheets, especially when such sheets are used as monoliths. However, the magnitude of the compressive stress is relatively low, typically less than 100 MPa. Conventional thermal strengthening is becoming less effective for relatively thin glasses, such as glass sheets having a thickness of less than about 2 mm.

  In the thermal strengthening of a glass sheet, the glass sheet is heated to a temperature higher than the glass transition temperature of the glass, and then the surface of the sheet is rapidly cooled (“quenched”) while the internal area of the sheet is slower. Cool at speed. Its inner region cools slower because it is insulated by the thickness of the glass and the rather low thermal conductivity. This different cooling creates a residual compressive stress in the surface area of the glass, which is balanced by the residual tensile stress in the central area of the glass.

  Thermal strengthening of glass is distinguished from chemical strengthening of glass, in which surface compressive stress is caused by changes in the chemical composition of the glass in a region close to the surface due to processes such as ion diffusion. In some processes based on ion diffusion, glass is replaced by exchanging smaller ions near its surface with larger ions to provide compressive stress (also called negative tensile stress) at or near the glass surface. The outside of may be strengthened. The compressive stress is believed to limit crack initiation and / or propagation.

  Thermal strengthening of glass is also distinguished from mechanical strengthening of glass where the exterior of the glass is strengthened or placed by combining two types of glass. In such a process, layers of glass compositions having different coefficients of thermal expansion are combined or laminated together while hot. For example, by sandwiching a molten glass with a higher coefficient of thermal expansion (CTE) between layers of molten glass with a lower CTE, when the glass cools, the positive tension in the inner glass compresses the outer layer. Again, a compressive stress is formed on the surface to balance the positive tensile stress. This surface compressive stress provides reinforcement.

  Tempered glass has advantages over untempered glass. The surface compression (or compressive stress) of this tempered glass provides greater fracture resistance than untempered glass. In particular, automotive glass breaking modes include breakers, collisions with debris along the road, manufacturing, shipping, mounting and bending in use. The increase in strength is generally proportional to the amount of surface compressive stress. If a tempered glass sheet has a sufficient level of thermal strengthening for its thickness, when the glass breaks, the glass generally breaks into smaller pieces rather than large or elongated shards with sharp edges . As defined in various established standards, a sufficiently small piece or glass that breaks into “dices” is safety glass, or “fully quenched” glass, or sometimes simply “quenched” Also known as glass. As used herein, “fully tempered” refers to a tempered glass that breaks into such a die, as defined by various established standards.

  Since the degree of strengthening depends on the temperature difference between the surface and the center of the glass sheet being quenched, thinner glass requires a faster cooling rate to achieve a given stress. Also, thinner glass generally requires higher values of surface compressive stress and central tensile stress in order to dice into small particles upon failure. Therefore, it is very difficult, if not impossible, to achieve the desired level of strengthening in glass having a thickness of about 3 mm or less.

  Aspects of the present disclosure also broadly relate to thin heat strengthened glass sheets that exhibit a stress profile. Such a sheet can be used for automotive applications as described above.

  The present disclosure relates, in part, to highly reinforced thin automotive glass sheets and articles, and methods, processes that achieve surprisingly high levels of thermal strengthening of automotive glass sheets at unachieved thicknesses in the past And system. In various embodiments, the processes and methods of the present disclosure provide for the automotive glass thickness limits provided by conventional convection gas thermal tempering processes and the need to contact the automotive glass with a liquid or solid heat sink and It is considered that the heat transfer rate is exceeded. In such systems and processes, automotive glass is only in contact with gas during quenching. The disclosed system and method includes heat up to “sufficient quenching” or dicing behavior in automotive glass sheets that are as thin as at least 0.1 mm thick (in at least some possible embodiments). Allows strengthening; in some embodiments, this strengthening is imparted to thin automotive glass sheets that also have low roughness and high flatness caused by the absence of liquid or solid contact during quenching. In various embodiments, the properties of these beneficial automotive glass sheet materials are provided by systems and methods that have substantially lower quenching power requirements compared to conventional convective automotive glass tempering systems.

  One embodiment of the present disclosure relates to a process for thermally strengthening an automotive glass material. The process includes providing an article formed from a glass material. The process includes heating the article above the glass transition temperature of the glass material. The process includes moving the heated article into a cooling station. The cooling station includes a heat sink having a heat sink surface facing the heated article and a gas gap separating the heat sink surface from the heated article such that the heat sink surface does not contact the heated article. The process includes cooling the article to a temperature below the glass transition temperature of the glass material so that surface compressive stress and median tensile stress occur in the heated article. The article is transferred by transferring heat energy from the heated article to the heat sink by conduction across the gap so that more than 20% of the thermal energy exiting the heated article traverses the gap and is received by the heat sink. To be cooled.

Another aspect of the present disclosure relates to a system for thermally strengthening an automotive glass sheet. The system includes a heating station that includes a heating element that supplies heat to the automotive glass sheet, the automotive glass sheet comprising a first major surface, a second major surface, and first and second major surfaces thereof. Having a thickness between. The system includes a cooling station that includes opposing first and second heat sink surfaces defining a passage therebetween such that an automotive glass sheet is located in the passage during cooling. The system includes a gas bearing that supplies pressurized gas to the passage so that the automotive glass sheet is supported within the passage without touching the first and second heat sink surfaces, the gas bearing comprising: Define the gap area. The gas bearing supplies gas to the passage so that the total mass flow rate of gas into the passage is greater than zero and less than 2 k / g C _p per square meter of gap area, where k is the heat transfer The thermal conductivity of the gas in the passage evaluated in direction, g is the distance between the automotive glass sheet and the heat sink surface, and C _p is the specific heat capacity of the gas in the passage.

  Another embodiment of the present disclosure relates to a reinforced automotive glass-based article that is disposed within an opening of a vehicle. As used herein, the phrase “glass-based” is used in its broadest sense to include any object made entirely or partially of glass. Glass-based articles include amorphous materials (eg, glass) and materials that contain an amorphous phase and a crystalline phase (eg, glass ceramic). Unless otherwise stated, all compositions of such materials are expressed in mole percent (mol%) based on oxide.

In one or more embodiments, the article comprises 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. Have In one or more embodiments, the article has an average thickness between the first and second major surfaces of less than 2 mm. As used herein, the term thickness refers to the average thickness. In one or more embodiments, at least some ion content and chemical composition of both the first major surface and the second major surface are the same as at least some ion content and chemical composition of the inner region. It is. In one or more embodiments, the first major surface and the second major surface are under compressive stress, the inner region is under tensile stress, and the compressive stress is greater than 150 MPa. In one or more embodiments, the surface roughness of the first major surface is _{a Ra} roughness between 0.2 nm and 2.0 nm over an area of about 15 micrometers x 15 micrometers. In one or more embodiments, the first major surface, the second major surface, or both the first major surface and the second major surface of the article have an area greater than 2500 mm ² . In one or more embodiments, the first major surface, the second major surface, or both the first major surface and the second major surface exhibit a stress birefringence of about 10 nm / cm or less.

Another embodiment of the present disclosure relates to a laminate for a vehicle. In one or more embodiments, the laminate includes a first glass-based layer, a second glass-based layer, and at least one intermediate layer. The second glass-based layer is opposite the first main surface, the second main surface defining the thickness t, and between the first and second main surfaces. Contains the located internal region. In one or more embodiments, at least one intermediate layer is at least partially coextensive with the first glass-based layer and is bonded directly or indirectly to the side of the first glass-based layer. Has been. In one or more embodiments, the second glass-based layer is at least partially coextensive with the at least one intermediate layer and is directly opposite to the intermediate layer opposite the first glass-based layer. Combined indirectly or indirectly. In one or more embodiments, the second glass-based layer has a thickness of less than 2 mm between the first major surface and the second major surface. In one or more embodiments, in the second glass-based layer, the ion content and chemical composition of at least a portion of both the first major surface and the second major surface is at least one of the inner region. Part ion content and chemical composition. In one or more embodiments, the first and second major surfaces are under compressive stress, the inner region is under tensile stress, and the compressive stress is greater than 150 MPa. In one or more embodiments, the surface roughness of the first major surface is _{a Ra} roughness between 0.2 nm and 2.0 nm over an area of about 15 micrometers x 15 micrometers. In one or more embodiments, the first major surface, the second major surface, or both the first major surface and the second major surface of the second glass-based layer are about 10 nm / cm or less. The stress birefringence of is shown.

Another embodiment of the present disclosure relates to a vehicle having an opening containing a laminate structure. In one or more embodiments, the laminate includes a first glass-based layer, a second glass-based layer, and at least one intermediate layer. The second glass-based layer is opposite the first major surface, the second major surface separated by thickness, and between the first and second major surfaces. Contains the located internal region. In one or more embodiments, the at least one intermediate layer is at least partially coextensive with the first glass-based layer and is directly or indirectly on the side of the first glass-based layer. Are combined. In one or more embodiments, the second glass-based layer is at least partially coextensive with the at least one intermediate layer and is directly opposite to the intermediate layer opposite the first glass-based layer. Combined indirectly or indirectly. In one or more embodiments, the first major surface is 100 μm center runout accuracy (TIR (total indicator run-out)) along any 50 mm or less profile of the first major surface. It is flat. In one or more embodiments, the second glass-based layer has a softening temperature of T _softening expressed in units of ° C, an _annealing temperature of T _{slow cooling} expressed in units of ° C, and a unit of ° C. _Is included, which includes a glass having a fictive surface temperature measured on the first major surface of this second glass-based layer, denoted by T _fs . In one or more embodiments, the second glass-based layer has a dimensionless surface virtual temperature parameter θs given by (T _fs -T _{slow cooling} ) / (T _softening -T _{slow cooling} ). In one or more embodiments, the parameter θs is in the range of 0.20 to 0.9.

Another embodiment of the present disclosure relates to a vehicle having an opening containing a laminate structure. In one or more embodiments, the laminate comprises a first glass-based layer, a second glass-based layer, and at least one intermediate layer between the first and second glass-based layers. . In one or more embodiments, the second glass-based layer includes a first major surface, a second major surface opposite to the first major surface, and first and second major surfaces. Having a thickness between. In one or more embodiments, the first major surface is flat with 100 μm runout accuracy (TIR) along any 50 mm or less profile of the first major surface. In one or more embodiments, the second glass-based layer is 1 / cold line CTE represented by alpha ^S _CTE at ° C., 1 / hot line CTE represented by alpha ^L _CTE at ° C., in GPa Made from a glass material having a modulus of elasticity of E, a strain temperature of T _strain expressed in units of ° C, and a softening temperature of T _softening expressed in units of ° C. In still another embodiment, the first main surface of the second glass-based layer is expressed in units of less than 600 MPa and MPa.

Has a larger, thermally induced surface compressive stress, where P ₁ is

And P ₂ is given by

H is 0.020 cal / s · cm ² · ° C. (about 828 W / m ² K) or more.

  Additional features and advantages are set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from the description, the written description, the claims, and the accompanying drawings. Will be appreciated by implementing the embodiments as described in.

  It will be understood that both the foregoing general description and the following detailed description are exemplary only, and are intended to provide an overview or skeleton for understanding the nature and characteristics of the claims.

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

A graph of the fan output required for "sufficient quenching" as a function of glass thickness Graph of blower output required for “sufficient quenching” as a function of glass thickness for previous process or machine O and latest process or machine N Graph of previous curve O and latest curve N of FIG. 2 adjusted to match and overlay on the graph of FIG. A perspective view of an automotive glass-based article or sheet according to an exemplary embodiment 4 is a partial cross-sectional view of the thermally tempered glass sheet of FIG. 4 according to an exemplary embodiment. Graph showing estimated tensile stress versus thickness for a glass-based article according to an exemplary embodiment Explanatory drawing which shows a part of the crushed glass-type article | item by illustrative embodiment Graph plotting number of debris per square centimeter as a function of experimental positive tensile stress A graph plotting the magnitude of negative tensile stress at the surface as a function of the experimental initial hot zone temperature, showing the threshold for dicing Graph plotting the dimensionless surface virtual temperature parameter θs for the virtual temperature obtained by one or more embodiments of the method and system of the present invention. Graph of surface compressive stress calculated by simulation for various glass compositions plotted against the proposed temperability parameter Ψ for the various compositions shown. Graph of parameter P ₁ as a function of heat transfer coefficient h Graph of parameter P ₂ as a function of heat transfer coefficient h A graph of MPa of surface compressive stress of a glass sheet as a function of sheet thickness t, expressed in millimeters, showing the area of performance newly opened according to one or more embodiments of the disclosed systems and methods. Graph showing compressive stress as a function of thickness plotted for selected exemplary embodiments of tempered glass sheets of the present disclosure Flow diagram illustrating some aspects of a method according to the present disclosure Flow diagram illustrating some aspects of another method according to the present disclosure In contrast to the prior art, the graph of FIG. 3 including region R and points A, B, A 'and B' marked thereon, indicating the region in which the disclosed method and system allows operation. Another graph of region R and points A, B, A 'and B' shown adjacent to the reduced size copy of FIG. 2 (positioned with respect to the scale). Graph of heat transfer coefficient required for strengthening as a function of glass thickness Sectional view of a glass sheet being cooled by conduction rather than convection, according to an exemplary embodiment Sectional view of a conduction enhancement system according to an exemplary embodiment A cutaway perspective view of another embodiment of a system similar to that of FIG. 22 according to an exemplary embodiment. Cutaway perspective view of an alternative embodiment of the inset feature of FIG. 23 according to an exemplary embodiment FIG. 23 is a cutaway perspective view of yet another alternative embodiment of the inset feature of FIG. 23 according to an exemplary embodiment. Flow diagram illustrating some aspects of yet another method according to an exemplary embodiment. A perspective view of a building with glass windows according to an exemplary embodiment A perspective view of a display on a counter according to an exemplary embodiment FIG. 4 is an exploded perspective view of a device including a glass-based article according to an exemplary embodiment. A perspective view of an automotive glass-based article or sheet according to an exemplary embodiment Sectional view of an automotive laminate according to some embodiments of the present disclosure 1 is a perspective view of an automotive laminate according to some embodiments of the present disclosure. A side view of a vehicle including an automotive article according to one or more embodiments of the present disclosure

  Applicants believe that there is a need for improved heat treatment of automotive glass, both in methods and systems for thermally strengthening automotive glass, and the resulting thermally strengthened automotive glass sheet itself. Recognized. Thinner for a variety of applications including, for example, windows, windshields, rear windows, front or tail lights or mirrors, head-up displays, and rear displays in various vehicles (eg, vehicles, automobiles, trains, aircraft, etc.) High optical quality automotive glass sheet materials and products comprising such glass sheets are useful. Glass is very strong in compression but is relatively weak against tension at the surface. By providing the sheet surface with a compression balanced by tension in the middle without an exposed surface, the useful strength of automotive glass sheets is dramatically increased. However, conventional thermal strengthening of automotive glass is generally cheaper and faster compared to alternative strengthening methods (eg, chemical strengthening, laminate based strengthening), while conventional thermal strengthening of automotive glass is a thinner vehicle. It is not known that it is not effective for strengthening industrial glass (for example, glass sheets for automobiles of 2 to 3 mm or less). Conventional methods of heat strengthening glass are typically considered to be limited to thicker glass sheets. This is because the level of strengthening depends on the temperature difference that occurs between the surface and the center of the rapidly cooling glass sheet. Also, due to the relatively uniform cooling that typically occurs throughout thin glass sheets due to thermal conductivity limitations of conventional tempering methods, there is a significant temperature difference between the surface and the center of the thin automotive glass sheet. Difficult to achieve.

  On the other hand, strengthening thin automotive glass by ion exchange can be cumbersome and time consuming, such as requiring immersion of the automotive glass in a chemical bath for a long period of time. Laminating different types of glass directly on each other would require complex manufacturing processes, such as involving a fusion draw process with double isopipe.

  Thus, for automobiles having a stress profile that results in the strengthening of automotive glass for various uses in windows, windshields, displays, etc., manufactured by processes that are less resource intensive and / or less cumbersome than conventional processes There is a need for glass-based articles. In particular, the processes and systems described herein form an automotive glass article having a stress profile that reinforces the exterior of the automotive glass, which in turn acts to mitigate cracks and damage. A variety of other desirable automotive glass qualities (eg, shape, surface quality, visible light transmission, flexibility, etc.) can be enabled to facilitate use in a variety of automotive glass applications.

  The present description provides improved methods and systems that utilize thermal strengthening to produce highly reinforced automotive glass materials, and particularly highly reinforced thin automotive glass sheets. The method and system solve various limitations of the conventional automotive glass tempering process, with thicknesses 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 0.0. Allows a high level of strengthening in automotive glass sheets less than 25 mm and less than about 0.1 mm. In particular, the Applicant has given a very high thermal conductivity to strengthen (even to a sufficient quenching level) even in very thin automotive glass sheets, and the surface and center of the automotive glass sheet. Have developed systems and methods that produce a sufficiently large temperature difference between the two.

Overview of Conventional Thermal Strengthening Techniques and Limitations Traditional industrial processes for thermal strengthening of glass are as follows: a glass sheet at a given temperature in a radiant energy furnace or convection furnace (or a “combined mode” furnace using both techniques). And then gas cooling ("quenching"), typically by convection by blowing a large amount of ambient air against or along the glass surface. This gas cooling process is mainly convective so that when the gas carries heat away from the hot glass sheet, heat transfer is due to mass motion of the fluid (collective motion) through diffusion and advection.

  In conventional strengthening processes, certain factors can limit the amount of strengthening typically considered possible in glass sheets, particularly thin glass sheets. In part, there is a limitation because 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 that is achieved during quenching. However, the greater the temperature difference during quenching, the easier the glass breaks during quenching. By starting quenching at a higher initial glass temperature for a given cooling rate, breakage can be reduced. Also, higher onset temperatures typically allow tempered glass sheets to achieve sufficient temperability afforded by fast cooling rates. However, raising the temperature of the sheet at the start of quenching also has its own potential drawbacks. For example, a high initial glass temperature can lead to excessive deformation of the sheet as the sheet becomes softer, again limiting the temperature difference that can be achieved practically.

  In conventional strengthening processes, the thickness of the sheet also imposes significant limitations on the temperature difference that can be achieved during quenching. The thinner the sheet, the smaller the temperature difference between the surface and the center for a given cooling rate during quenching. This is because the thickness of the glass for insulating the center from the surface is smaller. Therefore, thermal strengthening of thin glass typically requires a faster cooling rate (compared to that of thicker glass), and therefore to remove heat faster from the outer surface of the glass, Typically, significant heat consumption is required to produce a strengthening level of temperature difference between the inner and outer portions of the glass sheet.

  As an example, FIG. 1 “fully quenches” soda-lime glass (“SLG”) as a function of glass thickness in millimeters, based on an industry standard thermal strengthening process developed 35 years ago. "The power (kilowatt per square meter of glass sheet area) required by the blower used to blow enough ambient air to". The required power increases exponentially as the glass used becomes thinner. Therefore, a glass sheet with a thickness of about 3 mm has been the thinnest fully thermally quenched commercial glass available for many years.

  In addition, the thinner the sheet, the greater the tendency of the glass to deform with a certain softness (ie with a certain viscosity). Therefore, reducing the thickness directly reduces the achievable temperature difference and increases the likelihood of sheet deformation, thus using the higher sheet temperature to achieve the full benefit of faster cooling rates However, it also tends to reduce the opportunity to prevent glass breakage caused by faster cooling rates. Thus, in the conventional convection gas glass tempering process, increase the air velocity, decrease the distance from the air nozzle opening to the glass sheet surface, increase the temperature of the glass (at the start of cooling), and Accordingly, faster cooling rates are achieved by reducing the temperature of the cooling air.

As a more recent example, the performance curve of Figure 2 (prior art) using the latest glass heat strengthening equipment was published. This improved equipment continues to use the traditional air convection process to cool the glass, but with the rollers used to support the glass during heating, at least the glass in the last stage of heating. It replaces a system that uses air to support it. With no roller contact, the glass can be heated to a higher temperature (and higher softness / lower viscosity) prior to quenching, and reportedly produces a 2 mm thick fully quenched glass. it can. As shown in FIG. 2, the reported blower output required to strengthen a 2 mm thick sheet uses air to support the glass (curve N) compared to the use of a roller (curve O). ) at a higher temperature becomes possible by, it has decreased from 1200 kW / m ² to 400 kW / m ^2.

While showing the advancement to produce a fully tempered 2 mm thick glass, as shown in FIG. 3 (Prior Art), the previous curve O of FIG. 2 and the latest to match the scale of FIG. Adjusting curve N, the performance improvement achieved by the latest convection strengthening process (shown in FIG. 2) is relatively small and is merely a gradual in the previous understanding of energy demand in convection strengthening of glass sheets. It is a change. In FIG. 3, the previous curve O and the latest curve N of FIG. 2 have been adjusted to coincide with the graph of FIG. 1 and overlaid on it (for ease of viewing the latest curve N, the previous curve N Curve O is 240 kW / m ² with the top cut off). From FIG. 3, it is clear that the technique represented by curve N changes only slightly the performance curve of the convection gas quench process when the glass thickness is reduced from 3 mm to 2 mm. Its high operating point (400 kW / m ² blower power for ² mm glass) shows the extreme increase in power still needed to process thinner glass in this way. The sudden increase in airflow, and hence the required power, is a matter of both engineering practice and economy, while producing fully tempered glass using conventional convection gas tempering methods. This suggests the difficulty of making the thickness less than 2 mm. Moreover, the very large airflow required can deform the shape of the thinner sheet. Thus, 2 mm is sufficient in a glass with a CTE lower than the coefficient of thermal expansion (“CTE”) of soda-lime glass to reach full quenching of a glass having a thickness of less than 2 mm or using thermal strengthening. In order to achieve a good quench, the Applicant has found that another strengthening method / system is required.

  Thermal intensification methods that replace current commercial convective gas fortification have also been tried, but each has certain drawbacks to convection gas fortification. In particular, typical alternative thermal intensification methods that achieve faster cooling rates generally require at least some liquid or solid contact with the glass surface, not just gas contact. Such contact with the glass sheet can adversely affect the quality of the glass surface, the flatness of the glass, and / or the uniformity of the strengthening process. These defects may be perceived by the human eye, especially when viewed in reflected light. As described in more detail below, in at least some embodiments, the conductive thermal enhancement system of the present disclosure reduces or eliminates such contact-related defects.

  Liquid contact enhancement in the form of immersion in a liquid bath or fluid, as well as in the form of sprays, has been used to achieve faster cooling rates than convective gas enhancement, which can be applied to the sheet during the cooling process. There is a defect that excessive thermal fluctuations occur. In immersion or immersion-like spraying or liquid flow, large thermal fluctuations over a small area can occur due to convection spontaneously occurring in the liquid bath or liquid flow. In finer sprays, significant thermal fluctuations also occur due to the effect of individual spray droplets and nozzle spray patterns. Excessive thermal fluctuations tend to cause glass breakage during thermal strengthening due to liquid contact, which can be mitigated by limiting the cooling rate, but limiting the cooling rate can result in the strength that can be achieved. Will also decline. In addition, the essential handling of the sheet (to position or hold the sheet in a liquid bath or liquid stream or liquid spray) also results in physical stress and excessive thermal fluctuations from physical contact with the sheet. Prone to breakage during strengthening, limiting cooling rate and resulting strength. Finally, some liquid cooling methods, such as oil immersion and quenching of fast cooling rates by various spraying techniques, change the glass surface during such cooling and produce glass material from the glass surface to produce a satisfactory finish. May need to be removed later.

  Solid contact thermal strengthening comprises the step of contacting the surface of the hot glass with a cooler solid surface. As with liquid contact enhancement, excessive thermal fluctuations such as found in liquid contact enhancement can easily occur during the quenching process. Any imperfection in the surface finish, quenching surface, or sheet thickness consistency of the glass sheet will result in incomplete contact over a certain area of the sheet, and this incomplete contact will cause the glass to be processed during processing. May cause large thermal fluctuations that tend to damage the sheet and, if the sheet remains, may cause undesirable birefringence. Moreover, when the high temperature glass sheet is brought into contact with a solid object, surface defects such as chips, cracks, cracks and scratches can be formed. Achieving good physical contact over the entire surface of the glass sheet can increase difficulties as the size of the sheet increases. Physical contact with the solid surface can add mechanical stress to the rapidly cooling sheet and increase the likelihood that the sheet will break during the process. Furthermore, the extremely high rate of temperature change at the beginning of contact can cause breakage during sheet processing, and thus contact cooling of thin glass substrates has not been commercially viable.

Summary of Applicant's Heat-Toughened Glass and Associated Conductive Cooling Process and Method The present disclosure does not cause various deficiencies commonly found in conventional processes, for example, without damaging the surface of automotive glass Efficient, efficient and even thermal strengthening of thin automotive glass sheets on a commercial scale, such as without inducing birefringence, non-uniform strengthening and / or without unacceptable breakage In order to do so, it surpasses the conventional process described above. In one or more embodiments, the resulting thermally reinforced thin automotive glass sheet has a thickness of about 10 nm / cm or less (eg, 9.5 nm / cm or less, 9 nm / cm or less, 8.5 nm / cm or less, 8 nm Stress birefringence of less than / cm, 7.5 nm / cm or less, or about 7 nm / cm or less). Thin (to a sufficient quenching level) reinforced automotive glass sheet not previously obtained can be produced by one or more of the embodiments disclosed herein. The systems and processes described herein accomplish this by providing a very high heat transfer rate in a precise manner with good physical control and gentle handling of automotive glass. In a particular embodiment, the process and system described herein is capable of treating thin automotive glass sheets at higher relative temperatures at the beginning of cooling to provide higher levels of thermal strengthening. A human-specified small gap gas bearing is utilized in the cooling / quenching zone. As described below, this small gap gas bearing cooling / quenching zone has a much higher heat transfer rate due to conductive heat transfer to the heat sink across the gap than using convective cooling based on atmospheric flow. To achieve. This high speed conductive heat transfer is achieved without contacting the automotive glass with a liquid or solid material by supporting the automotive glass on a gas bearing in the gap. As described below, Applicants have determined that, in at least some embodiments, the processes and systems described herein are heat tempered automotive glass, particularly heat, having one or more unique properties. It has also been found to form reinforced thin automotive glass.

