CN108883977A - The building glass and related system and method for heat enhancing - Google Patents

Abstract

A reinforced architectural glass or glass-ceramic sheet or article is provided, along with a method and system for manufacturing said reinforced architectural glass or glass-ceramic sheet or article. The method includes cooling the architectural glass sheet by non-contact heat conduction for a sufficient time to fix the surface compression and central tension of the sheet. The method produces a thermally reinforced architectural glass sheet that can be incorporated into one or more panes of a single-pane or multi-pane window.

Description

Thermally enhanced architectural glass and related systems and methods

technical field

This application is based on patent law requirements of U.S. Provisional Application Serial No. 62/236296 filed October 2, 2015 and U.S. Provisional Application Serial No. 62/288851 filed January 29, 2016 and U.S. Provisional Application Serial No. 62/288851 filed January 29, 2016 Priority Interest in Application Serial No. 62/288669 and Priority Interest Claimed under the Patents Act: U.S. Application Serial No. 14/814232 filed July 30, 2015 and U.S. Application Serial No. 14/814232 filed July 30, 2015 Serial No. 14/814274 and U.S. Application Serial No. 14/814293 filed July 30, 2015 and U.S. Application Serial No. 14/814303 filed July 30, 2015 and U.S. Application Serial No. 14 filed July 30, 2015 /814363 and U.S. Application Serial No. 14/814319, filed July 30, 2015, and U.S. Application Serial No. 14/814335, filed July 30, 2015, the entire contents of which are hereby incorporated by reference The method is incorporated into this article as a whole.

Background technique

The present disclosure relates generally to thermally regulated architectural glass, and in particular to thermally strengthened architectural glass and to related methods and systems for thermally strengthening architectural glass, particularly for thin architectural glass sheets.

In the thermal (or "physical") strengthening of architectural glass sheets, a sheet of architectural glass is heated to an elevated temperature above the glass transition temperature of the glass, and then the surface of the sheet is rapidly cooled ("quenched") while the sheet The inner area of the cools down at a slower rate. Internal areas cool more slowly because they are insulated by the thickness and rather low thermal conductivity of the architectural glass. The unequal cooling produces residual compressive stresses in the surface region of the architectural glass, which are balanced by residual tensile stresses in the central region of the architectural glass.

Thermal strengthening of glass is distinguished from chemical strengthening of glass in which surface compressive stresses are created by changing the chemical composition of the glass in regions near the surface (by methods such as ion diffusion). In some methods based on ion diffusion, the outer part of the glass can be strengthened by exchanging larger ions for smaller ions near the surface of the glass, so that compressive stress (also known as negative tensile stress) is applied on or near the surface . Compressive stress is believed to limit crack initiation and/or propagation.

Thermal strengthening of glass is also distinguished from glass that is strengthened by methods in which the outer part of the glass is strengthened or arranged by combining two types of glass. In such methods, layers of glass compositions having different coefficients of thermal expansion are combined or laminated together when warmer. For example, by sandwiching molten glass with a higher CTE between layers of molten glass with a lower coefficient of thermal expansion (CTE), as the glass cools, the positive tension in the inner glass compresses the outer layers, again creating compression on the surface. stress to balance the normal tensile stress. This surface compressive stress provides reinforcement.

Thermally strengthened architectural glass has advantages over unreinforced architectural glass. The surface compression of reinforced architectural glass provides greater fracture resistance compared to unreinforced architectural glass. The increase in strength is generally proportional to the amount of surface compressive stress. If the sheet has a sufficient level of thermal enhancement relative to its thickness, then if the sheet is damaged it will generally break into small pieces rather than large pieces with sharp edges or elongated pieces. Glass divided into sufficiently small pieces or "cuts," as defined by various established standards, may be referred to as safety glass or "fully tempered" glass, or sometimes simply "tempered" glass.

Because the degree of strengthening depends on the temperature difference between the surface and center of the glass sheet during quenching, thinner glasses require higher cooling rates to achieve a given stress. Also, thinner glasses typically require higher values of surface compressive stress and central tensile stress to achieve dicing into small particles upon fracture. Therefore, achieving the desired level of toughening in glass with a thickness of about 3mm or less has been very challenging, if not impossible.

Aspects of the present disclosure also generally relate to architectural glass or glass-ceramic having stress distribution for enhancing the exterior portion thereof. Architectural glass and glass-ceramic articles, such as architectural glass sheets, are useful in a wide variety of applications. Examples of these applications include architectural windows, single and multiple pane windows, interior and exterior windows, vacuum insulated glazing, and safety glazing for use in buildings, homes, hotels, offices, and other similar structures.

Contents of the invention

The present disclosure relates, in part, to highly reinforced thin architectural glass sheets and articles, and to methods, processes and systems for achieving surprisingly high thermal strengthening of glass sheets at thicknesses not achieved in the past. In various embodiments, it is believed that the processes and methods of the present disclosure exceed the architectural glass thickness limitations and heat transfer rates provided by conventional convective gas thermal enhancement methods without the need to contact the architectural glass with liquid or solid heat sinks. In such systems and methods, the architectural glass is only in contact with the gas during quenching. The disclosed systems and methods enable thermal enhancement in architectural glass sheets as thin as at least 0.1 mm in thickness, including achieving "full toughening" or dicing behavior; (in at least some contemplated embodiments) and in some embodiments Among them, this reinforcement is provided in thin architectural glass sheets that also have low roughness and high flatness due to lack of liquid or solid contact during quenching. In various embodiments, these advantageous forms of architectural glass sheet material are provided by systems and methods that require significantly lower quenching power than conventional convective glass tempering systems.

One embodiment of the present disclosure relates to a method for thermally strengthening architectural glazing materials. The method includes providing an article formed from an architectural glass material. The method includes heating the article above the glass transition temperature of the architectural glass material. The method includes moving the heated article into a cooling station. The cooling station includes a radiator having a radiator surface facing the heated article and an air gap separating the radiator surface from the heated article such that the radiator surface does not contact the heated article. The method includes cooling the heated article to a temperature below the glass transition temperature such that surface compressive stress and central tensile stress are generated within the article. The article is cooled by transferring heat energy from the article to the heat sink by convection across the gap such that more than 20% of the heat energy leaving the heated article crosses the gap and is absorbed by the Radiator reception.

Another embodiment of the present disclosure relates to a system for thermally strengthening architectural glass sheets. The system includes a heating station including a heating element that delivers heat to the glass sheet, and the glass sheet includes a first major surface, a second major surface, and a gap between the first major surface and the second major surface. thickness. The system includes a cooling station including opposing first and second heat sink surfaces defining a channel therebetween such that during cooling, the The glass sheet is located in the channel. The system includes a gas bearing delivering pressurized gas to the channel such that the glass sheet is supported within the channel without contacting the first and second heat sink surfaces, and the gas bearing defines a gap area. The gas bearing delivers the gas into the channel such that for a square meter gap area, the total gas mass flow rate into the channel is greater than zero and less than 2k/ _gCp , where k is the thermal conductivity of the gas within the channel evaluated in the direction of heat transfer, g is the distance between the glass sheet and the surface of the heat sink, and _Cp is the specific heat capacity of the gas in the channel.

Another embodiment of the present disclosure relates to reinforced architectural glass or glass-ceramic articles. The article includes a first major surface, a second major surface opposite the first major surface, and an interior region between the first major surface and the second major surface. The article comprises an average thickness between the first major surface and the second major surface of less than 4 mm. The article comprises at least 70% by weight silica. At least a portion of the first and second major surfaces have the same ion content and chemical composition as at least a portion of the interior region. The first major surface and the second major surface are under compressive stress and the inner region is under tensile stress, and the compressive stress is greater than 150 MPa. The surface roughness of the first major surface is between 0.2 and 1.5 nm _Ra roughness.

Another embodiment of the present disclosure relates to architectural glass or glass-ceramic layers in architectural windows. In an embodiment, the window includes a first glass-based layer and a second glass-based layer. In an embodiment, the first glass-based layer includes first and second major surfaces, a first body formed of a first glass material, and a first outer edge. In an embodiment, the second glass-based layer includes first and second major surfaces, a second body formed from a second glass material, and a second outer edge. The second glass-based layer is spaced apart from the first glass-based layer by a first distance and disposed substantially parallel to the first glass-based layer by the first distance. In an embodiment, the second glass-based layer includes an interior region between the first major surface and the second major surface of the second glass-based layer. In an embodiment, the second glass-based layer includes at least a portion of the first and second major surfaces having the same ionic content and chemical composition as at least a portion of the interior region. In an embodiment, the first major surface and the second major surface are under compressive stress and the inner region is under tensile stress, and the compressive stress is greater than 150 MPa. In an embodiment, the surface roughness of the first major surface of the second glass-based layer is between 0.2 and 2.0 nm _Ra roughness.

Another embodiment of the present disclosure relates to an architectural glass or glass-ceramic layer in a window of a building. In an embodiment, the window includes a first glass-based layer and a second glass-based layer. In an embodiment, the first glass-based layer includes first and second major surfaces, a first body formed of a first glass material, and a first outer edge. In an embodiment, the second glass-based layer includes first and second major surfaces, a second body formed from a second glass material, and a second outer edge. The first major surface and the second major surface of the second glass-based layer are separated by a thickness t. The second glass-based layer is spaced apart from the first glass-based layer by a first distance and disposed substantially parallel to the first glass-based layer by the first distance. In an embodiment, the first major surface is flat to the extent of a Total Indicated Runout (TIR) of 100 μm along any 50 mm or less profile of the first major surface of the second glass-based layer. In an embodiment, the second glass-based layer comprises a glass material having a low temperature linear CTE α ^S _CTE expressed in 1/°C, a high temperature linear CTE α ^L _CTE expressed in 1/°C, an elasticity in GPa Modulus E, _strain temperature Tstrain in °C and _softening temperature Tsoften in °C. In other embodiments, the first major surface of the second glass-based layer has a thermally induced surface compressive stress less than 600 MPa and greater than

in MPa;

where P1 is _given by

P2 is _given by

And h is greater than or equal to 0.020 cal/s·cm ² ·°C.

Another embodiment of the present disclosure relates to architectural glass or glass-ceramic layers in architectural windows. In an embodiment, the window includes a first pane of glass and a second pane of glass. In an embodiment, a first glass sheet includes first and second major surfaces, a first body formed from a first glass material, and a first outer edge. In an embodiment, the second glass sheet includes first and second major surfaces, a second body formed from a second glass material, and a second outer edge. The second glass sheet is spaced a first distance from the first glass sheet and is disposed substantially parallel to the first glass sheet at the first distance. In an embodiment, along any 50 mm or less profile of the first major surface of the second glass sheet, the first major surface is flat to the extent of a total indicated runout (TIR) of 100 μm. In an embodiment, the second glass sheet comprises glass having a _softening temperature Tsoftened in °C and an _annealing temperature Tanneal expressed in °C and measured on the first major surface of the second glass sheet The fictive surface temperature expressed by Tfs when expressed in °C. In an embodiment, the second glass sheet has a dimensionless surface fictive temperature parameter θs given by (Tfs - T _anneal )/(T _softening - T _anneal ). In an embodiment, the parameter θs is in the range of 0.20 to 0.9.

Additional features and advantages will be set forth in the following detailed description, and some of these features and advantages will be apparent to those skilled in the art from the description, or from practice of the written description and claims hereof and appended Some of these features and advantages are recognized by the embodiments described in the figures.

It is to be understood that both the foregoing summary and the following detailed description are exemplary only, and are intended to provide an overview or framework by which to understand the nature and character 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 implementations, and together with the description serve to explain principles and operations of the various implementations.

Description of drawings

Figure 1 (prior art) is a graph of the blower power required for "full tempering" as a function of glass thickness.

Figure 2 (Prior Art) is a graph of the blower power required for "full tempering" depending on glass thickness for an old method or machine O and a newer method or machine N.

Figure 3 (Prior Art) is a graph of the old curve O and new curve N of Figure 2 scaled to match the graph of Figure 1 and superimposed thereon.

4 is a perspective view of an architectural glass or glass-ceramic article or sheet according to an exemplary embodiment.

5 is a diagrammatic partial cross-section of the thermally enhanced architectural glass sheet of FIG. 4 according to an exemplary embodiment.

6 is a graphical representation of estimated tensile stress versus thickness for an architectural glass or glass-ceramic article according to an exemplary embodiment.

Figure 7 illustrates a portion of a fractured glass or glass-ceramic article according to an exemplary embodiment.

Figure 8 is a graph of fracture per square centimeter as a function of normal tensile stress from experiments.

Figure 9 is a graph of the magnitude of negative surface tensile stress as a function of initial hot zone temperature from experiments showing the threshold for achieving dicing.

Figure 10 is a graph of the dimensionless surface fictive temperature parameter θs for fictive temperatures obtained by one or more embodiments of the methods and systems of the present invention.

Figure 11 is a graph of surface compressive stress calculated by simulation for different glass compositions, plotted against the suggested temperability parameter Ψ for the various compositions shown.

Figures 12 and 13 are graphs of _two parameters P1 and P2 as _a function of the heat transfer coefficient h.

14 is a graph of surface compression (in MPa) of a glass sheet as a function of sheet thickness t (in millimeters) showing newly opened performance area.

15 is a graph showing compressive stress as a function of thickness plotted for selected exemplary embodiments of tempered glass sheets of the present disclosure.

16 is a flowchart illustrating some aspects of a method according to the present disclosure.

17 is a flowchart illustrating aspects of another method according to the present disclosure.

18 is a graph of FIG. 3 with region R and points A, B, A' and B' labeled thereon to illustrate the region in which the disclosed method and system allow operation (compared to the prior art).

Figure 19 is another representation of region R and points A, B, A' and B' of Figure 18, but shown adjacent (and positioned relative to scale) to the reduced-size copy of Figure 2 .

Figure 20 (Prior Art) is a graph of the required heat transfer coefficient required for tempering as a function of glass thickness.

21 is a diagrammatic cross-section of a glass sheet cooled by conduction rather than convection, according to an exemplary embodiment.

22 is a schematic cross-sectional view of a conduction enhancement system according to an exemplary embodiment.

23 is a perspective cutaway view of another embodiment of a system similar to that of FIG. 22, according to an exemplary embodiment.

24 is a perspective cutaway view of an alternative embodiment of the insertion feature of FIG. 23 according to an exemplary embodiment.

25 is a perspective cross-sectional view of yet another alternative embodiment of the insertion feature of FIG. 23, according to an exemplary embodiment.

26 is a flowchart illustrating aspects of yet another method according to an exemplary embodiment.

27 is a perspective view of a building with architectural glazing according to an exemplary embodiment.

28 is a perspective view of a display on a countertop according to an exemplary embodiment.

29 is an exploded perspective view of a device including a glass or glass-ceramic article according to an exemplary embodiment.

30 is a perspective view of a glass or glass-ceramic article or sheet according to an exemplary embodiment.

Figure 31 is an architectural window viewed from the exterior of a building, according to one embodiment.

32-33 are cross-sectional views of a perimeter edge of a dual pane window as seen along line 1 - 1 of FIG. 31 , according to an exemplary embodiment.

34 is a cross-sectional view of the perimeter edge of the triple pane window seen along line 1 - 1 of FIG. 31 according to an exemplary embodiment.

35 is a front view of an exemplary vacuum insulated glass (VIG) window, according to an exemplary embodiment.

36 is a cross-sectional view of the perimeter edge of the dual pane VIG window seen along line 1 - 1 of FIG. 35 according to an exemplary embodiment.

37 is a close-up cross-sectional view of an exemplary glass-bump spacer.

38 is a cross-sectional view of the perimeter edge of a triple-pane VIG window having a middle glass-based layer with a glass-bump spacer formed on the middle-based layer as seen along line 1-1 of FIG. 35. In both surfaces of the layer of glass.

39 is a cross-sectional view of the perimeter edge of an exemplary triple-pane VIG window with a rear glass-based layer instead of a middle glass-based layer as seen along line 1-1 of FIG. 35 . The second set of glass-bump spacers in the layer.

40 is a cross-sectional view of the perimeter edge of an exemplary triple-pane VIG window with glass-based layers formed at the front and rear instead of the middle, as seen along line 1-1 of FIG. 35. A first set of glass-bump spacers and a second set of glass-bump spacers in a glass-based layer.

Detailed ways

Applicants have recognized a need for improvements in the heat treatment of architectural glass, both in methods and systems for heat-strengthened architectural glass, and in the resulting heat-strengthened architectural glass sheet itself. For example, thinner but highly optical quality architectural glass sheet materials (e.g., architectural glass panes) and products comprising such architectural glass sheets are useful for many applications, including building, home, office, and similar structures. Layers or panes for interior and exterior single and multiple pane windows, architectural windows, vacuum insulated glass (VIG) windows, etc. It should be appreciated that glass is very compressible but relatively weak against surface tension. By providing compression at the surface of the sheet, which is balanced by tension at the center with no exposed surface, the useful strength of the sheet of architectural glass is significantly increased. However, while conventional thermal architectural glass reinforcement is generally cheaper and faster relative to alternative reinforcement methods (e.g., chemical reinforcement, lamination-based reinforcement), sheet of architectural glass), conventional thermal architectural glass reinforcement is known to be ineffective. Conventional thermal glass strengthening methods are generally considered limited to thicker glass sheets because the level of strengthening depends on the temperature difference created between the surface and center of the glass sheet during the quenching method; Relatively uniform cooling across the thin glass sheet makes it difficult to achieve significant temperature differences between the surface and the center of the thin architectural glass sheet.

On the other hand, strengthening thin architectural glass by ion exchange can be time-consuming and cumbersome, such as requiring an extended period of time in the architectural glass chemical bath. Directly laminating different types of architectural glass to each other may require complex manufacturing methods, such as fusion drawing involving double isopipes.

Accordingly, there is a need for architectural glass or glass-ceramic articles with specific stress distributions that result in the reinforcement of architectural glass for various uses, such as use in windows, countertops, fixtures, etc., through A method that is less resource intensive and/or less cumbersome than traditional methods is made. Specifically, the methods and systems discussed herein form architectural glazing articles with enhanced stress distribution of the exterior portion of the architectural glass, which in turn serves to mitigate cracking and failure while allowing for various other desired architectural glass qualities (e.g., geometric shape , surface quality, visible light transmittance, flexibility, etc.) in order to facilitate the use in various architectural glass applications.

The present specification provides improved methods and systems for producing highly reinforced architectural glass materials, and in particular highly reinforced thin architectural glass sheets, using thermal strengthening. Methods and systems address various limitations of conventional architectural glass strengthening methods, thereby allowing architectural glass sheets at thicknesses less than about 3 mm, less than 2 mm, less than 1.5 mm, less than 1.0 mm, less than 0.5 mm, less than about 0.25 mm, and less than about 0.1 mm achieve high levels of enhancement. In particular, applicants have developed systems and methods that provide very high rates of heat transfer, thereby creating a temperature differential between the surface and center of an architectural glass sheet large enough to provide reinforcement or toughening even in very thin architectural glass sheets.

Review and Limitation of Conventional Thermal Tempering Technology

Conventional industrial methods for thermally strengthening glass involve heating a glass sheet to a predetermined temperature in a radiant or convection furnace (or a "combined mode" furnace using both technologies), then typically by passing it against or along The glass surface is gas cooled ("quenched") by convective flow of large volumes of ambient air. This gas cooling method is primarily convective, whereby heat transfer (by diffusion and advection) occurs through mass motion (collective motion) of the fluid as the gas carries heat away from the hot glass sheet.

In conventional tempering methods, certain factors can limit the amount of reinforcement generally considered possible in glass sheets, especially thin glass sheets. There is a limit in part because the amount of compressive stress on the finished sheet is directly related to the magnitude of the temperature difference between the surface and center of the sheet achieved during quenching. However, the greater the temperature difference during quenching, the greater the possibility of glass cracking during quenching. For a given cooling rate, cracking can be reduced by starting the quench from a higher initial glass temperature. Additionally, higher onset temperatures generally allow tempered glass sheets to realize the full strengthening potential offered by high cooling rates. However, increasing the sheet temperature at the start of quenching also has its potential disadvantages. For example, a higher initial glass temperature may cause excessive deformation of the sheet as it becomes softer, limiting the practically achievable temperature difference.

In conventional tempering methods, sheet thickness also imposes a significant limit on the achievable temperature difference during quenching. For a given cooling rate during quenching, the thinner the sheet, the smaller the temperature difference between the surface and the center. This is due to the smaller thickness of glass used to insulate the center from the surface. Thus, thermal enhancement of thin glass generally requires a higher cooling rate (compared to thermal enhancement of thicker glass), and thus more rapid removal of heat from the outer surface of the glass generally requires significant energy expenditure in order to produce a glass sheet. The level of enhancement of the temperature difference between the interior and exterior.

As an example, Figure 1 shows the power (in kilowatts per square meter of glass sheet area) required by a blower employed to blow enough ambient air to "fully toughen" soda lime glass ("SLG"), which Depends on glass thickness in millimeters, based on an industry standard thermal strengthening method developed 35 years ago. As the glass used becomes thinner, the power required increases exponentially. As a result, the approximately 3 mm thick sheet of glass is the thinnest fully thermally tempered commercial glass available for many years.

Furthermore, the thinner the sheet, the more likely the glass will deform at a given softness (ie, at a given viscosity). Therefore, reducing the thickness directly reduces the achievable temperature difference and tends to reduce the full benefit of using higher sheet temperatures to obtain the higher cooling rate and prevent glass damage caused by the higher cooling rate because of the increased risk of sheet deformation. Chance of breaking. Therefore, in conventional convective gas glass strengthening methods, higher cooling rates are achieved by increasing the air velocity, reducing the distance from the air nozzle opening to the surface of the glass sheet, increasing the temperature of the glass (at the beginning of cooling), and Optionally reduce the temperature of the cooling air.

As a recent example, the performance curve of Figure 2 (Prior Art) was published using a prior art glass heat strengthening device. This improved apparatus continues to use the traditional blown convection method of cooling the glass, but replaces the rollers used to support the glass during heating with a system of supporting the glass with air during at least the final stage of heating. Without roller contact, the glass can be heated to higher temperatures (and higher softness/lower viscosity) prior to quenching, reportedly allowing the production of fully tempered glass 2mm thick. As shown in Figure 2, the reported blower power required to reinforce a 2 mm thick sheet varies from 1200 kW/ m ² is reduced to 400kW/m ² .