  Some embodiments of automotive glass sheets processed by the methods and / or systems according to the present disclosure have a higher level of permanently thermally induced stress than previously known. While not intending to be bound by theory, it is believed that the level of thermally induced stress achieved is obtained for a combination of reasons. The high uniformity of heat transfer in the process detailed here reduces or eliminates the physical and undesirable thermal stresses in the automotive glass, resulting in a high heat transfer rate without breaking the automotive glass sheet. Can be strengthened. Furthermore, the method of the present invention can be performed at lower glass sheet viscosities (higher initial temperatures at the beginning of quenching), yet still maintain the desired glass flatness and shape, thereby reducing cooling The temperature change in the process is much greater and therefore the level of thermal enhancement achieved is increased.

Heat strengthened automotive glass sheet As noted above, Applicants have developed systems and processes for forming heat strengthened automotive glass sheets, particularly thin automotive glass sheets, and are discussed in this section. As such, a heat strengthened thin automotive glass sheet formed as described herein may have one or more unique properties and / or that have not previously been achieved by conventional heat strengthening or other strengthening methods. Or have a combination of properties.

Thermally reinforced automotive glass sheet structure and dimensions Referring to FIGS. 4 and 5, there is shown a thermally reinforced automotive glass sheet having high surface compressive stress and / or high central tension, according to an exemplary embodiment. ing. FIG. 4 shows a perspective view of a thermally reinforced automotive glass-based article or sheet 500, and FIG. 5 shows a partial cross-sectional view of a thermally reinforced automotive glass sheet 500, according to one or more embodiments. It is. You may provide the glass sheet 500 for motor vehicles in opening of a vehicle (for example, an aircraft, a train, a motor vehicle, etc.).

  As shown in FIG. 4, a reinforced automotive glass-based article 500 (eg, a sheet, beam, plate) has a first major surface 510 and a second major surface 520 (half as disclosed herein). Which may be transparent and is indicated by a dotted line on the back of the sheet 500), and a body 522 extending therebetween. The second major surface 520 extends from the first major surface 510 such that the thickness t of the reinforced automotive glass sheet 500 is defined as the distance between the first and second major surfaces 510, 520. On the opposite side of the body 522, its thickness t is also the depth dimension. The width w of the reinforced automotive glass 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 automotive glass-based sheet 500 is defined as the 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. The

  In the illustrated embodiment, the thickness t of the automotive glass sheet 500 is less than the length l of the automotive glass sheet 500. In another exemplary embodiment, the thickness t of the automotive glass sheet 500 is less than the width w of the automotive glass sheet 500. In yet another exemplary embodiment, the thickness t of the automotive glass sheet 500 is less than both the length l and the width w of the automotive glass sheet 500. As shown in FIG. 5, the automotive glass sheet 500 is balanced by a first thermally induced central tensile stress (ie, tension) region 550 in the central portion of the sheet. It further has permanent thermally induced compressive stress regions 530 and 540 at and / or near the second major surface 510, 520.

  The methods and systems can be used to form reinforced automotive glass sheets having a wide thickness range. In various embodiments, the thickness t of the automotive glass sheet 500 is 0.2 mm, 0.28 mm, 0.4 mm, 0.5 mm, 0.55 mm, 0.7 mm, 1 mm, in addition to the endpoint values. It ranges from 0.1 mm to 5.7 or 6.0 mm, including 1.1 mm, 1.5 mm, 1.8 mm, 2 mm, and 3.2 mm. Possible embodiments are 0.1 to 20 mm, 0.1 to 16 mm, 0.1 to 12 mm, 0.1 to 8 mm, 0.1 to 6 mm, 0.1 to 4 mm, 0.1 to 3 mm, 0 .1 to 2 mm, 0.1 to less than 2 mm, 0.1 to 1.5 mm, 0.1 to 1 mm, 0.1 to 0.7 mm, 0.1 to 0.5 mm, and 0.1 to 0.3 mm A heat-strengthened automotive glass sheet 500 having a thickness t in the range of

  In some embodiments, automotive glass sheets with a thickness of 3 mm or less are used. In some embodiments, the automotive glass has a thickness of about (eg, plus or minus 1%) 8 mm or less, about 6 mm or less, about 3 mm or less, about 2.5 mm or less, about 2 mm or less, about 1 0.8 mm or less, about 1.6 mm or less, about 1.4 mm or less, about 1.2 mm or less, about 1 mm or less, about 0.8 mm or less, about 0.7 mm or less, about 0.6 mm or less, about 0.5 mm or less, It is about 0.4 mm or less, about 0.3 mm or less, or about 0.28 mm or less. In one or more embodiments, the automotive glass sheet is as thin as 0.1 mm. In other embodiments, the thickness of the automotive glass sheet is less than 2 mm and may range from about 0.1 mm to 2 mm. In some embodiments, the heat-strengthened automotive glass sheet has a high aspect ratio—ie, a large ratio of length and width to thickness. The thermal intensification process described here does not rely on high pressure or high volume air, so after intensification through the use of the gas bearing and high heat transfer system described herein, various factors such as surface roughness and flatness It is possible to maintain the characteristics of an automotive glass sheet. Similarly, the thermal tempering process described herein provides high aspect ratio automotive glass sheets (ie, automotive glass sheets with a high ratio of length to thickness and / or width to thickness). Can be heat strengthened while maintaining the desired or required shape. Specifically, strengthening sheets having a length to thickness and / or width to thickness ratio (“aspect ratio”) of approximately at least 10: 1, at least 20: 1, and up to 1000: 1 and beyond. it can. In possible 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: 1 can be reinforced.

  According to an exemplary embodiment, the length l of the reinforced automotive glass-based sheet 500 is greater than or equal to the width w, such as more than twice the width w, more than five times the width w, and / or the width w. 50 times or less. In some such embodiments, the width w of the reinforced automotive glass-based sheet 500 is greater than or equal to the thickness t, such as greater than twice the thickness t, greater than five times the thickness t, and the like. / Or 50 times or less of the thickness t.

  For example, in some embodiments, such as for the applications disclosed with respect to FIGS. 27-30 described below, the length l of the automotive glass-based sheet 500 is at least 3 cm, at least 5 cm, at least 7.5 cm, At least 1 cm, such as at least 20 cm, at least 50 cm, and / or 50 m or less, such as 10 m or less, 7.5 m or less, 5 m or less. In some such embodiments, the width w of the automotive glass-based sheet 500 is at least 3 cm, at least 5 cm, at least 7.5 cm, at least 20 cm, at least 1 cm, such as at least 50 cm, and / or 10 m or less, 7 It is 50 m or less such as 5 m or less and 5 m or less. Referring to FIG. 4, the thickness t of the automotive glass article in the form of a sheet 500 is 2.5 cm or less, 1 cm or less, 5 mm or less in possible embodiments, such as 0.8 mm or less. Less than 5 cm, such as 5 mm or less, 2 mm or less, 1.7 mm or less, 1.5 mm or less, 1.2 mm or less, and even 1 mm or less, and / or thickness t is at least 50 μm, at least 100 μm, at least 300 μm, etc. At least 10 μm.

  In other possible embodiments, the automotive glass-based article may be of a size other than that disclosed herein. In possible embodiments, the length l, width w, and / or thickness t of the automotive glass-based article may vary, such as for more complex shapes (generally see FIG. 30). Here, the dimensions disclosed herein apply at least to the corresponding automotive glass-based article embodiments having the above-described definitions of length l, width w, and thickness t with respect to each other.

In some embodiments, at least one of the first or second major surfaces 510, 520 of the automotive glass sheet 500 has a relatively large surface area. In various embodiments, the area of the first and / or second major surface 510 and 520, 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 2500 cm ^2, at least at least 100 mm ^2, such as 5000 cm ^2, and / or 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, 2500 m ² or less, such as 100 cm ² or less. Thus, the automotive glass-based sheet 500 may have a relatively large surface area; this is particularly the thickness of the automotive glass sheet described herein, unless the method and system disclosed herein. It may be difficult or impossible to heat strengthen while still having surface quality, and / or strain uniformity. In addition, unless dependent on the method and system disclosed herein, the negative of the stress profile, particularly the stress profile (see generally FIG. 6), without relying on changes in the type of automotive glass or ion exchange. It may be difficult or impossible to achieve the tensile stress portion.

Compressive and tensile stresses of thermally reinforced automotive glass sheets As noted above, the thermally reinforced sheets described herein may have unexpectedly high surface compression, for example, in regions 530 and 540 shown in FIG. Stresses, such as the region 550 shown in FIG. 5, may have a surprisingly high central tensile stress and / or a unique stress profile (see FIG. 6). This is due to the small thickness and / or other unique physical properties of the automotive glass sheet 500 described herein (eg, very low roughness, high flatness, various optical properties, virtual temperature, This is especially true when considering characteristics).

  The compressive stress (eg, in regions 530, 540 shown in FIG. 5) of the automotive glass formed by the processes and systems disclosed herein may vary as a function of the automotive glass thickness t. In various embodiments, automotive glass having a thickness of 3 mm or less, for example, glass sheet 500, has a compressive stress (eg, surface compressive stress) of at least 80 MPa, 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 400 MPa, and / or 1 GPa or less. In contemplated embodiments, the automotive glass having a thickness of 2 mm or less has a compressive stress of 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, at least 400 MPa, and / or 1 GPa or less. In contemplated embodiments, the automotive glass having a thickness of 1.5 mm or less has a compressive stress of 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 1 GPa. It is as follows. In possible embodiments, the automotive glass with a thickness of 1 mm or less has a compressive stress of 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 / or 1 GPa or less. In possible embodiments, the automotive glass with a thickness of 0.5 mm or less has a compressive stress of 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 / or 1 GPa or less. .

  In some embodiments, the thermally induced central tension (eg, in region 550 shown in FIG. 5) in the automotive glass formed by the processes and systems disclosed herein is greater than 40 MPa, May be more than 50 MPa, more than 75 MPa, more than 100 MPa. In other embodiments, the thermally induced median tension may be less than 300 MPa, or less than 400 MPa. In some embodiments, the thermally induced median tension can be about 50 MPa to about 300 MPa, about 60 MPa to about 200 MPa, about 70 MPa to about 150 MPa, or about 80 MPa to about 140 MPa. In some embodiments, the heat strengthened automotive glass sheet has a high thickness, i.e., is particularly thin. The systems and methods described herein allow very high heat transfer rates to be applied so that significant thermal effects, for example, a median tension of at least 10 or even at least 20 MPa, a sheet of SLG less than 0.3 mm thick Can be generated. In fact, a very thin sheet, at least as thin as 0.1 mm, can be heat strengthened. Specific levels of achieved and achievable thermal stress, considered as a function of thickness and other variables, are described in more detail herein.

  Referring to FIG. 6, the conceptual stress profile 560 of the tempered automotive glass-based sheet 500 of FIG. 4 at room temperature and standard atmospheric pressure of 25 ° C. is reinforced automotive glass under positive tensile stress. An inner portion 550 of the system sheet 500 and a portion 530 of the reinforced automotive glass-based sheet 500 that is external to and adjacent to the inner portion 550 under negative tensile stress (eg, positive compressive stress), 540 is shown. Applicants believe that the negative tensile stress strengthens the reinforced automotive glass-based sheet 500, at least in part, by limiting crack initiation and / or propagation of cracks therein. Yes.

  Given the relatively large surface area and / or thin thickness of the reinforced automotive glass-based sheet 500 as disclosed herein, it is external to the positive tensile stress of the inner portion 550 and its inner portion 550, and The abrupt transition of the tensile stress in the stress profile 560 between the negative tensile stresses of adjacent portions 530, 540 is considered unique to the technique of the present invention. This abrupt transition may be part of the thickness of the article where the change occurs, such as a distance of 1 mm or less, such as a distance of 500 μm, 250 μm, 100 μm, etc. , The distance used to quantify the rate of change), the magnitude of the stress (eg, the difference between the positive and negative tensile stress peak values + σ, −σ, 100 MPa, 200 MPa, 250 MPa, 300 MPa , 400 MPa), which may be expressed as the rate of change in tensile stress (ie, slope). In some such embodiments, the rate of change of tensile stress does not exceed 7000 MPa divided by 1 mm, such as 5000 MPa or less divided by 1 mm. In possible embodiments, the difference between the positive and negative tensile stress peak values is at least 50 MPa, such as 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 / or 50 GPa or less. It is. In possible embodiments, the magnitude of the peak negative tensile stress of the automotive glass-based sheet 500 is at least 50 MPa, such as 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. is there. The steep tensile curve transition caused by the systems and methods described herein is capable of achieving a greater magnitude of negative tensile stress at the surface of an automotive glass sheet for a given thickness and / or It is believed to demonstrate the ability to produce thinner automotive glass articles to high negative tensile stresses, such as achieving the dicing breakability disclosed in. Conventional heat strengthening techniques will not be able to achieve such steep tensile stress curves.

  According to exemplary embodiments, the high rate of change in tensile stress is at least 5% of automotive glass sheet 500 thickness, at least 10% of thickness, at least 15% of thickness, or at least 25 of thickness. At least one of the above-described magnitudes or more maintained over the thickness profile of the stress profile 560 that is at least 2% of the thickness, such as%. In possible embodiments, the strengthening is centered around a depth between 20% and 80% of the thickness from the first major surface where the rate of change in tensile stress is high. As such, it extends deeply into the reinforced automotive glass-based sheet 500, thereby further distinguishing it from, for example, chemical strengthening. Specifically, in one or more embodiments, the automotive glass sheet 500 is about 10% or more of the thickness measured from the first major surface (ie, about 0.1 t or more from the first major surface). May include depth of compression (DOC), indicating a change from compression to tension. For example, the DOC (measured from the first main surface) of the automotive glass sheet 500 is about 0.1 t or more, 0.11 t or more, 0.12 t or more, 0.13 t or more, 0.14 t or more, 0. It may be 15t or more, 0.16t or more, 0.17t or more, 0.18t or more, 0.19t or more, 0.2t or more, or 0.21t or more.

  In at least some possible embodiments, the reinforced automotive glass-based article includes a change in its composition with respect to ionic content, conceptually shown as a dotted line 562 in FIG. More particularly, the composition of the reinforced automotive glass-based article 500 in such an embodiment includes exchanged or implanted ions that affect the stress profile 560. In some such embodiments, the negative tensile stress is also a result of the thermal strengthening disclosed herein, so that the exchanged or implanted ions are in the strengthened automotive glass-based article 500. It does not extend completely into portions 530,540.

  Accordingly, the curves of the tensile stress profile 560 with enhanced ion exchange strength include discontinuities or abrupt changes 564 in the direction in which the tangents of the curves differ from each other on either side of the discontinuities or abrupt changes 564. The abrupt change 564 is located within the portions 530, 540 that are under negative tensile stress such that the tensile stress is negative on both sides immediately adjacent to the discontinuity or abrupt change 564. The discontinuity or sudden change 564 may correspond to different ion content depths. However, in some such embodiments, other portions 530, 540 under negative tensile stress still have the same composition with respect to ionic content as portion 550 under positive tensile stress. .

  In other words, with respect to at least some reinforced automotive glass-based articles 500, reinforced, under negative tensile stress, with or without ion exchange or implantation, external to inner portion 550 and adjacent thereto. The composition of at least a portion of the portions 530 and 540 of the automotive glass-based sheet 500 is the same as the composition of at least a portion of the inner portion 550 under positive tensile stress. In such embodiments, at least some of the negative tensile stress in the stress profile is independent of changes in the composition (eg, ionic composition) of the reinforced automotive glass-based sheet 500. Such a structure would simplify the composition of the reinforced automotive glass-based sheet 500 at least in part by providing sufficient strength without and / or without chemical strengthening. . Further, such a structure reduces stress concentrations in the reinforced automotive glass-based sheet 500 due to compositional discontinuities / changes, possibly peeling and / or peeling at the compositional discontinuities. Or it may reduce the chance of cracking.

Fracture performance of thermally strengthened automotive glass sheet If sufficient energy is stored in the tensile stress region 550, the glass sheet will break like safety glass when subjected to sufficient impact, or “Dice”. As used herein, an automotive glass sheet is considered to be diced when an automotive glass sheet having an area of 25 cm ² is broken into 40 or more pieces. In some embodiments, dicing is performed when the automotive glass sheet is “sufficiently quenched” (ie, for 2 mm or larger glass, the glass sheet has a compressive stress of at least 65 MPa or an edge compression of at least 67 MPa. ) Used as a qualitative measure. In various embodiments, the automotive glass sheet 500 has sufficient tensile stress in the tensile stress region 550 such that a 25 cm ² piece of the automotive glass sheet 500 breaks into 40 or more pieces.

  Referring to FIG. 7, an automotive glass-based article 610 having properties such as those disclosed herein with respect to the glass-based sheet, such as sheet 500, may be used using a prick punch or other instrument and / or generally in the United States. It is crushed according to standards association (ANSI) Z97.1 (impact test) and ASTM 1048 standards. According to the illustrated embodiment, the glass-based article 610 is reinforced to the extent that dicing occurs during crushing to form a plurality of small granular masses 616 (eg, pieces, fragments). In some embodiments, the automotive glass-based article 610 is a glass-based article 610 in a crush test in which an impact is applied by a hammer or punch to initiate cracks that cause the automotive glass to become granular pieces. It has sufficient thermally induced stress to produce more than 40 granular lumps 616 within an area of 50 × 50 mm. A standard office thumbtack 612 with a metal pin length 614 of about 1 cm is shown for reference.

According to various possible embodiments, regardless of the thin thickness of the reinforced automotive glass-based article 610, its stress profile (see generally FIG. 6) is the same as the reinforced automotive glass-based article. 610, when it is crushed, in particular small granular mass 616, for example, less than 50 mm ² or of the area of the first or second major surface, less than 20 mm ^2, less than 10 mm ^2, 90 mm ^2, such as less than 5 mm ² Provides high friability of the reinforced automotive glass-based article 610 so that it can break to less than and / or at least 10 mm ² . In some such embodiments, the friability of the reinforced automotive glass-based article 610 is at least 20% of the granular mass 616 (eg, when the reinforced automotive glass-based article is crushed) , At least 50%, at least 70%, at least 95%) such that the area of at least one of the first or second major faces is one of the above-mentioned quantities.

In some embodiments, a particularly thin automotive glass-based article 610 that may be manufactured, at least in part, using the techniques of the present invention with tensile stress as disclosed herein. Because of the shape, the friability of the reinforced automotive glass-based article 610 is particularly low when the reinforced automotive glass-based article 610 is crushed, such as having a low volume granular mass. less than 40 mm ^3, less than 30 mm ^3, less than 50 mm ^3, such as less than 25 mm ^3, and / or is such break in at least 50 [mu] m ³ things.

In some embodiments, at least in part, a particularly large portion of an automotive glass-based article 610 that may be manufactured using the techniques of the present invention with tensile stress as disclosed herein. Due to the area, the friability of the reinforced automotive glass-based article 610 is such that when the reinforced automotive glass-based article 610 is crushed, the volume of at least 50 μm ³ is at least 200, at least 400. , Such as at least 1000, at least 4000 granular lumps 616, such as at least 50 μm ³ in volume.

Referring now to FIGS. 8 and 9, a glass comprising at least 70% by weight silicon dioxide, and / or at least 10% by weight sodium oxide, and / or at least 7% by weight calcium oxide, disclosed herein. Experiments were performed on 1.1 mm thick glass sheets reinforced using the same equipment and processes. As shown in FIG. 8, it has been found that the number of granular lumps 616 per square centimeter of glass is generally related to the magnitude of the positive tensile stress at the center of each automotive glass-based article 610. Similarly, as shown in FIG. 9, the crushability of each glass-based article 610 depends on the size of the gap between the surface of the glass sheet being quenched and the heat sink / gas bearing and the gas used in that gap. Based on the thermal conductivity of the glass, the temperature of the glass in the hot zone (see, eg, FIGS. 21, 22 and 23), and cal / cm ² · s effectively applied to the glass surface during quenching It was also found to be related to the calculated predicted heat transfer coefficient (h) in ° C. units (SI unit is W / m ² · K).

Virtual Temperature of Heat-Tempered Automotive Glass Sheet In various embodiments, a thermally strengthened glass sheet (eg, automotive glass sheet 500) formed by the systems and methods described herein has a high virtual temperature. Have In various embodiments, it is understood that the high fictive temperature of the automotive glass material described herein is related to the high level of reinforcement, high central tensile stress, and / or high compressive surface stress of the automotive glass sheet 500. Let's be done. The surface fictive temperature may be determined by any suitable method including differential scanning calorimetry, Brillouin spectroscopy, or Raman spectroscopy.

  According to an exemplary embodiment, the automotive glass-based sheet 500 is, in some embodiments, at or on the first and / or second major surfaces 510, 520, as for soda lime glass. Some of them, such as nearby, have a particularly high fictive temperature, such as at least 500 ° C, at least 600 ° C, and even at least 700 ° C. According to an exemplary embodiment, the automotive glass-based sheet 500 is at least 30 parts higher, at least 10 degrees Celsius, such as at or near the first and / or second major surfaces 510, 520. It has a particularly high fictive temperature as compared to slow-cooled automotive glass of the same chemical composition, such as high, at least 50 ° C, at least 70 ° C, or even at least 100 ° C higher. At least in part, due to the abrupt transition from the hot zone to the cooling zone in the reinforced system (see, eg, FIGS. 21, 22 and 23), a high fictive temperature is disclosed in the book disclosed herein. May be achieved by inventive techniques. Applicants believe that high fictive temperatures may correspond to or be associated with increased damage resistance of automotive glass.

  In some methods of determining the surface fictive temperature, it may be necessary to break the automotive glass to remove the stress induced by the heat strengthening process in order to measure the fictive temperature fairly accurately. It is well known that the characteristic structural bands measured by Raman spectroscopy shift in a controlled manner with respect to both fictive temperature and stress applied to the silicate automotive glass. If the stress is known, this shift can be used to non-destructively measure the fictive temperature of the heat strengthened automotive glass sheet.

Referring generally to FIG. 10, a hypothetical temperature determination for some example automotive glass articles is shown. The effect of stress on the Raman spectrum of silica glass is described by 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). Has been reported. Commercially available glasses containing 65% by weight or more of silica show substantially the same reaction. The reported stress response is related to uniaxial stress, but in the single biaxial stress state (σ _xx = σ _yy ) as observed in tempered glass, the peak is expected to be uniaxial stress. It can be predicted to shift 2 times. Peak around 1090 cm ^-1 in the soda-lime glass and glass 2 corresponds to the peak of 1050 cm ^-1 observed in silica glass. The effect of stress on the 1050 cm ⁻¹ peak in silica and the corresponding peaks in SLG and other silicate glasses is expressed as a function of stress σ in units of MPa: a) ω (cm ⁻¹ ) = 1054. 93−0.00232 · σ.

Calibration curves for Raman band positions as a function of fictive temperature for SLG and another glass, glass 2, were generated. The glass samples were heat treated at various times that were 2-3 times longer than the structural relaxation time calculated by τ = 10 × η / G, where η is the viscosity and G is the modulus. After the heat treatment, the glass was quenched in water to fix the fictive temperature at the heat treatment temperature. The glass surface is then placed in the range of 200-1800 cm ⁻¹ with micro-Raman using a 442 nm laser, 10-30 seconds exposure time, and 100% output at 50 × magnification and 1-2 μm spot size. Measured over time. The peak position at 1000-1200 cm ⁻¹ was fitted using computer software, in this case Renishaw WiRE version 4.1. A good fitting of the 1090 cm ⁻¹ Raman peak measured in the SLG on the air side as a function of the fictive temperature Tf (° C.) is obtained by the equation b) ω (cm ⁻¹ ) = 1110.66-0.0282 · Tf . For glass 2, good fitting is obtained by the formula c) ω (cm ⁻¹ ) = 11102.00−0.0231 · Tf.

Using the relationships established in equations a), b), and c), a correction factor for surface compressive stress can be used to represent the fictive temperature of the automotive glass as a function of the measured Raman peak position. A compressive stress σ _{C of} 100 MPa causes a shift in the Raman band position corresponding to a decrease in fictive temperature of about 15 to 20 ° C. The following equation is applicable to SLG:

The formulas applicable to glass 2 are:

It is.

In these equations, ω is the measured peak wavenumber of the peak near 1090 cm ⁻¹ , σ _C is the surface compressive stress measured by any suitable technique, and stress corrected measurement of the fictive temperature in units of ° C. Is done. As a demonstration of the increased damage resistance associated with the determined fictive temperature, four glass sheet samples were prepared, two of which were subjected to surface compressive stress (CS) of about 70 and 110 MPa by conventional tempering methods. A prepared 6 mm soda lime glass (SLG) sheet, the remaining two being 1.1 mm SLGs prepared to approximately the same level of CS by the methods and systems disclosed herein. Two additional sheets of one of each thickness were used as controls. Standard Vickers indentation was performed on the surface of each test sheet. Various levels of force were applied for 15 seconds each, and after 24 hours, each indentation was examined. As shown in Table I, a 50% crack threshold (the average number of cracks that appear is defined as a load that is two of the four points of the indenter that tends to crack) was measured for each sample. .

Table I shows that the Vickers crack initiation threshold for SLG processed by conventional convective gas fortification (reflected in 6 mm sheet) is substantially the same as for SLG sheet after slow cooling or as supplied. , From 0 and 1 Newton (N) to about 1 to less than 2 Newton. This is a surface fictive temperature (T _fs ) of about 25 to 35 ° C. with respect to the glass transition temperature given by conventional strengthening (defined as T _g = 550 ° C., η = 10 ^12-13.3 poise for SLG). Or a relatively mild increase in the Tf _surface ). In contrast, with the reinforcement using the method and system of the present invention, the Vickers crack initiation threshold was improved to over 10N, a 10-fold increase over the Vickers damage resistance afforded by conventional reinforcement. For glasses in which the invention was implemented, the value of T _fs minus T _s was at least 50 ° C., or at least 75 ° C., or at least 90 ° C., or in the range of about 75 ° C. to 100 ° C. Even in one or more embodiments that include a low level of heat strengthening, the glass in which the present invention is implemented can still provide increased resistance at levels such as, for example, 5N. In certain possible embodiments, the 50% crack threshold after a 15 second Vickers crack initiation test can be 5N or higher, 10N or higher, 20N or higher, or 30N or higher.

  The following dimensionless virtual temperature parameter θ can be used to compare the relative performance of the heat strengthening process with respect to the obtained virtual temperature. In this case, the surface fictive temperature θs is given by:

_Where T _fs is the fictive temperature of the surface, T _{slow cooling} (the glass temperature at a viscosity of η = 10 ^13.2 poise) is the slow cooling point, and T _softening (the glass temperature at a viscosity of η = 10 ^7.6 poise) Is the softening point of the glass of the sheet. FIG. 10 is a plot of θs versus measured surface fictive temperature as a function of heat transfer coefficient h applied during thermal strengthening of two different glasses. As shown in FIG. 10, the results of the two different glasses overlap fairly closely with each other. This means that the parameter θ provides a means for comparing the fictive temperatures of different glasses that are directly compared with respect to the heat transfer coefficient h required for production. The vertical range of the results at each h corresponds to the variation in the initial temperature T _O at the start of quenching. In one or more embodiments, the parameter θs is about (eg, plus or minus 10%) 0.2 to about 0.9, or 0.21 to 0.09, or 0.22 to 0.09, Or from 0.23 to 0.09, or from 0.24 to 0.09, or from 0.25 to 0.09, or from 0.30 to 0.09, or from 0.40 to 0.09, or from 0.5 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, and even 0.65 to 0.9.

The hardenability parameters of thermally tempered automotive glass sheets, however, at higher heat transfer rates (eg, about 800 W / m ² K and higher), high glass temperatures or “liquidus” CTEs begin to affect tempering performance. . Thus, under such conditions, a hardenability parameter Ψ based on an approximation of the integral over the CTE value that varies across the viscosity curve has proved useful:

In the formula, α ^S _CTE is a low-temperature line CTE represented by 1 / ° C. (° C. ⁻¹ ) (corresponding to an average linear expansion coefficient of 0 to 300 ° C. for glass), and α ^L _CTE is 1 / ° C. a (° C. ^-1) represented by the high temperature line CTE (corresponding to a high temperature plateau value it has been confirmed that occurs somewhere between the softening point and glass transition point), E is not GPa (MPa ) (This allows the value of the (dimensionless) parameter Ψ to generally be in the range between 0 and 1), and the T _strain is the strain of the glass expressed in degrees Celsius. It is the point temperature (η = 10 glass temperature at a viscosity of ^14.7 poise), and T _softening is the softening point of the glass expressed in ° C. (η = temperature of glass at a viscosity of 10 ^7.6 poise).

In order to determine the strengthening parameter Ψ, a glass with various properties was modeled for the thermal strengthening process and the resulting surface compressive stress. Glasses were modeled in the same starting viscosity and different heat transfer coefficient of 10 ^8.2 poise. The various glass properties are shown in Table II, along with the calculated values for each glass temperature and each hardenability parameter Ψ at 10 ^8.2 poise.

The results in Table II show that ψ is proportional to the thermal quenching performance of the glass. This correlation is further illustrated in FIG. 11 which shows an example for a high heat transfer coefficient (2093 W / m ² K (0.05 cal / s · cm ² · ° C.) heat transfer coefficient) and a glass sheet thickness of only 1 mm. . As can be seen, the variation in compressive stress produced in the seven different glasses correlates well with the proposed variation in the hardenability parameter Ψ.

In another aspect, the heat transfer coefficient of the heat strengthened glass sheet and the relationship to surface compressive stress and central tensile stress, for any glass, the heat transfer coefficient h (expressed in cal / cm ² · s · ° C.) At any given value, the surface compressive stress (σ _CS , MPa) vs. thickness (t, mm) curve (over a range of t from 0 to 6 mm) can be fitted to a hyperbola. I know, where P ₁ and P ₂ are:

Or a curve of compressive stress σ _CS (glass, h, t):

In the formula, each of the constants P ₁ and P ₂ in the above (6) or (7) is:

and

It is a continuous function of the heat transfer value h expressed by The constants P ₁ and P ₂ are shown graphically as a function of h in FIGS. 12 and 13, respectively. Therefore, by using the value of P ₁ for a given h and the value of P ₂ corresponding to the same h in the previous equation (6) or (7), that h as a function of thickness t A curve corresponding to the surface compressive stress (CS) that can be obtained is defined.

In some embodiments, a similar equation is used, simply by dividing the expected compressive stress under the same conduction by 2, especially for thicknesses of 6 mm or less, and heats such as 800 W / m ² K or more. The median tension (CT) of the thermally reinforced automotive glass sheet in the transfer coefficient can be predicted. Therefore, the expected median tension is

Can be obtained from In the formula, the P _1CT and P _2CT:

and

It is required as follows. In some embodiments, h and _hCT may have the same value for a given physical situation of thermal enhancement. However, in some embodiments, they may fluctuate, resulting in separate variables, and when variation occurs between them, the typical 2: 1 ratio of CS / CT is not maintained Can be incorporated into the performance curve.

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

In some embodiments, the heat transfer value ratio (h and h _CT ) is about 0.024 to about 0.15 cal / s · cm ² · ° C. (about 1004 to about 6280 W / m ² K), about 0 .026 to about 0.10 cal / s · cm ² · ° C. (about 1089 to about 4187 W / m ² K), or about 0.026 to about 0.075 cal / s · cm ² · ° C. (about 1089 to 3140 W / m ² K).

FIG. 14 shows the MPa of surface compression of a glass sheet as a function of thickness t (mm) according to the graph of C (h, t) · Ψ (SLG) against a selected value of h according to equations 6-9 above. Ψ (SLG) corresponds to the ψ value of SLG in Table II. Lines indicated by the GC, the gas convection enhancements ^{0.02cal / s · cm 2 · ℃} ( or 840W / m ² K) from ^{0.03cal / s · cm 2 · ℃} ( or 1250W / m ² K) The estimated range of maximum stress versus achievable SLG sheet thickness is shown, and these heat transfer coefficient levels are about 704 ° C. at a heated glass viscosity of 10 ^8.2 poise, or higher than the convective gas process capability. Can be used in the process.

An example of the maximum reported sheet CS value based on the gas convection intensification process is indicated by the Δ symbol labeled gas convection in the legend. The value 601 indicates the published product performance capability of a commercial facility, while the value 602 is based on an oral report at a glass processing conference. The line indicated by LC is obtained with a heat transfer coefficient h of 0.0625 cal / s · cm ² · ° C. (or about 2600 W / m ² K), and an initial heated glass viscosity of 10 ^8.2 poise or treatment at about 704 ° C. FIG. 5 shows a maximum stress curve versus SLG sheet thickness that is assumed to be realizable by liquid contact enhancement. An example of the maximum reported sheet CS value based on the liquid contact enhancement process is indicated by a circle marked as liquid contact in the legend. The greater of the two values at 2 mm thickness is based on a report of strengthening of borosilicate automotive glass sheets, and the achieved stress is (Ψ _SLG ) / (Ψ _borosilicate for direct comparison with scale changes. The scale of the figure is changed by _acid ).

The line shown at 704 represents one of the disclosed methods and systems at a heat transfer rate of 0.20 cal / s · cm ² · ° C. (or about 8370 W / m ² K) and an initial temperature of 704 ° C. just prior to quenching. The stress realizable by the above embodiment is shown. The stress levels on the automotive glass sheet that can be achieved in this way show almost the same range of improvements to the liquid fortified strength level that liquid fortification shows for modern gas convection fortification. The line shown at 704 is not an upper limit, but at higher temperatures (at the lower viscosity of automotive glass) for good control of the shape and flatness achievable with thermal strengthening of small gap gas bearings, In the embodiment, it is shown that a higher value can be realized. The line shown at 730 is 0.20 cal / s · cm ² · ° C. (or about 8370 W / m ² K) at the starting temperature of the SLG sheet at 730 ° C. which is very close to or higher than the softening point of automotive glass. ) Shows a part of the further enhanced performance realized by the heat transfer coefficient. In particular, the combination of high heat transfer rates and the use of high initial temperatures, enabled by good handling and control of sheet flatness and shape in narrow gas bearings, significantly improves compressive stress and thus automotive glass sheet strength. Is realized in this way, and the improvement at a thickness of 2 mm or less is particularly remarkable.

  FIG. 15 is described above with compressive stress as a function of thickness plotted for selected examples of tempered glass sheets that are 2 mm or less, but manufactured according to one or more embodiments of the present disclosure. FIG. 15 illustrates the line of FIG. 14 and illustrates the best combination of thermal enhancement level and thickness enabled by the present disclosure.

Thermally reinforced automotive glass sheet with low surface roughness and high flatness In various embodiments , the thermally reinforced automotive glass sheet disclosed herein, such as sheet 500, has high thermal stresses. , Both with low formation surface roughness. The processes and methods disclosed herein can thermally strengthen automotive glass sheets without increasing the surface roughness of the forming surface. For example, the air side surface of incoming float automotive glass and the surface of incoming fusion formed automotive glass were characterized by atomic force microscopy (AFM) before and after treatment. The _Ra surface roughness is less than 1 nm (0.6-0.7 nm) for incoming 1.1 mm thick soda lime float automotive glass, and the _Ra surface roughness is the heat generated by the process of the present invention. It did not increase with reinforcement. Similarly, _Ra surface roughness of less than 0.3 nm (0.2-0.3 nm) for a 1.1 mm thick sheet of fused automotive glass was maintained by thermal strengthening according to the present disclosure. . Thus, a thermally strengthened automotive glass sheet has a surface roughness on at least a first major surface of at least 10 × 10 μm over an area of 0.2 to 1.5 nm _Ra roughness, 0.2 To 0.7 nm, 0.2 to 0.4 nm, or even 0.2 to 0.3 nm. The surface roughness may be measured over an area of 10 × 10 μm in exemplary embodiments, or in some embodiments 15 × 15 μm.

In some possible embodiments, the heat-strengthened automotive glass sheet disclosed herein has both high thermal stress and low formation surface roughness and / or coating surface. The processes and methods disclosed herein do not increase the surface roughness of the smooth as-formed or as-supplied surface of an automotive glass sheet, and likewise are sensitive low E coatings or reflections. Automotive glass sheets can be heat strengthened without damaging the protective coating or other coatings. The air side surface of the incoming float automotive glass and the surface of the incoming fusion formed automotive glass were characterized by atomic force microscopy (AFM) before and after treatment. The _Ra surface roughness was less than 1 nm (such as 0.6 to 0.7 nm) for incoming 1.1 mm soda lime float automotive glass and was not increased by thermal strengthening according to the present disclosure. The _Ra surface roughness is less than 0.3 nm (such as 0.2 to 0.3 nm) for a 1.1 mm sheet of incoming fusion-formed automotive glass, as well as the heat according to the present disclosure. It did not increase with reinforcement. Accordingly, in contemplated embodiments, the heat-strengthened automotive glass sheet according to the present disclosure is at least 0.2 nm and / or 0.7 nm or less, 0.4 nm or less, or even 0.3 nm or less. Having a surface roughness on at least the first major surface in the range of R _a roughness of 5 nm or less, or having a heat-strengthening sheet thereon having a type of coating that may be applied prior to strengthening, or These low roughness values and coating combinations are obtained from the process according to the invention used as starting material for the corresponding automotive glass sheets. According to Applicants' understanding, such preservation of surface quality and / or surface coatings previously required the use of convective gas fortification or possibly low heat transfer liquid fortification processes. This limits the heat strengthening effect over the full range that can be utilized by the process and method of the present invention.

  In another embodiment, the heat strengthened automotive glass sheet described herein has a high flatness. In various embodiments, the tempering systems described herein utilize controlled gas bearings to support automotive glass material during transfer and heating, and in some embodiments, automotive glass Can be used to facilitate control and / or improvement of sheet flatness, thereby obtaining higher flatness than previously obtained, especially for thin and / or highly reinforced automotive glass sheets it can. For example, a sheet of at least 0.6 mm can be reinforced to have improved post-strengthening flatness. The flatness of the heat-strengthened automotive glass sheet embodying the present invention has a core runout accuracy (TIR of 100 μm or less along an arbitrary 50 mm length along one of the first or second main surfaces. ), A TIR of 300 μm or less within a length of 50 mm on one of the first or second major surfaces, a TIR of 200 μm or less within a length of 50 mm on one of the first or second major surfaces; It can have a TIR of 100 μm or less, or a TIR of 70 μm or less. In the illustrated embodiment, flatness is measured along any 50 mm or less profile of the automotive glass sheet. In contemplated embodiments, a sheet having the thickness disclosed herein may have a TIR flatness of 100 μm or less, a TIR flatness of 70 μm or less, a TIR flatness of 50 μm or less, etc. Having a TIR flatness of 200 μm or less within a length of 20 mm on one of the major surfaces.

  According to possible embodiments, the reinforced automotive glass-based article described herein (eg, automotive glass sheet 500 shown in FIG. 4) is along a 1 cm longitudinal extension of the body 522. Thus, the thickness t has a high degree of dimensional consistency such that the thickness t changes only to 50 μm or less, such as 10 μm or less, 5 μm or less, or 2 μm or less. Such dimensional consistency is a predetermined thickness, area, as disclosed herein, due to practical considerations such as cold plate alignment and / or surface irregularities that may distort the dimensions. And / or the magnitude of the negative tensile stress would not be achievable with solid quenching.

  According to possible embodiments, the reinforced automotive glass-based article described herein has a 1 cm longitudinal profile along the straight line within 20 μm, within 10 μm, within 5 μm, within 2 μm, etc. A flat major surface (eg, of FIG. 4) such that the 1 cm width profile within 50 μm and / or along it is within 50 μm such as within 20 μm, within 10 μm, within 5 μm, within 2 μm, etc. There are at least one first and second main surfaces 510, 520) of the reinforced automotive glass sheet 500. Such high flatness is due to practical considerations such as warping or bending of automotive glass strengthened in these processes due to liquid convection and related forces, as disclosed herein. For a given thickness, area, and / or magnitude of negative tensile stress, liquid quenching would not be achievable.

CTE of heat-strengthened automotive glass sheet
Another aspect includes a thermally enhanced low coefficient of thermal expansion (CTE) sheet. As described above (see, for example, Equations 7 and 10), the effect of thermal strengthening greatly depends on the CTE of the automotive glass constituting the automotive glass sheet. However, due to the thermal strengthening of low CTE automotive glass, reinforced automotive glass compositions having advantageous properties such as high chemical resistance or better compatibility with electronic devices due to low alkali content. May be obtained. Automotive glass sheets having a CTE of 65, 60, 55, 50, 45, 40, and even 35 × 10 ⁻⁶ ° C. ⁻¹ or less are less than 4 mm, less than 3.5 mm, less than 3 mm, and even less than 2 mm With this thickness, a breaking pattern (“dicing”) like safety glass becomes possible. Automotive glass having a CTE value of 40 × 10 ⁻⁶ ° C. ⁻¹ or less can be tempered using the process described herein. Such low CTE automotive glass reinforced by the systems and methods described herein may have similar surface compression to SLG sheets reinforced with conventional commercial (gas convection) processes at the same thickness. it can. In some embodiments, the compressive stress of the low CTE automotive glass is 1 cm or less, 5 mm or less, 3 mm or less, 2 mm or less, 1.5 mm or less, 1 mm or less, 0.75 mm or less, 0.5 mm or less, 0. For automotive glass sheets having a thickness of 3 mm or less, 0.2 mm or less, or 0.1 mm or less, at least 50 MPa, 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 obtain.

  The glass sheet for automobiles formed according to the present disclosure includes, for example, electronic components in laminated bodies such as glass side windows, windshields, windows, and glass / interlayer / glass laminated bodies used for rearview mirrors. There are many uses in displays. Stronger and thinner laminates can be produced, resulting in reduced mass and cost and increased fuel efficiency. Heat-strengthened thin sheets can be cold bent and laminated to the thicker automotive glass formed, providing an easy and reliable manufacturing process that does not require any thermoforming of the thin sheet It is desirable to be given.

Alpha of thermally tempered automotive glass sheet Table IV below shows the results obtained by the method of the present disclosure (designated “Method Source” I in the table) and obtained within the tempering process. The figure of merit alpha, a rough measure of the heat exchange coefficient, is shown. Alpha is:

And expressed in units of ° C / mm, where CS is the physical compressive stress (MPa), t is the thickness in millimeters, CTE is the heat exchange coefficient in ° C ^-1 , E is the elastic modulus of the glass of (MPa).

Samples 1 and 3 are reproducible values obtained from the disclosed process, with sample 1 using air and sample 3 using helium as the gas in the process. Sample 2 exhibits a “champion” value using air within the process of the present invention, ie, has not been reliably reproduced until now. All automotive glass samples (Samples 1-3) treated by the process of the present disclosure exceeded alpha at 117 ° C./mm. Applicants believe that the alpha gradient with thickness will have an inherent tendency to decrease with decreasing glass thickness. The glass disclosed herein has, in some embodiments, an alpha greater than 20t + 77, where t is the glass thickness in mm.

Thermal Strengthening System and Process In various embodiments, a process for strengthening an automotive glass sheet includes at least a portion of an automotive glass sheet, such as an automotive glass sheet 500, wherein the sheet is quenched. Supporting or guiding a refrigerated automotive glass sheet having one or more of the stated properties into a cooling or quenching zone. In various embodiments, an automotive glass sheet is at least partially supported by a gas flow or pressure supplied to a gap between the surface of the automotive glass sheet and one or more heatsinks. . In general, the temperature of an automotive glass sheet is higher than the glass transition temperature when the sheet is placed in a cooling zone, and in various embodiments, the automotive glass sheet is more thermally conductive than convection. Cooled in the cooling area. Conduction is a heat transfer process in which energy is transferred by the interaction between adjacent molecules, and convection is a fluid (e.g., when the heated fluid moves away from the heat source and is replaced by a cooler fluid) It is a heat transfer process in which energy is transferred by the movement of air, helium, etc.). Thus, the system of the present invention differs significantly from conventional convection-based glass strengthening systems where the main form of heat transfer during cooling of automotive glass sheets is convective.

In some embodiments, the overall process for strengthening an automotive glass sheet includes heating the automotive glass sheet in a high temperature zone and then cooling the automotive glass sheet in a cooling zone. Including. An automotive glass sheet has a transition temperature, which is the temperature at which the automotive glass viscosity has a value of η = 10 ¹² to 10 ^13.3 poise. The automotive glass is heated sufficiently to bring the automotive glass sheet above the transition temperature and then placed in a cooling zone. If desired, automotive glass can be transferred from the hot zone to the cold zone via the transition zone. Within the cooling zone, the surface of the automotive glass sheet is located adjacent to one heat sink on either side of the automotive glass sheet, each facing one of the automotive glass surfaces and its heat sink. There is a gap between the surface and the surface. Gas is supplied into the gap through a number of openings in the heat sink, and in some embodiments, the supplied gas causes the automotive glass to move between the heat sinks so that the surface of the automotive glass does not contact the heat sink. To form an air bearing to be supported. Within the cooling zone, the automotive glass sheet is cooled by conduction rather than convection and is cooled sufficiently to allow thermally induced surface compression and thermally induced central tension to be fixed or formed on the sheet. , Given increased strength as described herein. In various embodiments, primarily cooling by conduction is accomplished by having a very small gap size in the cooling zone so that the automotive glass sheet is close to but not in contact with the opposing surface of the heat sink. .

  The apparatus enabling the described process provides a heating zone for heating the automotive glass sheet to a temperature above the transition temperature, and a tempered automotive glass sheet by cooling the heated automotive glass sheet. And a cooling area for performing. The apparatus can include an optional transition zone between the heating zone and the cooling zone. The cooling zone may include a heat sink having a pair of opposing surfaces that define a gap in which the heated automotive glass sheet is accommodated. The cooling zone can include a pair of gas bearings disposed on opposite surfaces of the gap that serve to support the automotive glass sheet within the gap. This gap can be configured to cool the heated automotive glass sheet by conduction rather than convection. In some embodiments, the gas bearing can include a plurality of openings for supplying gas to the gap, the surface of the gas bearing being more conductive than convection from a heated automotive glass sheet. Works as a heat sink that can take heat away.

  With the disclosed strengthening process and equipment (generally see FIGS. 21-25), automotive glass-based articles (generally see FIGS. 4-7 and 27-30) in accordance with the present form of heat strengthening. Can be strengthened. The process has a steep tensile stress vs. thickness / depth curve (see generally FIG. 6), in particular, a steep slope near the surface of an automotive glass-based article, thereby causing ion exchange or different Without the need for strengthening by lamination of automotive glass, automotive glass-based articles can be strengthened to a particularly high level of negative tensile stress for a given thickness near the surface of each article. However, in some embodiments, the thermal strengthening process disclosed herein may be enhanced by ion exchange or glass-to-glass lamination. The thermal strengthening process disclosed herein is limited to conventional thermal strengthening due to limitations in alignment of contact quench equipment, cooling speed limitations of conventional convection systems, and / or warpage damage associated with liquid quench strengthening. It enables particularly high levels of reinforcement in large area articles (eg, sheets) that would be too large for reinforcement by the method. The process disclosed herein is due to susceptibility to breakage or crushing of thin automotive glass-based articles and the contact forces associated with solid or liquid quenching during the tempering process and / or the limitation of the cooling rate of conventional convective tempering. For example, high levels of reinforcement are made specifically functional, especially in thin sheets that would be too thin for reinforcement by conventional reinforcement methods. However, in other possible embodiments, automotive glass-based articles such as those disclosed herein may be manufactured by at least some solid or liquid quenching, such as in combination with the unique tempering process disclosed herein. May be.

  One embodiment of a method according to the present disclosure is shown in the flow diagram of FIG. The method or process 100 includes providing 140 the automotive glass sheet at a temperature above the transition temperature of the automotive glass sheet. The method or process 100 also includes a step 160 of supporting the automotive glass sheet at least in part by gas (by gas flow and pressure). Step 160 involves thermally induced surface compressive stress and thermally induced while the automotive glass sheet is supported by gas, 1) by conduction rather than convection by gas to the heat sink, and 2) at ambient temperature. Cooling the sheet sufficiently to form or fix a central tensile stress to the sheet.

  According to a variation of the embodiment of FIG. 16 shown as method 100 ′ in the flow diagram of FIG. 17, this method involves the glass sheet such that the automotive glass sheet is above the transition temperature of the automotive glass. A step 110 of sufficient heating may be included. As part of, or in preparation for, cooling step 160, method 100 ′ includes first and second heat sink surfaces (generally see FIGS. 21-25), each having an opening therein, in step 120. It further includes the step of providing a heat sink (either alone or separately). In step 130A, the method includes positioning the first sheet surface across the first gap and facing the first heat sink surface, and in step 130B, passing the second gap across the second heat sink surface. The method further includes the step of disposing the second sheet surface so as to face the surface. The heat sink surface can include openings and / or can be porous. The method 100 ′ is sufficient in step 160 to strengthen automotive glass (eg, thermally induced surface compressive stress and thermally induced by conduction rather than gas convection to the respective heat sink surfaces). Cooling the sheet (sufficiently to form or fix the applied central tension stress to the plate). Step 160 can also include supplying a gas to the first and second gaps through an opening or a porous heat sink, and in some such embodiments, the gas is adjacent to the heat sink. To form an air bearing that supports the automotive glass sheet. In some embodiments, the gas is supplied only through the openings in the heat sink, or only through the pores of the porous heat sink, or through the pores and openings.

  These and other related methods of the present disclosure are opposed to the current mainstream technology of gas convection cooling by using conduction instead of convection as the primary mode of cooling. Instead of heat exchange between solid and gas (from glass to air), the method described herein uses a small amount of gas (e.g., a glass surface and the like) to both initiate and complete cooling to provide heat strengthening. Use solid-to-solid (glass to heat sink) heat exchange mediated across small gaps (without physical contact between heatsinks). There is some convection when gas (eg, air bearing gas) flows into a small gap, but direct conduction through the gas to the heat sink across the gap is the main cooling mode. Applicants have determined that due to the predominance of conductive heat transfer, convection increases the heat transfer rate over the main cooling process.

  Because conduction between solids (even across gaps) allows for faster heat flow than convection, the increase in cooling rate required for thinner automotive glass sheets can be constrained by gas velocity and volume. Absent. According to various embodiments, the gas flow and gap size support the seat to control the stiffness of the gas cushion in the gap, without the constraints typically imposed by the gas flow and gap size in the convection system. In order to maintain the flatness and / or shape of the sheet during thermal strengthening and / or to handle the sheet at a fast cooling rate It can be selected, controlled, or optimized for other purposes such as balancing ease. For example, in some embodiments, cooling is not convective, so helium is an economically viable alternative to air in the disclosed system because of the very small gas flow rate that supports the gas bearing. In such embodiments, helium provides about five times the thermal conductivity of air. Even helium at a price assumed to be several times that sold today is an economically viable alternative to the disclosed system at low flow rates.

  Furthermore, the system and method described herein provides a conventional convection-based reinforced system because the system of the present disclosure reduces the volume of air flowing over the automotive glass sheet being cooled (as compared to a convection system). The potential risk of deformation of the hot thin sheet of automotive glass typically caused by the high volume of high velocity airflow required is reduced. This also allows the softer and hotter automotive glass sheets to be handled with no or minimal distortion and further improves the degree of reinforcement that can be achieved. By eliminating the need for a large air flow, high-speed, cooler air flows into the quenching chamber (moving against a fast air stream) and into the adjacent part of the furnace used to heat the sheet Problems that may be seen in avoiding cooling it are also reduced.

  In addition, the use of conduction through gas will reduce contact damage, warpage, shaping, etc., associated with conventional liquid or solid contact quench enhancements. Using a gas as an intermediate conductor maintains the surface quality of the article being processed by avoiding contact between solids. By mediating higher conduction velocities in the gas, gas contact is also avoided. Several types of liquid quenching can introduce undesirable distortions in automotive glass surfaces, spatial variations in reinforcement, and contamination. These embodiments are inevitably non-contact (excluding contact by gas) but provide very fast cooling. In other embodiments, as mentioned above, solid or liquid contact may be included.