Although it represents a process capable of producing fully tempered 2mm thick glass, as shown in Figure 3 (Prior Art), scaling the old curve O and new curve N of Figure 2 to match the scale of Figure 1 shows the passing of the state of the art The performance improvement achieved by the convective tempering method (shown in Figure 2) of 2009 is relatively small and is only an incremental change in the previous understanding of the energy requirements in the convective enhancement of glass sheets. In Figure 3, the old curve O and new curve N of Figure 2 are scaled to match the graph of Figure 1 and overlaid on top of it (where the old curve O is truncated at the top of ^240kW /m2 to facilitate viewing of the new curve N) . It can be seen from Figure 3 that the technology represented by curve N only slightly changes the performance curve of the convective gas quenching method when the glass thickness is reduced from 3mm to 2mm. The high operating point (400 kW/m2 blower power for ^2mm glass) shows that the power required to process thinner glass by this method is still greatly increased. The drastic increase in airflow, and thus the power required, shows that it is difficult (as a matter of engineering practice and economics) to achieve thicknesses below 2 mm while using conventional convective gas intensification methods to produce fully tempered glass. In addition, the very high air flow required may also distort the shape of the flakes. Therefore, in order to achieve full tempering of glass less than 2 mm thick, or to achieve full tempering of 2 mm in glass having a coefficient of thermal expansion ("CTE") lower than that of soda lime glass using thermal tempering, applicants have determined that it is necessary to use Another tempering method/system.

Alternative thermal enhancement methods to current commercial convective gas enhancement have also been attempted, but each method has certain disadvantages in terms of convective gas enhancement. Specifically, typical alternative thermal enhancement methods to achieve higher cooling rates generally require at least some liquid or solid to be in contact with the glass surface, rather than just a gas. Such contact with the glass sheet may adversely affect glass surface quality, glass flatness, and/or uniformity of the strengthening method. These imperfections are sometimes detectable by the human eye, especially when viewed in reflected light. As described in more detail below, at least in some embodiments, the thermally conductive tempering systems of the present disclosure reduce or eliminate such contact-related defects.

Liquid contact enhancement (in the form of immersion in a liquid bath or flowing liquid, and in the form of a spray) has been used to achieve higher cooling rates than convective gas enhancement, but has the disadvantage of causing excessive thermal changes on the sheet during the cooling process. shortcoming. In an immersion or immersion-like spray or flow of a liquid, large thermal changes may occur in a small area due to spontaneously generated convective airflow within the liquid bath or liquid flow. In finer sprays, the effects of discrete spray droplets and nozzle spray patterns also produce significant thermal variations. Excessive thermal changes tend to cause glass cracking during thermal intensification by liquid contact, which can be mitigated by limiting the cooling rate, but limiting the cooling rate also reduces the achievable resulting strength. In addition, the necessary handling of the sheet (positioning or holding it in a liquid bath or in a liquid flow or liquid spray) also tends to cause cracks during reinforcement due to physical stress and excessive thermal changes due to physical contact with the sheet And limit the cooling rate and resulting mildness. Finally, some liquid cooling methods (such as high cooling rate quenching by oil immersion and various spray techniques) can modify the glass surface during such cooling, requiring later removal of glass material from the glass sheet surface to produce a satisfactory finish.

Solid contact thermal enhancement involves bringing the hot glass surface into contact with a cooler solid surface. Excessive thermal changes may be prone to occur during quenching, as seen in liquid contact enhancement. Any defect in the surface finish of the glass sheet, the tempered surface, or the uniformity of the sheet thickness can result in poor contact in one area of the sheet, and this poor contact can lead to large thermal changes that tend to break the glass during handling And can also lead to undesired birefringence if the sheet survives. Additionally, bringing the hot glass sheet into contact with a solid object can result in the formation of surface defects such as chips, grates, fissures, cracks, scratches, and the like. Achieving good physical contact across the entire surface of the glass sheet can also become increasingly difficult as the sheet size increases. Physical contact with solid surfaces can also mechanically compress the sheet during quenching, increasing the likelihood of breaking the sheet during this process. Furthermore, the extremely high rate of temperature change upon initiation of contact can lead to cracking during thin sheet handling, and thus contact cooling of thin glass substrates is not commercially viable.

Overview of Applicant's Thermally Enhanced Architectural Glass and Related Conduction Cooling Processes and Methods

The present disclosure goes beyond the conventional methods described above to effectively, efficiently and uniformly thermally strengthen thin sheets of architectural glass on a commercial scale without the various drawbacks common in conventional methods, e.g., without damaging the architectural glass surface, without inducing birefringence, No uneven reinforcement, and/or unacceptable cracking, etc. Thinner sheets of thermally tempered/reinforced architectural glass that were not previously available can be produced by one or more of the embodiments disclosed herein. The systems and methods discussed herein accomplish this by providing very high heat transfer rates in a precise manner with good physical control and gentle handling of the architectural glass. In specific embodiments, the methods and systems discussed herein utilize a small gap gas bearing in the cooling/quenching section, which applicants have determined allows for processing of thin architectural glass sheets at higher relative temperatures at the onset of cooling , resulting in a higher level of thermal enhancement. As described below, this small gap gas bearing cooling/quenching section achieves very high heat transfer rates by conduction of heat across the gap to the heat sink rather than using convective cooling based on high air flow. This high rate of heat transfer is achieved by supporting the architectural glass on gas bearings within the gap without bringing the architectural glass into contact with liquid or solid materials. As described below, applicants have also determined that, in at least some embodiments, the methods and systems discussed herein form heat-strengthened architectural glass (particularly heat-strengthened thin architectural glass) that has one or more unique properties.

Some embodiments of architectural glass sheets treated by methods and/or systems according to the present disclosure have higher levels of permanent thermally induced stress than previously known. Without wishing to be bound by theory, it is believed that the achieved level of thermally induced stress may be achieved due to a combination of causes. The high uniformity of heat transfer in the methods detailed herein reduces or eliminates physical and undesired thermal stresses in the architectural glass, thereby allowing sheets of architectural glass to be tempered at higher heat transfer rates without cracking. In addition, the present method can be performed at lower architectural glass sheet viscosities (higher initial temperatures at the onset of quenching) while still maintaining the desired architectural glass flatness and shape, which provides greater flexibility in cooling methods The temperature is varied, thereby increasing the level of thermal enhancement achieved.

Thermally Tempered Architectural Glass Sheets

As noted above, applicants have developed systems and methods for forming thermally enhanced architectural glass sheets, particularly thin architectural glass sheets, and as discussed in this section, the thermally enhanced thin architectural glass formed as discussed herein The flakes have one or more unique properties and/or combinations of properties not previously achievable by conventional thermal or other tempering methods.

Structure and Dimensions of Thermally Tempered Architectural Glass Sheets

Referring to Figures 4 and 5, thermally strengthened architectural glass sheets having high surface compressive stress and/or high central tension are shown according to exemplary embodiments. Figure 4 shows a perspective view of a heat-strengthened architectural glass or glass-ceramic article or sheet 500, and Figure 5 is a diagrammatic partial cross-section of a heat-strengthened architectural glass sheet 500 according to one or more embodiments. Sheet 500 may also be referred to herein as a pane or as a glass-based layer.

As shown in FIG. 4 , a reinforced architectural glass or glass-ceramic article 500 (e.g., sheet, beam, plate) includes a first major surface 510, a second major surface 520 (dashed line to the backside of sheet 500, as described herein may be translucent as disclosed), and a body 522 extending therebetween. The second major surface 520 is on the side of the main body 522 opposite the first major surface 510 such that the thickness t of the reinforced architectural glass or glass-ceramic sheet 500 is defined as the distance between the first major surface 510 and the second major surface 520 , where the thickness t is also the dimension of the depth. The width w of the reinforced architectural glass or glass-ceramic sheet 500 is defined as a first dimension of one of the first major surface 510 and the second major surface 520 that is normal to the thickness t. The length l of the reinforced architectural glass or glass-ceramic sheet 500 is defined as a second dimension of one of the first major surface 510 and the second major surface 520 that is orthogonal to the thickness t and the width w.

In an exemplary embodiment, the thickness t of the sheet of architectural glass 500 is less than the length 1 of the sheet of architectural glass 500 . In other exemplary embodiments, the thickness t of the sheet of architectural glass 500 is less than the width w of the sheet of architectural glass 500 . In still other exemplary embodiments, the thickness t of the sheet of architectural glass 500 is less than both the length l and the width w of the sheet of architectural glass 500 . As shown in FIG. 5 , architectural glass sheet 500 also has regions of permanent thermally induced compressive stress 530 and 540 at and/or near first major surface 510 and second major surface 520 through permanent thermally induced compressive stress in the central portion of the sheet. Thermally induced central tensile stress (ie tension) region 550 to balance.

Methods and systems can be used to form reinforced architectural glass sheets having a wide range of thicknesses. In various embodiments, the thickness t of the architectural glass sheet 500 ranges from 0.1 mm to 5.7 mm or 6.0 mm, including 0.2 mm, 0.28 mm, 0.4 mm, 0.5 mm, 0.55 mm, 0.7 mm, except for endpoint values. mm, 1mm, 1.1mm, 1.5mm, 1.8mm, 2mm and 3.2mm. Contemplated embodiments include thermally strengthened architectural glass sheets 500 having thicknesses ranging from 0.1 mm to 20 mm, from 0.1 mm to 16 mm, from 0.1 mm to 12 mm, from 0.1 mm to 8 mm, from 0.1 mm to 6 mm, from 0.1 mm to 4mm, from 0.1mm to 3mm, from 0.1mm to 2mm, from 0.1mm to less than 2mm, from 0.1mm to 1.5mm, from 0.1mm to 1mm, from 0.1mm to 0.7mm, from 0.1mm to 0.5mm and From 0.1mm to 0.3mm.

In some embodiments, architectural glass sheets with a thickness of 3 mm or less are used. In some embodiments, the architectural glass thickness is 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 1.8mm or less, about 1.6mm or less, about 1.4mm or less, about 1.2mm or less, about 1mm or less, about 0.8mm or less, about 0.7mm or less, about 0.6 mm or less, about 0.5 mm or less, about 0.4 mm or less, about 0.3 mm or less, or about 0.28 mm or less.

In some embodiments, the thermally strengthened architectural glass sheet has a high aspect ratio—ie, a large ratio of length and width to thickness. Because the thermal tempering methods discussed herein do not rely on high pressures or large volumes of air, various architectural glass sheet properties (such as surface roughness and flatness) can be maintained after tempering by using the gas bearing and high heat transfer rate systems discussed herein . Similarly, the thermal tempering methods discussed herein allow for the thermal strengthening of high aspect ratio architectural glass sheets (i.e., higher length-to-thickness ratios, or higher width-to-thickness ratios, or both) while maintaining the desired or necessary shape. architectural glass). In particular, sheets having length-to-thickness ratios and/or width-to-thickness ratios ("aspect ratios") of about at least 10:1, at least 20:1, and up to and exceeding 1000:1 can be reinforced. In contemplated embodiments, sheets having an aspect ratio of at least 200:1, at least 500:1, at least 1000:1, at least 2000:1, at least 4000:1 may be reinforced.

According to an exemplary embodiment, the length l of the reinforced architectural glass or glass-ceramic sheet 500 is greater than or equal to the width w, such as greater than twice the width w, greater than five times the width w, and/or not greater than fifty times the width w. In some such embodiments, the width w of the reinforced architectural glass or glass-ceramic 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/or not greater than fifty times the thickness t. times.

In some embodiments, such as for the applications disclosed with respect to FIGS. 27-30 discussed below, for example, the architectural glass or glass-ceramic sheet 500 has a length 1 of at least 1 cm, such as at least 3 cm, at least 5 cm, at least 7.5 cm, at least 20 cm, At least 50cm, and/or not greater than 50m, such as not greater than 10m, not greater than 7.5m, not greater than 5m. In some such embodiments, the architectural glass or glass-ceramic sheet 500 has a length w of at least 1 cm, such as at least 3 cm, at least 5 cm, at least 7.5 cm, at least 20 cm, at least 50 cm, and/or not greater than 50 m, such as not greater than 10 m , not greater than 7.5m, not greater than 5m. Referring to Figure 4, the architectural glass or glass-ceramic is in the form of a sheet 500 having a thickness t of less than 5 cm, such as 2.5 cm or less, 1 cm or less, 5 mm or less, 2.5 mm or less , 2 mm or less, 1.7 mm or less, 1.5 mm or less, 1.2 mm or less, or in contemplated embodiments even 1 mm or less, such as 0.8 mm or less; and/or thickness t It is at least 10 μm, such as at least 50 μm, at least 100 μm, at least 300 μm.

In other contemplated embodiments, architectural glass or glass-ceramic articles may be dimensioned differently than disclosed herein. In contemplated embodiments, the length l, width w and/or thickness t of the architectural glass or glass-ceramic article may vary relative to each other, for example for more complex geometries (see generally FIG. 30 ), where the dimensions disclosed herein are at least Applies to all aspects of the corresponding architectural glass or glass-ceramic article with the above definitions of length l, width w and thickness t.

In some embodiments, at least one of the first surface 510 or the second surface 520 of the architectural glass sheet 500 has a relatively large surface area. In various embodiments, the area of the first surface 510 and/or the second surface 520 is at least 100 mm ² , such as 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 5000 cm ² , and/or not more than 2500 m ² , such as not more than 100 m ² , not more than 5000 cm ² , not more than 2500 cm ² , not more than 1000 cm ² , not more than 500 cm ² , not more than 100 cm ² . As such, architectural glass or glass-ceramic sheet 500 may have a relatively large surface area; it may be difficult or impossible to thermally strengthen, except by the methods and systems disclosed herein, especially while having the thickness, surface quality, and /or strain uniformity. Furthermore, stress distribution, particularly the negative tensile stress portion of the stress distribution, may be difficult or impossible to achieve without reliance on ion exchange or architectural glass type changes other than by the methods and systems disclosed herein (see generally FIG. 6 ).

Compressive stress and tensile stress of heat-strengthened architectural glass sheets

As noted above, the heat-strengthened architectural glass sheets discussed herein can have unexpectedly high surface compressive stress (e.g., in regions 530, 540 shown in FIG. 5 ), unexpectedly high central tensile stress (e.g., in FIG. shown in region 550) and/or unique stress distributions (see FIG. 6). In consideration of the low thickness and/or other unique physical properties (e.g., very low roughness, high flatness, various optical properties, fictive temperature properties, etc.) of architectural glass sheet 500 as discussed herein, this is very real.

The compressive stress (eg, in regions 530 , 540 shown in FIG. 5 ) of architectural glass formed by the methods and systems disclosed herein may vary depending on the thickness t of the glass. In various embodiments, the compressive stress (e.g., surface compressive stress) of architectural glass (e.g., architectural glass sheet 500) having a thickness of 3 mm or less is as follows: at least 45 MPa, at least 60 MPa, 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 not greater than 1 GPa. In contemplated embodiments, architectural glass having a thickness of 2 mm or less has a compressive stress of at least 45 MPa, at least 60 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, at least 300 MPa, at least 350 MPa , at least 400Mpa and/or not greater than 1GPa. In contemplated embodiments, architectural glass having a thickness of 1.5 mm or less has a compressive stress as follows: at least 45 MPa, at least 60 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, at least 300 MPa, at least 350Mpa and/or not greater than 1GPa. In contemplated embodiments, architectural glass having a thickness of 1 mm or less has a compressive stress of at least 45 MPa, at least 60 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, at least 300 MPa and/or Not greater than 1GPa. In contemplated embodiments, architectural glass having a thickness of 0.5 mm or less has a compressive stress of at least 45 MPa, at least 60 MPa, 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 Or not greater than 1GPa.

In some embodiments, the thermally induced central tension in architectural glass formed by the methods and systems disclosed herein (e.g., in region 550 shown in FIG. Greater than 100MPa. In other embodiments, the thermally induced central tension may be less than 300 MPa or less than 400 MPa. In some embodiments, the thermally induced central tension may be from about 30 MPa to about 300 MPa, 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 architectural glass sheet has relatively thin, ie, is exceptionally thin. Because of the very high heat transfer rates that can be imposed by the systems and methods discussed herein, significant thermal effects (eg, central tensions of at least 10 MPa or even at least 20 MPa) can be generated in SLG sheets less than 0.3 mm thick. In fact, very thin sheets (ie sheets as thin as at least 0.1 mm) can be thermally enhanced. The specific thermal stress levels achieved and achievable, believed to depend on thickness and other variables, are described in further detail herein.

Referring to FIG. 6 , a conceptual stress curve 560 (at room temperature 25° C. and standard atmospheric pressure) of the reinforced architectural glass or glass-ceramic sheet 500 of FIG. 4 shows the inner portion 550 of the reinforced architectural glass or glass-ceramic sheet 500 under normal tensile stress. , and portions 530, 540 of the reinforced architectural glass or glass-ceramic sheet 500 outside and adjacent to the inner portion 550 under negative tensile stress (eg, positive compressive stress). Applicants believe that the negative tensile stress at least partially strengthens the reinforced architectural glass or glass-ceramic sheet 500 by limiting the initiation and/or propagation of cracks through the architectural glass or glass-ceramic sheet 500 .

Believed to be unique to the present technology, given the relatively large surface area and/or thin thickness of reinforced architectural glass or glass-ceramic sheet 500, as disclosed herein, the tensile stress in stress distribution 560 is between There is a sharp transition between the positive tensile stress of the inner portion 550 and the negative tensile stress of the portions 530 , 540 outside and adjacent to the inner portion 550 . This sharp transition can be understood as the rate of change (i.e. slope) of the tensile stress, which can be expressed as the magnitude of the stress (for example, 100MPa, 200MPa, 250MPa, 300MPa, 400MPa, i.e. positive tensile stress + σ and negative tensile stress - the difference in the peak value of σ) divided by the distance of the thickness where the change occurs (such as a distance of 1 mm, such as a distance of 500 μm, 250 μm, 100 μm), (this is the distance used to quantify the rate of change, which may be a fraction of the thickness of the article, Not necessarily the size of the product geometry). In some such embodiments, the change in tensile stress is no more than 7000 MPa divided by 1 mm, such as no greater than 5000 MPa divided by 1 mm. In contemplated embodiments, the difference between the peak values of the positive tensile stress and the negative tensile stress 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 not greater than 50 GPa . In contemplated embodiments, the magnitude of the peak negative tensile stress of the architectural glass or glass-ceramic 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. The sharp transition in the tensile stress curve produced by the systems and methods discussed herein is believed to be indicative of the ability to achieve higher magnitudes of negative tensile stress at the surface of the architectural glass sheet for a given thickness, and/or to manufacture thinner architectural glass articles to achieve The ability to have higher levels of negative tensile stress, such as to achieve the fragmentation potential of the dicing as disclosed herein. Conventional thermal tempering methods may not be able to achieve such a sharp tensile stress profile.

According to an exemplary embodiment, the high rate of change of the tensile stress is at least one or more of the above magnitudes sustained over the thickness-wise extension of the stress profile 560, i.e. at least 2% of the thickness of the architectural glass sheet 500, such as At least 5% thickness, at least 10% thickness, at least 15% thickness, or at least 25% thickness. In a contemplated embodiment, the reinforcement extends deep into the reinforced architectural glass or glass-ceramic sheet 500 such that the thickness direction extension with a high rate of change of tensile stress is centered between 20% and 80% of the thickness from the first surface. At depth, this can eg further differentiate chemical toughening.

In at least some contemplated embodiments, reinforced architectural glass or glass-ceramic articles include changes in their composition in terms of ion content, shown conceptually as dotted line 562 in FIG. 6 . More specifically, in such embodiments, the composition of the reinforced architectural glass or glass-ceramic article 500 includes exchanged or implanted ions that affect the stress distribution 560 . In some such embodiments, the exchanged or implanted ions do not fully extend through the portions 530, 540 of the reinforced architectural glass or glass-ceramic article 500 under negative tensile stress, as negative tensile stress is also a result of thermal tempering as disclosed herein.

Thus, the curve of the tensile stress profile 560 with increasing ion exchange strength includes the discontinuity or abrupt change 564 in directions where the tangents to the curve differ from each other on either side of the discontinuity or abrupt change 564 . The discontinuity 564 is located within the portions 530 , 540 under negative tensile stress such that the tensile stress is negative on either side immediately adjacent the discontinuity or discontinuity 564 . The discontinuities or abrupt changes 564 may correspond to depths of differing ionic content, however in some such embodiments, other portions of the portions 530, 540 under negative tensile stress still have the same ionic content as the portion 550 under positive tensile stress. same composition.

In other words, for at least some reinforced architectural glass or glass-ceramic articles 500, with or without ion exchange or implantation, at least a portion of the portions 530, 540 of the architectural glass or glass-ceramic sheet 500 (which are under negative tensile stress Under and outside of the inner portion 550 and adjacent to the inner portion 550) is the same composition as at least a portion of the inner portion 550 (under normal tensile stress). In such embodiments, at least some of the negative tensile stress of the stress profile is independent of changes in the composition (eg, ionic composition) of the reinforced architectural glass or glass-ceramic sheet 500 . Such a structure may simplify, at least in part, the composition of reinforcing architectural glass or glass-ceramic sheet 500 by providing sufficient strength without and/or with less use of chemical toughening. In addition, such structures can reduce stress concentrations within the reinforced architectural glass or glass-ceramic sheet 500 due to discontinuities/changes in the composition, thereby reducing the likelihood of delamination and/or cracking at compositional discontinuities. possibility.

Fracture properties of thermally tempered architectural glass sheets

If enough energy is stored in the tensile stress region 550, architectural glass will break like safety glass or "cut" when sufficiently damaged. As used herein, a piece of architectural glass is considered to be diced when a piece of architectural glass with an area of 25 ^cm2 breaks into 40 or more pieces. In some embodiments, cutouts are used as a qualitative measure to indicate that a piece of architectural glass is "fully toughened" (i.e., for architectural glass 2 mm thick or thicker, where the piece of architectural glass has a compressive stress of at least 65 MPa or an edge of at least 67 MPa compression). In various embodiments, the architectural glass sheet 500 has sufficient tensile stress in the tensile stress region 550 such that a 25 cm ² piece of architectural glass sheet 500 breaks into 40 or more pieces.

Referring to FIG. 7, an architectural glass or glass-ceramic article 610 having properties as disclosed herein with respect to architectural glass or glass-ceramic sheets, such as sheet 500, has been fractured, for example, using a center punch or other instrument and/or generally according to U.S. National Standards Institute (ANSI) Z97.1 (Impact Test) and ASTM 1048 standards. According to an exemplary embodiment, the architectural glass or glass-ceramic article 610 has been reinforced to such an extent that it chops when broken, thereby forming a plurality of small particle masses 616 (eg, chips, flakes). In some embodiments, the architectural glass or glass-ceramic article 610 has sufficient thermally induced stress to break the architectural glass or glass-ceramic article 610 in a fragmentation test in which an impact is applied with a hammer or punch to cause the architectural glass to crack into particle pieces. A plurality of particle masses 616 of not less than 40 are generated within a 50 mm x 50 mm area of 610 . A standard office pushpin 612 with a metal pin length 614 of approximately 1 cm is shown for reference.

According to various contemplated embodiments, despite the thinner thickness of the architecturally reinforced glass or glass-ceramic article 610, the stress distribution (see generally FIG. 6) imparts a high fragmentation potential to the reinforced architectural glass or glass-ceramic article 610 such that upon fracture , the reinforced architectural glass or glass-ceramic article 610 is broken into particularly small particle masses 616 having an area on either the first surface or the second surface of less than 90 mm ² , such as less than 50 mm ² , such as less than 20 mm ² , such as less than 10 mm ² , such as less than 5 mm ² , and/or at least 10 μm ² . In some such embodiments, the fragmentation potential of the reinforced architectural glass or glass-ceramic article 610 is such that when the reinforced architectural glass or glass-ceramic article breaks, at least 20% (e.g., at least 50%, at least 70%) of the particle mass 616 , at least 95%) has an area of at least one of the first surface or the second surface of one of the aforementioned amounts.

Due at least in part to the exceptionally thin geometry of architectural glass or glass-ceramic articles 610 that may in some embodiments be fabricated using the techniques of the present invention through the tensile stresses disclosed herein, the enhanced fracture potential of architectural glass or glass-ceramic articles 610 makes Upon fracture, the reinforced architectural glass or glass-ceramic article 610 breaks into particularly low-volume clumps of particles having a volume of less than 50 mm ³ , such as less than 40 mm ³ , such as less than 30 mm ³ , such as less than 25 mm ³ , and/or A volume of at least 50 μm ³ .

Due at least in part to the exceptionally large area of architectural glass or glass-ceramic articles 610 that can be fabricated in some embodiments using the techniques of the present invention through the tensile stresses disclosed herein, the enhanced fragmentation potential of architectural glass or glass-ceramic articles 610 makes it possible to Upon fracture, the reinforced architectural glass or glass-ceramic article 610 breaks into at least 100 particle masses 616 having a volume ^of at least 50 μm, such as at least 200, at least 400, at least 1000, at least 4000 particles having a volume ^of at least 50 μm Block 616.

Referring now to Figures 8 and 9, experiments were performed on 1.1 mm thick glass sheets comprising glass comprising at least 70% by weight silica, and/or at least 10% by weight sodium oxide, and/or at least 7% calcium oxide by weight and enhanced using the apparatus and methods disclosed herein. As shown in FIG. 8 , it has been found that the number of particle masses 616 per square centimeter of glass generally correlates with the magnitude of the normal tensile stress at the center of the corresponding glass or glass-ceramic article 610 . Similarly, as shown in FIG. 9 , fragmentation of the corresponding glass or glass-ceramic article 610 was also found based on the size of the gap between the surface of the glass sheet and the heat sink/gas bearing during quenching and based on the thermal conductivity of the gas used in the gap. The potential is related to the temperature of the glass in the hot zone (see eg Figures 21, 22 and 23), and the calculated expected heat transfer coefficient (h) (in cal/cm ² ·s°C (the metric unit is watt/m ² ·°K) as the unit).

Fictitious temperature of thermally tempered architectural glass sheets

In various embodiments, the thermally enhanced architectural glass sheet (eg, architectural glass sheet 500 ) formed by the systems and methods discussed herein has a high fictive temperature. It will be appreciated that, in various embodiments, the high fictive temperatures of the architectural glass materials discussed herein correlate with high tempering levels, high central tensile stresses, and/or high surface compressive stresses of the architectural glass sheet 500 . The surface fictive temperature can be determined by any suitable method, including differential scanning calorimetry, Brillouin spectroscopy, or Raman spectroscopy.

According to an exemplary embodiment, a portion of the architectural glass or glass-ceramic sheet 500 (such as at or near the first surface 510 and/or the second surface 520) has a particularly high fictive temperature, such as at least 500° C., such as at least 600° C., Or in some embodiments even at least 700°C (such as for soda lime glass). According to an exemplary embodiment, a portion of architectural glass or glass-ceramic sheet 500 (such as at or near first surface 510 and/or second surface 520) has a particularly high fictive temperature relative to annealed glass of the same chemical composition, such as At least 10°C or higher, at least 30°C or higher, at least 50°C or higher, at least 70°C or higher, or even at least 100°C or higher. High fictive temperatures can be achieved by the presently disclosed inventive techniques due at least in part to the rapid transition from hot to cool regions in the enhanced system (see, eg, Figures 21, 22 and 23). Applicants believe that high fictive temperatures may correspond to or be associated with increased glass damage resistance.

In some methods of determining the fictive temperature of a surface, it may be necessary to break the glass to relieve the "tempering stress" caused by the thermal enhancement method in order to measure the fictive temperature with reasonable accuracy. It is well known that characteristic structural bands measured by Raman spectroscopy are shifted in a controlled manner with respect to fictive temperature and with respect to applied stress in silicate glasses. If the tempering stress is known, this offset can be used to non-destructively measure the fictive temperature of the thermally strengthened glass sheet.

Referring generally to FIG. 10 , determination of fictive temperature for several exemplary architectural glazing by tempering method. Stress on the Raman spectrum of silica glass was reported in "The effects of tensile stress on the Ramanspectrum of silica glass" J.Non-Cryst.Solids, 106 380-383 (1988) by D. RTallant, TAMichalske and WLSmith Impact. Commercial glasses with 65% by weight silica or higher have essentially the same response. Although the reported stress response is for uniaxial stress, in the case of a uniaxial stress regime such as that observed in tempered glass, σ _xx = σ _yy , it would be expected that this peak would be shifted by Twice the expected deflection for uniaxial stress. The peak around ¹⁰⁹⁰ cm in soda lime glass and glass 2 corresponds to the peak at ¹⁰⁵⁰ cm observed in quartz glass. The effect of stress on the peak at 1050 cm ⁻¹ in silica and the corresponding peak in SLG and other silicate glasses can be expressed by the equation a) ω(cm ⁻¹ )=1054.93−0.00232σ as function of stress σ in MPa.

Calibration curves were generated from Raman band positions as a function of fictive temperature for SLG and another glass (Glass 2). Glass samples were heat treated for different 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 shear modulus. After heat treatment, the glass was quenched in water to freeze the fictive temperature at the heat treatment temperature. Then, using a 442 nm laser in the range of ^200-1800 cm, exposure time of 10-30 s and power of 100%, at magnification of 50x and spot size of 1-2 μm, microscopic Raman spectroscopy to measure glass surfaces. In this case, computer software (Renishaw WiRE version 4.1) was used to match the peak position at 1000-1200 cm ⁻¹ . A good fit (as the fictive temperature Tf in °C) of the Raman peak at 1090 cm ⁻¹ measured in the SLG on the air side is given by the equation b) ω(cm ⁻¹ )=1110.66−0.0282·Tf function). For glass 2, a good fit is given by the equation c)ω(cm ⁻¹ )=1102.00-0.0231·Tf.

By using the relationships established in equations a), b) and c), the fictive temperature of architectural glass can be expressed as a function of the measured Raman peak position and a correction factor due to surface compressive stress. A compressive stress σ _c of 100 MPa shifts the Raman band positions, corresponding to a decrease in the fictive temperature of about 15 to 20 degrees Celsius.

The following formula applies to SLG:

The equation for glass 2 is:

In these equations, ω is the measured peak wavenumber for the peak around 1090 cm and σ is the surface compressive stress measured by any suitable technique, resulting in a stress ^- corrected measurement of the fictive temperature in ° _C . As a demonstration of the increased damage resistance associated with the determined fictive temperature, four glass sheet samples were prepared, two 6 mm soda lime glass (SLG) sheets by conventional tempering methods to surface pressures of approximately 70 MPa and 110 MPa Stress (CS), and two 1.1 mm SLG sheets were prepared to approximately the same level of CS by the methods and systems disclosed herein. Two additional sheets were used as controls, each sheet having its own thickness. The surface of each test sheet was subjected to a standard Vickers indentation. The indentations were checked individually after applying different levels of force for 15 seconds each and waiting for 24 hours. As shown in Table I, a 50% cracking threshold (defined as the average number of cracks that occur is the load at two of the four points of the indenter that tends to initiate cracking) was determined for each sample.

Table I shows that the Vickers crack initiation threshold (reflected in the 6mm sheet) of SLG treated by conventional convective gas tempering is basically the same as that of the annealed or soon-to-be-delivered SLG sheet, i.e. from zero N to one N (N) rises between about one cow and less than two cows. This corresponds to a surface fictive temperature ( _Tfs or Tf _surface ) of about 25°C to 35°C relative to the glass transition temperature ( _Tg = 550°C, defined as η = ^1012-13.3 Poise for SLG) provided by conventional tempering Relatively moderate rise in correlation. In contrast, by tempering using the present method and system, the Vickers crack initiation threshold is increased to greater than 10 N, a 10-fold increase in Vickers damage resistance conferred by conventional tempering. In the embodied glass, _Tfs minus _Tg is at least 50°C, or at least 75°C, or at least 90°C, or in the range from about 75°C to 100°C. Even in embodiments that include lower levels of thermal enhancement, the embodied glass may still, for example, provide increased resistance (such as a level of 5N). In certain contemplated embodiments, the 50% cracking threshold after a 15 second Vickers crack initiation test may be equal to or greater than 5N, 10N, 20N, or 30N.

The following dimensionless fictive temperature parameter Θ can be used to compare the relative performance of thermal enhancement methods in terms of generated fictive temperature. In this case, given in terms of surface fictive temperature θs:

θs=(T _fs -T _annealing )l(T _softening -T _annealing ) (3)

where Tfs is the fictive surface temperature, _Tanneal (glass temperature at viscosity η = ^1013.2 poises) is the annealing point, and _Tsoften (glass temperature at viscosity η = ^107.6 poises) is the softening point of the sheet glass. Figure 10 is a graph of θs of the measured surface fictive temperature as a function of the heat transfer rate h applied during the thermal intensification of two different glasses. As shown in Figure 10, the results for the two different glasses superimpose fairly closely to each other. This means that the parameter θ provides a means for directly comparing the fictive temperatures of different glasses, related to the heat transfer rate h required to produce them. The vertical range of results under each h corresponds to the change in the value of the initial temperature _T0 at the onset of quenching. In embodiments, the parameter θs comprises from 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 0.23 to 0.09, or 0.24 to 0.09, or 0.25 to 0.09, or or Even 0.65 to 0.9.

Tempering parameters of thermally tempered architectural glass sheets

In various embodiments, thermally enhanced architectural glass sheets (eg, architectural glass sheet 500 ) formed by the systems and methods discussed herein have high tempering and/or heat transfer values. The "specific thermal stress" of glass is given by:

where α is the (low temperature linear) CTE of the glass, E is the elastic modulus of the glass material, and μ is the Poisson's ratio of the glass material. This value is used to indicate the level of stress developed within a given glass composition when subjected to a temperature gradient. It can also be used as an estimator of thermal "temperability". However, at higher heat transfer rates (eg, like at about 800 W/ ^m2K and above), the high temperature or "liquidus" CTE of the glass starts to affect the tempering properties. Therefore, under such conditions, the temperability parameter Ψ is found to be useful based on an approximation of the integral of the changing CTE value over the viscosity curve:

Among them, α ^S _CTE is the low-temperature linear CTE expressed in 1/°C (°C ^-1 ) (equivalent to the average linear expansion coefficient of glass from 0-300°C), and α ^L _CTE is expressed in 1/°C (°C ^-1 ). High-temperature linear CTE (equivalent to the observed high-temperature plateau value to occur somewhere between the glass transition point and softening point), E is the elastic modulus of the glass expressed in GPa (not MPa) (its allowable (dimensionless) parameter The value of Ψ usually ranges between 0 and 1), Tstrain is the glass _strain point temperature in °C (glass temperature at viscosity η = ^1014.7 poise), and Tsoftening is the glass _softening point in °C ( Glass temperature at viscosity η = ^107.6 poise).

For glasses with different properties, the thermal strengthening method and the resulting compressive surface stresses are modeled to determine the toughening parameter Ψ. Glasses were modeled at the same starting viscosity of 10 ^8.2 Poise and at different heat transfer coefficients. The properties of the various glasses, as well as the temperature of each glass at 10 ^8.2 poise, and the calculated value of the temperability parameter Ψ for each glass are shown in Table II.

Table II

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

The results in Table II show that Ψ is proportional to the thermal enhancement properties of the glass. This correlation is further shown in Figure 11, which provides a concrete example of a high heat transfer rate (heat transfer coefficient of 2093 W/m ² K (0.05 cal/s·cm ² ·°C)) and a glass sheet thickness of only 1 mm . As shown, the variations in the resulting compressive stresses for the seven different glasses correlate well with variations in the suggested temperability parameter Ψ.

Thermally tempered architectural glass sheet heat transfer coefficient and its relationship with surface compressive stress and central stress

^In another aspect, it has been found that, for any glass, the surface compressive stress (σ _cs , in MPa ₎ versus thickness (t in mm) (in the range 0mm to 6mm ₎ , where P1 and P2 are functions of h such that:

Or substituting Ψ into the expression, the curve of compressive stress σ _cs (Glass,h,t) is given by:

Wherein the constants P ₁ and P ₂ in the above (6) or (7) are respectively continuous functions of the heat transfer value h, given by the following formula:

as well as

In Figures ₁₂ and ₁₃ , the constants P1, P2 are plotted as a function of h, respectively. Thus, by using the value of P ₁ for a given h and the corresponding P ₂ for that same h in expressions (6) or (7) above, the corresponding surface compressive stress (CS ) curve as a function of thickness t.

In some embodiments, a similar expression can be used to predict the central tension (CT) of a sheet of thermally strengthened architectural glass (particularly with a thickness of 6 mm or less) by simply dividing the compressive stress predicted at the same conduction by 2 and heat transfer coefficients (such as above 800 W/m ² K). Therefore, the expected central tension can be given by:

where P _1CT and P _2CT are given by:

d and

In some embodiments, h and _hCT may have the same value for a given physical instance of thermal enhancement. However, in some embodiments they can vary, and providing individual variables and allowing variation between them allows (within the descriptive performance curve) to capture instances where the typical ratio of 2:1 CS/CT does not hold.

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

Table III

In some embodiments, the heat transfer value rate (h and h _CT ) can be from about 0.024 to about 0.15, about 0.026 to about 0.10, or about 0.026 to about 0.075 cal/s·cm ² ·°C.

Figure 14 shows the new open performance space in MPa depending on the surface compression of the glass sheet of thickness t (in mm), by a selected value of h C(h,t) according to Equations 6-9 above • A graph of Ψ(SLG), where Ψ(SLG) corresponds to the Ψ value of SLG in Table II. The trace marked GC represents the estimated range of maximum stress relative thinness of SLG sheets achievable by gas convection tempering, i.e. from 0.02 cal/s cm ² °C (or 840 W/m ² K) to 0.03 cal/s· cm ² ·°C or 1250 W/m ² K, assuming that these heat transfer coefficient levels can be used in the process at a heated glass viscosity of 10 ^8.2 poise, or about 704°C (above the capabilities of convective gas methods).

An example of the highest reported sheet CS value based on the gas convection tempering method is shown by the triangle marker labeled gas in the legend. Value 601 represents the advertised product performance capability of commercial equipment, while value 602 is based on an oral presentation at a glass processing conference. The trace labeled LC represents the maximum stress-versus-thinness curve of the SLG sheet estimated to be achievable by liquid contact tempering, from a heat transfer rate of 0.0625 cal/s cm ² °C (or about 2600 W/m ² K) h is given, also assuming processing at an initial heated glass viscosity of 10 ^8.2 poise or about 704°C. An example of the highest reported sheet CS value based on the liquid contact tempering method is shown by the circle marked liquid in the legend. The higher of the two values at 2mm thickness is based on reports of tempering of borosilicate architectural glass sheets and has been scaled for direct comparison by (Ψ _slg )/(Ψ _borosilicate ) for graph scaling achieved stresses.

The trace labeled 704 represents the heat transfer through the presently disclosed method and system at a heat transfer rate of 0.20 cal/s cm ² ·°C (or approximately 8370 W/m ² K) and an onset temperature of 704°C (just before quenching). One or more embodiments of the achievable stress. The stress levels on architectural glass sheets thus achievable represent almost the same range of improvement as liquid tempering strength levels, as liquid tempering represents prior art gas convective tempering. But the trace marked 704 is not an upper limit - embodiments have been shown to be feasible above this value due to the thermally enhanced shape and Good control of flatness. The trace labeled 730 shows the passage of 0.20 cal/s·cm ² ·°C (or approximately 8370 W/m ² K) at an SLG sheet onset temperature of 730°C (very close to or above the softening point of architectural glass) Some additional enhancements to heat transfer rates. Significant improvements in compressive stress and thus strength of architectural glass sheets are thereby achieved, in particular through the combination of high heat transfer rates and the use of high-efficiency materials through good handling and control of sheet flatness and shape in hermetic gas bearings The high initial temperature achieved, and this improvement is particularly noticeable at thicknesses of 2 mm and below.

Figure 15 shows the traces of Figure 14 above at 2 mm and below, but with compressive stress as a function of thickness plotted for selected examples of tempered glass sheets produced by one or more embodiments of the present disclosure, showing The extreme combination of thermal enhancement levels and thinness publicly achieved.

Thermally tempered architectural glass sheets with low surface roughness and high flatness

In various embodiments, thermally enhanced architectural glass sheets disclosed herein, such as sheet 500, have high thermal stress and low formed surface roughness. The processes and methods disclosed herein can thermally strengthen architectural glass sheets without increasing the surface roughness of the formed surface. For example, incoming float architectural glass airside surfaces and incoming fusion-formed architectural glass surfaces were characterized by atomic force microscopy (AFM) before and after processing. The R _a surface roughness is less than 1 nm (0.6-0.7 nm) for incoming 1.1 mm soda lime float architectural glass, and according to the present method, the R _a surface roughness is not increased by thermal enhancement. Similarly, according to the present disclosure, the R _a surface roughness of 1.1 mm fused-formed architectural glass sheets is maintained less than 0.3 nm (0.2-0.3) by thermal strengthening. Thus, the surface roughness (i.e. _Ra roughness) of the thermally enhanced architectural glass sheet on at least the first surface ranges from 0.2 nm to 1.5 nm, 0.2 nm to 0.7 nm, 0.2 nm, at least over an area of 10 μm x 10 μm to 0.4nm, even such as 0.2nm to 0.3nm. In exemplary embodiments, surface roughness may be measured over an area of 10 μm x 10 μm, or in some embodiments, may be measured over an area of 15 μm x 15 μm.

In some contemplated embodiments, the thermally strengthened architectural glass sheets disclosed herein have both high thermal stress and low formed and/or coated surfaces. The processes and methods disclosed herein allow for thermal strengthening of architectural glass sheets without increasing the surface roughness of the smooth formed or delivered surface of the architectural glass sheet, and likewise without damaging sensitive low-E or anti-reflective coatings or other coating. The incoming float architectural glass airside surface and the incoming fusion-formed architectural glass surface were characterized by atomic force microscopy (AFM) before and after processing. The R _a surface roughness is less than 1 nm, such as 0.6 nm to 0.7 nm, for entry on the air side of 1.1 mm soda lime float architectural glass and is not increased by thermal enhancement according to the present disclosure. The R _a surface roughness is less than 0.3 nm, such as 0.2 nm to 0.3 nm, for entry on 1.1 mm fusion formed architectural glass sheet and is also not increased by thermal enhancement according to the present disclosure. Thus, in contemplated embodiments, according to the present disclosure, the thermally enhanced architectural glass sheet has a surface roughness on at least a first surface in the range of at least 0.2 nm and/or not greater than 1.5 nm (such as not greater than 0.7 nm, such as _Ra roughness not greater than 0.4 nm, or even such as not greater than 0.3 nm); or having a thermally enhanced sheet with a coating thereon of the type that can be applied prior to strengthening; or having these The combination of low roughness values and coatings is obtained from the method of the invention used with corresponding architectural glass sheets as starting material. It is the applicant's understanding that such preservation of surface quality and/or surface coating previously required the use of convective gas tempering or possibly low heat transfer liquid tempering methods, which generate limited heat relative to the overall range available through current processes and methods Reinforcement effect.

In another embodiment, the heat-strengthened architectural glass sheets described herein have a high flatness. In various embodiments, the reinforcement systems discussed herein utilize controlled gas bearings to support architectural glass materials during transport and heating, and in some embodiments, can be used to assist in the control and/or improve the flatness of architectural glass sheets , resulting in higher flatness than previously achievable, especially for thin and/or highly reinforced architectural glass sheets. For example, sheets of at least 0.6 mm can be reinforced with improved post-reinforced flatness. The flatness of the thermally enhanced architectural glass sheet embodied herein may include a total indicator run-out (TIR) of 100 μm or less along any 50 mm length of one of its first or second surfaces, TIR of 300 μm or less over a length of 50 mm on one of the two surfaces, TIR of 200 μm or less, TIR of 100 μm or less, or 70 μm or less over a length of 50 mm on one of the first or second surfaces Smaller TIRs. In an exemplary embodiment, flatness is measured along any contour of the architectural glass sheet that is 50 mm or less. In contemplated embodiments, a sheet having a thickness as disclosed herein has a flatness of TIR of 200 μm or less, such as a flatness of 100 μm or less, over a length of 20 mm on either the first surface or the second surface TIR, TIR where the flatness is 70 μm or less, and TIR where the flatness is 50 μm or less.