Another advantage of avoiding power consumption large air flow rate of the heat enhancement system / process is in the power savings are achieved and energy by using a solid-gas-solid conduction as the primary Automotive cooling mechanism . Points A and B in FIGS. 18 and 19 show an evaluation of the upper limit of air bearing peak power usage per square meter of automotive glass sheet with a relatively high flow of compressed air supply. The actual lower peak power usage of the compressed air can be as small as 1/16 of the indicated value. Points A and B do not include active cooling of the heat sink, but in some embodiments may include active cooling, especially if the machine is in continuous, quasi-continuous, or high frequency operation.

  Referring again to FIGS. 18 and 19, the thermal load corresponding to a 300 ° C. decrease in the temperature of the automotive glass sheet is within the time limit of 2.1 seconds for point A ′ and 1 second for point B ′. Assuming that within the limits, the heat to mechanical (or electricity) efficiency ratio is achieved by an active cooling system of 7.5 to 1, points A and B when active cooling of the heat sink surface is considered. The points A ′ and B ′ show the conservatively estimated peak power levels for air bearing operation at L. (these points roughly correspond to the glass sheets actually strengthened with the apparatus described herein). .

The four points in region R of FIGS. 18 and 19 illustrate (at least to some extent) the importance of the improvement that can be obtained with the disclosed methods and systems, but since the power demand is the stated amount, Note that the full advantage is likely to be significantly underestimated in these figures. For example, as indicated by curve N, the blower peak power is not efficiently turned on and off, and typically a large fan that still rotates (but is less loaded) when no air is needed. It is necessary to have a ventilated passage with a gate to shut off. The peak power demand of a fluid cooling system, such as a cooling water plant, shown at points A ′ and B ′ as an example that can be easily achieved by the present disclosure, can generally be accommodated much more efficiently and addresses fully continuous operation. Only then will the effective peak power be much smaller and approach A ′ and B ′. Therefore, the total energy demand difference will tend to be larger than the peak power demand difference shown in the figure. In some embodiments, the process described herein is less than 120 kW / m ² for the thermal toughening of automotive glass sheet thickness less than 2 mm, less than 100 kW / m ^2, of less than 80 kW / m ² Has peak power.

Heat Transfer from Thin Automotive Glass Sheet During Thermal Strengthening Generally, heat transfer from a thin automotive glass sheet in the disclosed systems and processes includes a conductive member, a convection member and a radiating member. As described above and described in detail herein, the thermal strengthening system of the present disclosure reinforces thin automotive glass by utilizing conductive heat transfer as the primary mechanism for quenching thin automotive glass sheets. .

  The following is the applicant's understanding of the underlying theory. Whether a sufficiently fast cooling rate for a thin automotive glass sheet (such as 2 millimeters or less) can actually be achieved by conduction by a gas such as air—and if so, such a rate is Asking whether it can be achieved with a gap size probably comes to the mind of one skilled in the art of glass strengthening (conduction effects are usually small enough to support convection and radiation-only analysis and are usually negligible) Will.

  The amount of heat conduction under conditions embodied in the process using the system described herein can be determined as follows. First, for thermal enhancement by conduction as in the present disclosure, the thermal conductivity of the gas in the gap must be evaluated in the direction of conduction along the thermal gradient. The hot air at or near the surface of the sheet being cooled is at or near room temperature at or near the surface of the heat sink ((dry) room temperature air (25 ° C.) has a nominal thermal conductivity of about 0. Has a much higher thermal conductivity than cooler air (such as 026 W / m · K). At the start of cooling, an approximation is used that assumes that the air across the gap is at the average temperature of the two opposite surfaces. The automotive glass sheet may be at a temperature of, for example, 670 ° C. at the start of cooling, while the heat sink surface may be initiated at, for example, 30 ° C. Therefore, the average temperature of the air in the gap will be 350 ° C. The dry air then has a thermal conductivity of about 0.047 W / m · K, more than 75% higher than its thermal conductivity at room temperature, and the sheet has a fairly high surface and thickness consistency. Assuming that it is finished, it is high enough to conduct a large amount of thermal energy through a sized gap in the system of the present disclosure, as described below.

For illustration purposes, the Q _conduction of the conduction component of the heat transfer rate through the gap of distance g, where the gap has an area A _g (any direction perpendicular to the direction of the gap distance g) is:

Where k is the thermal conductivity of the material (gas) in the gap, evaluated in the direction of heat conduction (or vice versa), and T _s is the temperature of the automotive glass surface. Yes, T _HS is the temperature of the heat sink surface (or heat source surface for other embodiments). As described above, since the thermal conductivity of gas changes with temperature, in order to accurately evaluate k, it is necessary to integrate the thermal conductivity of the gas along (or against) the direction of the conduction heat flow. However, as a good approximation, k may be interpreted as the value of k for the gas in the gap at the average of the temperatures T _s and T _HS of the two surfaces.

  Reconstructing equation (14) in units of heat transfer coefficient (unit of heat flow output per K per square meter):

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) in the gap divided by the length of the gap (meters). And the value of wattage per degree of temperature difference per square meter is obtained. Table V shows the heat transfer coefficient (k / g) due to conduction alone for a gap filled with air and helium, each with a gap size from 10 μm to 200 μm in 10 μm increments.

  FIG. 20 (prior art) is an industry standard from about 35 years ago showing the heat transfer coefficient required to obtain a fully quenched glass sheet as a function of mm thickness under certain hypothetical conditions. (A reference line is added at 2 mm). As can be seen by comparing Table V with FIG. 20, a gap of about 40 μm filled with air allows complete quenching of 2 mm thick automotive glass by conduction. Slightly below 40 micrometers is a fairly small gap, but planar porous air bearings for conveyor applications will generally operate reliably with gaps as small as 20 micrometers. Therefore, 37 micrometers can be achieved in the air gap supplied by the pores of the heat sink surface. When helium (or hydrogen with similar thermal conductivity) is used as a gas, a 2 mm thick automotive glass can be sufficiently quenched with a gap of about 200 μm. Using helium or hydrogen as the gas allows gap sizes about 5 times larger with the same heat transfer coefficient. In other words, using helium or hydrogen as the gas in the gap increases the heat transfer coefficient used for quenching with the same gap size by a factor of about five. Thus, even with air, the spacing is not unrealistic, and with high conductivity gases, gap spacing is relatively easily achieved even with sheet thicknesses less than 2 millimeters.

In addition to cooling through a gas by conduction rather than convection, another embodiment includes heating (or heating and / or cooling) through a gas by conduction rather than convection. With regard to the relative contribution of conduction and convection, the Q _conv component of the convection of the heat transfer coefficient across the gap (or gaps), whether heating or cooling, is:

In the formula,

Is the mass flow rate of the gas, Cp is the specific heat capacity of the gas, T _i is the inlet temperature of the gas when flowing into the gap, e is, a gas that flows into the gap, the sheet surface and the heat sink / heat source Efficiency of heat exchange with the surface (the “wall” of the gap). The value of e varies from 0 (indicating zero heat exchange between the surface and the gas) to 1 (indicating that the gas has sufficiently reached the surface temperature). The value of e can be calculated by those skilled in the art of heat transfer, for example using the e-NTU method.

However, typically, 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 very close to 1, which means that the gas will average on both sides before leaving the gap. It is heated to be almost completely equal to the average temperature of the two surfaces. Assuming e = 1 (slightly overestimating the convective heat transfer coefficient) and assuming that gas is supplied to the gap through the surface of the heat sink / heat source, the initial temperature of the gas in the gap is the heat sink / It can be assumed that the surface temperature of the heat source is the same (T _i = T _HS ). Next, the heat transfer coefficient by convection is:

And can be simplified.

  At temperatures typically useful for thermal strengthening or heat treatment of automotive glass and similar materials, radiant heat transfer from the sheet being processed is relatively small. Thus, if the sheet (eg, sheet 200 shown in FIG. 21) is cooled (or heated too much), mainly by conduction within the region of the gap (eg, gaps 204a, 204b shown in FIG. 21), To heat (assuming the amount of radiation from a heat source):

Only necessary. Combining (18) with equations (14) and (17), the following conditions:

Is maintained and this substantially ensures that the sheets in the region of the subject gap are cooled (or heated) primarily by conduction. Therefore, the mass flow rate of gas

Is, 2 kA _g / gC less than _p, i.e. it should be a gap area per square meter 2k / gC less than _p. In some embodiments,

Where B is the ratio of convection cooling to conduction cooling. As used herein, B is a positive constant less than 1 and greater than 0, and specifically has a value of 2/3 or less, or even 4/5 or 9/10 or less. In general,

Controls the position of an automotive glass sheet (eg, the sheet 200 shown in FIG. 21 relative to the heat sink surface (eg, the heat sink surfaces 201b, 202b shown in FIG. 21)) or the position of the heat exchange surface itself. Should be kept as low as possible, consistent with the need for a gas flow to do so. The ratio of convection cooling to conduction cooling may be any value from less than 1 to 1 × 10 ⁻⁸ . In some embodiments, B is less than 0.9, less than 0.8, less than 0.7, less than 0.6, less than 0.5, less than 0.4, less than 0.1, 5 × 10 ^−. Less than ² , 1 × 10 ^{−2 or} less, 5 × 10 ^{−3 or} less, 1 × 10 ^{−3 or} less, 5 × 10 ^{−4 or} less, 1 × 10 ^{−4 or} less, 5 × 10 ^{−5 or} less, 1 × 10 ⁻⁵ , less than 5 × 10 ^-6, less than 1 × 10 ^-6, less than 5 × 10 ^-7, less than 1 × 10 ^-7, less than 5 × 10 ^-8, or less than 1 × 10 ^-8. In some embodiments,

Is minimal and is consistent with the need to use gas flow to support and control the position of the sheet relative to the heat sink surface. In other embodiments,

Should be selected to control the position of the heat exchange surface itself relative to the sheet.

In various embodiments, the mass flow rate of a gas in the conduction-based cooling system of the present disclosure

Is substantially lower than conventional convection-based enhancement systems. This substantially lower gas flow allows the conduction system to operate with substantially reduced power usage, as described herein. Further, in at least some embodiments, the reduced gas flow rate also provides a substantially quieter cooling system compared to conventional convective cooling systems. In such embodiments, reducing noise reduces the likelihood of hearing damage and further reduces driver safety by reducing or eliminating the need for the driver to use hearing protection equipment. It will increase.

Of course, in one or more embodiments in which a sheet of automotive glass material is supported on an air bearing between opposing heat sink surfaces, both surfaces of the automotive glass sheet are conductive to both heat sink surfaces. Heat transfer occurs. Therefore, in such an embodiment, the automotive glass sheet has first and second sheet surfaces, and the first gap is located between the first sheet surface and the first heat sink surface. The first sheet surface (eg, the lower surface of an automotive glass sheet) is positioned adjacent to the first heat sink surface (eg, the lower heat sink surface), and the second gap is the second sheet surface A second sheet surface (e.g., the top surface of an automotive glass sheet) is positioned adjacent to the second heat sink surface (e.g., the upper heat sink surface) so as to be positioned between the first and second heat sink surfaces Thus, the automotive glass sheet is cooled. In such an embodiment, heat conduction can 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 such an embodiment, the first gap has a length across the first gap of g ₁ and the area of the first gap of A _g1 , and the second gap is the second gap of g ₂ . the length spanning the gap and a second gap area of the a _g2. In such an embodiment, a first flow of a first gas is supplied to the first gap and a second flow of the second gas is supplied to the second gap. Of course, as in the previous discussion, the first gas has a heat capacity C _p1 and a thermal conductivity k ₁ and the first flow is the mass flow rate.

Supplied in. In such an embodiment,

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

Supplied in. In such an embodiment,

Is greater than zero and less than (2k _{2 Ag 2} ) / (g ₂ C _p2 ). In such an embodiment, the first and second streams contact the automotive glass sheet such that the automotive glass sheet is supported without touching the heat sink surface. In this way, the sheet is cooled by conduction rather than convection in such a way that surface compressive stress and median tension are created in the sheet.

Automotive glass tempering system with a high conductivity cooling zone Referring to FIG. 21, there is shown a schematic cross-sectional view of a high conductivity glass cooling / quenching station and a glass sheet being cooled by conduction rather than convection. The hot glass sheet 200 has its first and second (main) surfaces 200a, 200b, each of which spans a respective gap 204a and 204b of each of the first and second heat sinks 201a, 202a. Facing the respective first and second surfaces 201b, 202b. The gas 230 is supplied through the first and second surfaces 201b, 202b as indicated by the arrows and supplied to the gaps 204a, 204b for the automobile at the center or other suitable location between the heat sinks 201a, 202a. Help maintain the glass sheet. Air or another gas can leave through the edges of the heat sinks 201a, 202a, as indicated by arrow 240. By selecting the size of the gaps 204a, 204b and the gas and flow rate of the gas 230 according to the discussion herein, the automotive glass sheet 200 is cooled more by conduction than by convection. In certain embodiments, the automotive glass sheet 200 comprises more than 20%, specifically more than 50%, more specifically more than 80% of the thermal energy from a heated article such as the automotive glass sheet 200, It is cooled by heat sinks 201a and 202a to be 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 interstitial distance such that the heated automotive glass sheet is cooled by conduction rather than convection. Of course, the size of the gaps 204a and 204b is generally the distance between the major surface of the automotive glass and the opposing heat sink surface.

  In some embodiments, the gaps 204a and 204b are about (eg, plus or minus 1%) 100 μm or more (eg, about 100 μm to about 200 μm, about 100 μm to about 190 μm, about 100 μm to about 180 μm, about 100 μm to about 100 μm A thickness of about 170 μm, about 100 μm to about 160 μm, about 100 μm to about 150 μm, about 110 μm to about 200 μm, about 120 μm to about 200 μm, about 130 μm to about 200 μm, or about 140 μm to about 200 μm). is there. In other embodiments, the gaps 204a and 204b are about (eg, plus or minus 1%) 100 μm or less (eg, about 10 μm to about 100 μm, about 20 μm to about 100 μm, about 30 μm to about 100 μm, about 40 μm to about 100 μm). , About 10 μm to about 90 μm, about 10 μm to about 80 μm, about 10 μm to about 70 μm, about 10 μm to about 60 μm, or about 10 μm to about 50 μm.

  The heat sinks 201a, 202a may be solid or porous. Suitable materials include, but are not limited to, aluminum, bronze, carbon or graphite, stainless steel, and the like. The size of the heat sink is sufficient to accommodate the size of the glass sheet and can be designed to transfer heat efficiently and effectively without significantly changing the heat sink temperature. If the heat sinks 201a and / or 202a are porous, they can further include additional openings or holes for the gas to flow, or a porous structure can be used to provide fluidity, or It can be both. In some embodiments, the heat sink further includes a passage through which fluid can flow for temperature control of the heat sink and is described in more detail in FIGS. 23-25 and below.

  Eliminating the high gas flow rates of the prior art would allow the use of very small openings or pores 206, as shown in FIG. 21, in the heat sink surface to supply gas into the gap. In some embodiments, the aperture is less than 2 mm, less than 1.5 mm, less than 1 mm, less than 0.5 mm, less than 0.25 mm when measured in the minimum direction (eg, diameter for a circular aperture), Alternatively, it may be 200 μm or less, 150 μm or less, 100 μm or less, 50 μm or less, 30 μm or less, 20 μm or less, or 10 μm. In some embodiments, the aperture is about (eg, plus or minus 1%) from 10 μm to about 1 mm, from about 20 μm to about 1 mm, or from about 50 μm to about 1 mm.

  The spacing between adjacent openings 206 can be about (eg, plus or minus 1%) from 10 μm to about 3 mm, from about 20 μm to about 2 mm, or from about 50 μm to about 1 mm, measured between the edges of the openings. Small openings or pores function as individual flow restrictors to provide high performance gas bearing type kinetics, for example, high levels of rigidity and seat support consistency to position the seat and control the gap size Thereby obtaining a high uniformity of thermal strengthening effect to avoid or reduce stress birefringence. Furthermore, because very small pores or openings can be used, the relative amount of solid material at the heat sink surface facing the sheet surface across the gap can be maximized, thereby increasing the conduction heat flow.

  According to various embodiments, the use of such an aperture 206 as the only passage for supplying gas to the gaps 204a, 204b desirably opens in a direction that is nearly perpendicular to the heat sink surfaces 201b, 202b. Using 206, the air bearing type dynamics are optimized and from larger openings or by gas flow from sources other than through the heat sink surfaces 201b, 202b adjacent to the seat 200 or other excess Lateral flow ensures that it is not impaired. In other embodiments, the gas may be supplied to the gaps 204a, 204b through other sources in addition to the openings 206 or pores or the like. Thus, aspects of the present disclosure can save power and energy through the use of low gas flow and solid / gas / solid conduction over conventional convection enhancement processes and the like.

  22-25 illustrate an exemplary embodiment of an automotive glass tempering system 300 according to the present disclosure. FIG. 22 shows a schematic cross-sectional view of a system 300 that can cool an automotive glass sheet by conduction of heat from the automotive glass sheet by airflow into a conductive heat sink. The apparatus includes a hot zone 310, a cold zone 330, and a transfer gas bearing 320. The transfer gas bearing 320 removes the automotive glass article (eg, automotive glass sheet 400a) from the hot zone 310 to the cold zone 330 such that there is no contact or substantially no contact between the automotive glass and the bearing. Move or point to. The hot zone 310 has gas bearings 312, each supplied from a hot air plenum 318, which has a cartridge heater 314 inserted in a hole through the bearing 312, which is a gas bearing in the hot zone. It serves to heat 312 to the desired starting process temperature. The automotive glass sheet (hot zone) 400a is maintained between the gas bearings 312 in the hot zone for a period long enough to achieve a desired precooling temperature (eg, higher than the transition temperature).

  In some embodiments, heating of the sheet in the hot zone may be performed primarily by conduction of heat from the heat sink through a thin gas barrier. The conductive heating process used in the hot zone is similar to the cooling process described herein, but can be reversed (eg, applying heat into the glass sheet).

  In some embodiments, the gap 316 between the hot zone gas bearing 312 and the automotive glass sheet 400a is relatively large, from about 0.05 inches (1.27 mm) to about 0.125 inches (3. 175 mm) or more, because the automotive glass sheet 400a can be heated relatively slowly, and heat radiation from the hot gas bearing 312 into the automotive glass sheet 400a is suitable for this purpose. . In other embodiments, the hot zone gap size may be as small as 150 micrometers per side, or as much as 500 micrometers per side. In some embodiments, a smaller gap may be advantageous because it causes the bearing to have a better “rigidity”, ie center the automotive glass, so that the automotive glass is This is because it can have the ability to flatten automotive glass while in the softened state. In some embodiments, the process may reshape the automotive glass sheet (planarize the automotive glass sheet) in an initial heating step, for example, by pressure supplied by the gas bearing 312. In some embodiments, top and bottom hot zone gas bearings can be present on the actuator, which can continuously change the width of the gap, or the automobile when the gap is large The automotive glass can be carried into the hot zone and then the gap can be reduced to flatten the automotive glass when it is still in a soft state.

  The process temperature depends on a number of factors including the composition of the automotive glass, the thickness of the automotive glass, the nature of the automotive glass (such as CTE), and the desired level of strengthening. In general, the starting process temperature can be any value between the automotive glass transition temperature and the Littleton softening point, or in some embodiments, can be even higher. In the case of SLG, for example, the system 300 heats the automotive glass sheet 400a between about 640 to about 730 ° C. or between about 690 to about 730 ° C. (eg, plus or minus 1%). In some embodiments, the system 300 removes the automotive glass sheet 400a from about (eg, plus or minus 1%) 620 to about 800 ° C., about 640 to about 770 ° C., about 660 to about 750 ° C., about 680 Heat to a temperature of about 750 ° C, about 690 to about 740 ° C, or about 690 to about 730 ° C.

  The automotive glass sheet 400a is heated to its desired starting process temperature (eg, higher than the automotive glass transition temperature) and then moved from the hot zone 310 to the cold zone 330 using any suitable means. In some embodiments, the movement of the automotive glass sheet 400a from the hot zone 310 to the cold zone 330 may be such that (1) the automotive glass sheet moves to the cold zone due to gravity acting on the automotive glass sheet. (2) shut off the gas flow from the leftmost outlet of the hot zone 310 (in this embodiment the side is sealed), thereby releasing all gas from the gas bearing Are pushed out of the rightmost outlet of the cold zone, applying a fluid force on the automotive glass sheet 400a and moving it to the cold zone 330, or (3) of (1) and (2) Can be done by combination.

  Gas may be supplied to the transfer gas bearing 320 by the transfer gas bearing plenum 328. The thickness of the solid material behind the surface of the transfer gas bearing 320 may be thin, of low thermal mass and / or low thermal conductivity, reducing heat conduction from the hot zone 310 to the cold zone 330. it can. The transfer gas bearing 320 can function as a thermal insulation or heat transfer layer between the two zones 310 and 330 and serves as a transition from the larger gap 316 in the hot zone to the smaller gap 336 in the cold zone 330. be able to. In addition, the low thermal mass and / or low thermal conductivity of the transfer gas bearing 320 limits the amount of heat transfer and thus the cooling experienced by the automotive glass sheet 400a while passing through the transfer gas bearing 320.

  Once the automotive glass sheet (cold zone) 400b has moved into the cold zone 330 and into the passage 330a, it is prevented from exiting the right exit by mechanical stop means or other suitable shut-off mechanism shown as a stop gate 341. Stopped. The automotive glass sheet 400b is sufficiently central to pass through the automotive glass transition (for example, in the case of a 1 mm thick SLG, this example corresponds to about 325 ° C. at the surface, below about 490 ° C.). Once cooled, the stop gate 341 can be moved to remove the obstruction in the cold zone passage 330a and then the automotive glass sheet 400b can be removed from the system 300. If desired, the automotive glass sheet 400b may remain in the cold zone 330 to some temperature near room temperature before removal.

  As described above, in the high temperature zone 310, the automotive glass sheet 400 is heated to a temperature higher than the automotive glass transition temperature of the automotive glass sheet. In the embodiment shown in FIG. 22, the cold zone 330 receives the heated automotive glass sheet 400b through the opening 330b, transfers the automotive glass sheet 400b, and cools the automotive glass sheet 400b in the cold zone. Including a passage 330a. In one or more embodiments, the passage 330a includes a transport system that can include gas bearings, roller wheels, conveyor belts, or other means for physically transporting the automotive glass sheet to the cold zone. . As shown in FIG. 22, the cold zone 330 includes a gas bearing 332 that is a supply plenum 338 that is separate from the hot zone plenum 318 and the transfer plenum 328.

  As shown in FIG. 22, the cold zone 330 includes one or more heat sinks 331 disposed adjacent to the passage 330a. If two heat sinks are used, such heat sinks can be located on opposite sides of the passage 330a, facing each other across the passage gap 330a. In some embodiments, the heat sink includes a plurality of openings 331a that form part of the gas bearing 332, and the surface of the cold gas bearing 332 in the cold zone 330 functions as two heat sink surfaces. Due to the low gas flow rate in the passage 330a and the small size of the passage gap 330a, the automotive glass sheet 400b mainly crosses the gap into the solid heat sink 331 without the automotive glass sheet 400b touching the heat sink surface. It is cooled in the cold zone 330 by conduction of heat from the automotive glass sheet.

  In some embodiments, the heat sink and / or its surface may be segmented. As described above, in some embodiments, the heat sink may be porous, and in such embodiments, the opening through which the gas in the gas bearing 332 is supplied is the porous heat sink. The pores. The plurality of openings 332b, the gas source, and the passage gap 330a can be in fluid communication. In some embodiments, gas forms a gas cushion, total or bearing through passage 331a and into passage gap 330a. The gas cushion of some embodiments prevents the automotive glass sheet 400b from contacting the surface of the heat sink 331. The gas also functions as a gas that cools the automotive glass sheet 400b by conduction rather than convection.

  Since cooling occurs substantially by heat conduction between the solids across the gap, it may be necessary to address the problem that convection does not exist with dominant cooling. For example, for large thin sheet reinforcement, the sheet can be (1) optionally introduced quickly into the cold zone at a speed higher than that typically used for convection-based quenching, and (2) Heat and cool a number of sheets one after another in a continuous flow with only a slight spacing between (2) so that a thermal equilibrium is reached such that the leading and trailing edges of a large sheet have a similar thermal history The process can be operated in a quasi-continuous manner where the heat sink is actively cooled.

  In some embodiments, the gas flowing through opening 331a cools the heat sink. In some embodiments, the gas flowing through the opening facilitates heat conduction from the automotive glass into the heat sink across the gap and also cools the heat sink 331. In some cases, another gas or fluid may be used to cool the heat sink 331. For example, the heat sink 331 can include a passage 334 through which a cooling fluid for cooling the heat sink 331 is flowed, as described more fully with respect to FIG. The passage 334 can be sealed.

  If two heat sinks are used (ie, a first heat sink and a second heat sink), one or more gas sources can be used to supply gas to the passage gap 330a. These gas sources can include the same gas or different gases. Thus, the passage gap 330a can include one type of gas, a mixture of gases from different gas sources, or the same gas source. Exemplary gases include air, nitrogen, carbon dioxide, helium or other noble gases, hydrogen, and various combinations thereof. The gas may be described by the thermal conductivity when entering the passage 330a just before starting the conductive cooling of the automotive glass sheet 400b. In some cases, the gas is about (eg, plus or minus 1%) 0.02 W / (m · K) or more, about 0.025 W / (m · K) or more, about 0.03 W / (m · K). ) Or more, about 0.035 W / (m · K) or more, about 0.04 W / (m · K) or more, about 0.045 W / (m · K) or more, about 0.05 W / (m · K) or more, About 0.06 W / (m · K) or more, about 0.07 W / (m · K) or more, about 0.08 W / (m · K) or more, about 0.09 W / (m · K) or more, about 0 .1 W / (m · K) or more, about 0.15 W / (m · K) or more, or about 0.2 W / (m · K) or more).

The process and system of the present invention described herein allows for a high heat transfer rate, which, as mentioned above, provides a temperature difference that is toughening, even in very thin automotive glass sheets. Can occur. Using air as a gas in the gap between the automotive glass sheet and the heat sink, heat transfer rates of 350, 450, 550, 650, 750, 1000, and 1200 kW / m ² or higher can be achieved. Only possible with conduction. When helium or hydrogen is used, a heat transfer coefficient of 5000 kW / m ² or more can be achieved.

  The heat sink 331 of one or more embodiments may be fixed or movable to change the thickness of the passage gap 330a. The thickness of the automotive glass sheet 400b may be in the range of about 0.4 to about 0.6 times the thickness of the passage gap 300a, defined as the distance between the opposing surfaces of the heat sink 331 ( For example, the upper surface and the lower surface of the heat sink 331 in the arrangement of FIG. In some cases, the passage gap is configured to have a thickness sufficient for the heated automotive glass sheet to be cooled by conduction rather than convection.

  In some embodiments, the distance between the major surface of the automotive glass sheet 400b and the heat sink surface when the automotive glass sheet 400b is being carried through or located within the passage 330a ( For example, the gap size mentioned above is about (eg, plus or minus 1%) 100 μm or more (eg, about 100 μm to about 200 μm, about 100 μm to about 190 μm, about 100 μm to about 180 μm, about 100 μm to about 170 μm, About 100 μm to about 160 μm, about 100 μm to about 150 μm, about 110 μm to about 200 μm, about 120 μm to about 200 μm, about 130 μm to about 200 μm, or about 140 μm to about 200 μm. May have. In some embodiments, when the automotive glass sheet 400b is being conveyed through the passageway, the distance between the automotive glass sheet and the heat sink surface (one or more gaps 336) is about (eg, plus Or minus 1%) 100 μm or less (eg, about 10 μm to about 100 μm, about 20 μm to about 100 μm, about 30 μm to about 100 μm, about 40 μm to about 100 μm, about 10 μm to about 90 μm, about 10 μm to about 80 μm, about 10 μm to about The passage gap may have a thickness such as 70 μm, about 10 μm to about 60 μm, or about 10 μm to about 50 μm. The total thickness of the passage gap 330a depends on the thickness of the glass sheet for automobile 400b, but it is assumed that the thickness of the glass sheet for automobile is added to twice the distance between the heat sink surface and the glass sheet for automobile. Generally can be characterized. In some embodiments, the distance or gap 336 between the automotive glass sheet and the heat sink may not be equal. In such an embodiment, the total thickness of the passage gap 330a can be characterized as the sum of the distance between the automotive glass sheet and each heat sink surface plus the thickness of the automotive glass sheet.

  In some cases, the total thickness of the passage gap is less than about (eg, plus or minus 1%) 2500 μm (eg, about 120 μm to about 2500 μm, about 150 μm to about 2500 μm, about 200 μm to about 2500 μm, about 300 μm to about 2500 μm. About 400 μm to about 2500 μm, about 500 μm to about 2500 μm, about 600 μm to about 2500 μm, about 700 μm to about 2500 μm, about 800 μm to about 2500 μm, about 900 μm to about 2500 μm, about 1000 μm to about 2500 μm, about 120 μm to about 2250 μm, about 120 μm to about 2000 μm, about 120 μm to about 1800 μm, about 120 μm to about 1600 μm, about 120 μm to about 1500 μm, about 120 μm to about 1400 μm, about 120 μm to about 1300 μm, about 120 μm to about 1200 μm, or in the range of about 120 μm to about 1000 μm). In some cases, the total thickness of the passage gap is about 2500 μm or more (eg, about 2500 μm to about 10,000 μm, about 2500 μm to about 9,000 μm, about 2500 μm to about 8,000 μm, about 2500 μm to about 7,000 μm, About 2500 μm to about 6,000 μm, about 2500 μm to about 5,000 μm, about 2500 μm to about 4,000 μm, about 2750 μm to about 10,000 μm, about 3000 μm to about 10,000 μm, about 3500 μm to about 10,000 μm, about 4000 μm To about 10,000 μm, about 4500 μm to about 10,000 μm, or about 5000 μm to about 10,000 μm).

  The opening 331a in the heat sink 331 can be disposed perpendicular to the heat sink surface, or 20 degrees or less from the vertical to the heat sink surface (eg, about (eg, plus or minus 1%) 15 degrees or less, about 10 degrees or less or about 5 degrees or less).

  In some embodiments, the material behind the heat sink (cold bearing 332) surface is any suitable material having a high heat transfer rate including metals (eg, stainless steel, copper, aluminum), ceramics, and carbon. There is no problem. This material can be relatively thicker than the material behind the surface of the transfer bearing 320 as shown in FIG. 22 so that the heat sink can readily accept a relatively large amount of thermal energy. In the illustrated embodiment, the material of the heat sink 331 is stainless steel.

  FIG. 23 is a cut-away perspective view of an apparatus similar to that of FIG. 22, but reversed from right to left and mounted / removed gas bearing 342 with the automotive glass sheet 400c disposed thereon. Is further included next to the cold zone 330 of the apparatus 300. The apparatus of FIG. 23 also uses a narrow passage gap (not shown) in the hot zone 310, transfer bearing 320, and cold zone 330.

  The inset in FIG. 23 shows an alternative embodiment of the cold zone gas bearing 332a, which is actively cooled by a coolant passage 334 between the gas bearing supply holes 333, and the supply holes Feeds into an opening in the surface of the bearing 332a. The coolant passage 334 is defined between a heat sink segment 333b that combines with each other to form a heat sink 331 and a surface facing the automotive glass sheet 400b.

  The coolant passage 334 can be located very close to the surface of the heat sink 331 in the solid material of the gas bearing 332 and the solid between the heat sink / gas bearing surface and the edge closest to the surface of the coolant passage 334. The area of bearing material has the same width as the edge of the coolant passage 334 closest to the surface. 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 passage 334 and the surface facing the automotive glass sheet 400b. This is different from typical convective gas cooling equipment because high gas flow requires a large space in the center of the array of gas nozzles 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 surface of the automotive glass. This reduced cross-sectional area is generally located between the active cooling fluid and the automotive glass sheet being processed in order to form a high volume passage of heated bulk gas back from the sheet.

  FIG. 24 shows yet another embodiment of a cold zone gas bearing 332 similar to the inset of FIG. In this embodiment, the coolant passage 334 includes a gas bearing supply member 335 including a gas bearing supply hole 333, a gas bearing surface member 337a for supplying the automotive glass sheet 400b so as to face the surface of the gas bearing 332, and Is formed between. FIG. 25 has a structure similar to that of the embodiment of FIG. 24, but has a porous member 339 between the bearing plate member 337b and the automotive glass sheet 400b, so that the porous member 339 is the automotive glass sheet. Yet another alternative cold zone gas bearing 332c is shown forming a surface facing 400b.

  In various embodiments, the automotive glass tempering process and system described herein with respect to FIGS. 16-26 can be used to produce any of the characteristics, features, dimensions, physical properties of the automotive glass article embodiments described herein. It should be understood that automotive glass-based articles (such as automotive glass sheet 500) having any combination of properties and the like can also be used or actuated to form.

  The automotive glass sheets that have been subjected to the heat strengthening process described herein can be further processed by ion exchange to further improve their strength. Upon ion exchange of the surface of a heat strengthened automotive glass as described herein, in some such possible embodiments, the aforementioned compressive stress is at least 20 MPa, such as at least 50 MPa, such as at least 70 MPa, such as It can be increased by 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 or less.

Systems and Processes for Thermal Conditioning and / or Heating of Automotive Glass Sheets The processes and systems described herein are in addition to thermally strengthening thin automotive glass sheets, as well as further thermal conditioning. Can be used for process. Although cooling is specifically described herein, the system and process can be used to transfer heat to an automotive glass sheet by a conductive method. Thus, additional embodiments of the disclosed process include heating through a gas by conduction rather than convection. Such a process or method 700 is illustrated in the flow diagram of FIG.

Method 700 includes two main steps. Step 710 of the first step includes providing an article, such as an automotive glass sheet, having at least one surface. Step 720 of the second step includes heating or cooling from a part of the surface of the article to the entire surface of the article. Step 720 is performed by conduction rather than convection by gas entering and exiting the heat source or heat sink source, as shown in sub-step 720a, completing the thermal conditioning of the article or a portion of the surface of the article in sub-step 720b. The cooling / heating conduction in step 720 is performed at a high heat transfer rate of at least 450 kW / m ^{2 in} the partial area in substep 720b.

  For example, an article can be thermally conditioned by cooling or heating from a portion of the surface of the article to the entire surface of the article (the portion having an area) by conduction rather than convection. That is, it can be either heated or cooled, and its conduction is mediated by a gas entering or exiting the heat sink or heat source, and is used to regulate the thermal conditioning of the article or part of the article surface, regardless of contact between solids. It is sufficient for completion and its conduction is heated or cooled at a rate of at least 450, 550, 650, 750, 800, 900, 1000, 1100, 1200, 1500, 2000, 3000, 4000, or even 5000 kW / square meter or more For at least some time.

  In addition to strengthening, the high heat output transfer rates provided by the systems and methods described herein allow for during strengthening, edge strengthening of automotive glass, firing or sintering of ceramic, glass, or other materials, etc. Any kind of heat treatment or conditioning including heating and cooling is possible. Furthermore, since heat is extracted or supplied primarily by conduction, surface smoothness and quality are maintained while tightly controlling the thermal history and distribution of the article being processed. Thus, in yet another aspect of the present disclosure, heat is extracted or supplied primarily by conduction, yet the smoothness and quality of the surface is maintained, so that the thermal history and heat distribution of the article being processed is tight. Control is given. Thus, using the systems and methods of the present disclosure, changing the gap, changing the heat sink / heat source material, changing the heat sink / heat source temperature, changing the gas mixture (all of these in the path of the sheet as it is moved) Both in the thickness direction and in the direction in which the surface of the sheet is, depending on the position, along or across the path of the sheet, or not only the position but can also potentially change with time (for most of the variables)) Thus, it is possible to intentionally change the stress profile obtained in the strengthening process.

Devices, products and structures comprising tempered glass sheets The tempered glass-based articles and sheets described herein have a wide range of applications in a wide range of articles, devices, products, structures and the like.

  Referring to FIG. 27, a structure 1010 such as a building, a house, or a vehicle includes a glass-based article 1012 in the form of a window, a part of a wall (for example, a surface), a partition plate, or the like. In a possible embodiment, the glass-based article 1012 has a negative tensile stress at or near its surface where the glass-based article 1012 is balanced with a positive tensile stress therein, as disclosed herein. Can be strengthened to have Furthermore, the glass-based article 1012 may be present in the outdoor environment by having silicon dioxide at a relatively high content, such as at least 70% by weight silicon dioxide, such as at least 75% by weight, and / or It can have a composition that resists corrosion.

According to an exemplary embodiment, the glass-based article 1012 has a major surface that is perpendicular to its thickness (see generally sheet 500 as shown in FIG. 4), the major surface being , Having a large area (eg, at least 5 cm ² , at least 9 cm ² , at least 15 cm ² , at least 50 cm ² , at least 250 cm ² ) compared to glass-based articles used in other applications (eg, lenses, battery members, etc.) . In contemplated embodiments, the total light transmission through the glass-based article 1012 is such that the glass-based article 1012 is less than 5 cm, less than 3 cm, less than 2 cm, less than 1.75 cm, less than 1.5 cm, less than 1 cm, less than 5 cm. 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, less than 0.6 mm, less than 0.5 mm, less than 0.4 mm, less than 0.2 mm, and / or at least 50 At least 50% (eg, at least 65%, at least 75%) at wavelengths from about 300 nm to about 800 nm when having a thickness as disclosed herein, such as a thickness of at least 10 micrometers, such as micrometers. It is.

  The thin thickness of the automotive glass-based article 1012 is less than that of a conventional article because of the high level of strength of the glass-based article 1012 provided by the inventive process disclosed herein. Will not adversely affect the function of the glass-based article 1012 in this application. Thin glass-based article 1012 may be particularly useful in such construction, automotive, or other applications. This is because glass-based articles 1012 will be lighter than conventional such articles and will reduce the mass of the corresponding overall structure. For automobiles, this will result in higher fuel efficiency. For buildings, the structure will be more robust or less resource intensive. In other possible embodiments, the glass-based articles disclosed herein may have areas that are smaller in size, thicker, and less light transmissive and / or, for example, FIG. It can be used for various applications such as those disclosed with respect to 27-32.

Referring to FIG. 28, the surface 1110 may function as part of a counter and / or display, manufactured as disclosed herein, and / or described herein as a stress profile, structure and / or physical. It comprises a glass-based article 1112 having any combination of properties. In some embodiments, the total transmittance through the glass-based article 1112 is at least about 30% (eg, at least 50%) at an infrared wavelength of about 800 nm to about 1500 nm, and the surface 1110 as a sink top surface. Use is promoted. In some embodiments, the glass-based article 1112 has a coefficient of thermal expansion (CTE) of about 10 × 10 ⁻⁷ / ° C. to about 140 × 10 ⁻⁷ / ° C., about 20 × 10 ⁻⁷ / ° C. to about 120. × 10 ⁻⁷ / ° C., about 30 × 10 ⁻⁷ / ° C. to about 100 × 10 ⁻⁷ / ° C., about 40 × 10 ⁻⁷ / ° C. to about 100 × 10 ⁻⁷ / ° C., about 50 × 10 ⁻⁷ / ° C. From about 100 × 10 ⁻⁷ / ° C., or from about 60 × 10 ⁻⁷ / ° C. to about 120 × 10 ⁻⁷ / ° C. In various embodiments, the process is ideally suited for glass compositions with moderate to high CTE. Examples of glasses that work well for the processes described herein include alkali aluminosilicate glasses such as Corning® Gorilla® Glass, aluminoborosilicate glass, and soda lime glass. In some embodiments, the CTE of the glass used is greater than 40 × 10 ⁻⁷ / ° C., greater than 50 × 10 ⁻⁷ / ° C., greater than 60 × 10 ⁻⁷ / ° C., and 70 × 10 ⁻⁷ / ° C. More than 80 × 10 ⁻⁷ / ° C. or more than 90 × 10 ⁻⁷ / ° C. Some such CTEs may be particularly low for thermal strengthening as disclosed herein, and the degree of negative tensile stress is 50 MPa or less and / or at least 10 MPa.

  Referring to FIG. 29, a device 1210 (eg, a portable computer, tablet, portable computer, mobile phone, television, display bulletin board, etc.) is manufactured and / or disclosed herein. One or more glass-based articles 1212, 1214, 1216 having any combination of stress profiles, structures and / or physical properties, and further comprising an electronic component 1218 and a housing 1220. In possible embodiments, the housing 1220 may be or include a glass-based article as disclosed herein. In possible embodiments, the substrate 1222 of the electrical component 1218 may be a glass-based article disclosed herein.

  In some embodiments, the glass-based articles 1212, 1214 may function as front and backplane substrates, and the glass-based article 1216 may function as a cover glass in the device 1210. According to an exemplary embodiment, glass-based article 1216 of device 1210 is an alkali aluminosilicate glass. Such a composition may allow glass-based article 1216 to be tempered by thermal strengthening, as disclosed herein, and further strengthened by ion exchange, particularly at or near its surface. High negative tensile stress (eg, at least 200 MPa, at least 250 MPa) may be applied. In other embodiments, the glass-based article 1216 may include sodium carbonate, calcium oxide, calcium magnesium carbonate, silicon dioxide (eg, at least 70% by weight), aluminum oxide, and / or other components, where May be enhanced by the inventive process disclosed in. The glass-based article 1216 may be particularly thin or otherwise structured, such as having any of the dimensions as disclosed herein.

  Referring now to FIG. 30, automotive glass manufactured according to the process disclosed herein and / or having any combination of stress profile, structure and / or physical properties as disclosed herein. System article 1310 has a curvature and / or a variable cross-sectional dimension D. Such articles may have the thicknesses disclosed herein as an average of dimension D or as a maximum of dimension D. Although the automotive glass-based article 1310 is shown as a curved sheet, other shapes, such as more complex shapes, may be reinforced by the process disclosed herein. In possible embodiments, the automotive glass-based article 1310 may be used as an automotive window (eg, sunroof, windshield, rear window, etc.), as a lens, as a container, or for other uses.

  In various embodiments, a glass material manufactured according to the process disclosed herein and / or having any combination of stress profiles, structures and / or physical properties as disclosed herein is: It is useful for forming at least one sheet of glass, polymer, interlayer, and glass laminate as used in many automotive applications. Stronger and thinner laminates can be produced, resulting in mass and cost savings and increased fuel efficiency. It is desirable that a heat-strengthened thin sheet can be cold formed (see generally FIG. 32) (ie, can be formed without hot forming / shaping) as described herein. Automotive glass systems manufactured according to the processes disclosed herein and / or having any combination of stress profiles, structures and / or physical properties as disclosed herein and attached to a vehicle or automobile Article 1310 will provide mass and cost savings, soundproofing benefits, and increased fuel efficiency.

  Referring now to FIG. 31, a cross-sectional view of an exemplary automotive laminate 1410 is provided. The automotive laminate 1410 is attached to any vehicle or autopropelled vehicle (eg, aircraft, train, automobile, etc.). For example, the automobile laminate 1410 is attached to an inner opening or an outer opening of a vehicle or an automobile. The openings may be for windshields, rear windows, sunroofs or moon roofs, side or door windows, side windows, internal display panels, display covers, interactive touch screens, dashboard surfaces. In one or more embodiments, the laminate 1410 may be movable with respect to a vehicle or automobile opening. In other embodiments, the laminate 1410 is disposed adjacent to a display in an automobile. The automotive laminate 1410 has advantages over other conventional monoliths and laminates that do not include any of the thermally tempered glass-based articles of the present disclosure. These benefits include higher impact resistance, a lighter mass that improves fuel efficiency, and improved sound insulation properties.

  In one or more embodiments, the automotive laminate 1410 includes a first glass-based layer 1412, a second glass-based layer 1416, and at least one intermediate layer 1414 therebetween. Each of the first and second glass-based layers 1412 and 1416 has first main surfaces 1413 and 1417 opposite to the second main surfaces 1415 and 1419, respectively. Any major surface of the glass-based layers 1412, 1416 of the laminate 1410 may have features for user tactile feedback. For example, raised protrusions, protrusions, contours, or steps are non-limiting surface features for haptic feedback. In one or more embodiments, the intermediate layer 1414 is at least partially coextensive with the first glass-based layer 1412 and / or the second glass-based layer 1416. In one or more embodiments, the intermediate layer 1414 is coupled directly and / or indirectly to one of the major surfaces of each of the first and second glass-based layers 1412, 1416 to form a laminate structure 1410. Form. In one or more embodiments, the intermediate layer 1414 may include a polymeric material. The polymeric material may include polyvinyl butyral (PVB), polycarbonate, soundproof PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastic materials, and combinations thereof.

  At least one or both of the first and second glass-based layers 1412, 1416 are manufactured according to the systems and methods disclosed herein and / or stress profiles, structures and / or as disclosed herein. A heat-strengthened glass-based sheet having any combination of physical properties. In one or more embodiments, the second glass-based layer 1416 is a thermally strengthened glass-based layer (eg, FIG. 4) according to the present disclosure, while the first glass-based layer 1412 is thermally strengthened. Glass layer, chemically strengthened glass layer, mechanically strengthened glass layer, thermally and chemically strengthened glass layer, thermally and mechanically strengthened glass layer, or chemically and mechanically Tempered glass layer. In the example of the laminate 1410, both the first and second glass-based layers 1412, 1416 include a heat strengthened soda lime glass sheet according to the present disclosure. In one or more embodiments, if only one of the first and second glass-based layers 1412, 1416 is reinforced as described herein, the other of the first and second glass-based layers. May not be strengthened. As used herein, the unstrengthened glass-based layer may be slowly cooled.

  In one embodiment, one of the first glass-based layer and the second glass-based layer may be different from the automotive glass sheet 500 described herein, such as 250 MPa or more, 300 MPa or more, for example , 400 MPa or more, 450 MPa or more, 500 MPa or more, 550 MPa or more, 600 MPa or more, 650 MPa or more, 700 MPa or more, 750 MPa or more, or 800 MPa or more. In one embodiment, such a tempered glass-based layer (ie, one of the first glass-based layer and the second glass-based layer that is different from the automotive glass sheet 500) is the glass It may have a DOC of about 10% (0.1 t) or more of the thickness of the system layer (as described herein), or about 17% (0.17 t) or more of its thickness. For example, DOC is about 0.1 t or more, 0.11 t or more, 0.12 t or more, 0.13 t or more, 0.14 t or more, 0.15 t or more, 0.16 t or more, 0.17 t or more, 0.18 t or more. , 0.19 t or more, 0.2 t or more, or about 0.21 t or more. The tempered glass-based layer different from the automotive glass sheet 500 is 10 MPa or more, 20 MPa or more, 30 MPa or more, 40 MPa or more (for example, 42 MPa, 45 MPa, or 50 MPa or more), but less than 200 MPa (for example, 175 MPa or less, 150 MPa or less, 125 MPa or less, 100 MPa or less, 95 MPa or less, 90 MPa or less, 85 MPa or less, 80 MPa or less, 75 MPa or less, 70 MPa or less, 65 MPa or less, 60 MPa or less, 55 MPa or less.

  In one or more embodiments of the automotive laminate 1410, one or both of the first and second glass-based layers 1412, 1416 may be soda lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali May be made from materials including aluminoline silicate glass or alkali aluminoborosilicate glass. In one or more embodiments, one or both of the first and second glass-based layers 1412, 1416 may have the same or different glass composition and / or properties according to various embodiments of the present disclosure. . The thickness of the first and second glass-based layers 1412 and 1416 may be the same or different.

  In one or more embodiments, the automotive laminate 1410 may have a thickness of 6.85 mm or less, or 5.85 mm or less, and the thickness of the automotive laminate 1410 is the first glass system. This is the total thickness of the layer 1412, the second glass-based layer 1416, and the intermediate layer 1414. In various embodiments, the thickness of the automotive laminate 1410 ranges from about 1.8 mm to about 6.85 mm, or from about 1.8 mm to about 5.85 mm, or from about 1.8 mm to about 5 0.0 mm range, or about 2.1 mm to about 6.85 mm range, or about 2.1 mm to about 5.85 mm range, or about 2.1 mm to about 5.0 mm range, or about 2.4 mm In the range of about 6.85 mm, or in the range of about 2.4 mm to about 5.85 mm, or in the range of about 2.4 mm to about 5.0 mm, or in the range of about 3.4 mm to about 6.85 mm, or about 3. It may be in the range of 4 mm to about 5.85 mm, or in the range of about 3.4 mm to about 5.0 mm.

  In one or more embodiments, the automotive laminate 1410 exhibits a radius of curvature of less than 1000 mm, or less than 750 mm, or less than 500 mm, or less than 300 mm. The laminate, the first glass-based layer and / or the second glass-based layer are substantially free from wrinkles.

  In one or more embodiments, the second glass-based layer 1416 is relatively thin compared to the first glass-based layer 1412. In other words, the first glass layer 1412 is thicker than the second glass layer 1416. In one or more embodiments, the thickness of the first glass-based layer 1412 may be more than twice the thickness of the second glass-based layer 1416. In one or more embodiments, the thickness of the first glass-based layer 1412 can range from about 1.5 times to about 2.5 times the thickness of the second glass-based layer 1416. .

  In one or more embodiments, the first glass-based layer 1412 and the second glass-based layer 1416 can be the same thickness, and the first glass-based layer is the second glass-based layer. The thickness of both the first glass-based layer 1412 and the second glass-based layer 1416 is more rigid or has greater rigidity compared to the system layer, and in a very particular embodiment, It is in the range of 0.2 mm and 1.6 mm.

  In various embodiments, the thickness of one or both of the first glass-based layer 1412 and the second glass-based layer 1416 ranges from about 0.1 mm to about 2 mm, or from about 0.2 mm. A range from about 2 mm, or a range from about 0.3 mm to about 2 mm, or a range from about 0.4 mm to about 2 mm, or a range from about 0.5 mm to about 2 mm, or from about 0.6 mm to about 2 mm. A range from about 0.7 mm to about 2 mm, or a range from about 0.8 mm to about 2 mm, or a range from about 0.9 mm to about 2 mm, or a range from about 1 mm to about 2 mm, Or about 1.1 mm to about 2 mm, or about 1.2 mm to about 2 mm, or about 1.3 mm to about 2 mm, or about 1.4 m. To about 2 mm, or about 1.5 mm to about 2 mm, or about 0.1 mm to about 1.9 mm, or about 0.1 mm to about 1.8 mm, or about 0 .1 mm to about 1.7 mm, or about 0.1 mm to about 1.6 mm, or about 0.1 mm to about 1.5 mm, or about 0.1 mm to about 1.4 mm Or about 0.1 mm to about 1.3 mm, or about 0.1 mm to about 1.2 mm, or about 0.1 mm to about 1.2 mm, or about 0.1 mm. To about 1 mm, or about 0.2 mm to about 1 mm, or about 0.1 mm to about 0.7 mm, or about 0.2 mm to about 0.7 mm, or about .3 mm to about 0.7 mm, or about 0.4 mm to about 0.7 mm, or about 0.2 mm to about 0.6 mm, or about 0.3 mm to about 0.6 mm Or about 0.4 mm to about 0.6 mm, or about 0.2 mm to about 0.5 mm, or about 0.3 mm to about 0.5 mm, or about 0.2 mm. To about 0.4 mm.

  In one or more embodiments, the thickness of the first glass-based layer 1412 may be greater than the thickness of the second glass-based layer 1416. In one or more embodiments, the thickness of the first glass-based layer is 4.0 mm or less, or 3.85 mm or less. In various embodiments, the thickness of the first glass-based layer ranges from about 1.4 mm to about 3.85 mm, or from about 1.4 mm to about 3.5 mm, or from about 1.4 mm to about 3.0 mm range, or about 1.4 mm to about 2.8 mm range, or about 1.4 mm to about 2.5 mm range, or about 1.4 mm to about 2.0 mm range, or about 1.5 mm To about 3.85 mm, or about 1.5 mm to about 3.5 mm, or about 1.5 mm to about 3.0 mm, or about 1.5 mm to about 2.8 mm, or about 1 In the range of 0.5 mm to about 2.5 mm, or in the range of about 1.5 mm to about 2.0 mm, or in the range of about 1.6 mm to about 3.85 mm, or in the range of about 1.6 mm to about 3.5 mm, or About 1.6mm to about 3 0 mm, or about 1.6 mm to about 2.8 mm, or about 1.6 mm to about 2.5 mm, or about 1.6 mm to about 2.0 mm, or about 1.8 mm to about It may be in the range of 3.5 mm, or in the range of about 2.0 mm to about 3.0 mm.