According to contemplated embodiments, the reinforced architectural glass or glass-ceramic articles discussed herein (e.g., the architectural glass sheet or panel 500 shown in FIG. The change in thickness t is not more than 50 μm, such as not more than 10 μm, not more than 5 μm, not more than 2 μm. Due to practical considerations such as cooling plate alignment and/or surface irregularities that may distort the size, as disclosed herein, for a given thickness, area, and/or negative tensile stress magnitude, this dimensional uniformity may be Not achievable by solid quenching.

According to contemplated embodiments, the reinforced architectural glass or glass-ceramic articles discussed herein have at least one major surface (e.g., first surface 510 and second surface 520 of reinforced architectural glass or glass-ceramic sheet 500 in FIG. 4 ) that is planar such that the distribution of 1 cm along its length remains within 50 μm of a straight line, such as within 20 μm, 10 μm, 5 μm, 2 μm; and/or the distribution of 1 cm along its width remains within 50 μm of a straight line, such as 20 μm, Within 10μm, 5μm, 2μm. Due to practical considerations such as warping or bending of architectural glass reinforced in these methods due to convection of fluids and associated forces, as disclosed herein, for a given thickness, area, and/or negative tensile stress magnitude, this This high flatness may not be achievable by liquid quenching.

Heat Enhanced Architectural Glass Sheet CTE

Another aspect includes thermally enhanced low coefficient of thermal expansion (CTE) architectural glass sheets. As discussed above (see, eg, Equations 7 and 10), the thermal enhancement effect depends significantly on the CTE of the architectural glass making up the architectural glass sheet. However, thermal reinforcement of low CTE architectural glass can provide reinforced architectural glass compositions with advantageous properties, such as increased chemical resistance, or better compatibility with electronic devices due to low alkali content. Sheets of architectural glass with CTEs of 65, 60, 55, 50, 45, 40 and even 35x10 ^-6 °C ^-1 and below can have a fracture pattern ("cut") like safety glass with a thickness of less than 4 mm, less than 3.5 mm, less than 3mm, or even less than 2mm. Architectural glass having a CTE value of 40x10 ^-6 °C ^-1 and below can be reinforced using the methods described herein. At the same thickness, such low CTE architectural glass reinforced by the systems and methods discussed herein can have similar surface compression to SLG sheets reinforced by conventional commercial (gas convection) methods. In some embodiments, for architectural glass sheets having a thickness of: no greater than 1 cm, no greater than 5 mm, no greater than 3 mm, no greater than 2 mm, no greater than 1.5 mm, no greater than 1 mm, no greater than 0.75 mm, no greater than 0.5 mm, No greater than 0.3 mm, no greater than 0.2 mm, or no greater than 0.1 mm, the compressive stress of the low CTE architectural glass may comprise 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.

Architectural glass sheets formed according to the present disclosure have a variety of applications, for example, in single-pane and multi-pane windows (such as architectural glass-interlayer-architectural glass laminates used in architectural glass panes). Stronger and thinner laminates can be produced, resulting in weight and cost savings and improved fuel efficiency. Ideally, the thermally enhanced thin sheet could be cold bent and laminated to the formed thicker architectural glass, providing a simple and reliable manufacturing method without requiring any thermoforming of the thin sheet.

Alpha of Thermally Tempered Architectural Glass Sheets

Table IV below presents the results obtained by the method of the present disclosure (identified in the table as "Method Source" I) and the figure of merit Alpha as a rough measure of the heat transfer coefficient obtained in the tempering method. Alpha is given by:

where CS is the physical compressive stress in MPa, t is the thickness in millimeters, CTE is the coefficient of thermal expansion in °C ^-1 , and E is the glass elasticity in (MPa), and the output The unit is ℃/mm.

Table IV

Sample 1 and Sample 3 are reproducible values obtained from the disclosed method, Sample 1 using air as the gas in the method and Sample 3 using helium as the gas in the method. Sample 2 represents the "champion" value for the use of air in this method, ie not reliably repeatable so far. The glass samples (Samples 1-3) treated by the method of the present disclosure all exceeded Alpha at 117°C/mm. Applicants believe that there may be an inherent tendency for the slope of Alpha versus thickness to decrease as the thickness of the glass decreases. The architectural glass disclosed herein has an Alpha greater than 20t+77, where t is the thickness of the glass, in some embodiments, in mm.

Thermal Enhancement Systems and Methods

In various embodiments, the process for strengthening a sheet of architectural glass includes supporting or directing at least a portion of a sheet of architectural glass, such as architectural glass sheet 500, into a cooling or quenching zone where the sheet is cooled or quenched. The rapid cooling results in a reinforced architectural glass sheet having one or more of the properties discussed herein. In various embodiments, the sheet of architectural glass is at least partially supported by the flow or pressure of gas delivered to the gap between the surface of the sheet of architectural glass and the one or more heat sinks. Generally, the sheet of architectural glass is at a temperature above the transition temperature of the architectural glass as the sheet moves into the cooling zone, and in various embodiments, the sheet of architectural glass is cooled by conduction rather than convection within the cooling zone . Conduction is the method of heat transfer that transfers energy through the interaction between adjacent molecules, and convection is the method of heat transfer that transfers energy through the motion of a fluid (e.g., air, helium, etc.), such as where a heated fluid moves away from a heat source. open and replaced by cooler fluid. Thus, the present system differs significantly from conventional convection-based glass strengthening/tempering systems in which the dominant mode of heat transfer during cooling of the glass sheet is convection.

In some embodiments, the overall process for strengthening architectural glass sheets includes heating the architectural glass sheets in a hot zone and then cooling the architectural glass sheets in a cooling zone. Sheets of architectural glass have a transition temperature at which the architectural glass has a viscosity value of η = 10 ¹² -10 ^13.3 poise. The architectural glass is heated sufficiently to bring the architectural glass sheet above the transition temperature, and then the architectural glass is moved into the cooling zone. Optionally, the architectural glass can transition from a hot zone to a cool zone through a transition zone. In the cooling zone, the architectural glass sheet surfaces are positioned adjacent to heat sinks, one on either side of the architectural glass sheet, with each a gap between one architectural glass surface and the opposing surface of the heat sink. Gas is delivered into the gap through a plurality of orifices in the heat sink, and in some embodiments, this delivered gas forms an air bearing that supports the architectural glass between the heat sinks so that the architectural glass surface does not heatsink contacts. Within the cooling zone, the sheet of architectural glass is cooled by conduction rather than by convection, and is cooled sufficiently to fix or generate thermally induced surface compression and thermally induced central tension of the sheet, which provides increased strength as discussed herein. In various embodiments, cooling primarily by conduction is achieved by having a very low gap size within the cooling zone, such that the architectural glass sheet approaches but does not contact the opposing surface of the heat sink.

Apparatus for carrying out the described process may include a heating zone for heating the architectural glass sheet to a temperature above the transition temperature, and a cooling zone for cooling the heated architectural glass sheet to provide a reinforced architectural glass sheet. The apparatus may 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 defining a gap within which the heated sheet of architectural glass is received. The cooling zone may include a pair of gas bearings disposed on opposite sides of the gap for supporting the sheet of architectural glass within the gap. The gap may be configured to cool the heated sheet of architectural glass by conduction rather than convection. In some embodiments, the gas bearing may include multiple orifices for delivering gas to the gap, and the gas bearing surface acts as a heat sink, capable of conducting heat away from the heated architectural glass sheet by conduction rather than convection.

The reinforcement methods and apparatus disclosed herein (see generally FIGS. 21-25 ) allow for reinforcement of architectural glass or glass-ceramic articles (see generally FIGS. 4-7 and 27-30 ) by thermally tempering versions of the present invention. The method allows for a steep tensile stress versus thickness/depth curve (see generally FIG. 6 ), especially steepness in the slope near the surface of an architectural glass or glass-ceramic article, which makes it possible to Architectural glass or glass-ceramic articles are reinforced to particularly high levels of negative tensile stress without the need for reinforcement by ion exchange or lamination of different architectural glasses. However, in some embodiments, the thermal tempering methods disclosed herein can be enhanced with ion exchange or applied to glass-to-glass lamination. The thermal tempering methods disclosed herein enable particularly high levels of reinforcement in large area articles (e.g., sheets) that may be too large for reinforcement by conventional thermal tempering methods, such as due to the limitations of contact quenching equipment. Alignment limitations, cooling rate limitations of conventional convection systems, and/or warpage damage associated with liquid quench tempering. The methods disclosed herein uniquely allow high levels of reinforcement in particularly thin sheets that may be too thin for reinforcement by conventional tempering methods, such as due to thin architectural glass or glass during the reinforcement method. Sensitivity to cracking or fracturing of ceramic articles and contact forces associated with solid or liquid quenching, and/or cooling rate limitations due to conventional convective hardening. However, in other contemplated embodiments, the architectural glass or glass-ceramic articles disclosed herein may be made by at least some solid or liquid quenching, such as in combination with the unique strengthening methods disclosed herein.

One embodiment of a method according to the present disclosure is shown in the flowchart of FIG. 16 . Method or process 100 includes a step 140 of providing a sheet of architectural glass at a temperature above the transition temperature of the sheet of architectural glass. The method or process 100 also includes a step 160 of supporting the sheet of architectural glass at least in part with the gas (by gas flow and pressure). Step 160 involves, while the sheet of architectural glass is supported by the gas, cooling the sheet: 1) by conduction rather than by convection (through the gas to the heat sink), and 2) at ambient temperature sufficient to generate or hold the sheet in heat surface compressive stress and thermally induced central tensile stress.

According to a variation of the embodiment of FIG. 16 (depicted as method 100' in the flowchart of FIG. 17), the method may include step 110 of heating the sheet of architectural glass sufficiently such that the sheet is above the transition temperature of the architectural glass. As part of or in preparation for cooling step 160, at step 120, method 100' also includes providing a heat sink (whether as a single piece) having a first heat sink surface and a second heat sink surface (see generally FIGS. 21-25 ). Also as a separate piece), each heat sink surface has an aperture therein. In step 130A, the method further includes positioning a first sheet surface facing the first heat sink surface across the first gap, and in step 130B, the method further includes positioning a second sheet facing the second heat sink surface across the second gap material surface. The heat sink surface may include apertures and/or may be porous. In step 160, the method 100' may also include cooling the panels by conduction rather than by convection (through the gas to the respective heat sink surfaces), sufficient to strengthen the architectural glass (e.g., to sufficiently create or fix a thermotropic surface in the sheet compressive stress and thermally induced central tensile stress). Step 160 may also include delivering gas to the first and second gaps through the orifice or porous heat sink, and in some such embodiments, delivering the gas to form an air bearing that supports the sheet of architectural glass near the heat sink. In some embodiments, the gas is delivered only through the orifices of the heat sink or only through one or more holes and orifices of the porous heat sink.

These and other related approaches of the present disclosure go against current dominant gas convective cooling techniques by using conduction as the dominant cooling mode rather than convection. Instead of solid-to-gas (glass-to-air) heat exchange, the method described here uses solid-to-solid (glass-to-radiator) heat exchange through a small amount of gas (e.g., no gap between the glass surface and the physical contact) mediate in small gaps to initiate and complete cooling that produces thermal enhancement. While there is some convection as gas (eg, air bearing gas) flows into the small gap, direct trans-gap conduction through the gas and into the heat sink is the dominant cooling mode. Applicants have determined that the advantage of heat conduction increases the rate of heat transfer relative to convection-based cooling methods.

Because solid-to-solid conduction (even across gaps) allows faster heat flow than convection, the increased cooling rate required for thinner architectural glass sheets is not limited by gas velocity and volume. According to various embodiments, the gas flow and gap size can be selected, controlled, or optimized for other purposes without the constraints typically imposed by gas flow and gap size in convective systems, such as for controlling a gas cushion in the gap. Stiffness, for supporting the sheet, for flattening or otherwise shaping the sheet, for optimizing thermal conduction, for maintaining sheet flatness and/or shape during thermal enhancement, and/or for balancing the sheet Ease of handling and high cooling rates. For example, in some embodiments, because cooling is not by convection, helium becomes an economically viable alternative to air in systems of the present disclosure due to the very low gas flow rates supporting the gas bearings, and in such implementations In scheme, helium provides about five times the thermal conductivity of air. Even if the price is assumed to be several times that currently available, helium becomes an economically viable alternative at the low flow rates of the disclosed system.

Furthermore, because the systems of the present disclosure reduce the volume of air flowing over the architectural glass sheet (relative to convective systems) during cooling, the systems and methods discussed herein reduce the high speeds typically required in conventional convection-based tempering systems. , Potential risk of deformation of hot thin architectural glass sheets due to high volume air movement. This also allows softer, higher temperature sheets of architectural glass to be processed with no or minimal deformation, further improving the degree of reinforcement achievable. Eliminating high air velocity also alleviates the problems sometimes seen in conveying the sheet to the quench chamber (moving against the high air flow) and preventing high flow, cooler air from entering and cooling the furnace used to heat the plates Adjacent section.

Furthermore, the use of conduction through gas can mitigate contact damage, warping, forming, etc. associated with conventional liquid contact or solid contact quench tempering. The use of gas as an intermediate conductor preserves the surface quality of processed articles by avoiding solid-solid contact. The high conduction rate mediated by the gas also avoids liquid contact. Some types of liquid quenching can cause undesired deformations, spatial variations in tempering, and contamination of architectural glass surfaces. These embodiments primarily provide non-contact (except gas) but very high velocity cooling. In other embodiments, solid or liquid contacting may be involved, as described above.

Power Consumption of Thermal Tempering Systems/Methods

Another advantage of avoiding high air velocity is the power and energy savings achieved by using solid-gas-solid conduction as the primary architectural glass cooling mechanism. Points A and B of Figures 18 and 19 represent a high end estimate of peak power usage of the air bearing per square meter of architectural glass sheet (by compressed air supply at relatively high flow). Actual low-end peak power usage for compressed air may be as little as 1/16 of the value shown. Points A and B do not include active cooling of the heat sink, however, it may be included in some embodiments, especially if the machine is in continuous, quasi-continuous, or high frequency operation.

Referring again to Figures 18 and 19, points A' and B' represent conservatively estimated peak power levels for air bearing operation at points A and B when active cooling of the heat sink surface is taken into account, assuming thermal-mechanical (or An active cooling system with an electrical) efficiency ratio of 7.5 to 1 to accomplish a thermal load equivalent to a 300°C drop in architectural glass sheet temperature (within a time frame of 2.1 seconds for point A' and 1 second for point B' Inside). (These points correspond approximately to the pieces of architectural glass that are actually tempered in the apparatus described herein.)

While the four points within region R of FIGS. 18 and 19 illustrate the importance (at least to some extent) of the improvements obtainable by the methods and systems of the present disclosure, it should be noted that since power requirements are Quantities are represented, so full returns may be significantly underestimated in the figures. For example, as represented by curve N, the peak power of the blower cannot be turned on and off efficiently, often requiring a gated airway to block large fans that still spin (but with reduced load) when air is not needed. The peak power demand (represented by points A' and B') of a fluid cooling system such as a chilled water plant, for example, which is readily implemented according to the present disclosure, can generally be more efficiently accommodated, and will significantly reduce the effective peak power so that only at near full It is only close to A' and B' during continuous operation. Therefore, as shown, the variance in total energy demand will tend to be greater than the variance in peak energy demand. In some embodiments, the processes described herein have a peak power of less than 120 Kw/m ² , less than 100 Kw/m ² , less than 80 KW/m ² to thermally strengthen architectural glass sheets having a thickness of 2 mm or less.

Heat transfer from thin architectural glass sheets during thermal tempering

In general, in the systems and methods of the present invention, heat transfer from a thin sheet of architectural glass includes a conductive component, a convective component, and a radiative component. As noted above and explained in detail herein, the thermal tempering system of the present disclosure provides thin architectural glass tempering by utilizing heat conduction as the primary mechanism for quenching thin architectural glass sheets.

The following is the applicant's understanding of the underlying theory. One of ordinary skill in the art of glass tempering can readily conceive, where conduction effects are often so small that they are generally ignored in favor of analyzing convection and radiation separately, to ask whether thinner glass is actually achievable by conduction through a gas such as air. Sufficiently high cooling rates for architectural glass sheets (such as at 2 mm and below) - and if so, whether such rates can be achieved at practical gap sizes.

The heat conduction under the conditions embodied in the method using the system described herein can be determined via the following. First, in the context of thermal enhancement by conduction as in the present disclosure, the thermal conductivity of the gas within the gap must be evaluated in the direction of conduction along the thermal slope. High temperature air at or near the surface of the sheet being cooled has a significantly higher thermal conductivity than lower temperature air, such as room temperature or near room temperature air at or near the surface of a heat sink ((dry) room temperature The nominal thermal conductivity of air (25°C) is about 0.026W/m·K). An approximation is used that assumes that the air across the gap is at the average temperature of the two opposing surfaces at the start of cooling. At the start of cooling, the architectural glass sheet may eg be at a temperature of 670°C, whereas the heat sink surface may eg start at 30°C. Therefore, the average temperature of the air in the gap will be 350°C, at which temperature dry air has a thermal conductivity of about 0.047 W/m·K; more than 75% higher than its thermal conductivity at room temperature and high enough to A substantial amount of heat energy is conducted through gaps of this size within the system of the present invention, as discussed below, assuming the sheet is finished to a reasonable degree of surface and thickness uniformity.

To illustrate, Q _cond , the conduction component (in a direction perpendicular to the direction of the gap distance g) of the rate of heat transfer through a gap of distance g (which has an area A _g ) can be given by is given by:

where k is the thermal conductivity of the material (gas) in the gap evaluated in the direction of heat conduction (or in the opposite direction), Ts is the temperature of the building glass surface, and _TH is the heat sink surface (or in other embodiments the heat source surface) temperature. As mentioned above, a rigorous assessment of k would require incorporating the thermal conductivity of the gas along (or against) the direction of conductive heat flow, since the thermal conductivity of a gas varies with temperature—but as a good approximation, at two surface temperatures Ts Under the average value of T HS and T _HS , k can be regarded as the k value of the gas in the gap.

Reconstructing equation (14) in units of heat transfer coefficient (in heat flux power/m2/Kelvin) gives:

So the effective heat transfer coefficient for conduction across the gap is the thermal conductivity (in W/m K) of the medium in the gap (air in this case) divided by the gap length (in meters), giving The temperature difference in units of Watt/square meter/degree. Table V presents the heat transfer coefficients (k/g) for air-filled and helium-filled gaps for conduction-only gap sizes from 10 μm up to 200 μm in steps of 10 μm.

Table V

Figure 20 (Prior Art) shows an industry standard curve from about 35 years ago (reference line at 2mm added) whereby the tempering method requires the heat transfer coefficient (as measured in mm) to fully temper a glass sheet under certain assumed conditions function of thickness in units). As can be seen from the comparison of Table V with Figure 20, an air-filled gap of about 40 μm can allow the complete toughening of 2 mm thick architectural glass by conduction. While a little less than 40 microns is a fairly small clearance, planar porous air bearings in conveyor applications can often operate reliably with clearances as low as 20 microns. Thus, for the air gap fed through the holes in the surface of the heat sink, 37 microns can be achieved. Using helium (or hydrogen, with similar thermal conductivity) as the gas, a gap of about 200 μm can be used to fully toughen 2 mm thick architectural glass. Using helium or hydrogen as the gas allows about 5 times larger gap size for the same heat transfer coefficient. In other words, in the case of using helium or hydrogen as the gas in the gap, the gap increases the heat transfer coefficient available for quenching by about 5 times at the same gap size. So even in the case of air, the spacing is not impractical, and under high-conductivity gases, gap spacing is relatively easy to achieve, even for sheet thicknesses of less than 2 mm.

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

where m is the mass flow rate of the gas, Cp is the specific heat capacity of the gas, _Ti is the gas entry temperature as the gas flows into the gap, and e is the gas flowing in the gap, the surface of the sheet, and the surface of the heat sink/heat source (" The effectiveness of heat exchange between walls"). The value of e varies from 0 (indicating zero surface-to-gas heat exchange) to 1 (indicating the temperature at which the gas fully reaches the surface). Those skilled in the art of heat transfer can use, for example, the e-NTU method to calculate the value of e.

In general, however, if the gap between the surface of the sheet and the surface of the heat sink/source is small, the value of e will be very close to equal 1, which means that the gas is almost completely heated - on average, equal to two surfaces Average value of temperature on either side - before it leaves the gap. Assuming e = 1 (slightly overestimating the rate of convective heat transfer), and the gas is supplied to the gap through the surface of the heat sink/heat source, it can be assumed that the initial temperature of the gas in the gap is the same as that of the surface of the heat sink/heat source (T _i =T _HS ). The rate of heat transfer due to convection can then be simplified to:

At temperatures typical for thermal enhancement or heat treatment of architectural glass and similar materials, the radiative heat transfer outward from the sheet under treatment is relatively small. To cool (or heat, assuming the amount of radiation from the heat source is not too high when heating) a sheet (e.g., sheet 200 shown in FIG. In the area of gaps 204a, 204b), it is therefore only required that:

Q _cond > Q _conv (18)

Combining (18) with equations (14) and (17) gives the following conditions:

It, when held, will substantially ensure that the sheet is cooled (or heated) mainly by conduction in the gap region in question. Therefore, the mass flow rate m of gas should be less than 2 kA _g /gC _p or 2 k/gC _p per square meter of interstitial area. In one embodiment, m<B(2kA _g /gC _p ), where B is the ratio of convective cooling to conductive cooling. As used herein, B is a normal number less than one and greater than zero, specifically having a value of 2/3 or less, or even 4/5 or 9/10 or less. In general, m should be kept as low as possible consistent with using gas flow to control architectural glass sheets (e.g., sheet 200 shown in FIG. , 202b) or the location of the heat exchange surface itself. The ratio of convective cooling to conductive cooling can be anywhere from less than 1 to 1×10 ⁻⁸ . In some embodiments, B is less than 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.1, ^5x10-2 , ^1x10-2 , ^5x10-3 , ^1x10-3 , ^5x10-4 , ^1x10-4 , ^5x10-5 , ^1x10-5 , ^5x10-6 , ^1x10-6 , ^5x10-7 , ^1x10-7 , ^5x10-8 , or ^1x10-8 . In some embodiments, m is minimized consistent with the need to use gas flow to support and control the position of the sheet relative to the surface of the heat sink. In other embodiments, m should be chosen to control the position of the heat exchange surface itself relative to the sheet.