  The first and second glass-based layers 1412, 1416 may have any major surface dimensions and / or physical properties as disclosed herein. In an exemplary embodiment, automotive laminate 1410 includes first and second glass-based layers 1412, 1416, and PVB, which are heat-strengthened soda lime glass sheets manufactured according to the systems and methods disclosed herein. Alternatively, an intermediate layer 1414 containing soundproof PVB may be provided.

  In one or more embodiments, one of the first glass-based layer 1412 or the second glass-based layer 1416 may be cold formed (along with an intervening intermediate layer 1414). In the exemplary cold-formed laminate shown in FIG. 32, a second glass-based layer 1516 is laminated to a relatively thicker first glass-based layer 1512. The first glass-based layer 1512, the second glass-based layer 1516, or both the first glass-based layer and the second glass-based layer may include the automotive glass sheet 500 described herein. 32, the first glass-based layer 1512 has a first surface 1513 and a second surface 1515 in contact with the intermediate layer 1514, and the second glass-based layer 1516 has a third surface in contact with the intermediate layer 1514. 1517 and a fourth surface 1519. The indicator of the cold-formed laminate is that the fourth surface 1519 has a larger surface CS than the third surface 1517. Thus, the cold formed laminate may have a high compressive stress level at the fourth surface 1519, making it more resistant to crushing due to wear.

  In one or more embodiments, the respective compressive stresses on the third surface 1517 and the fourth surface 1519 are substantially equal prior to the cold forming process. In one or more embodiments where the second glass-based layer 1516 is not tempered (as defined herein), the third surface 1517 and the fourth surface 1519 are appreciably prior to cold forming. The compressive stress is not shown. In one or more embodiments in which the second glass-based layer 1516 is reinforced (as defined herein), the third surface 1517 and the fourth surface 1519 are substantially relative to each other prior to cold forming. Shows equal compressive stress. In one or more embodiments, after cold forming, the compressive stress on fourth surface 1519 increases (ie, the compressive stress on fourth surface 1519 is greater after cold forming than before cold forming). ). While not being bound by theory, this cold forming process increases the compressive stress of the glass-based layer being formed (ie, the second glass-based layer), resulting in tensile stress imparted during bending and / or forming operations. Offset. In one or more embodiments, the cold forming process causes the third surface of the glass-based layer (ie, third surface 1517) to experience tensile stress, while the fourth surface of the glass-based layer ( That is, the fourth surface 1519) experiences compressive stress.

  When using a reinforced second glass-based layer 1516, the third and fourth surfaces (1517, 1519) are already under compressive stress, and therefore the third surface 1517 experiences greater tensile stress. . This allows the reinforced second glass-based layer 1516 to follow a tighter curved surface.

  In one or more embodiments, the thickness of the second glass-based layer 1516 is less than the thickness of the first glass-based layer 1512. This thickness difference means that the second glass-based layer 1516 will give less force and be more flexible to follow the shape of the first glass-based layer 1512. Furthermore, the thinner second glass-based layer 1516 will more easily deform to compensate for the shape mismatch and gaps caused by the shape of the first glass-based layer 1512. In one or more embodiments, the thin tempered second glass-based layer 1516 exhibits greater flexibility, especially during cold forming. In one or more embodiments, the second glass-based layer 1516 provides a substantially uniform distance between the second surface 1515 and the third surface 1517 according to the first glass-based layer 1512, which is intermediate. Filled with layers.

  In some non-limiting embodiments, the cold-formed laminate 1510 can be equal to or slightly higher than the softening temperature of the interlayer material (eg, 1414, 1514) (eg, from about 100 ° C. to about 120 ° C) temperature, ie, an exemplary cold forming process performed at a temperature below the softening temperature of the respective glass layer. In one embodiment, the cold-formed laminate comprises: an intermediate layer disposed between a first glass-based layer (curved) and a second glass-based layer (which may be flat) Forming a stack; applying pressure to the stack and pressing the second glass-based layer against the intermediate layer, the intermediate layer being pressed against the first glass-based layer; May be formed by heating to a temperature of less than 400 ° C. to form a cold-formed laminate in which the shape of the second glass-based layer follows the first glass-based layer. Such a process can be performed using a vacuum bag or ring in an autoclave or another suitable apparatus. The cross-sectional stress profile of an exemplary inner glass layer (e.g., layer 1516), as described in WO2015 / 031594, which is hereby incorporated by reference in its entirety, and shown therein in FIGS. 8A-8B. Will vary from substantially symmetric to asymmetric according to some embodiments of the present disclosure.

  In one or more embodiments, the first glass-based layer, the second glass-based layer, the laminate or combination thereof may have a complex curved shape, and may be cold formed as necessary. May be. As shown in FIG. 32, the first glass-based layer 1512 has at least one concave surface (eg, surface 1515) and a first that provides a first surface of the laminate that is intricately curved and has a thickness therebetween. It may have at least one convex surface (eg, surface 1513) that provides a second surface of the laminate opposite the surface. In the cold forming embodiment, the second glass-based layer 1516 is intricately curved and has a thickness therebetween, at least one concave surface (eg, fourth surface 1519) and at least one convex surface (eg, There may be a third surface 1517).

  As used herein, the phrase “complexly curved” refers to a non-planar shape having curvature along two different orthogonal axes. Examples of intricately curved shapes include those with simple curves or compound curves, also called non-developable shapes, including but not limited to spherical, aspheric, and toroidal surfaces Is mentioned. Complexly curved laminates or sheets according to embodiments disclosed herein may also include such surface segments or portions, or may consist of a combination of such curves and surfaces. In one or more embodiments, a complex curved laminate or sheet may have a compound curve that includes a major radius and a cross curvature. A complex curved laminate or sheet according to one or more embodiments may have separate radii of curvature in two independent directions. According to one or more embodiments, a complex curved laminate or sheet may therefore be characterized as having a “cross curvature”, in which case the laminate or sheet is a predetermined It is curved along an axis that is parallel to the dimension (ie, the first axis) and is also curved along an axis that is perpendicular to the same dimension (ie, the second axis). The curvature of the laminate or sheet can be even more complex when a significant minimum radius is combined with a significant cross curvature and / or bending depth. Some laminates or sheets may include bends along axes that are not perpendicular to each other. As a non-limiting example, the complex curved laminate or sheet has a length and width dimension of 0.5 m × 1.0 m, a radius of curvature of 2 to 2.5 m along the minor axis, and along the major axis. May have a radius of curvature of 4 to 5 meters. In one or more embodiments, the complex curved laminate or sheet may have a radius of curvature of 5 m or less along at least one axis. In one or more embodiments, the complex curved laminate or sheet has a radius of curvature of 5 m or less along at least a first axis and a second axis perpendicular to the first axis. May have. In one or more embodiments, the complex curved laminate or sheet has a radius of curvature no greater than 5 meters along at least a first axis and a second axis that is not perpendicular to the first axis. May have.

  In one or more embodiments, one or more of the intermediate layer 1414, the first glass-based layer 1412, and the second glass-based layer 1416 have a first edge having a first thickness and a first thickness. A second edge opposite the first edge, with a second thickness greater than the first thickness.

  In one or more embodiments, the automotive glass article described herein may be placed in a vehicle. For example, FIG. 33 illustrates a vehicle 1600 that includes a glass-based article 1630 according to a vehicle body 1610, at least one opening 1620, and one or more embodiments described herein disposed therein. In one or more embodiments, the vehicle may include an internal surface (not shown) with a glass-based layer disposed on the internal surface. In one or more embodiments, the interior surface includes a display and a glass-based layer is disposed on the display.

  Thermally tempered glass-based sheets manufactured according to the systems and methods disclosed herein and / or having any combination of stress profiles, structures and / or physical properties as disclosed herein, International Publication No. 2014/022663 (MULTI-LAYER TRANSPARENT LIGHT-WEIGHT SAFETY GLAZINGS), International Publication No. 2014/176059 (LAMINATED GLASS STRUCTURES HAVING HIGH GLASS TO POLYMER INTERLAYER ADHESION), International Publication No. 2015/031594 (THIN GLASS LAMINATE STRUCTURES), International Publication No. 2015/054112 (GLASS LAMINATE STRUCTURES HAVING IMPROVED EDGE STRENGTH), International Publication No. 2015/088886 (NON-YELLOWING GLASS LAMINATE STRUCTURE), International Publication No. 2013/063207 (GLASS ARTICLES WITH INFRARED REFLECTIV METHODS FOR MAKING THE SAME), International Publication No. 201 No. 178173 (LAMINATED GLASS ARTICLE AND METHOD FOR FORMING THE SAME), US Patent Application No. 14/638224 (GLASS LAMINATE STRUCTURES FOR HEAD-UP DISPLAY SYSTEM), US Provisional Patent Application No. 61/970972 (GLASS ARTICLE), No. 62/011305 (LAMINATING THIN GLASS STRUCTURES), No. 62/121076 (THIN LAMINATE STRUCTURES WITH ENHANCED ACOUSTIC PERFORMANCE), No. 62/159477 (SURFACE DISPLAY UNITS WITH OPAQUE SCREEN), US Patent Application No. 14 / As disclosed in each specification of 699263 (STRENGTHENED GLASS AND COMPOSITIONS THEREOF), instead of one or more glass layers in an automotive laminate (eg, FIG. 31) and a method of forming the laminate. Or it may be applied to it. The entire disclosure of each of these is hereby incorporated by reference.

  The automotive glass-based article 1310 and the automotive laminates 1410, 1510 may include a glass material that is substantially optically transparent, clear, and free of light scattering. In such embodiments, the glass material is about 85% or more, about 86% or more, about 87% or more, about 88% or more, about 89% or more, about 90% or more, about 91% or more, or about May exhibit an average light transmission over a wavelength range of about 400 nm to about 780 nm, greater than 92%. In one or more alternative embodiments, the glass material is opaque or less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5% , Less than about 4%, less than about 3%, less than about 2%, less than about 1%, or less than about 0%, may exhibit an average light transmittance over a wavelength range of about 400 nm to about 780 nm. In some embodiments, these light reflectance and transmittance values may be total reflectance or total transmittance (taking into account the reflectance or transmittance on both major surfaces of the glass material). . The glass material may exhibit colors such as white, black, red, blue, green, yellow, orange, etc. as required.

Glass-based materials for heat-strengthened automotive glass sheets The described systems and methods can be used to heat strengthen various automotive glass-based materials.

The processes and systems described herein may generally be used with almost any glass composition, and some embodiments can be used with glass laminates, glass ceramics, and / or ceramics. The glass compositions and properties listed below are also applicable to one or more of the glass-based layers in the glass laminate structure described herein (eg, 1410 in FIG. 31, 1510 in FIG. 32). In various embodiments, the process can be used for glass compositions having a high CTE. In one or more embodiments, automotive glass tempered by the processes and systems described herein includes alkali aluminosilicate glass such as “Corning”, “Gorilla” Glass, SLG, no soda or alkali glass. . In some embodiments, the CTE of automotive glass tempered by the processes and systems described herein is greater than 40 × 10 ⁻⁷ / ° C., greater than 50 × 10 ⁻⁷ / ° C., and 60 × 10 ^−7. / ° C., 70 × 10 ⁻⁷ / ° C., 80 × 10 ⁻⁷ / ° C., or 90 × 10 ⁻⁷ / ° C. Suitable glasses are US Pat. No. 8759238 entitled “ION EXCHANGEABLE GLASS WITH HIGH CRACK INITIATION THRESHOLD”, US Pat. No. 9156724 entitled “ION EXCHANGEABLE GLASS WITH HIGH CRACK INITIATION THRESHOLD”, “ION EXCHANGEABLE GLASS WITH HIGH CRACK INITIATION THRESHOLD” U.S. Patent No. 8765262 entitled "ZIRCON COMPATIBLE, ION EXCHANGEABLE GLASS WITH HIGH DAMAGE RESISTANCE", U.S. Patent No. 89951927, "ZIRCON COMPATIBLE, ION EXCHANGEABLE GLASS WITH HIGH DAMAGE RESISTANCE", U.S. Patent No. 8946103, " U.S. Pat. No. 8,802,581 entitled “ZIRCON COMPATIBLE GLASSES FOR DOWN DRAW” and U.S. Patent Application Publication No. 2014/0106172 entitled “ION EXCHANGEABLE GLASS WITH HIGH DAMAGE RESISTANCE”. The disclosure is cited here.

  In some applications and embodiments, an automotive glass (such as an automotive glass sheet 500) reinforced by the processes and systems described herein may have a composition configured for chemical durability. is there. In some such embodiments, the composition comprises at least 70% by weight silicon dioxide, and / or at least 10% by weight sodium oxide, and / or at least 7% by weight calcium oxide. Conventional articles of such composition may be difficult to chemically strengthen to deep depths and / or because of their low thickness, if not impossible, due to fragility and power of conventional processes, etc. It may be difficult to heat strengthen by conventional processes to a sufficiently large negative surface tensile stress. However, in contemplated embodiments, in the inventive process disclosed herein, such a composition causes negative tensile stresses to occur on the first and second major surfaces (e.g., the major surfaces of an automotive glass sheet 500). Up to a distance of at least 10% of the thickness of the reinforced automotive glass-based sheet from at least one of the surfaces 510, 520), for example at least 12% of the thickness, at least 15% of the thickness, at least of the thickness Each reinforced automotive glass system up to a distance of 16%, at least 17% of thickness, at least 18% of thickness, at least 19% of thickness, at least 20% of thickness, or at least 21% of thickness Reinforced automotive glass-based articles or sheets, such as automotive glass sheet 500, extending into the sheet are possible.

  In some embodiments, an automotive glass-based sheet and article reinforced as described herein may include one or more coatings disposed on the glass prior to thermal strengthening of the automotive glass sheet. Have The process described herein can be used to produce a tempered automotive glass sheet having one or more coatings, and in some such embodiments, the coating is thermally enhanced. Previously placed on automotive glass and unaffected by heat strengthening process. Special coatings that are conveniently maintained on the automotive glass sheet of the present disclosure include low E coatings, reflective coatings, antireflective coatings, anti-fingerprint coatings, cut-off filters, pyrolytic coatings, and the like.

  According to an exemplary embodiment, the automotive glass-based sheet or article described herein, eg, articles 1212, 1214 of device 1210 shown in FIG. 29, is an aluminoborosilicate glass. In some embodiments, the automotive glass-based sheets or articles described herein, such as the articles 1212, 1214 of the device 1210 shown in FIG. 29, are generally non-alkaline glass, yet still here Having a stress profile and structure as disclosed in US Pat. Such a composition would reduce the degree of glass relaxation and promote transistor coupling thereto. In some embodiments, the automotive glass sheet / article described herein is a flexible automotive glass sheet. In other embodiments, the automotive glass sheet / article described herein comprises a laminate of two or more glass sheets.

In some possible embodiments, the automotive glass (such as automotive glass sheet 500) reinforced by the processes and systems described herein is an amorphous material, a crystalline material, or a combination thereof (glass ceramic material). Etc.). Automotive glass (such as automotive glass sheet 500) reinforced by the processes and systems described herein may be an alkali aluminosilicate glass, an alkali-containing borosilicate glass, an alkali aluminosilicate glass, or an alkali aluminoborosilicate glass. May be included. In one or more embodiments, automotive glass (such as automotive glass sheet 500) reinforced by the processes and systems described herein is in mole percent (mol%) in its non-ion-exchanged portion. In terms of SiO ₂ in the range of about (plus or minus 1%) 40 to about 80 mol%, Al ₂ O _{3 in} the range of about 10 to about 30 mol%, B _{2 in} the range of about 0 to about 10 mol%. May include a glass having a composition comprising O ₃ , R ₂ O in the range of about 0 mol% to about 20 mol%, and / or RO in the range of about 0 to about 15 mol%. In some possible embodiments, the composition comprises either 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%. There is. In some possible embodiments, TiO ₂ may be present from about 0 to about 2 mole percent.

In some possible embodiments, the composition used in the reinforced automotive glass-based sheet or article described herein includes 0 to 2 mole percent Na ₂ SO ₄ , NaCl, At least one clarifier selected from the group comprising NaF, NaBr, K ₂ SO ₄ , KCl, KF, KBr, and SnO ₂ may be batch formulated. The automotive glass composition according to one or more embodiments has from about 0 to about 2 mole percent, from about 0 to about 1 mole percent, from about 0.1 to about 2 mole percent, from about 0.1 to about 1 mole percent. Or SnO ₂ in the range of about 1 to about 2 mol%. The disclosed automotive glass composition for reinforced automotive glass-based sheet 500 is substantially free of As ₂ O ₃ and / or Sb ₂ O ₃ in some embodiments. There is.

In possible embodiments, the reinforced automotive glass-based sheet or article described herein comprises an alkali aluminosilicate glass composition or an alkali aluminoborosilicate glass composition that is further reinforced by an ion exchange process. Sometimes. An example automotive glass composition includes SiO ₂ , B ₂ O ₃ , and Na ₂ O, where (SiO ₂ + B ₂ O ₃ ) ≧ 66 mol% and / or Na ₂ O ≧ 9 mol%. It is. In certain embodiments, the automotive glass composition comprises at least 6% by weight aluminum oxide. In a further embodiment, the reinforced automotive glass-based sheet or article described herein has one or more alkaline earth oxides such that the alkaline earth oxide content is at least 5% by weight. It may contain the glass composition for motor vehicles which has this. Suitable automotive glass compositions further comprise at least one of K ₂ O, MgO, and CaO in some embodiments. In a special embodiment, the automotive glass composition used in the reinforced glass-based sheet or article described herein is 61-75 mol% SiO ₂ , 7-15 mol% Al ₂ O _3. , 0-12 mol% of B ₂ O _3, 9 to 21 mol% of Na ₂ O, 0 to 4 mol% of K ₂ O, 0 to 7 mol% of MgO, and / or 0-3 mol% of CaO Can be included.

The glass composition of a further exemplary suitable strengthened glass-based sheet or article for a motor vehicle set forth herein, 60-70 mol% of SiO _2, having 6 to 14 mol% of Al ₂ O _3, 0 to 15 mol % of B ₂ O _3, 0~15 mol% of Li ₂ O, 0 to 20 mol% of Na ₂ O, 0 mol% of K ₂ O, 0 to 8 mol% of MgO, 0 mol% Of CaO, 0-5 mol% ZrO ₂ , 0-1 mol% SnO ₂ , 0-1 mol% CeO ₂ , less than 50 ppm As ₂ O ₃ , and less than 50 ppm Sb ₂ O ₃ , Mol% ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20 mol%, and / or 0 mol% ≦ (MgO + CaO) ≦ 10 mol%. Yet another exemplary glass compositions suitable for enhanced glass-based sheet or article for a motor vehicle set forth herein, from 63.5 to 66.5 mol% of SiO _2, 8 to 12 mol% of Al ₂ O _3, 0-3 mol% of B ₂ O _3, 0 to 5 mol% of Li ₂ O, 8 to 18 mol% of Na ₂ O, 0 to 5 mol% of K ₂ O, 1 to 7 mol% of MgO , 0-2.5 mol% of CaO, 0 to 3 mol% of ZrO _2, 0.05 to 0.25 mol% of SnO _2, 0.05 to 0.5 mol% of CeO _2, 50 ppm less of As ₂ O ₃ and less than 50 ppm Sb ₂ O ₃ , 14 mol% ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 18 mol%, and / or 2 mol% ≦ (MgO + CaO) ≦ 7 mol%.

In particular contemplated embodiments, the alkali aluminosilicate glass composition suitable for the reinforced automotive glass-based sheet or article described herein includes alumina, at least one alkali metal, and some implementations. In an embodiment, comprising more than 50 mol% SiO ₂ , in other embodiments at least 58 mol% SiO ₂ , and in still other embodiments at least 60 mol% SiO ₂ , in a ratio (Al ₂ O ₃ + B ₂ O ₃ ) / Σ modifier (ie, the sum of modifiers) is greater than 1, where in this ratio, the components are expressed in mole% and the modifier is an alkali metal oxide. . This automotive glass composition comprises, in a special embodiment, 58-72 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, the ratio (Al ₂ O ₃ + B ₂ O ₃ ) / Σ modifier (ie the sum of modifiers) is greater than 1. . In yet another embodiment, automotive glass based sheet 500 which has been enhanced, 64-68 mol% of SiO _2, 12 to 16 mol% of Na ₂ O, 8 to 12 mol% of 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, 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%, may include an alkali aluminosilicate glass composition . In an alternative embodiment, the reinforced automotive glass-based sheet or article described herein has 2 mol% or more of Al ₂ O ₃ and / or ZrO ₂ , or 4 mol% or more of Al ₂ O ₃ and And / or an alkali aluminosilicate glass composition containing ZrO ₂ .

In possible embodiments, examples of suitable glass ceramics for the reinforced automotive glass-based sheets or articles described herein include the Li ₂ O.Al ₂ O ₃ .SiO ₂ system (ie, LAS). Main crystal phase containing glass ceramic, MgO.Al ₂ O ₃ .SiO ₂ (ie MAS) glass ceramic, and / or β-quartz solid solution, β-spodumene solid solution, cordierite, and lithium disilicate. A glass ceramic containing may be mentioned.

  The reinforced automotive glass-based sheet or article described herein may be characterized by the manner in which it is formed. For example, the reinforced automotive glass-based sheets or articles described herein are float moldable (ie, formed by a float process), downdrawable, and particularly fusion moldable or slot drawable (ie, fusion) And may be characterized by a downdraw method such as a draw method or a slot draw method).

  Floatable toughened automotive glass-based sheets or articles may be characterized by a smooth surface and consistent thickness, and float molten glass over a molten metal, typically a tin floor Manufactured by. In the illustrated process, the molten glass system fed onto the surface of the molten tin bed forms a floating glass ribbon. As the glass-based ribbon flows along the tin bath, the temperature gradually decreases until the glass-based ribbon solidifies into a solid automotive glass-based article that is lifted from tin to the roller. Once the automotive glass article is removed from the bath, it can be further cooled and annealed to reduce internal stress. When the automotive glass-based article is a glass ceramic, the automotive glass-based article formed from the float process can be subjected to a ceramization process in which one or more crystal phases are generated.

  The downdraw process produces automotive glass-based articles having a consistent thickness and a consistent thickness. Since the average bending strength of the automotive glass-based article is controlled by the amount and size of surface flaws, the solid surface with minimal contact has a higher initial strength. If this high-strength automotive glass-based article is then further reinforced (eg chemically), the resulting strength is higher than the strength of the automotive glass-based article having a lapped and polished surface. obtain. The downdrawn automotive glass-based article will be stretched to a thickness of less than about 2 mm. Moreover, down-drawn automotive glass-based articles have a very flat and smooth surface that can be used for end use without costly grinding and polishing. When the automotive glass-based article is a glass ceramic, the automotive glass-based article formed by the downdraw method can be subjected to a ceramization process in which one or more crystal phases are generated.

  The fusion draw method uses, for example, a drawing tank having a passage for receiving molten glass raw material. The passage has weirs that are open at the top along the longitudinal direction of the passage on both sides of the passage. When the passage is filled with molten material, the molten glass overflows over the weir. The molten glass flows down as two flowing glass films on the outer surface of the drawing tank due to gravity. These outer surfaces of the drawing tank extend downward and inward so that they join at the lower edge of the drawing tank. The two flowing glass films are joined and fused at this edge to form one flowing automotive glass article. This fusion draw method provides the advantage that none of the outer surfaces of the resulting automotive glass article is in contact with any part of the device, because the two glass films flowing across the passage are fused together. Therefore, the surface properties of glass articles for automobiles formed by the fusion draw method are not affected by such contact. When the automotive glass-based article is a glass ceramic, the automotive glass-based article formed by the fusion method can be subjected to a ceramization process in which one or more crystal phases are generated.

  The slot draw method is different from the fusion draw method. In the slot draw method, molten raw material glass is provided to a drawing vessel. There is an open slot at the bottom of the draw tank, which has a nozzle that extends over its length. The molten glass flows through the slots / nozzles and is drawn downward into a slow cooling region as a continuous automotive glass article. If the automotive glass article is a glass ceramic, the automotive glass article formed by the slot draw method can be subjected to a ceramization process in which one or more crystalline phases are produced.

  In some embodiments, the automotive glass article includes U.S. Pat. No. 8,713,972, U.S. Pat. No. 9,0038,35, U.S. Patent Application Publication No. 2015/0027169, all of which are incorporated herein by reference. It may be formed using a thin rolling process, such as described in the specification and US Patent Application Publication No. 2005/0099618. More specifically, the automotive glass-based article provides a vertical flow of molten glass and a pair of moldings in which the supplied flow of molten glass is maintained at a surface temperature of about 500 ° C or higher or about 600 ° C or higher. Forming a molded glass ribbon having a molding thickness by molding with a roll, and dimensionally finishing the molded glass ribbon with a pair of dimension finishing rolls maintained at a surface temperature of about 400 ° C. or less to obtain a desired thickness smaller than the molding thickness. It may be formed by producing a dimensionally finished glass ribbon having a thickness and a desired thickness consistency. The apparatus used to form the glass ribbon is a glass supply apparatus for supplying a molten glass supply stream; a pair of forming rolls maintained at a surface temperature of about 500 ° C. or more, between the forming rolls. Are spaced closely adjacent to each other to define a glass forming gap, the glass forming gap accepts a molten glass feed stream and thins the molten glass feed stream between the forming rolls, A forming roll positioned vertically below the glass feeder to form a formed glass ribbon having a forming thickness; and a pair of dimension finishing rolls maintained at a surface temperature of about 400 ° C. or less, wherein the dimension finishing The glass dimension finish gaps are spaced closely adjacent to each other to define a glass dimension finish gap between the rolls, which receives the molded glass ribbon and forms By reducing the Rasuribon, to produce a glass ribbon which is dimensioned finish having a desired thickness and a desired thickness consistency, which may comprise a dimension finishing rolls are positioned vertically below the forming roll.

  In some cases, the thin rolling method may be used when the fusion method or slot draw method cannot be used due to the viscosity of automotive glass. For example, when automotive glass exhibits a liquidus viscosity of less than 100 kP, a thin rolling method can be used to form automotive glass-based articles. The automotive glass-based article may be acid polished or otherwise treated to eliminate or reduce the effects of surface flaws.

In possible embodiments, the automotive glass-based sheets or articles described herein have different compositions on the sides. In one surface of the automobile glass-based sheet 500, the composition of example, SiO ₂ of 69 to 75 wt%, 0 to 1.5 wt% of Al ₂ O _3, 8 to 12 wt% of CaO, 0 to 0 .1 wt% of Cl, Fe of 0~500ppm, 0~500ppm of K, from 0.0 to 4.5 wt% of MgO, 12 to 15 wt% Na ₂ O, 0 to 0.5 wt% of SO _3, SnO ₂ 0 to 0.5 wt%, 0-0.1 wt% of SrO, 0 to 0.1 wt% of TiO _2, 0 to 0.1 wt% of ZnO, and / or 0-0 1% by mass of ZrO ₂ . In the other aspect of the automotive glass-based sheet or article described herein, an exemplary composition is 73.16 wt% SiO ₂ , 0.076 wt% Al ₂ O ₃ , 9.91 wt% CaO. 0.014 mass% Cl, 0.1 mass% Fe ₂ O ₃ , 0.029 mass% K ₂ O, 2.792 mass% MgO, 13.054 mass% Na ₂ O,. 174% by weight of SO _3, SnO ₂ 0.001 wt%, 0.01 wt% SrO, TiO ₂ 0.01 wt%, 0.002 wt% of ZnO, and / or 0.005 wt% ZrO ₂ .

In the embodiments other possible, the composition of the automotive glass-based sheets or articles mentioned herein, SiO ₂ of 55 to 85 wt%, 0-30 wt% of Al ₂ O _3, 0 to 20 wt% B ₂ O ₃ , 0 to 25 mass% Na ₂ O, 0 to 20 mass% CaO, 0 to 20 mass% K ₂ O, 0 to 15 mass% MgO, 5 to 20 mass% BaO, It contains 0.002 to 0.06 mass% Fe ₂ O ₃ and / or 0.0001 to 0.06 mass% Cr ₂ O ₃ . In the embodiments other possible, the composition of the automotive glass-based sheet or article described herein is 60 to 72 mol% of SiO _2, from 3.4 to 8 mol% of Al ₂ O _3, 13 to 16 mol% of Na ₂ O, 0 to 1 mol% of K ₂ O, from 3.3 to 6 mol% of MgO, 0 to 0.2 mol% of TiO _2, 0.01 to 0.15 mol% of Fe ₂ O ₃ , 6.5-9 mol% CaO, and / or 0.02-0.4 mol% SO ₃ .

Device Setup-As previously described in detail, the device of the present invention includes three zones: a hot zone, a transition zone, and a cooling or quench zone. The gap between the top and bottom thermal bearings (heat sinks) in the hot zone and quench zone is set to the desired spacing. The gas flow rates in the hot zone, transition zone, and quench zone are set to ensure that the automotive glass material, sheet or component is centered on the air bearing. The hot zone is preheated to the desired T ₀ and then the automotive glass article is quenched from that temperature. To ensure uniform heating, the automotive glass article is preheated in a separate preheating device such as a batch furnace or a continuous furnace. In general, automotive glass sheets are preheated for more than 5 minutes before being placed in the hot zone. In the case of soda-lime glass, preheating is performed at about 450 ° C. After the preheating phase, the glass article is placed in a hot zone and allowed to equilibrate, where equilibration is when the glass is uniform at T ₀ . T ₀ can be determined by the desired level of strengthening, but is generally maintained within a range between the softening point and the glass transition temperature. The time for equilibration depends at least on the glass thickness. For example, in the case of an automotive glass sheet of about 1.1 mm or less, equilibration takes place in about 10 seconds. In the case of a 3 mm automotive glass sheet, equilibration takes place in about 10 to 30 seconds. For thicker sheets up to about 6 mm, the equilibration time may be about 60 seconds. Once the automotive glass is equilibrated to T ₀ , the automotive glass is quickly transferred over the air bearing through the transition zone to the cooling or quenching zone. The automotive glass article is quickly struck to a temperature below the glass transition temperature Tg in the quench zone. Depending on the desired degree of quenching and / or the desired temperature of the automotive glass upon removal, the automotive glass sheet can be placed in the quenching zone for any period up to 1 second, 10 seconds, or several minutes or longer. Can be maintained. Upon removal, the automotive glass can be cooled before handling, if desired.

  The following examples are summarized in Table VI.

Example 1-A 5.7 mm thick soda lime silicate glass plate (e.g. at least 70 wt% silicon dioxide and / or at least 10 wt% sodium oxide and / or at least 7 wt% calcium oxide) Glass) is preheated at 450 ° C. for 10 minutes and then transferred to the hot zone where it is maintained at T ₀ of 690 ° C. for 60 seconds. After equilibration at T ₀ , it is quickly transferred to a quench zone filled with helium with a 91 μm gap (this gap is the distance between the surface of the glass sheet and the nearest heat sink), where 10 Hold for seconds. The resulting article has a surface compression of −312 MPa, a median tension of 127 MPa, and a flatness of 83 μm.

Example 2-A 5.7 mm thick soda lime silicate glass plate is preheated at 450 ° C. for 10 minutes and then transferred to the hot zone where it is maintained at T ₀ of 690 ° C. for 60 seconds. After equilibration, it is quickly transferred to a quench zone with a 91 μm gap where it is maintained for 10 seconds. The resulting article has a surface compression of −317 MPa, a median tension of 133 MPa, and a flatness of 89.7 micrometers.

Example 3-A 1.1 mm thick soda lime silicate glass plate is preheated at 450 ° C. for 10 minutes and then transferred to a hot zone where it is maintained at a T ₀ of 700 ° C. for 10 seconds. After equilibration, it is quickly transferred to a quench zone filled with helium with a gap of 56 μm, where it is maintained for 10 seconds. The obtained article has a measured surface fictive temperature of 661 ° C., a surface compression of −176 MPa, a median tension of 89 MPa, a flatness of 190 μm, and a Vickers crack threshold of 10 to 20 N.

Example 4-A 0.55 mm thick soda lime silicate glass plate is preheated at 450 ° C for 10 minutes and then transferred to a hot zone where it is maintained at T ₀ at 720 ° C for 10 seconds. After equilibration, if it is quickly transferred to a quench zone with a 25 μm gap and maintained there for 10 seconds, an effective heat transfer coefficient of 0.184 cal / (cm ² · s · ° C.) (7704 W / m ₀ K) is obtained. It is done. The resulting article has a surface compression of -176 MPa and a median tension of 63 MPa. Also, the flatness of the resulting reinforced article was about 168 micrometers (for a sample with an initial temperature of 710 ° C.) and 125 micrometers (for a sample with an initial temperature of 720 ° C.).

Example 5-A 1.5 mm thick "CORNING""GORILLA" Glass plate is preheated at 550 ° C. for 10 minutes and then transferred to a hot zone where it is maintained at T ₀ of 790 ° C. for 30 seconds. After equilibration, it is quickly transferred to a quench zone with a gap of 226 μm where it is maintained for 10 seconds. This glass article was measured to have a flatness of 113 μm before processing and 58 μm after processing, indicating an improvement.

Example 6-A 0.7 mm thick soda lime silicate glass plate is preheated at 450 ° C for 10 minutes and then transferred to a hot zone where it is maintained at T ₀ at 730 ° C for 10 seconds. After equilibration, it is quickly transferred to a quenching zone filled with helium, having a gap of 31 μm, and maintained there for 10 seconds, 0.149 cal / (cm ² · s · ° C.) (6238 W / m ² K) An effective heat transfer coefficient is obtained. The resulting article has a surface compression of −206 MPa, a median tension of 100 MPa, and a flatness of 82 μm. When crushed, this glass plate “dices” (using the standard terminology for dicing sheets with a thickness of 2 mm or more, ie a 5 × 5 cm square glass sheet into 40 or more pieces. Is observed), suggesting that the sheet has been fully quenched.

Example 7 - was preheated for 10 minutes Borofloat-33 glass plate having a thickness of 3.3mm at 550 ° C., then transferred to a hot zone, where maintained at T ₀ of 800 ° C. 30 seconds. After equilibration, it is quickly transferred to a quench zone with a gap of 119 μm where it is maintained for 10 seconds. The resulting article has a flatness of 120 μm. When partly crushed, this glass plate “dices” (using the standard terminology for dicing sheets with a thickness of 2 mm or more, ie a square glass plate of 5 × 5 cm has more than 40 It is observed that the sheet has been fully quenched.

Example 8-A 3.2 mm thick soda lime silicate glass plate is preheated at 450 ° C. for 10 minutes and then transferred to a hot zone where it is maintained at T ₀ of 690 ° C. for 30 seconds. After equilibration, it is quickly transferred to a quench zone with a 84 μm gap where it is maintained for 10 seconds. The resulting article has a surface compression of −218 MPa, a median tension of 105 MPa, and a flatness of 84 μm.

Example 9-A 0.3 mm thick soda lime silicate glass plate is preheated at 450 ° C for 10 minutes and then transferred to a hot zone where it is maintained at T ₀ at 630 ° C for 10 seconds. After equilibration, it is quickly transferred to a quench zone with a gap of 159 μm where it is maintained for 10 seconds. The resulting article has a film stress that can be observed by gray field polarimetry, suggesting that the glass contains thermal stress.

Example 10-A 0.1 mm thick "CORNING""GORILLA" Glass plate is preheated at 550 ° C for 10 minutes and then transferred to a hot zone where it is maintained at a T ₀ of 820 ° C for 10 seconds. After equilibration, if it is quickly transferred to a quench zone with a gap of 141 μm and maintained there for 10 seconds, an effective heat transfer coefficient of 0.033 cal / (cm ² · s · ° C.) (1382 W / m ² K) is obtained. It is done. When crushed, the resulting article exhibits behavior consistent with glass with residual stress.

Example 11-A 1.1 mm thick soda lime silicate glass plate is preheated at 450 ° C. for 10 minutes and then transferred to a hot zone where it is maintained at 700 ° C. T ₀ for 10 seconds. After equilibration, if transferred quickly to a quench zone with a gap of 65 μm and maintained there for 10 seconds, an effective heat transfer coefficient of 0.07 cal / (cm ² · s · ° C.) (2931 W / m ² K) is obtained. It is done. The obtained article has a measured surface fictive temperature of 657 ° C., a surface compression of −201 MPa, a central tension of 98 MPa, a flatness of 158 μm, and a Vickers crack threshold of 10 to 20 N.

Example 12-A 1.1 mm thick "CORNING""GORILLA" Glass plate is preheated at 550 ° C for 10 minutes and then transferred to a hot zone where it is maintained at a T ₀ of 810 ° C for 10 seconds. After equilibration, if transferred quickly to a quench zone with a gap of 86 μm and maintained there for 10 seconds, an effective heat transfer coefficient of 0.058 cal / (cm ² · s · ° C.) (2428 W / m ² K) is obtained. It is done. The obtained article has a measured surface fictive temperature of 711 ° C., a surface compression of −201 MPa, a median tension of 67 MPa, and a Vickers crack threshold of 20 to 30 N.

Example 13-A 1.1 mm thick "CORNING""GORILLA" Glass plate is preheated at 550 ° C for 10 minutes and then transferred to a hot zone where it is maintained at a T ₀ of 800 ° C for 10 seconds. After equilibration, it is quickly transferred to a quench zone with a 91 μm gap where it is maintained for 10 seconds. The obtained article has a measured surface fictive temperature of 747 ° C., a surface compression of −138 MPa, a median tension of 53 MPa, a flatness of 66 μm, and a Vickers crack threshold of 20 to 30 N.

  Additional Examples-Helium gas and a 5.7 mm thick sheet of glass containing at least 70% by weight silicon dioxide and / or at least 10% by weight sodium oxide and / or at least 7% by weight calcium oxide. Experiments were performed with gaps 204a, 204b (FIG. 21) of about 90 micrometers. The glass was heated to an initial temperature of about 690 ° C. and cooled rapidly. The resulting reinforced article had a negative tensile stress of about 300 Pa on its surface and a positive tensile stress of about 121 MPa at the center. Further, the flatness of the obtained reinforced article was about 106.9 micrometers.

  Additional Examples-In one experiment using the inventive technique disclosed herein, at least 70 wt% silicon dioxide, and / or at least 10 wt% sodium oxide, and / or at least 7 wt% oxidation Experiments were conducted on a 1.1 mm thick sheet of glass containing calcium with helium gas and gaps 204a, 204b (FIG. 21) of approximately 160 micrometers. The glass was heated to an initial temperature of about 680 ° C. and cooled rapidly. The resulting reinforced article had a negative tensile stress of about 112 Pa on its surface and a positive tensile stress of about 54 MPa at the center. Prior to tempering, the flatness of the sheet of glass was about 96 micrometers, while the flatness of the resulting reinforced article was about 60 micrometers. Therefore, this tempering process also made the tempered glass-based article flat.

Aspect (1) of the present disclosure is the vehicle laminate, wherein the laminate has a first glass-based layer; and has the same extent as the first glass-based layer. At least one intermediate layer bonded directly or indirectly to the side of the glass-based layer; a first main surface, a second main surface opposite the first main surface and defining a thickness t And a second glass-based layer including an inner region located between the first and second major surfaces; the second glass-based layer being at least partially with the at least one intermediate layer And is bonded directly or indirectly to the intermediate layer opposite the first glass-based layer; the first main surface and the second main surface of the second glass-based layer One or both of the surfaces has a stress birefringence of about 10 nm / cm or less; the first glass-based layer first The ionic content and chemical composition of at least a portion of both the surface and the second major surface are the same as the ionic content and chemical composition of at least a portion of the internal region of the second glass-based layer; One or both of the first and second main surfaces of the second glass-based layer have a surface compressive stress of more than 150 MPa; the surface of the first or second main surface of the second glass-based layer Roughness refers to a laminate that is an R _a roughness between 0.2 nm and 2.0 nm over an area of about 15 micrometers × 15 micrometers.

  Aspect (2) of the present disclosure relates to the laminate of aspect (1), wherein the thickness of the second glass-based layer is less than 2 mm.

  Aspect (3) of the present disclosure relates to the laminate of aspect (1) or aspect (2), wherein the thickness of the second glass-based layer is in the range from about 0.3 mm to about 2 mm.

  According to the aspect (4) of the present disclosure, a compression depth (DOC) in which the surface compressive stress is about 17% or more of the thickness from one or both of the first main surface and the second main surface. The present invention relates to any one of the laminates extending from (1) to (3).

Aspect (5) of the present disclosure relates to a laminate according to any one of Aspects (1) to (4), wherein the surface roughness is _{a Ra} roughness of 0.2 nm to 1.5 nm over the area.

  In the aspect (6) of the present disclosure, the first and second main surfaces of the second glass-based layer are along a 50 mm profile of the first and second main surfaces of the second glass-based layer. The present invention relates to a laminate according to any one of modes (1) to (5), which is flat with a core runout accuracy of at least 50 μm.

  In the aspect (7) of the present disclosure, the material of the intermediate layer is polyvinyl butyral (PVB), polycarbonate, soundproof PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomer, thermoplastic material, and their It is related with the laminated body in any one of aspect (1) to aspect (6) containing the material selected from the group which consists of a combination.

  Aspect (8) of the present disclosure relates to any one of the laminates of Aspects (1) to (7), wherein the first glass-based layer is soda-lime glass.

  Aspect (9) of the present disclosure relates to a laminate according to any one of Aspects (1) to (8), wherein the second glass-based layer includes the same glass material as the first glass-based layer.

  Aspect (10) of the present disclosure provides that the first glass-based layer is a thermally strengthened glass layer, a chemically strengthened glass layer, a mechanically strengthened glass layer, a thermally and chemically strengthened The present invention relates to a laminate according to any one of aspects (1) to (9), comprising a glass layer, a thermally and mechanically reinforced glass layer, or a chemically and mechanically reinforced glass layer.

  Aspect (11) of the present disclosure is such that the second glass-based layer is a thermally strengthened glass layer, a chemically strengthened glass layer, a mechanically strengthened glass layer, a thermally and chemically strengthened layer. The present invention relates to a laminate according to any one of aspects (1) to (10), comprising a glass layer, a thermally and mechanically reinforced glass layer, or a chemically and mechanically reinforced glass layer.

  Aspect (12) of the present disclosure relates to a laminate according to any one of aspects (1) to (11), wherein the average thickness of the second glass-based layer is from about 0.1 mm to about 1.5 mm.

  Aspect (13) of the present disclosure relates to any one of the laminates of Aspects (1) to (12), wherein the average thickness of the first glass-based layer is about 6 mm or less.

  Aspect (14) of the present disclosure relates to a laminate according to any one of Aspects (1) to (13), in which the average thicknesses of the first and second glass-based layers are different.

  Aspect (15) of the present disclosure relates to a laminate according to any one of aspects (1) to (13), wherein one of the first glass-based layer and the second glass-based layer is cold-formed. .

  Aspect (16) of the present disclosure is characterized in that the first glass-based layer is complicatedly curved and has a thickness therebetween, at least one concave surface providing the first surface of the laminate, and the first surface A third surface of the laminate having at least one convex surface that provides a second surface of the laminate opposite to the first, and wherein the second glass-based layer is complicatedly curved and has a thickness therebetween At least one concave surface for providing a fourth surface of the laminate opposite to the third surface; and the fourth surface has a compressive stress value greater than the compressive stress value of the third surface. It has to the laminated body of aspect (15) in which this 3rd surface and 4th surface have a compressive stress value so that it may have.

  Aspect (17) of the present disclosure relates to any one of the laminates according to aspects (1) to (16), wherein the laminate is in an opening of a vehicle.

  Aspect (18) of the present disclosure relates to the stacked body according to aspect (17), wherein the opening of the vehicle forms a window or is an opening for a display.

According to an aspect (19) of the present disclosure, in a vehicle including a main body, an opening in the main body, and a structure disposed in the opening, the structure has a first main surface, opposite to the first main surface. A first glass-based layer comprising a second major surface defining a thickness and an internal region located between the first and second major surfaces; wherein the thickness is less than 2 mm The ion content and chemical composition of at least a portion of both the first main surface and the second main surface are the same as the ion content and chemical component of at least a portion of the internal region; The first main surface and the second main surface are under compressive stress, the internal region is under tensile stress; the compressive stress is greater than 150 MPa; and the surface roughness of the first main surface is Over an area of about 15 micrometers x 15 micrometers, between 0.2 nm and 1.5 nm _a a roughness, one or both of said first major surface said second major surface has an area of 2500 mm ^2, more than a vehicle.

  Aspect (20) of the present disclosure is an aspect in which the surface compressive stress extends from one or both of the first main surface and the second main surface to a depth of 17% or more of the thickness ( The vehicle of 19).

Aspect (21) of the present disclosure relates to the vehicle according to aspect (19) or aspect (20), wherein the surface roughness is _{a Ra} roughness of 0.2 nm to 1.5 nm over the area.

  Aspect (22) of the present disclosure is the aspect (19) in which the first and second main surfaces are flat with a core runout accuracy of at least 50 μm along the 50 mm profile of the first and second main surfaces. ) To aspect (21).

  Aspect (23) of the present disclosure further includes a second glass-based layer and at least one intermediate layer between the first glass-based layer and the second glass-based layer. Aspect (22) relates to any one vehicle.

  Aspect (24) of the present disclosure provides that the intermediate layer comprises polyvinyl butyral (PVB), polycarbonate, soundproof PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastic materials, and combinations thereof. The vehicle according to aspect (23) is made of a material selected from the group consisting of:

  Aspect (25) of the present disclosure relates to the vehicle according to aspect (23) or aspect (24), wherein the second glass-based layer is soda-lime glass.

  Aspect (26) of the present disclosure is such that the second glass-based layer is a thermally strengthened glass layer, a chemically strengthened glass layer, a mechanically strengthened glass layer, a thermally and chemically strengthened The invention relates to a vehicle according to any one of aspects (23) to (25), comprising a glass layer, a thermally and mechanically tempered glass layer, or a chemically and mechanically tempered glass layer.

  In the aspect (27) of the present disclosure, the average thickness of the first and second glass-based layers is 1.5 mm or less, 1.0 mm or less, and 0.7 mm or less. An average thickness of 0.5 mm or less, an average thickness in the range of about 0.5 mm to about 1.0 mm, and an average thickness of about 0.5 mm to about 0.7 mm. 23) to aspect (26) any one of the vehicles.

  Aspect (28) of the present disclosure relates to a vehicle according to any one of aspects (23) to (26), wherein the thickness of the second glass-based layer is different from the thickness of the first glass-based layer.

  Aspect (29) of the present disclosure relates to the vehicle according to any one of aspects (19) to (28), wherein the structure is an automobile window, a sunroof, or a display cover.

  Aspect (30) of the present disclosure relates to a vehicle according to any one of aspects (19) to (29), wherein the first main surface or the second main surface has a feature for tactile feedback.

Aspect (31) of the present disclosure provides a vehicle having an opening including a laminate structure, in which the laminate structure includes a first glass-based layer; a second glass-based layer; and the first glass-based layer and the first glass-based layer. At least one intermediate layer between the second glass-based layer; the second glass-based layer having a first main surface and a second main surface to define a thickness; The first main surface of the second glass-based layer is flat with a core runout accuracy (TIR) of 100 μm along an arbitrary profile of 50 mm or less of the first main surface; Is the low temperature line _CTE of α ^S _CTE expressed in 1 / ° C, the high temperature line CTE of α ^L _CTE expressed in 1 / ° C, the elastic modulus of E expressed in GPa, and T expressed in units of ° C. made of glass material having a softening temperature of T _softening expressed in units of strain temperature, and ℃ _distortion; of the second glass-based layer One major surface is less than 600MPa and is expressed in units of MPa,

Has a larger, thermally induced surface compressive stress, where P ₁ is

And P ₂ is given by

And h is related to a vehicle that is 0.020 cal / s · cm ² · ° C. (about 828 W / m ² K) or more.

  Aspect (32) of the present disclosure relates to the vehicle of aspect (31), wherein the laminate structure is movable with respect to the opening of the vehicle.

  Aspect (33) of the present disclosure relates to the vehicle of aspect (31), further comprising a display, wherein the laminate structure is disposed adjacent to the display.

  Aspect (34) of the present disclosure is that the first glass-based layer is a thermally tempered glass layer, a chemically tempered glass layer, a mechanically tempered glass layer, a thermally and chemically tempered layer. The invention relates to any one of aspects (31) to (33), comprising a glass layer, a thermally and mechanically tempered glass layer, or a chemically and mechanically tempered glass layer.

  Aspect (35) of the present disclosure is such that the first glass-based layer comprises a chemically tempered glass layer, a thermally and chemically tempered glass layer, or a chemically and mechanically tempered glass layer. In addition, the present invention relates to any one of the modes (31) to (33), wherein the second glass-based layer has a surface compressive stress of about 200 MPa or more.

  Aspect (36) of the present disclosure relates to a vehicle according to any one of aspects (31) to (35), wherein the first glass-based layer has a compression depth (DOC) of about 10 micrometers or greater.

According to an aspect (37) of the present disclosure, in a vehicle having an opening including a laminate structure, the laminate structure is at least partially coextensive with the first glass-based layer; and the first glass-based layer. And having at least one intermediate layer directly or indirectly bonded to the side of the first glass-based layer; a first major surface, separated by a thickness t, opposite the first major surface And a second glass-based layer including an internal region located between the first and second main surfaces; wherein the second glass-based layer comprises the at least one Is at least partially coextensive with the intermediate layer and is directly or indirectly bonded to the intermediate layer opposite the first glass-based layer; the first main of the second glass-based layer A surface is along any 50 mm or less profile of the first major surface of the second glass-based layer, Is flat at 00μm the runout accuracy (TIR); wherein the second glass-based layer has a softening temperature of T _softening expressed in units of ° C., cooling temperature of T _annealing, expressed in units of ° C., And made from glass having a fictive surface temperature measured on the first major surface of the second glass-based layer, expressed as T _fs , when expressed in units of and ° C. The layer has a dimensionless surface virtual temperature parameter θs given by (T _fs −T _{slow cooling} ) / (T _softening− T _{slow cooling} ), which parameter θs is in the range of 0.20 to 0.9. Regarding vehicles.

  Aspect (38) of the present disclosure relates to the vehicle according to aspect (37), wherein the first glass-based layer is soda-lime glass.

  Aspect (39) of the present disclosure relates to the vehicle according to aspect (37) or aspect (38), wherein the second glass-based layer includes the same glass material as the first glass-based layer.

  Aspect (40) of the present disclosure relates to a vehicle according to any one of aspects (37) to (39), wherein one of the first glass-based layer and the second glass-based layer is cold-formed.

  Aspect (41) of the present disclosure is such that the material of the intermediate layer is polyvinyl butyral (PVB), polycarbonate, soundproof PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomer, thermoplastic material, and their The present invention relates to a vehicle according to any one of aspects (37) to (40), including a material selected from the group consisting of combinations.

  In the aspect (42) of the present disclosure, any one or more of the intermediate layer, the first glass-based layer, and the second glass-based layer includes a first edge having a first thickness and the first glass layer. The present invention relates to the vehicle according to any one of aspects (37) to (41), wherein the vehicle has a second edge that is opposite to the first edge and has a second thickness that is greater than one thickness.

  Aspect (43) of the present disclosure is such that the first glass-based layer is a thermally strengthened glass layer, a chemically strengthened glass layer, a mechanically strengthened glass layer, a thermally and chemically strengthened The invention relates to a vehicle according to any one of aspects (37) to (42), comprising a glass layer, a thermally and mechanically tempered glass layer, or a chemically and mechanically tempered glass layer.

  Aspect (44) of the present disclosure provides that the first glass-based layer comprises a chemically tempered glass layer, a thermally and chemically tempered glass layer, or a chemically and mechanically tempered glass layer. In addition, the present invention relates to the vehicle according to any one of aspects (37) to (43), wherein the second glass-based layer has a surface compressive stress of about 200 MPa or more.

  Aspect (45) of the present disclosure relates to a vehicle according to any one of aspects (37) to (44), wherein the first glass-based layer has a compressive stress layer depth (DOL) of about 10 micrometers or more. .