In various embodiments, the mass flow rate m of the gas within the conduction-based cooling system of the present disclosure is substantially lower compared to conventional convection-based tempering systems. As discussed herein, this substantially lower gas flow rate allows the conduction system to operate with substantially reduced power usage. Furthermore, in at least some embodiments, the reduced gas flow velocity also results in a substantially quieter cooling system compared to conventional convective cooling systems. In such embodiments, the reduction of noise can increase operator safety by reducing the likelihood of hearing damage and even reducing or eliminating the need for the operator to use hearing protection.

As will be appreciated, in embodiments where the sheet of architectural glass material is supported on air bearings between opposing heat sink surfaces, heat conduction will occur from both sides of the sheet of architectural glass to both heat sink surfaces. Thus, in such embodiments, the architectural glass sheet has a first sheet surface and a second sheet surface, and by positioning the first sheet surface (e.g., the lower surface of the architectural glass sheet) adjacent to the first heat sink surface (for example, the surface of the lower heat sink) such that the first gap is located between the first sheet surface and the first heat sink surface, and by positioning the second sheet surface (for example, the upper surface of the architectural glass sheet) as The sheet of architectural glass is cooled adjacent the second heat sink surface (eg, the surface of the upper heat sink) such that the second gap is between the second sheet surface and the second heat sink surface. In such embodiments, heat conduction is allowed to occur from the first sheet surface to the first heat sink surface and from the second sheet surface to the second heat sink surface. In such embodiments, the first gap has a length g ₁ across the first gap and a first gap area Ag ₁ , and the second gap has a length g ₂ across the second gap and a second gap area Ag ₂ . In such embodiments, a first flow of the first gas is provided to the first gap, and a second flow of the second gas is provided to the second gap. As will be appreciated, similar to the discussion above, the first gas has a heat capacity C _p1 and a thermal conductivity k ₁ , and the first flow is set to a mass flow rate m ₁ . In such embodiments, m ₁ 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 set to a mass flow rate m ₂ . In such embodiments, m ₂ is greater than zero and less than (2k ₂ A _g2 )/(g ₂ C _p2 ). In such embodiments, the first flow and the second flow contact the sheet of architectural glass such that the sheet of architectural glass is supported without contacting the surface of the heat sink. In this way, the sheet is cooled by conduction rather than by convection in such a way as to generate surface compressive stress and central tension of the sheet.

Architectural Glass Reinforcement Systems Including Highly Conductive Cooling Zones

Referring to FIG. 21 , a diagrammatic cross-section of a tempering method high conduction glass cooling/quenching station and a glass sheet cooled by conduction rather than convection. The first (major) surface 200a and the second (major) surface 200b of the hot glass sheet 200 span the corresponding gaps 204a and 204b, each facing the corresponding first surface 201b and the corresponding first heat sink 201a and the second heat sink 202a. The second surface 202b. As indicated by the arrows, a gas 230 is supplied through the first surface 201b and the second surface 202b to supply the gaps 204a, 204b and help keep the sheet of architectural glass centered or otherwise positioned between the heat sinks 201a, 202a. As indicated by arrows 240, air or other gases may exit, passing the edges of the heat sinks 201a, 202a. According to the discussion herein, by selecting the dimensions of the gaps 204a, 204b and the flow rates of the gas and gas 230, the sheet of architectural glass 200 will be cooled by conduction rather than by convection. In particular embodiments, the sheet of architectural glass 200 is cooled by radiators 201a and 202a so that more than 20%, particularly more than 50%, and more specifically more than 80% of the ) passes through gaps (such as gaps 204a and 204b) and is received by heat sinks 201a and 202a.

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

In some embodiments, gaps 204a and 204b can have a thickness of about (eg, plus or minus 1%) 100 μm or greater (eg, in the ranges of: 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). In other embodiments, gaps 204a and 204b can have a thickness of about (eg, plus or minus 1%) 100 μm or less (eg, in the ranges of: 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 of solid or porous configuration. Suitable materials include, but are not limited to, aluminum, bronze, carbon or graphite, stainless steel, and the like. The heat sink can be sized to be large enough to handle sheets of architectural glass and to transfer heat effectively and efficiently without significantly changing the heat sink temperature. Where heat sinks 201a and/or 202a are porous, they may still include additional orifices or holes for gas flow or may use a porous structure to provide flow, or both. In some embodiments, the heat sink also includes channels that allow fluid flow for controlling the temperature of the heat sink, described in more detail in FIGS. 23-25 and below.

Eliminating the high gas flow rates of the prior art may enable the use of very small orifices or holes 206 in the face of the heat sink, as shown in Figure 21, to provide gas to the gap. In some embodiments, the orifice may be less than 2 mm, less than 1.5 mm, less than 1 mm, less than 0.5 mm, less than 0.25 mm, or less than Or equal to 200 μm, 150 μm, 100 μm, 50 μm, 30 μm, 20 μm, or 10 μm. In some embodiments, the orifice is from about (eg, plus or minus 1%) 10 μm to about 1 mm, about 20 μm to about 1 mm, or about 50 μm to about 1 mm.

The spacing between adjacent apertures 206 may be from about (eg, plus or minus 1%) 10 μm to about 3 mm, about 20 μm to about 2 mm, or about 50 μm to about 1 mm when measured from edge to edge of the aperture. Small orifices or holes can be used as individual flow restrictors, providing high performance gas bearing type dynamics (such as high stiffness and consistency of sheet support) to position sheets and control gap size, allowing thermal enhancement effects High homogeneity to avoid or reduce stress birefringence. Furthermore, because very small holes or orifices can be used, the relative amount of solid matter at the surface of the heat sink facing the sheet surface across the gap can be maximized, thereby increasing conductive heat flow.

According to various embodiments, using such orifices 206 as the only path to provide gas to the gaps 204a, 204b, and desirably using orifices 206 located in a direction approximately perpendicular to the heat sink surfaces 201b, 202b, ensures air bearing Type dynamics are optimized and are not compromised by gas flow from larger orifices or from sources other than through adjacent heat sink surfaces 201b, 202b of sheet 200, or by other excessive lateral flow . In other embodiments, gas may be provided to the gaps 204a, 204b by other sources, such as in addition to the orifices 206 or holes. Thus, aspects of the present disclosure allow for power and energy savings (such as relative to conventional convective tempering methods) through the use of low gas flow and solid-gas-solid conduction.

22-25 illustrate an exemplary embodiment of an architectural glass reinforcement system 300 according to the present disclosure. Figure 22 shows a schematic cross-sectional view of a system 300 in which a sheet of architectural glass may be cooled by conduction of heat from the sheet of architectural glass through the gas into a conduction heat sink. The device includes a hot zone 310 , a cold zone 330 and a transition gas bearing 320 . Transition gas bearing 320 moves or directs the architectural glazing article (eg, architectural glass sheet 400a ) from hot zone 310 to cool zone 330 such that no or substantially no contact occurs between the architectural glass and the bearing. The hot zones 310 have gas bearings 312 each fed from a hot zone plenum 318 and the bearings 312 have cartridge heaters 314 inserted into holes through the bearings 312 for heating the hot zone gas bearings 312 to the desired starting process temperature. The architectural glass sheet (hot zone) 400a is held between the hot zone gas bearings 312 for a sufficient time to bring it to the desired pre-cooling temperature (eg, above the transition temperature).

In some embodiments, heating the sheet in the hot zone can be accomplished primarily by conducting heat from the heat sink through the thin gas barrier layer. The conductive heating method used in the hot zone can be similar to the cooling method described herein, but reversed (eg, pushing heat into the architectural glass sheet).

In some embodiments, the gap 316 between the hot zone gas bearing 312 and the architectural glass sheet 400a can be relatively large, on the order of 0.05" (1.27 mm) to 0.125" (3.175 mm) or more, because the architectural glass The sheet 400a can be heated relatively slowly and heat radiation from the hot gas bearing 312 into the sheet of architectural glass 400a is sufficient for this purpose. In other embodiments, the hot zone gap size may be as small as 150 microns per side or 500 microns per side. Smaller gaps may be advantageous in some embodiments because they enable better "stiffness" of the bearing - ie the ability to center and flatten the architectural glass while the glass is in its softened state. In some embodiments, the method may reform the architectural glass sheet - flatten it - during the initial heating step, for example, by pressure provided by gas bearing 312 . In some embodiments, the top and bottom hot zone bearings may be on actuators, allowing the gap width to be varied in a continuous manner, or alternatively, allowing architectural glass to be brought into the hot zone and then compress the gap when the gap is large In order to flatten the architectural glass while it is still soft.

The process temperature depends on many factors including architectural glass composition, architectural glass thickness, architectural glass properties (CTE, etc.), and desired level of reinforcement. In general, the starting process temperature can be anywhere between the architectural glass transition temperature and the Littleton softening point, or even higher in some embodiments. For example, for SLG, the system 300 heats the architectural glass sheet 400a to a temperature between about (eg, plus or minus 1%) 640°C to about 730°C, or about 690°C to about 730°C. In some embodiments, the system 300 heats the architectural glass sheet 400a to a temperature of from about (eg, plus or minus 1%) 620°C to about 800°C, about 640°C to about 770°C, about 660°C to about 750°C °C, from about 680°C to about 750°C, from about 690°C to about 740°C, or from about 690°C to about 730°C.

The sheet of architectural glass 400a is heated to its desired starting process temperature (eg, above the architectural glass transition temperature), and then moved from the hot zone 310 to the cool zone 330 using any suitable means. In some embodiments, moving the piece of architectural glass 400a from the hot zone 310 to the cool zone 330 can be accomplished by, for example, (1) tilting the entire assembly so that gravity acting on the piece of architectural glass forces it to move to the cool zone, (2) block air flow from the leftmost outlet of the hot zone 310 (closed sides in this embodiment), thereby forcing all gas from all gas bearings to exit the rightmost side outlet of the cold zone, causing the Fluid forces are exerted on the architectural glass sheet 400a and cause it to move to the cool zone 330, or (3) through a combination of (1) and (2).

Transition bearing plenum 328 may supply gas to transition gas bearing 320 . The thickness of solid material behind the surface of transition gas bearing 320 may be thin, have low thermal mass, and/or low thermal conductivity, allowing for reduced heat transfer from hot zone 310 to cold zone 330 . The transition gas bearing 320 may serve as a thermal break or transition between the two zones 310 and 330 and may be used to transition down from the larger gap 316 of the hot zone to the small gap 336 of the cold zone 330 . Furthermore, the low thermal mass and/or low thermal conductivity of the transition gas bearing 320 limits the heat transfer and thus limits the cooling experienced by the architectural glass pane 400a as it passes through the transition gas bearing 320 .

Once the sheet of architectural glass (cold zone) 400b moves into the cold zone 330 and into the channel 330a, it is prevented from exiting the right side exit by a mechanical stop or any other suitable blocking mechanism (shown as a stop door 341). Once the architectural glass sheet 400b has cooled sufficiently that the center has passed the architectural glass transition (e.g., in the case of a 1 mm thick SLG, to below about 490°C, corresponding in this example to about 325°C at the surface), then Stop door 341 may be moved, thereby unlocking cold zone channel 330a, and architectural glass sheet 400b may then be removed from system 300 . If desired, the sheet of architectural glass 400b may be left in the cold zone 330 until some temperature near room temperature before removal.

As described above, within the hot zone 310, the sheet of architectural glass 400 is heated to a temperature above the architectural glass transition temperature of the sheet of architectural glass. In the embodiment shown in FIG. 22, cold zone 330 includes a channel 330a for receiving heated architectural glass sheet 400b through opening 330b, conveying architectural glass sheet 400b, and cooling architectural glass sheet 400b in the cold zone. In one or more embodiments, the channel 330a includes a conveyor system that may include gas bearings, rollers, conveyor belts, or other means for physically transporting the architectural glass sheet through the cold zone. As shown in FIG. 22 , the cold zone 330 includes a gas bearing 332 fed by a plenum 338 separate from the hot zone plenum 318 and the transition plenum 328 .

As shown in Figure 22, the cold zone 330 includes one or more heat sinks 331 disposed adjacent to the channel 330a. Where two heat sinks are utilized, such heat sinks may be disposed on opposite sides of the channel 330a, facing each other across the channel gap 330a. In some embodiments, the heat sink includes a plurality of apertures 331a forming part of the gas bearing 332, and the surface of the cold gas bearing 332 of the cold zone 330 serves as the two heat sink surfaces. Due to the lower air velocity in the channel 330a and the smaller size of the channel gap 330a, the sheet of architectural glass 400b is cooled in the cold zone 330 primarily by heat conduction from the sheet of architectural glass, across the gap, and into the solid heat sink 331, The architectural glass sheet 400b does not contact the surface of the heat sink.

In some embodiments, the heat sink and/or its surface may be segmented. As noted above, in some embodiments, the heat sink may be porous, and in such embodiments, the orifices through which the gas for gas bearing 332 is delivered are the pores of the porous heat sink. The plurality of orifices 332b, the gas source, and the channel gap 330a may be in fluid communication. In some embodiments, gas flows through the orifice 331a to form a gas cushion, layer or bearing in the channel gap 330a. The air cushion of some embodiments prevents the architectural glass sheet 400b from contacting the surface of the heat sink 331 . The gas also acts as a gas through which the architectural glass sheet 400b cools by conduction rather than by convection.

Because cooling occurs essentially by solid-to-solid heat conduction across the gap, problems that do not exist in convective-dominated cooling may need to be addressed. For example, to temper large thin sheets, (1) the sheets can be introduced rapidly into the cold zone, optionally at higher speeds than are used in convection-based quenching, and/or (2) operated in quasi-continuous mode The method in which a plurality of sheets are heated and cooled one after the other in a continuous flow, with little space between the sheets, and in which heat sinks are actively cooled so that they come into thermal equilibrium, so that large sheets The leading and trailing edges of the wood have similar thermal histories.

In some embodiments, the gas flowing through the aperture 331a cools the heat sink. In some embodiments, the gas flowing through the apertures facilitates heat transfer from the architectural glass, across the gap, into the heat sink, and also cools the heat sink 331 . In some cases, a separate gas or fluid may be used to cool heat sink 331 . For example, heat sink 331 may include channels 334 for flowing cooling fluid therethrough to cool heat sink 331 , as described more fully with respect to FIG. 23 . Channel 334 may be closed.

Where two heat sinks are used (ie, a first heat sink and a second heat sink), one or more gas sources may be used to provide gas to channel gap 330a. The gas sources may comprise the same gas as each other or different gases. Thus, channel gap 330a may include one gas, a mixture of gases from different gas sources, or the same gas source. Exemplary gases include air, nitrogen, carbon dioxide, helium or other inert gases, hydrogen, and various combinations thereof. Just before the gas begins to conductively cool the sheet of architectural glass 400b, the gas can be described by its thermal conductivity as it enters the channel 330a. In some cases, the gas may have a thermal conductivity of about (eg, plus or minus ±1%) 0.02 W/(m·K) or greater, about 0.025 W/(m·K) or greater, about 0.03W/(m·K) or more, about 0.035W/(m·K) or more, about 0.04W/(m·K) or more, about 0.045W/(m·K) or more , about 0.05W/(m·K) or greater, about 0.06W/(m·K) or greater, about 0.07W/(m·K) or greater, about 0.08W/(m·K) or Greater, about 0.09W/(m·K) or greater, about 0.1W/(m·K) or greater, about 0.15W/(m·K) or greater, or about 0.2W/(m·K) or greater K) or greater.

The methods and systems described herein allow for high heat transfer rates which, as discussed above, allow for an enhanced degree of temperature differential even within very thin sheets of architectural glass. In the case of using air as the gas, there is a gap between the architectural glass sheet and the radiator, and the heat transfer rate can be as high as 350, 450, 550, 650, 750, 1000 and 1200kW/ ^m2 or more by conduction only . With the use of helium or hydrogen, heat transfer rates of 5000kW/ ^m2 or more can be achieved.

The heat sink 331 of one or more embodiments may be stationary, or may be movable to modify the thickness of the channel gap 330a. The thickness of the architectural glass sheet 400b may be oriented from about 0.4 times to about 0.6 times the thickness of the channel gap 300a defined as the opposing surface of the heat sink 331 (e.g., in the arrangement of FIG. The distance between the upper surface and the lower surface of the radiator 331). In some cases, the channel gap is configured to be of sufficient thickness such that the heated sheet of architectural glass is cooled by conduction rather than convection.

In some embodiments, the channel gap can have a thickness such that when the architectural glass sheet 400b is conveyed through or within the channel 330a, the distance between the major surface of the architectural glass sheet 400b and the surface of the heat sink (e.g., above The gap size in question) is about (e.g., plus or minus 1%) 100 μm or greater (e.g., in the following ranges: 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). In some embodiments, the channel gap can have a thickness such that when the architectural glass sheet 400b is conveyed through the channel, the distance between the architectural glass sheet and the heat sink surface (gap or gaps 336) is about (e.g., plus or minus 1%) 100 μm or less (for example, in the following ranges: 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 total thickness of the channel gap 330a depends on the thickness of the architectural glass sheet 400b, but can generally be characterized as twice the distance between the heat sink surface and the architectural glass sheet plus the thickness of the architectural glass sheet. In some embodiments, the distance or gap 336 between the architectural glass sheet and the heat sink may not be equal. In such embodiments, the total thickness of the channel gap 330a may be characterized as the sum of the distances between the architectural glass sheet and each heat sink surface plus the thickness of the architectural glass sheet.

In some cases, the total thickness of the channel gap can be less than about (eg, plus or minus 1%) 2500 μm (eg, in the range of: 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 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 about 120 μm to about 1200 μm 1000μm). In some cases, the total thickness of the channel gap can be about 2500 μm or more (e.g., in the range of 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 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 aperture 331a in the heat sink 331 may be positioned perpendicular to the heat sink surface or possibly at an angle of 20 degrees or less, such as about (e.g., plus or minus 1%) 15 degrees from perpendicular to the heat sink surface 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 can be any suitable material with a high heat transfer rate, including metals (eg, stainless steel, copper, aluminum), ceramics, carbon, and the like. As shown in FIG. 22, the material may be relatively thick compared to the material behind the surface of the transition bearing 320 so that the heat sink can readily accept a relatively large amount of thermal energy. In an exemplary embodiment, the material of heat sink 331 is stainless steel.

23 is a cutaway perspective section of an apparatus similar to that of FIG. 22 , although reversed from right to left, and also including a loading/unloading zone 340 next to the cold zone 330 of the system 300 , which includes a loading/unloading gas bearing 342 and a sheet of architectural glass 400c thereon. Also, the apparatus of FIG. 23 uses tight channel clearances in the hot zone 310, transition bearing 320, and cold zone 330 (not shown).

The inset in Figure 23 shows an alternative embodiment of a cold zone gas bearing 332a in which the gas bearing 322a is actively cooled by coolant passages 334 between the gas bearing feed holes 333 which feed into the surface of the bearing 322a. hole. Cooling channels 334 are defined between heat sink segments 333b that are assembled together to form heat sink 331 and its surface facing architectural glass sheet 400b.

Cooling passages 334 may be located in the solid material of gas bearing 332 very close to the surface of heat sink 331 with an area of solid bearing material existing between the heat sink/gas bearing surface and the closest surface edge of coolant passage 334 has the same width as the closest surface edge of the coolant channel 334 . Thus, in some embodiments, there are no regions of reduced cross-section in the solid material of the heat sink 331/gas bearing 332a between the coolant channel 334 and the surface facing the architectural glass 400b. This differs from typical convective gas cooling devices because high gas flow rates require significant space in the middle of the gas nozzle array for the gas flow to escape. Where active cooling is used, the heat sink 331 /gas bearing 332a has areas of reduced cross-section in the solid material of the gas nozzle design relative to the solid material closest to the architectural glass surface. The region of reduced cross-section is typically positioned between the active cooling fluid and the sheet of architectural glass being processed to provide a high volume path for the bulk of the heated gases returning from the sheet.

FIG. 24 shows yet another alternative embodiment of a cold zone gas bearing 332 that is similar to the cold zone gas bearing of the inset of FIG. 23 . In this embodiment, a coolant channel 334 is formed between a gas bearing supply member 335 including a gas bearing supply hole 333 and a gas bearing surface member 337a, which provides the sheet of architectural glass 400b facing the surface of the gas bearing 332 . Figure 25 shows yet another alternative cold zone gas bearing 332c having a similar structure to the embodiment of Figure 24 but with a porous member 339 between the bearing plate member 337b and the architectural glass sheet 400b such that the porous member 339 forms The surface facing the sheet of architectural glass 400b.

It should be understood that, in various embodiments, the architectural glass reinforcement methods and systems described herein with respect to FIGS. Architectural glass or glass-ceramic articles (such as architectural glass sheet 500 ) of any combination of properties, etc.

Architectural glass sheets that have been subjected to the thermal strengthening methods described herein can be further processed by subjecting them to ion exchange to further enhance their strength. In some such contemplated embodiments, ion-exchanging the surface of a heat-strengthened architectural glass as described herein may increase the aforementioned compressive stress by at least 20 MPa, such as at least 50 MPa, such as at least 70 MPa, such as at least 80 MPa, such as at least 100 MPa, Such as at least 150 MPa, such as at least 200 MPa, such as at least 300 MPa, such as at least 400 MPa, such as at least 500 MPa, such as at least 600 MPa and/or not greater than 1 GPa.