  Aspect (46) of the present disclosure relates to the vehicle according to any one of aspects (37) to (45), wherein the laminate structure is an automobile window, a sunroof, or a display cover.

  Aspect (47) of the present disclosure relates to a vehicle according to any one of aspects (37) to (46), wherein the laminate structure is movable with respect to an opening of the vehicle.

Aspect (48) of the present disclosure is an automobile having an inner surface; a glass-based layer disposed on the inner surface, wherein the second main surface is opposite to the first main surface and the first main surface. A glass-based layer having a surface and defining a thickness t; the glass-based layer is a low temperature line CTE of α ^S _CTE represented by 1 / ° C., α ^L _CTE represented by 1 / ° C. A high temperature line CTE, an elastic modulus of E expressed in GPa, a strain temperature of T _strain expressed in ° C and a softening temperature of T _softening expressed in ° C; The first main surface of the glass-based layer is expressed in units of less than 600 MPa and MPa.

Has a larger, thermally induced surface compressive stress, where P ₁ is

And P ₂ is given by

And h is related to a vehicle that is 0.020 cal / s · cm ² · ° C. (about 828 W / m ² K) or more.

  Aspect (49) of the present disclosure relates to the vehicle of aspect (48), wherein the surface compressive stress extends to a compression depth of about 0.17 × t or greater.

  Aspect (50) of the present disclosure relates to the vehicle of aspect (48) or aspect (49), wherein the glass-based layer has a compressive stress layer depth (DOL) of about 10 micrometers or greater.

  Aspect (51) of the present disclosure relates to a vehicle according to any one of aspects (48) to (50), wherein the internal surface includes a display, and the glass-based layer is disposed on the display.

  In the aspect (52) of the present disclosure, the first main surface of the glass-based layer is flat with a center runout accuracy (TIR) of 100 μm along an arbitrary profile of 50 nm or less of the first main surface. , Aspect (48) to Aspect (51).

In the aspect (53) of the present disclosure, the glass-based layer is represented by a softening temperature of T _softening expressed in units of ° C, a _{slow cooling} temperature of T _{slow cooling} expressed in units of ° C, and a unit of ° C. The glass-based layer has a surface fictive temperature measured on the first major surface of the glass-based layer, denoted by T _fs , and the glass-based layer is (T _fs -T _{slow cooling} ) / ( A dimensionless surface fictive temperature parameter θs given by (T _softening− T _{slow cooling} ), the parameter θs being in the range of 0.20 to 0.9, any one of aspects (48) to (52) Regarding vehicles.

  Aspect (54) of the present disclosure relates to a vehicle according to any one of aspects (48) to (53), wherein the glass-based layer is soda-lime glass.

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

  The structure and configuration of automotive glass-based sheets and laminates, as shown in the various exemplary embodiments, are merely illustrative. Although only some embodiments have been described in detail in this disclosure, many modifications (eg, size, dimensions, structure, etc.) have been made without substantially departing from the novel teachings and advantages of the subject matter described herein. The shape and ratio of various elements, parameter values, mounting arrangements, material use, color, orientation changes) are possible. Some elements illustrated as being integrally molded may be made up of a number of parts or elements, and the position of those elements may be reversed or otherwise changed and separated. The nature or number of elements or positions of can be varied or different. The order or order of the steps of any process, logic algorithm, or method may be varied or rearranged according to alternative embodiments. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the various exemplary embodiments without departing from the scope of the present technology.

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

Embodiment 1
In the vehicle laminate, the laminate is:
A first glass-based layer;
At least one intermediate layer that is at least partially coextensive with the first glass-based layer and is bonded directly or indirectly to the side of the first glass-based layer;
A first main surface, a second main surface opposite the first main surface and defining a thickness t, and a second including an internal region located between the first and second main surfaces A glass-based layer of
With
The second glass-based layer is at least partially coextensive with the at least one intermediate layer and is directly or indirectly bonded to the intermediate layer opposite the first glass-based layer. ,
One or both of the first main surface and the second main surface of the second glass-based layer have a stress birefringence of about 10 nm / cm or less, and the first main surface of the second glass-based layer The ion content and chemical composition of at least a portion of both the surface and the second major surface is the same as the ion content and chemical composition of at least a portion of the internal region of the second glass-based layer;
Either one or both of the first and second main surfaces of the second glass-based layer have a surface compressive stress of more than 150 MPa,
The surface roughness of the first or second major surface of the second glass-based layer is an _Ra roughness between 0.2 nm and 2.0 nm over an area of about 15 micrometers x 15 micrometers. There is a laminate.

Embodiment 2
The laminate according to embodiment 1, wherein the thickness of the second glass-based layer is less than 2 mm.

Embodiment 3
The laminate according to embodiment 1 or 2, wherein the thickness of the second glass-based layer is in the range of about 0.3 mm to about 2 mm.

Embodiment 4
From Embodiment 1, wherein the surface compressive stress extends from one or both of the first major surface and the second major surface to a compression depth (DOC) of about 17% or more of the thickness. 3. Laminated body as described in any one of 3.

Embodiment 5
The laminate according to any one of Embodiments 1 to 4, wherein the surface roughness is _{a Ra} roughness of 0.2 nm to 1.5 nm over the area.

Embodiment 6
The first and second main surfaces of the second glass-based layer are flat with a core runout accuracy of at least 50 μm along the 50 mm profile of the first and second main surfaces of the second glass-based layer. The laminated body according to any one of Embodiments 1 to 5.

Embodiment 7
The intermediate layer material is selected from the group consisting of polyvinyl butyral (PVB), polycarbonate, soundproof PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastic materials, and combinations thereof. The laminated body as described in any one of Embodiment 1 to 6 containing this.

Embodiment 8
The laminated body according to any one of Embodiments 1 to 7, wherein the first glass-based layer is soda-lime glass.

Embodiment 9
The laminated body according to any one of Embodiments 1 to 8, wherein the second glass-based layer contains the same glass material as the first glass-based layer.

Embodiment 10
The first glass-based layer is a thermally tempered glass layer, a chemically tempered glass layer, a mechanically tempered glass layer, a thermally and chemically tempered glass layer, thermally and mechanically Embodiment 10. A laminate according to any one of embodiments 1 to 9, comprising a tempered glass layer or a chemically and mechanically tempered glass layer.

Embodiment 11
The second glass-based layer is a thermally tempered glass layer, a chemically tempered glass layer, a mechanically tempered glass layer, a thermally and chemically tempered glass layer, thermally and mechanically Embodiment 11. A laminate according to any one of embodiments 1 to 10, comprising a tempered glass layer or a chemically and mechanically tempered glass layer.

Embodiment 12
The laminate of any one of embodiments 1 to 11, wherein the average thickness of the second glass-based layer is from about 0.1 mm to about 1.5 mm.

Embodiment 13
The laminated body according to any one of Embodiments 1 to 12, wherein the average thickness of the first glass-based layer is about 6 mm or less.

Embodiment 14
The laminated body according to any one of Embodiments 1 to 13, wherein the average thicknesses of the first and second glass-based layers are different.

Embodiment 15
The laminated body according to any one of Embodiments 1 to 14, wherein one of the first glass-based layer and the second glass-based layer is cold-formed.

Embodiment 16
At least one concave surface providing a first surface of the laminate and a second of the laminate opposite the first surface, the first glass-based layer being intricately curved and having a thickness therebetween Having at least one convex surface providing a surface;
The second glass-based layer is intricately curved and has a thickness therebetween, at least one concave surface providing a third surface of the laminate, and a fourth of the laminate opposite the third surface. Having at least one convex surface providing a surface;
The laminate according to embodiment 15, wherein the third surface and the fourth surface each have a compressive stress value such that the fourth surface has a compressive stress value greater than the compressive stress value of the third surface.

Embodiment 17
Embodiment 17. The laminate according to any one of Embodiments 1 to 16, wherein the laminate is in a vehicle opening.

Embodiment 18
The laminate according to embodiment 17, wherein the opening of the vehicle forms a window or is an opening for a display.

Embodiment 19
In a vehicle having a main body, an opening in the main body, and a structure disposed in the opening, the structure includes:
A first main surface, a second main surface opposite the first main surface and defining a thickness, and a first region comprising an interior region located between the first and second main surfaces Glass-based layer,
Have
The thickness is less than 2 mm;
The ion content and chemical composition of at least a portion of both the first main surface and the second main surface are the same as the ion content and chemical component of at least a portion of the internal region,
The first main surface and the second main surface are under compressive stress, and the inner region is under tensile stress;
The compressive stress is greater than 150 MPa;
The surface roughness of the first major surface is _Ra roughness between 0.2 nm and 1.5 nm over an area of approximately 15 micrometers x 15 micrometers;
The vehicle, wherein one or both of the first main surface and the second main surface has an area greater than 2500 mm ² .

Embodiment 20.
The vehicle according to embodiment 19, wherein the surface compressive stress extends from one or both of the first main surface and the second main surface to a depth of 17% or more of the thickness.

Embodiment 21.
The vehicle according to embodiment 19 or 20, wherein the surface roughness is _{a Ra} roughness of 0.2 nm to 1.5 nm over the area.

Embodiment 22
The first and second major surfaces according to any one of embodiments 19 to 21, wherein the first and second major surfaces are flat with a runout accuracy of at least 50 μm along the 50 mm profile of the first and second major surfaces. vehicle.

Embodiment 23
Embodiment 23. The vehicle according to any one of embodiments 19 to 22, further comprising a second glass-based layer and at least one intermediate layer between the first glass-based layer and the second glass-based layer.

Embodiment 24.
The intermediate layer is made from a material selected from the group consisting of polyvinyl butyral (PVB), polycarbonate, soundproof PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastic materials, and combinations thereof. Embodiment 24. The vehicle according to embodiment 23.

Embodiment 25
The vehicle according to embodiment 23 or 24, wherein the second glass-based layer is soda-lime glass.

Embodiment 26.
The second glass-based layer is a thermally tempered glass layer, a chemically tempered glass layer, a mechanically tempered glass layer, a thermally and chemically tempered glass layer, thermally and mechanically Embodiment 26. The vehicle according to any one of embodiments 23 to 25, comprising a tempered glass layer or a chemically and mechanically tempered glass layer.

Embodiment 27.
The average thickness of the first and second glass-based layers is 1.5 mm or less, 1.0 mm or less, 0.7 mm or less, 0.5 mm or less. Embodiment 23. Any one of Embodiments 23 to 26 selected from the group consisting of: an average thickness in the range of about 0.5 mm to about 1.0 mm; and an average thickness of about 0.5 mm to about 0.7 mm. Vehicle.

Embodiment 28.
28. The vehicle according to any one of embodiments 23 to 27, wherein the thickness of the second glass-based layer is different from the thickness of the first glass-based layer.

Embodiment 29.
29. A vehicle according to any one of embodiments 19 to 28, wherein the structure is a car window, sunroof, or display cover.

Embodiment 30.
Embodiment 30. The vehicle according to any one of embodiments 19 to 29, wherein the first main surface or the second main surface has features for tactile feedback.

Embodiment 31.
In a vehicle having an opening including a laminate structure, the laminate structure is:
The first glass-based layer,
A second glass-based layer, and at least one intermediate layer between the first glass-based layer and the second glass-based layer;
With
The second glass-based layer includes a first main surface and a second main surface to define a thickness, and the first main surface of the second glass-based layer is the first main surface. Along with any 50 mm or less profile of 100 μm with a runout accuracy (TIR) of 100 μm,
The second glass-based layer is composed of α ^S _CTE low-temperature line CTE expressed in 1 / ° C., α ^L _CTE high-temperature line CTE expressed in 1 / ° C., E elastic modulus expressed in GPa, Made of a glass material having a strain temperature of T _strain expressed in units of T, and a softening temperature of T _softening expressed in units of ° C.
The first main surface of the second glass-based layer is expressed in units of less than 600 MPa and MPa.

Has a larger, thermally induced surface compressive stress, where P ₁ is

And P ₂ is given by

And h is 0.020 cal / s · cm ² · ° C. (about 828 W / m ² K) or more.

Embodiment 32.
Embodiment 32. The vehicle of embodiment 31 wherein the laminate structure is movable with respect to the vehicle opening.

Embodiment 33.
The vehicle of embodiment 31, further comprising a display, wherein the laminate structure is disposed adjacent to the display.

Embodiment 34.
The first glass-based layer is a thermally tempered glass layer, a chemically tempered glass layer, a mechanically tempered glass layer, a thermally and chemically tempered glass layer, thermally and mechanically Embodiment 34. The vehicle according to any one of embodiments 31 to 33, comprising a tempered glass layer or a chemically and mechanically tempered glass layer.

Embodiment 35.
The first glass-based layer comprises a chemically tempered glass layer, a thermally and chemically tempered glass layer, or a chemically and mechanically tempered glass layer, and the second glass-based layer 34. The vehicle according to any one of embodiments 31 to 33, wherein the vehicle has a surface compressive stress of about 200 MPa or greater.

Embodiment 36.
36. The vehicle according to any one of embodiments 31-35, wherein the first glass-based layer has a depth of compression (DOC) of about 10 micrometers or greater.

Embodiment 37.
In a vehicle having an opening including a laminate structure, the laminate structure is:
A first glass-based layer;
At least one intermediate layer that is at least partially coextensive with the first glass-based layer and is bonded directly or indirectly to the side of the first glass-based layer;
A first main surface, a second main surface separated by a thickness t and opposite the first main surface, and a second including an interior region located between the first and second main surfaces A glass-based layer of
With
The second glass-based layer is at least partially coextensive with the at least one intermediate layer and is directly or indirectly bonded to the intermediate layer opposite the first glass-based layer. ,
The first main surface of the second glass-based layer is flat with a center deflection accuracy (TIR) of 100 μm along an arbitrary profile of 50 mm or less of the first main surface of the second glass-based layer. Yes,
The second glass-based layer has a softening temperature of T _softening expressed in units of ° C, an _annealing temperature of T _{slow cooling} expressed in units of ° C, and, when expressed in units of ° C, _Tfs . Made of glass having a surface fictive temperature measured on the first major surface of the second glass-based layer shown,
The second glass-based layer has a dimensionless surface virtual temperature parameter θs given by (T _fs −T _{slow cooling} ) / (T _softening− T _{slow cooling} ),
The vehicle wherein the parameter θs is in the range of 0.20 to 0.9.

Embodiment 38.
The vehicle according to embodiment 37, wherein the first glass-based layer is soda-lime glass.

Embodiment 39.
The vehicle according to embodiment 37 or 38, wherein the second glass-based layer comprises the same glass material as the first glass-based layer.

Embodiment 40.
The vehicle according to any one of Embodiments 37 to 39, wherein one of the first glass-based layer and the second glass-based layer is cold-formed.

Embodiment 41.
The intermediate layer material is selected from the group consisting of polyvinyl butyral (PVB), polycarbonate, soundproof PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastic materials, and combinations thereof. 41. The vehicle according to any one of embodiments 37-40, comprising:

Embodiment 42.
Any one or more of the intermediate layer, the first glass-based layer, and the second glass-based layer have a first edge having a first thickness and a second thickness that is thicker than the first thickness. 42. A vehicle according to any one of embodiments 37 to 41, having a second edge opposite the first edge.

Embodiment 43.
The first glass-based layer is a thermally tempered glass layer, a chemically tempered glass layer, a mechanically tempered glass layer, a thermally and chemically tempered glass layer, thermally and mechanically 43. A vehicle according to any one of embodiments 37 to 42, comprising a tempered glass layer or a chemically and mechanically tempered glass layer.

Embodiment 44.
The first glass-based layer comprises a chemically tempered glass layer, a thermally and chemically tempered glass layer, or a chemically and mechanically tempered glass layer, and the second glass-based layer Embodiment 44. The vehicle according to any one of embodiments 37 to 43, wherein the vehicle has a surface compressive stress of about 200 MPa or greater.

Embodiment 45.
45. The vehicle of any one of embodiments 37 to 44, wherein the first glass-based layer has a compressive stress layer depth (DOL) of about 10 micrometers or greater.

Embodiment 46.
46. The vehicle according to any one of embodiments 37 to 45, wherein the laminate structure is a car window, sunroof, or display cover.

Embodiment 47.
47. A vehicle according to any one of embodiments 37 to 46, wherein the laminate structure is movable with respect to the opening of the vehicle.

Embodiment 48.
In the vehicle,
An internal surface,
A glass-based layer disposed on the inner surface, wherein the glass-based layer has a first main surface and a second main surface opposite to the first main surface, and defines a thickness t; ,
With
The glass-based layer has an α ^S _CTE low-temperature line CTE represented by 1 / ° C., an α ^L _CTE high-temperature line CTE represented by 1 / ° C., an elastic modulus of E represented by GPa, and in units of ° C. Made from a glass material having a strain temperature of T _strain expressed, and a softening temperature of T _softening expressed in units of ° C;
The first main surface of the glass-based layer is expressed in units of less than 600 MPa and MPa.

Has a larger, thermally induced surface compressive stress, where P ₁ is

And P ₂ is given by

And h is 0.020 cal / s · cm ² · ° C. (about 828 W / m ² K) or more.

Embodiment 49.
49. The vehicle of embodiment 48, wherein the surface compressive stress extends to a compression depth of about 0.17 × t or greater.

Embodiment 50.
49. The vehicle of embodiment 48, wherein the glass-based layer has a compressive stress layer depth (DOL) of about 10 micrometers or greater.

Embodiment 51.
51. A vehicle according to embodiment 48 or 50, wherein the internal surface comprises a display and the glass-based layer is disposed on the display.

Embodiment 52.
Any one of embodiments 48 to 51, wherein the first principal surface of the glass-based layer is flat with a core runout accuracy (TIR) of 100 μm along any 50 nm or less profile of the first principal surface. Vehicle described in one.

Embodiment 53.
When the glass-based layer is represented by a softening temperature of T _softening expressed in units of ° C, an _annealing temperature of T _{slow cooling} expressed in units of ° C, and a unit of ° C, it is represented by _Tfs . Made of glass having a fictive surface temperature measured on the first major surface of the glass-based layer;
The glass-based layer has a dimensionless surface virtual temperature parameter θs given by (T _fs −T _{slow cooling} ) / (T _softening− T _{slow cooling} ),
53. The vehicle according to any one of embodiments 48 to 52, wherein the parameter θs is in the range of 0.20 to 0.9.

Embodiment 54.
54. The vehicle according to any one of embodiments 48-53, wherein the glass-based layer is soda lime glass.

200 High-temperature glass sheet 200a, 510 First main surface 200b, 520 Second main surface 201a, 201b Heat sink 204a, 204b Gap 206 Opening, pore 230 Gas 300 Automotive glass strengthening system 310 High-temperature zone 312, 332 Gas bearing 314 Cartridge heater 318 High temperature air plenum 320 Transfer gas bearing 328 Transfer gas bearing plenum 330 Low temperature zone 331 Solid heat sink 334 Passage 400a, 400b Automotive glass sheet 500, 610, 1212, 1214, 1216, 1310 Automotive glass-based article or sheet 522 Main body 530, 540 Area of compressive stress, part 550 Area of tensile stress, part 612 Office thumbtack 614 Length of metal pin 616 Granular mass 1010 Structure 1012, 1112 Glass-based article 1110 Surface 1210 Device 1218 Electrical component, electronic component 1220 Housing 1222 Substrate 1410 Laminate for automobile 1412, 1512 First glass-based layer 1414, 1514 Intermediate layer 1416, 1516 Second glass-based layer 1510 Cold-formed laminated body 1600 Vehicle 1610 Vehicle body 1620 Opening 1630 Glass-based article

Claims (15)

In the vehicle laminate, the laminate is:
A first glass-based layer;
At least one intermediate layer that is at least partially coextensive with the first glass-based layer and is bonded directly or indirectly to the side of the first glass-based layer;
A first main surface, a second main surface opposite the first main surface and defining a thickness t, and a second including an internal region located between the first and second main surfaces A glass-based layer of
With
The second glass-based layer is at least partially coextensive with the at least one intermediate layer and is directly or indirectly bonded to the intermediate layer opposite the first glass-based layer. ,
One or both of the first main surface and the second main surface of the second glass-based layer have a stress birefringence of about 10 nm / cm or less, and the first main surface of the second glass-based layer The ion content and chemical composition of at least a portion of both the surface and the second major surface is the same as the ion content and chemical composition of at least a portion of the internal region of the second glass-based layer;
Either one or both of the first and second main surfaces of the second glass-based layer have a surface compressive stress of more than 150 MPa,
The surface roughness of the first or second major surface of the second glass-based layer is an _Ra roughness between 0.2 nm and 2.0 nm over an area of about 15 micrometers x 15 micrometers. There is a laminate.   The laminate according to claim 1, wherein the second glass-based layer is cold-formed. At least one concave surface providing a first surface of the laminate and a second of the laminate opposite the first surface, the first glass-based layer being intricately curved and having a thickness therebetween Having at least one convex surface providing a surface;
The second glass-based layer is intricately curved and has a thickness therebetween, at least one concave surface providing a third surface of the laminate, and a fourth of the laminate opposite the third surface. Having at least one convex surface providing a surface;
The laminate according to claim 1 or 2, wherein each of the third surface and the fourth surface has a compressive stress value such that the fourth surface has a compressive stress value larger than that of the third surface.   The laminate according to any one of claims 1 to 3, wherein the thickness of the second glass-based layer is less than 2 mm.   The first and second main surfaces of the second glass-based layer are flat with a core runout accuracy of at least 50 μm along the 50 mm profile of the first and second main surfaces of the second glass-based layer. The laminate according to claim 1 or 4, wherein there is a laminate.   The laminate according to any one of claims 1 to 5, wherein the first and second glass-based layers are soda-lime glass.   The laminate according to any one of claims 1 to 6, wherein the second glass-based layer has an average thickness of about 0.1 mm to about 1.5 mm.   The laminate according to any one of claims 1 to 7, wherein the first and second glass-based layers have different average thicknesses.   The laminate according to any one of claims 1 to 8, wherein the laminate is in an opening of a vehicle. In a vehicle having a main body, an opening in the main body, and a structure disposed in the opening, the structure includes:
A first main surface, a second main surface opposite the first main surface and defining a thickness, and a first region comprising an interior region located between the first and second main surfaces Glass-based layer,
Have
The thickness is less than 2 mm;
The ion content and chemical composition of at least a portion of both the first main surface and the second main surface are the same as the ion content and chemical component of at least a portion of the internal region,
The first main surface and the second main surface are under compressive stress, and the inner region is under tensile stress;
The compressive stress is greater than 150 MPa;
The surface roughness of the first major surface is _Ra roughness between 0.2 nm and 1.5 nm over an area of approximately 15 micrometers x 15 micrometers;
The vehicle, wherein one or both of the first main surface and the second main surface has an area greater than 2500 mm ² .   The vehicle of claim 11, further comprising a second glass-based layer and at least one intermediate layer between the first glass-based layer and the second glass-based layer.   The average thickness of the first and second glass-based layers is 1.5 mm or less, 1.0 mm or less, 0.7 mm or less, 0.5 mm or less. 13. The vehicle of claim 11 or 12, wherein the vehicle is selected from the group consisting of: an average thickness in the range of about 0.5 mm to about 1.0 mm, and an average thickness of about 0.5 mm to about 0.7 mm. In a vehicle having an opening including a laminate structure, the laminate structure is:
The first glass-based layer,
A second glass-based layer, and at least one intermediate layer between the first glass-based layer and the second glass-based layer;
With
The second glass-based layer includes a first main surface and a second main surface to define a thickness, and the first main surface of the second glass-based layer is the first main surface. Along with any 50 mm or less profile of 100 μm with a runout accuracy (TIR) of 100 μm,
The second glass-based layer is composed of α ^S _CTE low-temperature line CTE expressed in 1 / ° C., α ^L _CTE high-temperature line CTE expressed in 1 / ° C., E elastic modulus expressed in GPa, Made of a glass material having a strain temperature of T _strain expressed in units of T, and a softening temperature of T _softening expressed in units of ° C.
The first main surface of the second glass-based layer is expressed in units of less than 600 MPa and MPa.

Has a larger, thermally induced surface compressive stress, where P ₁ is

And P ₂ is given by

And h is 0.020 cal / s · cm ² · ° C. (about 828 W / m ² K) or more. In a vehicle having an opening including a laminate structure, the laminate structure is:
A first glass-based layer;
At least one intermediate layer that is at least partially coextensive with the first glass-based layer and is bonded directly or indirectly to the side of the first glass-based layer;
A first main surface, a second main surface separated by a thickness t and opposite the first main surface, and a second including an interior region located between the first and second main surfaces A glass-based layer of
With
The second glass-based layer is at least partially coextensive with the at least one intermediate layer and is directly or indirectly bonded to the intermediate layer opposite the first glass-based layer. ,
The first main surface of the second glass-based layer is flat with a center deflection accuracy (TIR) of 100 μm along an arbitrary profile of 50 mm or less of the first main surface of the second glass-based layer. Yes,
The second glass-based layer has a softening temperature of T _softening expressed in units of ° C, an _annealing temperature of T _{slow cooling} expressed in units of ° C, and, when expressed in units of ° C, _Tfs . Made of glass having a surface fictive temperature measured on the first major surface of the second glass-based layer shown,
The second glass-based layer has a dimensionless surface virtual temperature parameter θs given by (T _fs −T _{slow cooling} ) / (T _softening− T _{slow cooling} ),
The vehicle wherein the parameter θs is in the range of 0.20 to 0.9. In the vehicle,
An internal surface,
A glass-based layer disposed on the inner surface, wherein the glass-based layer has a first main surface and a second main surface opposite to the first main surface, and defines a thickness t; ,
With
The glass-based layer has an α ^S _CTE low-temperature line CTE represented by 1 / ° C., an α ^L _CTE high-temperature line CTE represented by 1 / ° C., an elastic modulus of E represented by GPa, and in units of ° C. Made from a glass material having a strain temperature of T _strain expressed, and a softening temperature of T _softening expressed in units of ° C;
The first main surface of the glass-based layer is expressed in units of less than 600 MPa and MPa.

Has a larger, thermally induced surface compressive stress, where P ₁ is

And P ₂ is given by

And h is 0.020 cal / s · cm ² · ° C. (about 828 W / m ² K) or more.

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