Systems and processes for thermally regulating and/or heating architectural glass sheets

In addition to thermally enhancing architectural thin glass sheets, the methods and systems described herein can also be used for additional thermal conditioning processes. Although cooling is specifically discussed herein, the system and method may be used to transfer heat into a sheet of architectural glass by conduction. Accordingly, additional embodiments of the methods of the present disclosure include heating by conduction of the gas rather than by convection. Such a process or method 700 is shown in the flowchart of FIG. 26 .

Method 700 includes two main steps. The first step (step 710) includes providing an article (such as a sheet of architectural glass) having at least one surface. The second step (step 720) involves heating or cooling a portion of the surface of the article, up to and including the entire surface of the article. As shown in subsection 720a, step 720 is performed by conduction rather than convection (by passing gas to and from a heat source or heat sink source), and is performed in subsection 720b substantially so as to accomplish thermal conditioning of the article or surface portion of the article , and conduction of cooling/heating of step 720 is performed at a high heat transfer rate (at least 450 kW/m ² ) for the area of the portion in subsection 720b.

For example, an article can be thermally conditioned—that is, heated or cooled—by cooling or heating a portion of the surface of the article (up to and including the entire surface of the article (the portion with area)), by conduction rather than by convection, by going to and from a heat sink or a gas from a heat source rather than mediating said conduction by solid-to-solid contact is sufficient to accomplish thermal conditioning of the article or surface portion of the article, and during at least some of the time of heating or cooling at least 450, 550, 650, 750, 800 , 900, 1000, 1100, 1200, 1500, 2000, 3000, 4000, or even 5000 or more kW/square meters conduction is performed.

In addition to tempering, the high power transfer rates provided by the systems and methods discussed herein allow for all types of thermal processing or conditioning, including heating and cooling during tempering, edge reinforcement of architectural glass, firing of ceramics, glass, or other materials or sintering etc. Furthermore, since heat is extracted or delivered primarily by conduction, it provides tight control over the thermal history and distribution in the treated article while maintaining surface smoothness and quality. Thus, in yet another aspect of the present disclosure, tight control is provided over the thermal history and distribution in the treated article, since heat is extracted or delivered primarily by conduction, while maintaining surface smoothness and quality. Thus, the systems and methods of the present disclosure can be used to intentionally vary the stress distribution from the reinforcement method in the thickness direction and in the direction of the plane of the sheet by: changing the gap, changing the heat sink/heat source material, changing the heat sink / heat source temperature, changing gas mixture - and all of these can be varied by positioning along the sheet path, across the sheet path, or perhaps not just positioning while the sheet is moving (for most variables).

Devices, products and structures incorporating reinforced architectural glass sheets

The reinforced architectural glass or glass-ceramic articles and sheets described herein have broad utility in a wide range of articles, equipment, products, buildings, and the like. In exemplary embodiments, the reinforced architectural glass or glass-ceramic articles and sheets described herein constitute a portion or the entire pane of single-pane, multiple-pane, and vacuum insulated glass (VIG) windows.

27, an architectural object 1010 (such as a building, house, office, vehicle, etc.) includes architectural glass or glass-ceramic articles 1012 in the form of windows, portions of walls (e.g., surfaces), partitions, decorative panels, mirrors, etc. . In other embodiments, the architectural glass or glass-ceramic article 1012 may be included in a refrigerator door, oven door, similar appliance, or other indoor application. In contemplated embodiments, architectural glass or ceramic article 1012 may be reinforced such that architectural glass or ceramic article 1012 has negative tensile stress on or near its surface, which is balanced by positive tensile stress within it, as disclosed herein of. In addition, the architectural glass or glass-ceramic article 1012 can have a composition that is resistant to outdoor conditions by having a relatively high silica content, such as at least 70% by weight (such as at least 75% by weight) of silica. Chemicals and/or corrosion that may be present in the environment.

According to an exemplary embodiment, architectural glass or glass-ceramic article 1012 has a major surface perpendicular to its thickness (see generally sheet 500 shown in FIG. Glass or glass-ceramic articles with major surfaces 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 ). In contemplated embodiments, when the architectural glass or glass-ceramic article 1012 has a thickness as disclosed herein, the total light transmission through the architectural glass or glass-ceramic article 1012 is at least about 50% for wavelengths from about 300 nm to about 800 nm (e.g., at least 65%, at least 75%), such as the following thicknesses: less than 5cm, less than 3cm, less than 2cm, less than 1.75cm, less than 1.5cm, less than 1cm, less than 5mm, less than 3mm, less than 2mm, 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 10 microns, such as at least 50 microns.

Referring to FIG. 31 , an architectural window 1400 is shown from the exterior of an architectural object (eg, building, home, office, automobile, train, etc.). Of course, windows 1400 of various sizes and shapes (eg, FIG. 30 ) are possible in accordance with the present disclosure. In an embodiment, a window 1400 may be installed in a building 1010 as shown in FIG. 27 . Window 1400 can be a single pane, double pane, triple pane window, or even a quadruple pane window. At least one of the panes in window 1400 may be architectural glass or Glass ceramic products. In an embodiment, all panes in window 1400 comprise architectural glass or glass-ceramic sheets fabricated as disclosed herein (eg, FIG. 4 ). In alternative embodiments, one or more of the panes in window 1400 may comprise stress distribution, structure, surface roughness fabricated as disclosed herein and/or have any combination described herein. and/or other physical properties of the building's glass-based layers (ie, heat-enhanced waves or glass-ceramics).

Referring to an example of a dual-pane embodiment of a window 1400 shown in FIG. 32 (cross-section along line 1-1 at the peripheral edge of the window 1400 in FIG. 31 ), the window 1400 includes a first glass-based layer 4102 and A second glass-based layer 4202 with a space or sealed interior region 4401 in between. In an embodiment, the first glass-based layer 4102 and the second glass-based layer 4202 face each other, are spaced apart from each other, and are disposed substantially parallel to each other. In an embodiment, the first glass-based layer 4102 includes a body 4101 having an outer surface 4104 opposite an inner surface 4106 and an outer edge 4108 . Outer surface 4104 and inner surface 4106 may be referred to herein as major surfaces. In an embodiment, the first glass-based layer 4102 includes an interior region between the major surfaces 4104, 4106 that defines a thickness t. In an embodiment, the second glass-based layer 4202 includes a body 4201 having an outer surface 4206 opposite an inner surface 4204 and an outer edge 4208 . Outer surface 4206 and inner surface 4204 may be referred to herein as major surfaces. In an embodiment, the second glass-based layer 4202 includes an interior region between the major surfaces 4204, 4206 that defines a thickness t. The glass-based layers 4102, 4202 may act as interior panes or exterior panes of a building.

At least one or both of the first and second glass-based layers 4102, 4202 are fabricated according to the systems and methods disclosed herein and/or have any combination of stress distributions, structures disclosed herein , glass composition, surface roughness etc. and/or physical properties of thermally enhanced architectural glass or glass-ceramic sheets. In one or more embodiments, the second glass-based layer 4202 is a thermally enhanced architectural glass or glass-ceramic sheet according to the present disclosure (e.g., FIG. 4 ), while the first glass-based layer 4102 is a thermally enhanced glass layer. , a chemically strengthened glass layer, a mechanically strengthened glass layer, a thermally and chemically strengthened glass layer, a thermally and mechanically strengthened glass layer, or a chemically and mechanically strengthened glass layer. The first and second glass-based layers 4102, 4202 may be the same or different glass material compositions as disclosed herein.

In mechanical strengthening, regions of compressive stress (CS) are created by mismatches in the coefficients of thermal expansion between parts of the glass ply. In thermal enhancement, the CS region is formed by heating the glass layer to an elevated temperature above the glass transition temperature, near the glass softening point, and then cooling the glass surface region more rapidly than the interior region of the glass layer. Different cooling rates between the surface area and the inner area create residual surface CS.

Chemically strengthened glass substrates may include compressive stress (CS) regions and central tension (CT) regions generated by ion exchange methods. In chemically strengthened glass layers, replacing smaller ions with larger ions at temperatures below which the glass network can relax produces a distribution of ions across the surface of the glass layer that results in stress distribution. The larger volume of incoming ions creates CS on the surface portion of the layer and tension (CT) in the center of the glass.

Surface compressive stress (CS) and compressive layer height (DOL) were determined by a surface stress meter (FSM) using a commercially available instrument such as FSM-6000 manufactured by Luceo Co., Ltd. (Tokyo, Japan), and In ASTM 1422C-99 titled "Standard Specification for Chemically Strengthened Flat Glass" and ASTM 1279.1977 titled "Standard Test Method for Non-Destructive Photoelastic Measurement of Edge and Surface Stresses in Annealed, Heat-Strengthened, and Fully-Tempered Flat Glass" Methods for measuring CS and layer height are described in ASTM, the contents of which are incorporated herein by reference in their entirety. Surface stress measurements rely on accurate measurements of the stress optic coefficient (SOC) associated with the birefringence of the glass. SOC is then measured by those methods known in the art, such as fiber and four-point bending methods (described in ASTM Standard C770-98 (2008) entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient" two methods described above, the contents of which are incorporated herein by reference in their entirety), and the bulk cylinder method.

When FSM is used to measure compressive stress, CS is related to CT by the following approximate relationship:

where thickness is the total thickness of the reinforced glass substrate. Unless otherwise indicated, CT and CS are expressed herein in megapascals (MPa), while thickness and DOL or DOC are expressed in millimeters or microns.

In one embodiment, the chemically strengthened (alone or in combination with other strengthening mechanisms) glass layer may have a thickness of 250 MPa or greater, 300 MPa or greater (e.g., 400 MPa or greater, 450 MPa or greater, 500 MPa or greater, 550 MPa or greater) greater, 600 MPa or greater, 650 MPa or greater, 700 MPa or greater, 750 MPa or greater, or 800 MPa or greater) surface CS. In one embodiment, the chemically strengthened (alone or in combination with other strengthening mechanisms) glass layer can have a thickness of 10 μm or greater, 15 μm or greater, 20 μm or greater (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or greater) and/or 10MPa or greater, 20Mpa or greater, 30MPa or greater, 40MPa or greater (eg, 42Mpa, 45Mpa or 50Mpa or greater) but less than 100Mpa (eg, 95, 90, 85 , 80, 75, 70, 65, 60, 55MPa or less) CT. In one or more specific embodiments, the chemically strengthened (alone or in combination with other strengthening mechanisms) glass layer has one or more of: a surface CS greater than 500 MPa, a DOL greater than 10 μm, and a CT greater than 18 MPa.

The window 1400 may also include members 4421 between its panes. The member 4421 may be an edge seal (e.g., glass frit, laser edge seal, solder, rubber) formed around the respective edges of the glass sheets 4102, 4202 (to form a hermetic or non-hermetic seal), the edge of the glass sheets 4102, 4202. Metal studs between surfaces, low thermal conductivity material or glass-bump spacers 50 attached to or integrally formed with one or both glass sheets. Member 4421 may help to create a space between one or two distances 4001, 4002 between its glass sheets. The window 1400 may also include a frame 4420 around the edges of its glass panes.

Space 4401 includes distance 4001 between glass-based layers 4102 and 4202 . Distance 4001 may be about 50 microns to about 50 mm, or about 0.1 mm to about 25 mm, or about 0.1 mm to about 23 mm, or about 0.2 mm to about 22 mm, or about 0.3 mm to about 21 mm, or about 0.4 mm to about 20 m , or about 0.5mm to about 19mm, or about 0.6mm to about 18mm, or about 0.7mm to about 17mm, or about 2mm to about 15mm. The space 4401 may be sealed and include an insulating gas such as air or a rare gas (eg, argon, krypton, xenon). Alternatively, space 4401 may be sealed and comprise a vacuum pressure less than atmospheric pressure (eg, 10 ⁻⁴ Torr). One or both of the first and second glass-based layers 4102, 4202 may include a low-E layer 4110 on any major surface thereof. Low-E layer 4110 may be a film, coating, or layer on the major surfaces of glass-based layers 4102 and 4202 or within the body. As shown in FIG. 32, a low-E layer 4110 is located on the interior surface 4106 of the first glass-based layer 4102 adjacent the outside of the building volume. One or both of the first and second glass-based layers 4102, 4202 may include an indium tin oxide layer or film for use in active smart windows such as electrochromic windows. One or both of the first and second glass-based layers 4102, 4202 may also include reflective coatings, clear coatings, polymer coatings, conductive coatings, matting films, or combinations thereof.

Figure 33 shows an exemplary embodiment of a window 1400 in which one of the panes is a laminate comprising a glass-based layer 4202 laminated to a glass sheet 4300 with an interlayer 4250 therebetween. In an embodiment, interlayer 4250 is at least partially coextensive with glass-based layer 4202 and is directly and/or indirectly coupled to one side of glass sheet 4300 . In an embodiment, the interlayer 4250 may comprise a polymeric material. Polymeric materials may include polyvinyl butyral (PVB), polycarbonate, acoustic PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomers, thermoplastics, and combinations thereof. Glass-based layer 4102 may alternatively or additionally be configured as a laminate.

Referring to an example of a three-pane embodiment of a window 1400 shown in FIG. 34 (cross-section along line 1 - 1 at the perimeter edge of the window 1400 in FIG. 31 ), the window 1400 includes a third glass-based layer 4302 . In an embodiment, the third glass-based layer 4302 includes a body 4301 having an outer surface 4304 opposite an inner surface 4306 and an outer edge 4308 . Outer surface 4304 and inner surface 4306 may be referred to herein as major surfaces. In an embodiment, the third glass-based layer 4302 includes an interior region between the major surfaces 4304, 4306 that defines a thickness t. In an embodiment, the third glass-based layer 4302 faces the first glass-based layer 4102 and/or the second glass-based layer 4202 and is spaced from the first glass-based layer 4102 and/or the second glass-based layer 4202 Open and disposed substantially parallel to the first glass-based layer 4102 and/or the second glass-based layer 4202 (with a second space or sealed interior region 4402 therebetween). In the embodiment of FIG. 43 , the third glass-based layer 4302 is spaced apart from the second glass-based layer 4202 by a second spaced apart distance 4002 . Accordingly, the glass-based layer 4302 can act as an interior pane or exterior pane of a building. The third glass-based layer 4302 may also be an intermediate pane between the first glass-based layer 4102 and/or the second glass-based layer 4202 of the three-pane window 1400 .

The third glass-based layer can be fabricated according to the systems and methods disclosed herein and/or have any combination of stress distribution, glass composition, structure, surface roughness properties, and/or thermal enhancement of physical properties disclosed herein architectural glass or glass-ceramic sheets. In one or more embodiments, the third glass-based layer 4302 is a thermally strengthened glass layer, a chemically strengthened glass layer, a mechanically strengthened glass layer, a thermally and chemically strengthened glass layer, a thermally and mechanically strengthened glass layer, or a chemically strengthened and mechanically strengthened glass layers. The third glass-based layer 4302 can be any glass composition or similar glass material disclosed herein. The first, second and third glass-based layers 4102, 4202, 4302 can be the same or a completely different glass material composition as disclosed herein. The third glass-based layer 4302 can include a low-E layer 4110 on any major surface thereof. Low-E layer 4110 may be a film, coating, or layer on a major surface of glass-based layer 4302 or within a body. In an embodiment, a third glass-based layer 4302 is laminated to a glass sheet 4300 with an interlayer 4250 in between. In an embodiment, interlayer 4250 is at least partially coextensive with glass-based layer 4302 and is directly and/or indirectly coupled to one side of glass sheet 4300 . The third glass-based layer 4302 may include an indium tin oxide layer or film for use in active smart windows such as electrochromic windows. The third glass-based layer 4302 may also include reflective coatings, clear coatings, polymer coatings, conductive coatings, matting films, or combinations thereof.

The first glass-based layer, second glass-based layer, third glass-based layer 4102, 4202, 4302 may also be configured as a dual-pane or triple-pane vacuum insulated glass (VIG) window. FIG. 35 is a front view of an exemplary embodiment of a VIG window 1500 . The configuration of VIG window 1500 may be similar to that of dual pane or triple pane window 1400 . VIG window 1500 may contain two panes or three panes. 36 is a cross-sectional view of the exemplary dual-pane VIG window 1500 of FIG. 35 viewed in direction 1 - 1 . In one embodiment, the VIG window 1500 includes a first glass-based layer 4102 (i.e., a heat-strengthened glass or glass-ceramic article) spaced from and positioned substantially parallel to a second glass-based layer 4202. Layer 4202 of glass. The first and second glass sheets 4102 , 4202 each include an inner surface 4106 , 4204 opposite an outer surface 4104 , 4206 . The first and second glass-based layers 4102 , 4202 also each include at least one outer edge 4108 , 4208 . In other embodiments, the VIG window 1500 can include a third glass-based layer 4302 that includes an inner surface 4304 opposite an outer surface 4306 and at least one outer edge 4308 . The third glass-based layer 4302 can be positioned between and substantially parallel to the first and second glass sheets 4102, 4202, or with the first glass sheet 4102 or the second glass sheet 4102. The main surfaces of the two glass plates 4202 are opposite to each other. The first, second and third glass-based layers 4102, 4202, 4302 may comprise any glass or glass-ceramic composition disclosed herein. One, two, or all of the glass-based layers 4102, 4202, 4302 may include stress profiles, glass compositions, structures, surfaces fabricated according to the systems and methods disclosed herein and/or have any combination disclosed herein Thermally enhanced architectural glass or glass-ceramic sheets of roughness properties and/or physical properties. In one embodiment where the window 1500 is not shown, at least one of the glass-based layers 4102, 4202, 4302 is configured as a laminate and laminated to a glass sheet 4300 with an interlayer 4250 therebetween (similar to that shown in FIG. 33 ). Show). In an embodiment, interlayer 4250 is at least partially coextensive with applicable glass-based layers (4102, 4202, 4302) and is directly and/or indirectly coupled to one side of glass sheet 4300. In an embodiment, the interlayer 4250 may comprise a polymeric material. One, two, or all of the glass-based layers 4102, 4202, 4302 in the window 1500 may be configured as a laminate. One, two, or all of the glass-based layers 4102 , 4202 , 4302 in the window 1500 may include a low-E layer 4110 within its body or on one or both major surfaces in the window 1500 . One, two, or all of the glass-based layers 4102, 4202, 4302 in window 1500 may include indium tin oxide layers or films for use in active smart windows such as electrochromic windows. One, two, or all of the glass-based layers 4102, 4202, 4302 (including the fourth glass-based layer) in the window 1500 may further include reflective coatings, clear coatings, polymer coatings, conductive coatings, Matting film or combination thereof. Matte films of the present disclosure may be partially transparent or opaque. Additionally, matte films can be decorative and/or functional.

VIG window 1500 also includes spacer 50 . In an embodiment, the spacers 50 are a plurality of glass-bump spacers 50 integrally formed in the inner surface 4204 of the second glass-based layer 4202 . Glass-bump spacers 50 may also be formed on inner surface 4106 of glass-based layer 4102 . FIG. 3 is a close-up view of an exemplary glass-bump spacer 50 . The glass-bump spacer 50 may be integrally formed in the first or second glass-based layer 4102, 4202, or added to the VIG window 1500 as a separate or discrete element. When integrally formed, glass bumps 50 are formed from (and thus consist of) the same material as the glass-based layer. Exemplary methods of forming glass bumps 50 (including by laser-induced irradiation on the major surfaces of the glass-based layers herein) are discussed in U.S. Patent Nos. 8,679,599 and 8,821,999, the entire contents of which are incorporated by reference Incorporated into this article. An exemplary method of etching glass bumps 50 from a glass sheet 20B is provided, for example, in U.S. Patent Application No. 62/248,715 (Attorney Docket No. 62/248,715), entitled "VACUUM INSULATED GLASS UNITS ANDMETHODOLOGY FOR MANUFACTURING THE SAME," The entire content of said application is incorporated herein by reference. Glass-bump spacers 50 may be provided or formed from glass-based layers 4102, 4202, 4302 either before or after applying thermal enhancement techniques to architectural glass or glass-ceramic sheets as disclosed herein. Spacer 50 may also be a discrete metal, ceramic, aluminum, plastic or glass spacer between panes 20B and 20F.

In the exemplary embodiment, glass-bump spacers 50 are evenly spaced relative to each other. Because glass-bump spacers 50 are integrally formed in bodies 4101, 4201, 4301, they are substantially invisible when viewing VIG window 1500 at a regular (ie, substantially normal incidence) viewing angle. Therefore, the glass bumps 50 are shown by dotted lines (dashed lines) in FIG. 35 . As shown in FIG. 3 , glass bump 50 has a "tip" or "top portion" 51 . As described below, the top portion 51 need not be rounded as shown in FIG. 37 . For example, the top portion 51 may have a larger radius of curvature or even have a flat top portion. Glass bump geometries according to the present disclosure are provided in U.S. Patent Application Serial No. 14/808,790 (Attorney Docket SP15-169PZ), entitled "GLASS BUMPS ON GLASS ARTICLES AND METHODS OF LASER-INDUCED GROWTH," which The entire contents are incorporated herein by reference. In an embodiment, the glass-based layer 4102, 4202, 4302 is transmissive at 420nm to 750nm. In an exemplary embodiment, glass-bump spacers 50 have a height ("bump height") H in the range of 50 μm to 300 μm, or 75 μm to 150 μm, and/or even 100 μm to 120 μm. In an embodiment, the height H of the glass-bump spacers 50 may define the separation distances 4001 , 4002 .

In the embodiment of FIG. 36 , glass-bump spacers 50 contact front glass-based layer 4101 (at surface 4106 ) to maintain first distance 4001 between front glass plate 4102 and rear glass plate 4202 . In an embodiment, the glass-based layer in window 1500 in contact with glass-bump spacers 50 is a sheet of thermally enhanced architectural glass or glass-ceramic fabricated according to the systems and methods disclosed herein. The compressive stress of the major surface thereon can help minimize point stresses at the top portion 51 of each glass-bump spacer 50 caused by vacuum forces in the space 4401 and thermal contraction and expansion of the opposing panes. damage.

A member 4421 (eg, an edge seal) may be provided between at least a portion of each outer edge at the respective outer edge 4108 and 4208 to provide a hermetic seal. The edge seal between the front glass-based layer 4102 and the rear glass-based layer 4202 defines a sealed interior region 4401 . In an embodiment, the edge seal is at least partially induced by a laser. The edge seal may be a frit seal, a seal directly between the glass-based layers 4102, 4202, or a seal with a spacer or glass section between the glass-based layers 4102, 4202.

Space 4401 may be at least partially evacuated such that it has a vacuum pressure of less than one atmosphere or less than atmospheric pressure (e.g., 10-4 Torr, or even less than 10-6 Torr), which provides VIG window 1500 with the desired thermal and acoustic insulation nature. In an embodiment, the members 4421 around the respective outer edges 4108, 4208 of the front glass-based layer 4102 and the rear glass-based layer 4102, 4202 are located between the surfaces of the front glass-based layer 4102 and the rear glass-based layer 4202. An airtight sealed space 4401 is created between 4106 and 4204 .

FIG. 38 is a cross-sectional view similar to FIG. 36 and showing an exemplary embodiment of a three-pane VIG window 1500 . A first set of glass-bump spacers and a second set of glass-bump spacers 50 are formed in the front surface 4204 and the rear surface 4206 of the second glass-based layer 4202, respectively, to maintain distance from the first glass-based layer 4102. and a distance 4002 from the third glass-based layer 4302. In the exemplary embodiment shown in FIG. 38, multiple edge seals may be used, with one edge seal being used to seal at least corresponding portions of edges 4108 and 4208 and another edge seal being used to seal at least corresponding portions of edges 4208 and 4308. part. In another exemplary embodiment, a single edge seal 4421 is used to seal edges 4108 , 4208 and 4308 to define two sealed interior regions 4401 and 4402 .

Of course, glass bump spacers may be formed on any surface of any two of the three glass-based layers 4102 , 4202 , 4302 in the VIG window 1500 . Glass-based layers 4102, 4202, 4302 may be referred to herein as front, middle, and rear glass-based layers. FIG. 39 is similar to FIG. 38 and shows an alternative exemplary embodiment of the triple-pane VIG window 1500 of FIG. 35 viewed in direction 1 - 1 . In this embodiment, the second set of glass-bump spacers 50 is on the third glass-based layer 4302 rather than in the middle glass-based layer 4202 . Figure 39 also shows an exemplary embodiment using multiple members 4421 (eg, edge banding) as described above. FIG. 40 is similar to FIG. 38 and shows yet another alternative exemplary embodiment of a triple-pane VIG window 1500 in which the first set of glass-bump spacers 50 are on the front glass-based layer 4102 rather than in the middle. Layer 4202 of glass. Thus, in the embodiment shown in Figure 40, the glass-bump spacers 50 are formed in the inner and outer glass-based layers, while in the embodiment shown in Figure 38, the glass-bump spacers are formed in the middle glass-based layer. formed in the layer.

One, two, or all of the glass-based layers 4102, 4202, 4302 (including the fourth glass-based layer) in the VIG window 1500 may be fabricated according to the systems and methods disclosed herein and/or have Any combination of stress distribution, glass composition, structure, surface roughness properties, and/or physical properties of a thermally enhanced architectural glass or glass-ceramic sheet. In other embodiments, one, two, or all of the glass-based layers 4102, 4202, 4302 may be thermally strengthened glass layers, chemically strengthened glass layers, mechanically strengthened glass layers, thermally and chemically strengthened glass layers, thermally strengthened and mechanically strengthened glass plies or chemically and mechanically strengthened glass plies.

The thinner thickness of the architectural glass or glass-ceramic article 1012 may not compromise the functionality of the architectural glass or glass-ceramic article 1012 in architectural windows, automotive, or other applications relative to conventional articles because the architectural glass or glass-ceramic article 1012 provided by the inventive methods disclosed herein or The high level of strength of the glass-ceramic article 1012. Thin architectural glass or glass-ceramic articles 1012 may be particularly useful in such architectural windows or other applications as layers or panes, as architectural glass or glass-ceramic articles 1012 may be lighter than conventional such articles, thereby reducing the corresponding overall the weight of the structure. For cars, the result can be greater fuel efficiency. For buildings, the result can be lighter, stronger or less resource-intensive structures. In other contemplated embodiments, the architectural glass or glass-ceramic articles disclosed herein may have regions of smaller amplitude, greater thickness, transmit less light, and/or may be used in different applications, for example as described with respect to FIG. 27 -30 those applications that are exposed.

Referring to FIG. 28, a surface 1110 includes a glass or glass-ceramic article 1112 fabricated as disclosed herein and/or having any combination of stress distributions, structures, and/or physical properties discussed herein, and used as a countertop and/or as a surface for a display. part. In some embodiments, the total transmission through glass or glass-ceramic article 1012 is at least about 30% (eg, at least 50%) for infrared wavelengths from about 800 nm to about 1500 nm, thereby facilitating use of surface 1110 as a cooker. In some embodiments, the glass or glass-ceramic article 1112 has a coefficient of thermal expansion (CTE) of about ^10x10-7 °C ^-1 to about ^140x10-7 °C ^-1 , about ^20x10-7 °C ^-1 to about ^120x10-7 °C ^-1 , about 30x10 ^-7 ℃ ^-1 to about 100x10 ^-7 ℃ ^-1 , about 40x10 ^-7 ℃ ^-1 to about 100x10 ^-7 ℃ ^-1 , about 50x10 ^-7 ℃ ^-1 to about 100x10 ^-7 ℃ ^-1 , or from about 60x10 ^-7 °C ^-1 to about 120x10 ^-7 °C ^-1 . In various embodiments, the method is ideally suited for glass compositions having a moderate to high CTE. Exemplary glasses that work well with the methods described herein include alkali aluminosilicates such as glass, boroaluminosilicate and soda lime glass. In some embodiments, the glass used has a CTE of greater than 40, greater than 50, greater than 60, greater than 70, greater than 80, or greater than 90×10 ⁻⁷ /°C. As disclosed herein, some such CTEs may be particularly low for thermal tempering as described herein, wherein the degree of negative tensile stress is no greater than 50 MPa and/or at least 10 MPa.

Referring to FIG. 29, a device 1210 (e.g., a handheld computer, tablet computer, portable computer, cellular phone, television, display panel, etc.) includes one or more glass or glass-ceramic articles 1212, 1214, 1216, as disclosed herein. Manufacture and/or have any combination of stress distributions, structures and/or physical properties as disclosed herein, and also include electronic components 1218 and housing 1220 . In contemplated embodiments, housing 1220 may be or include a glass or glass-ceramic article as disclosed herein. In contemplated embodiments, the substrate 1222 for the electronic component 1218 may be a glass or glass-ceramic article as disclosed herein.

In some embodiments, glass or glass-ceramic articles 1212 , 1214 can be used as front and backplane substrates, and glass or glass-ceramic article 1216 can be used as a cover glass in device 1210 . According to an exemplary embodiment, the glass or glass-ceramic article 1216 of the device 1210 is an alkali aluminosilicate glass. Such a composition may allow the glass or glass-ceramic article 1216 to be strengthened by thermal tempering as disclosed herein, and may additionally be strengthened by ion exchange, thereby providing a particularly high degree of negative tensile stress at or near its surface (e.g. , at least 200MPa, at least 250MPa). In other embodiments, the glass or glass-ceramic article 1216 can include sodium carbonate, calcium oxide, calcium magnesium carbonate, silica (e.g., at least 70% by weight), alumina, and/or other components; Invention method to enhance. Glass or glass-ceramic article 1216 may be particularly thin or otherwise configured, such as having any dimensions as disclosed herein.

Referring now to FIG. 30, an architectural glass or glass-ceramic article 1310 manufactured according to the methods disclosed herein and/or having any combination of stress distribution, structure, and/or physical properties as disclosed herein has curvature and/or variable cross-sectional dimensions d. Such articles may have the thicknesses disclosed herein, such as the average value of dimension D or the maximum value of dimension D. While architectural glass or glass-ceramic article 1310 is shown as a curved sheet, other shapes, such as more complex shapes, can be enhanced by the methods disclosed herein. In contemplated embodiments, architectural glass or glass-ceramic article 1310 may be used as a window in a vehicle (eg, a sunroof) or in a building (as a roof window) or for other applications.

In various embodiments, glass materials manufactured according to the methods disclosed herein and/or having any combination of stress distribution, structure, and/or physical properties disclosed herein can be used to form at least one piece of architectural glass-polymer-interlayer - Glass laminate. Stronger and thinner laminates can be produced, resulting in weight and cost savings. Ideally, the thermally enhanced thin sheet could be cold bent (see generally Figure 30) and laminated to the formed thicker glass, providing a simple and reliable manufacturing method without requiring any thermoforming/forming of the thin sheet.

Glass and glass-ceramic materials for heat-strengthened architectural glass sheets

The systems and methods discussed can be used to thermally condition, strengthen and/or toughen a wide variety of architectural glass and/or glass-ceramic materials.

The methods and systems described herein can generally be used with virtually any architectural glass composition, and some embodiments can be used with architectural glass laminates, architectural glass-ceramics, and/or ceramics. In various embodiments, the method can be used with architectural glass compositions having a high CTE. In embodiments, architectural glass reinforced by the methods and systems described herein includes alkali aluminosilicates such as of glass), SLG, sodium-free or alkali-free glass, etc. In some embodiments, architectural glass enhanced by the processes and systems discussed herein has a CTE of greater than ^40x10-7 /°C, greater than ^50x10-7 /°C, greater than ^60x10-7 /°C, greater than ^70x10-7 /°C, greater than 80x10 ^-7 /°C or greater than 90x10 ^-7 /°C.

In some applications and embodiments, architectural glass reinforced by the methods and systems discussed herein, such as architectural glass sheet 500, may have a composition configured for chemical durability. In some such embodiments, the composition comprises at least 70% by weight silica, and/or at least 10% by weight sodium oxide, and/or at least 7% by weight calcium oxide. Conventional articles with such compositions may be difficult to chemically toughen to greater depths, and/or may be difficult, if not impossible, to thermally toughen by conventional means to a sufficient magnitude of negative surface tension stress for thinner thicknesses, Such as due to the fragility and strength of conventional methods. However, in contemplated embodiments, the inventive methods disclosed herein allow for reinforced architectural glass or glass-ceramic articles or sheets (such as architectural glass sheet 500) having such compositions, wherein negative tensile stress emanates from the first surface and the second surface. At least one of the surfaces (e.g., surface 510, surface 520 of architectural glass sheet 500) extends into the corresponding reinforced architectural glass or glass-ceramic sheet for a distance that is at least the thickness of the reinforced architectural glass or glass-ceramic sheet. 10%, such as at least 12% of thickness, 15% of thickness, 18% of thickness, 20% of thickness.

In some embodiments, architectural glass or glass-ceramic sheets and articles strengthened as discussed herein have one or more coatings placed on the architectural glass prior to thermal strengthening of the architectural glass sheet. The methods discussed herein can be used to produce reinforced architectural glass sheets with one or more coatings, and in some such embodiments, the coatings are placed on the architectural glass prior to thermal strengthening and the coatings are not affected by the thermal strengthening method . Specific coatings that are advantageously preserved on architectural glass sheets of the present disclosure include low-E coatings, reflective coatings, anti-reflective coatings, anti-fingerprint coatings, cut-off filters, pyrolytic coatings, and the like.

According to an exemplary embodiment, the glass or glass-ceramic sheets or articles discussed herein (eg, articles 1212, 1214 of device 1210 shown in FIG. 29) are boroaluminosilicate glass. In some embodiments, the glass or glass-ceramic sheets or articles discussed herein (eg, articles 1212, 1214 of device 1210 shown in FIG. 29 ) are generally non-alkaline glasses, but still have stress distributions and structures as disclosed herein. This composition reduces the degree of relaxation of architectural glass, thereby facilitating the coupling of electronic devices to it (such as electrochromic windows). In some embodiments, the architectural glass sheets/articles discussed herein are flexible architectural glass sheets. In other embodiments, the architectural glass sheets/articles discussed herein comprise laminates of two or more architectural glass sheets.

In some contemplated embodiments, architectural glass reinforced by the methods and systems discussed herein, such as architectural glass sheet 500, may include an amorphous substrate, a crystalline substrate, or a combination thereof, such as an architectural glass-ceramic substrate. Architectural glass reinforced by the methods and systems discussed herein, such as architectural glass sheet 500, may include alkali aluminosilicate glass, alkali-containing borosilicate glass, alkali aluminophosphate glass, or alkali aluminoborosilicate glass. Salt glass, photochromic glass, electrochromic glass or thermochromic glass. In one or more embodiments, architectural glass reinforced by the methods and systems discussed herein, such as architectural glass sheet 500, may include, in its non-ion-exchanged portion, a composition having Architectural glass comprising: about (eg, plus or minus 1%) SiO ₂ in the range of about (eg, plus or minus 1%) 40 mol % to about 80 mol %, Al ₂ O ₃ in the range of about 10 mol % to about 30 mol %, about 0 mol % to about B ₂ O ₃ in the range of about 10 mol%, R ₁₀ O in the range of about 0 mol% to about 20 mol%, and/or RO in the range of about 0 mol% to about 15 mol%. In some contemplated embodiments, the composition may include either or both of: ZrO2 in the range of about 0 mol% to about 5 mol% and _P2O5 in the range of about 0 mol% to about 15 mol%. In some contemplated embodiments, _Ti02 may be present at about 0 mol% to about 2 mol%.

In some contemplated embodiments, compositions for the reinforced glass or glass _- ceramic sheets or articles discussed herein may be dosed with 0-2 mol % of at least one fining agent selected from the group consisting of: _Na2SO4 , NaCl, NaF, NaBr, K ₂ SO ₄ , KCl, KF, KBr, and SnO ₂ . The architectural glass composition according to one or more embodiments may further include SnO ₂ in the following range: about 0 to about 2 mol %, about 0 to about 1 mol%, about 0.1 to about 2 mol%, about 0.1 to about 1 mol%, or about 1 to about 2 mol%. In some embodiments, the architectural glass compositions disclosed herein that reinforce architectural glass or glass-ceramic sheet 500 can be substantially free of AS ₂ O ₃ and/or Sb ₂ O ₃ .

In contemplated embodiments, the reinforced architectural glass or glass-ceramic sheets or articles discussed herein may include alkali aluminosilicate architectural glass compositions, or alkali aluminoborosilicate architectural glass compositions further strengthened by an ion exchange process thing. An exemplary architectural glass composition includes SiO ₂ , B ₂ O ₃ and Na ₂ O, wherein (SiO ₂ +B ₂ O ₃ )≧66 mol.% and/or Na ₂ O≧9 mol.%. In one embodiment, the architectural glass composition comprises at least 6% by weight alumina. In another embodiment, the reinforced architectural glass or glass-ceramic sheet or article discussed herein may comprise an architectural glass composition having one or more alkaline earth oxides such that the alkaline earth oxide content is at least 5% by weight. _In some embodiments, suitable architectural glass compositions further comprise at least one of K2O, MgO, and CaO. In a specific embodiment, the architectural glass composition used in the reinforced architectural glass or glass-ceramic sheet or article discussed herein may comprise 61-75 mol % SiO ₂ ; 7-15 mol % Al ₂ O ₃ ; 0-12 mol % 9-21 mol% Na ₂ O _; 0-4 mol% K ₂ O _; 0-7 mol% MgO; and/or 0-3 mol% CaO.

Another exemplary glass composition suitable for use in reinforcing architectural glass or glass-ceramic sheets or articles discussed herein includes: 60-70 mol.% SiO ₂ ; 6-14 mol.% Al ₂ O ₃ ; 0-15 mol.% B ₂ O ₃ ; 0-15 mol.% Li ₂ O; 0-20 mol.% Na ₂ O; 0-10 mol.% K ₂ O; 0-8 mol.% MgO; 0-10 mol.% CaO ; 0-5mol.%) ZrO ₂ ; 0-1mol.% SnO ₂ ; 0-1mol.% CeO ₂ ; AS ₂ O ₃ less than 50ppm; and Sb ₂ O ₃ less than 50ppm; (Li ₂ O+Na ₂ O+K ₂ O)≦20 mol.% and/or 0 mol.%≦(MgO+CaO)≦10 mol.%. Yet another exemplary glass composition suitable for use in reinforcing architectural glass or glass-ceramic sheets or articles discussed herein includes: 63.5-66.5 mol.% SiO ₂ ; 8-12 mol.% Al ₂ O ₃ ; 0-3 mol. % of B ₂ O ₃ ; 0-5mol.% of Li ₂ O; 8-18mol.% of Na ₂ O; 0-5mol.% of K ₂ O; 1-7mol.% of MgO; 0-2.5mol. % CaO; 0-3 mol.%) ZrO ₂ ; 0.05-0.25 mol.% SnO ₂ ; 0.05-0.5 mol.% CeO ₂ ; less than 50 ppm AS ₂ O ₃ ; and less than 50 ppm Sb ₂ O ₃ ; Wherein 14 mol.%≤(Li ₂ O+Na ₂ O+K ₂ O)≤18 mol.% and/or 2 mol.%≤(MgO+CaO)≤7 mol.%.

In particularly contemplated embodiments, alkali aluminosilicate glass compositions suitable for use in reinforcing architectural glass or glass-ceramic sheets or articles discussed herein comprise alumina, at least one alkali metal, and in some embodiments more than 50 mol.% SiO ₂ , including at least 58 mol.% SiO ₂ in other embodiments, and at least 60 mol.% SiO 2 in other embodiments, where (Al ₂ O ₃ +B ₂ O ₃ )/ The ratio of the Σ modifier (ie the total amount of the modifier) is greater than 1, wherein in the ratio, the component is expressed in mol.% and the modifier is an alkali metal oxide. In a specific embodiment, the architectural glass composition comprises: 58-72 mol.% SiO ₂ ; 9-17 mol.% Al ₂ O ₃ ; 2-12 mol.% B ₂ O ₃ ; 8-16 mol.% and/or 0-4mol.% K ₂ O, wherein the ratio of (Al ₂ O ₃ +B ₂ O _{3 )} /∑ modifier (ie the total amount of modifier) is greater than 1. In yet another embodiment, the reinforced architectural glass or glass-ceramic sheet 500 may comprise an alkali aluminosilicate glass composition comprising: 64-68 mol. % SiO ₂ ; 12-16 mol. % Na ₂ O; 8 -12mol.% of Al ₂ O ₃ ; 0-3mol.% of B ₂ O ₃ ; 2-5mol.% of K ₂ O; 4-6mol.% of MgO; and 0-5mol.% of CaO, of which 66mol .%≤SiO ₂ +B ₂ O ₃ +CaO≤69mol.%; Na ₂ O+K ₂ O+B ₂ O ₃ +MgO+CaO+SrO>10mol.%; 5mol.%≤MgO+CaO+SrO≤ 8mol.%; (Na2O ₊ B2O3 _{) -Al2O3≤2mol} .%; _2mol .% _{≤Na2O - Al2O3≤6mol} .% _; and 4mol.%≤ ₍ Na2O +K ₂ O)—Al ₂ O ₃ ≤10 mol.%. In alternative embodiments, the reinforced architectural glass or glass-ceramic sheets or articles discussed herein may include alkali aluminosilicate glass compositions comprising: 2 mol % or more of Al ₂ O ₃ and/or ZrO ₂ , or 4 mol% or more of Al ₂ O ₃ and/or ZrO ₂ .

In contemplated embodiments, examples of suitable glass-ceramics for the reinforced glass or glass-ceramic sheets or articles discussed herein may include _Li2O - _{Al2O3 - SiO2} system (ie LAS system) glass ceramics, MgO- Al ₂ O ₃ -SiO ₂ system (i.e. MAS system) glass ceramics, and/or glass ceramics comprising dominant crystalline phases including β-quartz solid solution, β-spodumene ss, cordierite, and pyrosilica Lithium Oxide. The reinforced architectural glass or glass-ceramic sheets or articles discussed herein may be characterized by the manner in which they are formed. For example, the reinforced architectural glass or glass-ceramic sheets or articles discussed herein may be characterized as float formable (i.e., formed by the float glass production process), down drawable, and in particular, melt formable, Or grooveable (ie, formed by a down method such as a fusion drawing method or a slot drawing method).

Float-formed reinforced architectural glass or glass-ceramic sheets or articles can be characterized by a smooth surface and consistent thickness, and are produced by placing molten architectural glass floats on a bed of molten metal, usually tin. In an exemplary method, molten architectural glass or glass-ceramic fed onto the surface of a bed of molten tin forms a float architectural glass or glass-ceramic ribbon. As the ribbon of architectural glass flows along the tin bath, the temperature gradually drops until the ribbon of architectural glass or glass-ceramic solidifies into a solid architectural glass or glass-ceramic article that can be lifted from the tin onto the drum. Once out of the tin bath, the architectural glass or glass-ceramic article can be further cooled and annealed to reduce internal stresses. Where the architectural glass or glass-ceramic article is a glass-ceramic, the architectural glass article formed by the float glass production process may be subjected to a ceramization process by which one or more crystalline phases are produced.

The down-draw method produces architectural glass or glass-ceramic articles with a consistent thickness relative to the pristine surface. Because the average flexural strength of an architectural glass or glass-ceramic article is controlled by the amount and size of surface defects, pristine surfaces with minimal contact have higher initial strength. When this high-strength architectural glass or glass-ceramic article is then further strengthened (eg chemically), the resulting strength can be higher than that of an architectural glass or glass-ceramic article with ground and polished surfaces. Down-drawn architectural glass or glass-ceramic articles can be drawn to a thickness of less than about 2 mm. Furthermore, down-drawn architectural glass or glass-ceramic articles have very flat, smooth surfaces that can be used in their end applications without costly grinding and polishing. Where the architectural glass or glass-ceramic article is a glass-ceramic, the architectural glass or glass-ceramic article formed by the down-draw process may be subjected to a ceramization process by which one or more crystalline phases are produced.

For example, the fusion draw method uses a draw tank having channels for receiving molten architectural glass feedstock. On both sides of the channel, the weirs of the channel are open at the top along the length of the channel. As the channel fills with molten material, molten architectural glass overflows the weir. Due to gravity, the molten architectural glass flows down the outer surface of the drawing tank as two flowing membranes of architectural glass. These outer surfaces of the draw channel extend downward and inward such that they join at the edge below the draw channel. The two flowing architectural glass films join at this edge to form a single flowing architectural glass article. An advantage of the fusion draw method is that because the two architectural glass films flowing over the channel are fused together, none of the outer surfaces of the resulting architectural glass article touch any part of the device. Thus, the surface properties of fusion drawn architectural glass articles are not affected by this contact. Where the architectural glass or glass-ceramic article is a glass-ceramic, the architectural glass or glass-ceramic article formed by the melting process can be subjected to a ceramization process by which one or more crystalline phases are produced.

The slot drawing method is different from the fusion drawing method. In the slot drawing method, molten raw glass is supplied to a drawing tank. The bottom of the draw tank has an open tank and a nozzle extending along the length of the tank. The molten glass flows through the slot/nozzle and is drawn as a continuous glass article down and into the annealing zone. Where the architectural glass or glass-ceramic article is a glass-ceramic, the architectural glass article formed by the slot drawing process may be subjected to a ceramization process by which one or more crystalline phases are produced.

In some embodiments, architectural glass articles may be formed using thin rolling processes as described in U.S. Patent No. 8,713,972, U.S. Patent No. 9,003,835, U.S. Patent Publication No. 2015/0027169, and U.S. Patent Publication No. 20050099618, the The contents are hereby incorporated by reference in their entirety. More specifically, architectural glass or glass-ceramic articles may be formed by: supplying a vertical stream of molten glass; and shaping the supplied stream of molten glass or glass-ceramic with a pair of forming rolls maintained at about 500°C or higher, or a surface temperature of about 600° C. or higher, to form a shaped architectural glass ribbon having a formed thickness; the formed glass ribbon is sized with a pair of sizing rollers held at about A surface temperature of 400° C. or less to produce a sized glass ribbon having a desired thickness less than that formed and a desired thickness consistency. Apparatus for forming a glass ribbon may include: a glass supply for supplying a supply stream of molten glass; a pair of forming rolls maintained at a surface temperature of about 500° C. or greater, the forming rolls spaced closely adjacent to each other open so as to define a glass forming gap between the forming rolls, wherein the glass forming gap is positioned vertically below the glass supply for receiving a supply flow of molten glass and to flow the supply flow of molten glass between the forming rolls Thin to form a shaped glass ribbon having a formed thickness; and a pair of sizing rolls maintained at a surface temperature of about 400° C. or less, the sizing rolls spaced closely adjacent to each other so that defining a glass sizing gap therebetween, wherein the glass sizing gap is positioned vertically below the forming rolls for receiving and thinning the shaped architectural glass ribbon to produce a sized ribbon of desired thickness and desired thickness consistency architectural glass strips.

In some cases, thin rolling methods may be used when the viscosity of architectural glass does not allow the use of fusion or slot draw methods. For example, thin rolling can be utilized to form architectural glass or glass-ceramic articles when the glass exhibits a liquidus viscosity of less than 100 kP. Architectural glass or glass-ceramic articles may be acid-polished or otherwise treated to remove or reduce the effects of surface imperfections.

In contemplated embodiments, the architectural glass or glass-ceramic sheets or articles discussed herein have compositions that vary from side surface to side. On one side of the architectural glass or glass-ceramic sheet 500, exemplary compositions are: 69-75% by weight SiO ₂ , 0-1.5% by weight Al ₂ O ₃ , 8-12% by weight CaO, 0-0.1 Weight % of Cl, 0-500 ppm of Fe, 0-500 ppm of K, 0.0-4.5 weight % of MgO, 12-15 weight % of Na ₂ O, 0-0.5 weight % of SO ₃ , 0-0.5 weight % of SnO ₂ , 0-0.1 wt % SrO, 0-0.1 wt % TiO ₂ , 0-0.1 wt % ZnO, and/or 0-0.1 wt % ZrO ₂ . On the other side of the architectural glass or glass-ceramic sheet or article discussed herein, an exemplary composition is: 73.16 wt % SiO ₂ , 0.076 wt % Al ₂ O ₃ , 9.91 wt % CaO, 0.014 wt % _Cl , 0.1 wt% _Fe2O3 , 0.029 wt% K2O, _2.792 wt% MgO, _13.054 wt% Na2O, 0.174 wt% SO3, 0.001 wt _{% SnO2} , 0.01 wt% SrO, 0.01 wt% TiO ₂ , 0.002 wt% ZnO, and/or 0.005 wt% ZrO ₂ .

In other contemplated embodiments, the compositions of the architectural glass or glass-ceramic sheets or articles discussed herein include: 55-85% by weight SiO ₂ , 0-30% by weight Al ₂ O ₃ , 0-20% by weight B ₂ O ₃ , 0-25% by weight of Na ₂ O, 0-20% by weight of CaO, 0-20% by weight of K ₂ O, 0-15% by weight of MgO, 5-20% by weight of BaO, 0.002 - 0.06% by weight of Fe ₂ O ₃ , and/or 0.0001-0.06% by weight of Cr ₂ O ₃ . In other contemplated embodiments, the compositions of the glass or glass-ceramic sheets or articles discussed herein include 60-72 mol % SiO ₂ , 3.4-8 mol % Al ₂ O ₃ , 13-16 mol % Na ₂ O, 0 - 1 mol% K ₂ O, 3.3-6 mol% MgO, 0-0.2 mol% TiO ₂ , 0.01-0.15 mol% Fe ₂ O ₃ , 6.5-9 mol% CaO, and/or 0.02-0.4 mol% of SO ₃ .

Example

Equipment Setup - As detailed above, the equipment included three zones - a hot zone, a transition zone and a cold or quench zone. The gap between the hot zone and the top and bottom thermal bearings (radiators) of the quench zone is set to the desired spacing. Set gas flow rates in the hot zone, transition zone and quench zone to ensure that architectural glazing materials, sheets or sections are centered on air bearings. The hot zone is preheated to the desired T ₀ from which the architectural _glazing will subsequently be quenched. To ensure uniform heating, the architectural glazing is preheated in a separate preheating device, such as a batch or continuous furnace. Typically, architectural glass sheets are preheated for more than 5 minutes before being loaded into the hot zone. For soda lime glass, preheat at around 450°C. After the preheating phase, the architectural glazing is loaded into the hot zone and allowed to equilibrate, where equilibration is where the architectural glazing is homogeneous at _T0 . T ₀ can be determined by the degree of strengthening/toughening desired, but generally remains in the range between the softening point and the glass transition temperature. The time to reach equilibrium depends at least on the thickness of the architectural glass. For example, for architectural glass sheets of about 1.1 mm or smaller, equilibration occurs in about 10 seconds. Equilibration occurs in about 10 seconds to 30 seconds for a 3mm sheet of architectural glass. For thicker sheets (up to about 6 mm), the equilibration time may be around 60 seconds. Once the architectural glass has equilibrated to T ₀ , it is rapidly transferred through the transition zone on the air bearing and into the cooling or quenching zone. Architectural glass products are rapidly quenched in the quenching zone to a temperature below the glass transition temperature Tg. Depending on the desired degree of quenching and/or the desired architectural glass temperature upon removal, the sheet of architectural glass may remain in the quenching zone for any period of time of 1 second, 10 seconds, or several minutes or longer. After removal, the architectural glass is optionally allowed to cool before processing.

Table VI summarizes the following examples.

Example 1 - A sheet of soda lime silicate glass (e.g., comprising at least 70% by weight of silicon dioxide, and/or at least 10% by weight of sodium oxide, and/or at least 7% by weight of calcium) at 450°C for 10 minutes, after which it was transferred to a hot zone where the glass sheet was held at a _T0 of 690°C for 60 seconds. After equilibrating to _T0 , the glass sheet was quickly transferred to a helium-filled quenching zone with a gap of 91 μm (where the gap is the distance between the surface of the glass sheet and the nearest heat sink), in which the The glass slide was held for 10 seconds. The resulting article had a surface compression of -312 MPa, a central tension of 127 MPa, and a flatness of 83 μm.

Example 2 - A sheet of soda lime silicate glass with a thickness of 5.7 mm was preheated at 450°C for 10 minutes before being transferred to a hot zone where the sheet was heated at a T of 690°C ₀ for 60 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 91 μm, where it was held for 10 seconds. The resulting article had a surface compression of -317 MPa, a central tension of 133 MPa, and a flatness of about 89.7 μm.

Example 3 - A sheet of soda lime silicate glass with a thickness of 1.1 mm was preheated at 450°C for 10 minutes before being transferred to a hot zone where the sheet was heated at a T of 700°C ₀ for 10 seconds. After equilibration, the glass sheet was quickly transferred to a helium-filled quench zone with a gap of 56 μm, where it was held for 10 seconds. The fictive temperature of the surface of the resulting article was measured to be 661°C, the surface compression was -176 MPa, the central tension was 89 MPa, the flatness was 190 μm, and the Vickers cracking threshold was 10-20N.

Example 4 - A sheet of soda lime silicate glass with a thickness of 0.55 mm was preheated at 450°C for 10 minutes before being transferred to a hot zone where the sheet was heated at a T of 720°C ₀ for 10 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 25 μm, where it was held for 10 seconds, resulting in an effective heat transfer rate of 0.184 cal/(cm ² -s-° C.) . The resulting article had a surface compression of -176 MPa and a central tension of 63 MPa. In addition, the resulting reinforced article had a flatness of about 168 microns for the sample with an initial temperature of 710°C and 125 microns for the sample with an initial temperature of 720°C.

Embodiment 5 - the thickness is 1.5mm The glass sheet was preheated at 550°C for 10 minutes before it was transferred to a hot zone where it was held at a _T0 of 790°C for 30 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 226 μm, where it was held for 10 seconds. The improvement in the flatness of the glass article was measured to be 113 μm (before treatment) and 58 μm (after treatment).

Example 6 - A sheet of soda lime silicate glass with a thickness of 0.7 mm was preheated at 450°C for 10 minutes before being transferred to a hot zone where the sheet was heated at a T of 730°C ₀ for 10 seconds. After equilibration, the glass sheet was quickly transferred to a helium-filled quench zone with a gap of 31 μm, where it was held for 10 seconds, resulting in an effective heat transfer rate of 0.149 cal/(cm ² - s-°C). The resulting article had a surface compression of -206 MPa, a central tension of 100 MPa, and a flatness of 82 μm. At breakage, glass flakes were observed to "chop" (the standard term used for sheet dicing of 2 mm thickness or greater - i.e. a 5x5 cm2 glass flake breaking into 40 or more flakes), indicating that the flakes The material is fully tempered.

Example 7 - A Borofloat-33 glass sheet with a thickness of 3.3 mm was preheated at 550°C for 10 minutes before being transferred to a hot zone where the glass sheet was heated _at a T of 800°C Hold for 30 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 119 μm, where it was held for 10 seconds. The flatness of the obtained article was 120 μm. When the part breaks, "chipping" (the standard term used for dicing of sheet material of 2 mm thickness or more - i.e. a 5x5 cm square glass sheet breaks into 40 or more pieces) is observed, indicating that the sheet The material is fully tempered.

Example 8 - A sheet of soda lime silicate glass with a thickness of 3.2mm was preheated at 450°C for 10 minutes before being transferred to a hot zone where the sheet was heated at a T of 690°C ₀ for 30 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 84 μm, where it was held for 10 seconds. The resulting article had a surface compression of -218 MPa, a central tension of 105 MPa, and a flatness of 84 μm.

Example 9 - A sheet of soda lime silicate glass with a thickness of 0.3 mm was preheated at 450°C for 10 minutes before being transferred to a hot zone where the sheet was heated at a T of 630°C ₀ for 10 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 159 μm, where it was held for 10 seconds. The resulting article had film stress observable by gray field polarimetry, indicating that the glass had incorporated thermal stress.

Embodiment 10 - the thickness is 0.1mm The glass sheet was preheated at 550°C for 10 minutes before it was transferred to a hot zone where it was held at a _T0 of 820°C for 10 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 141 μm, where it was held for 10 seconds, resulting in an effective heat transfer rate of 0.033 cal/( ^cm2 -s-°C) . At fracture, the resulting articles exhibit behavior consistent with residual stress glasses.

Example 11 - A sheet of soda lime silicate glass with a thickness of 1.1 mm was preheated at 450°C for 10 minutes before being transferred to a hot zone where the sheet was heated at a T of 700°C ₀ for 10 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 65 μm where it was held for 10 seconds resulting in an effective heat transfer rate of 0.07 cal/(cm ² -s-° C.) . The fictive temperature of the surface of the resulting article was measured to be 657°C, the surface compression was -201 MPa, the central tension was 98 MPa, the flatness was 158 μm, and the Vickers cracking threshold was 10-20N.

Embodiment 12 - the thickness is 1.1mm The glass sheet was preheated at 550°C for 10 minutes before it was transferred to a hot zone where it was held at a _T0 of 810°C for 10 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 86 μm where it was held for 10 seconds resulting in an effective heat transfer rate of 0.058 cal/(cm ² -s-°C) . The fictive temperature of the surface of the resulting article was measured to be 711 °C, the surface compression was -201 MPa, the central tension was 67 MPa, and the Vickers cracking threshold was 20-30N.

Embodiment 13 - the thickness is 1.1mm The glass sheet was preheated at 550°C for 10 minutes before it was transferred to a hot zone where it was held at a _T0 of 800°C for 10 seconds. After equilibration, the glass sheet was quickly transferred to a quench zone with a gap of 91 μm, where it was held for 10 seconds. The fictive temperature of the surface of the resulting article was measured to be 747°C, the surface compression was -138 MPa, the central tension was 53 MPa, the flatness was 66 μm, and the Vickers cracking threshold was 20-30N.

Table VI

Additional Example - Treatment of a 5.7mm thick glass sheet (comprising at least 70% by weight of silica and/or at least 10% by weight of sodium oxide and/or or at least 7% by weight of calcium oxide). The glass is heated to an initial temperature of about 690°C and rapidly cooled. The resulting reinforced article has a negative tensile stress of about 300 MPa on its surface and a positive tensile stress of about 121 MPa in the center. Furthermore, the flatness of the resulting reinforced article was about 106.9 microns.

Additional Example - In one embodiment using the inventive techniques disclosed herein, a glass sheet having a thickness of 1.1 mm (comprising at least 70% by weight of silicon and/or at least 10% by weight sodium oxide and/or at least 7% by weight calcium oxide). The glass is heated to an initial temperature of about 680°C and rapidly cooled. The resulting reinforced article has a negative tensile stress of about 112 MPa on its surface and a positive tensile stress of about 54 MPa in the center. Before reinforcement, the glass sheet had a flatness of about 96 microns, but the resulting reinforced article had a flatness of about 60 microns. Thus, the strengthening method also flattens the strengthened glass or glass-ceramic article.

Other aspects and advantages will be apparent from a reading of the entire specification and appended claims.

The construction and arrangement of architectural glass and glass-ceramics, as shown in the various exemplary embodiments, is illustrative only. Although only a few embodiments have been described in detail in this disclosure, many modifications are possible without materially departing from the novel teachings and advantages of the subject matter described herein (e.g., size, dimension, structure, shape of various elements and changes in proportions, values of parameters, installation arrangements, use of materials, colors, orientations). Some elements shown as integrally formed may be constructed of multiple parts or elements, the position of elements may be reversed or otherwise varied, and the nature or number of separate elements or positions may be altered or varied. According to alternative embodiments, the order or sequence of any method, logical algorithm, or method steps may be varied or re-sequenced. Other substitutions, modifications, changes, and omissions may also be made in the design, operating conditions, and arrangement of the various exemplary embodiments without departing from the technical scope of the present invention.

Claims (68)

1. a kind of window comprising：

First layer based on glass comprising the first main surface and the second main surface, formed by the first glass material it is first main Body and the first outer edge；

Second layer based on glass comprising the first main surface and the second main surface, formed by the second glass material it is second main Body and the second outer edge；

Described second based on glass level glass is based on described first with first distance to the described first layer based on glass Interlayer separate, and be arranged to be arranged essentially parallel to the described first layer based on glass with first distance；

Described second based on glass layer include being located at the described second first main surface of layer and described the based on glass Interior zone between two main surfaces；

Wherein described second based on glass first main surface of layer or one in second main surface at least one Partial ion concentration and chemical component with described second based on glass the interior zone of layer it is at least part of from Sub- content is identical with chemical component；

Wherein described second based on glass layer first main surface and second main surface be in greater than 60Mpa pressure Under stress, and the interior zone of the described second layer based on glass is under tensile stress；

Wherein the surface roughness of the described second first main surface of layer based on glass is coarse with 1.5nm Ra between 0.2 Between degree.

2. window as described in claim 1, wherein the described second stress based on glass in layer is depended on relative to institute State second based on glass first main surface of layer and the position of second main surface and change, wherein second base Have on described second less than 500 μm based on glass distance of the thickness of layer in the stress in the layer of glass At least slope of 200MPa.

3. the window as described in claim 1 or claim 2, wherein second main surface of the described second layer based on glass Surface roughness between 0.2 and 1.5nm Ra roughness.

4. window as claimed in any one of claims 1-3, wherein along the described first main of the described second layer based on glass The profile of the 50mm of surface and second main surface, the described second first main surface of layer and described based on glass Two main surfaces are flat in the degree of at least 50 μm of total instruction bounce.

5. such as window of any of claims 1-4, wherein first main surface of the described second layer based on glass The area with second main surface is at least 50cm²。

6. window according to any one of claims 1 to 5, wherein first glass material or second glass material are Soda-lime glass, contains alkali borosilicate glass, alkali aluminium phosphosilicate glass, alkali aluminium borosilicate glass, light at alkali alumina silicate glass Cause photo chromic glass, electrochomeric glass or thermochromism glass.

7. such as window of any of claims 1-6, wherein first glass material and second glass material are It is identical.

8. such as window of any of claims 1-7, wherein described first based on glass layer with described second be based on glass The first distance between the layer of glass includes rare gas or air.

9. further including third layer based on glass such as window of any of claims 1-8, the third is based on glass Layer there is the first main surface and the second main surface, the main body formed by third glass material and third outer edge；

Wherein the third based on glass layer with described second based on glass the opposite side of layer towards first base In the layer of glass, with the second distance spaced apart with described first based on glass interlayer separate, and be arranged to between second The distance separated is arranged essentially parallel to the described first layer based on glass.

10. window as claimed in claim 9, wherein first glass material, second glass material and the third glass Glass material is identical.

11. such as window of any of claims 1-10, wherein described first based on glass layer include hot-reinforced glass Layer, chemically strengthening glass layer, mechanical reinforcing glass layer, heat enhancing and chemically strengthening glass layer, heat enhancing and mechanical reinforcing glass Layer or Chemical enhancement and mechanical reinforcing glass layer.

12. the window as described in any one of claim 9-11, wherein the third glass material is soda-lime glass, alkali manosil AS Salt glass contains alkali borosilicate glass, alkali aluminium phosphosilicate glass, alkali aluminium borosilicate glass, photochromic glass, electroluminescent change Color glass or thermochromism glass.

13. the window as described in any one of claim 9-12, wherein layer includes hot-reinforced glass to the third based on glass Layer, chemically strengthening glass layer, mechanical reinforcing glass layer, heat enhancing and chemically strengthening glass layer, heat enhancing and mechanical reinforcing glass Layer or Chemical enhancement and mechanical reinforcing glass layer.

14. the window as described in any one of claim 1-7 and 9-13, wherein described first based on glass layer further include first Multiple projection of glass spacers, a projection of glass spacer more than described first by first main body from first main surface or A surface in second main surface is formed, and is made of first glass material, wherein the multiple glass is convex Rise spacer contact described second based on glass layer to keep the first distance spaced apart；

First edge sealing is formed at least about first outer edge and the second outer peripheral corresponding portion, so as to described One based on glass layer and described second limit the first sealing between layer based on glass interior zone,

Wherein the interior zone of first sealing has the vacuum pressure less than atmospheric pressure.

15. window as claimed in claim 14, wherein a projection of glass spacer more than described first is irradiated by laser beam in institute First is stated to be formed in first main surface or second main surface of layer based on glass.

16. the window as described in any one of claim 14-15 further includes a projection of glass spacer more than second, and described A projection of glass spacer more than two is integrally formed in described first based on glass in layer, be located at with more than described first a glass In the opposite main surface of the main surface of glass bump spacer, a projection of glass spacer is by first glass more than described second Glass material form and contact the third based on glass layer to keep the second distance spaced apart；And

(i) the second edge sealing is at least about first outer edge and the outer peripheral corresponding portion of the third, described first Layer and the third limit second sealing with the vacuum pressure less than atmospheric pressure between layer based on glass based on glass Interior zone, or (ii) described first edge sealing is further around the outer peripheral at least part of the third, with further Described first, layer and the third limit the vacuum pressure having less than atmospheric pressure between layer based on glass based on glass Second sealing interior zone.

17. window as claimed in claim 16, wherein a projection of glass spacer more than described second is irradiated by laser beam in institute First is stated to be formed in first main surface or second main surface of layer based on glass.

18. the window as described in any one of claim 14-15 further includes a projection of glass spacer more than second, and described A projection of glass spacer more than two is integrally formed in first main surface or described second of third layer based on glass In main surface, the neighbouring described first layer based on glass is opposite with more than described second a projection of glass spacers, and by described Third glass material form and contact described first based on glass layer to keep the second distance spaced apart；And

I) the second edge sealing is at least about first outer edge and the outer peripheral corresponding portion of the third, in first base Second sealing with the vacuum pressure less than atmospheric pressure is limited between the layer of glass and the third based on glass layer Interior zone or ii) first edge sealing is further around the outer peripheral at least part of the third, further in institute Stating first, layer and the third limit between layer have the of the vacuum pressure less than atmospheric pressure based on glass based on glass The interior zone of two sealings.

19. the window as described in any one of claim 1-18, wherein the first layer or the second layer based on glass based on glass At least one of further include Low emissivity layer.

20. the window as described in any one of claim 8-19, wherein layer further includes Low emissivity layer to the third based on glass.

21. the window as described in any one of claim 1-20, wherein described second based on glass layer pass through at least one and press from both sides Be pressed onto glass plate layer by layer, the interlayer with described second layer is at least partly coextensive based on glass and directly or indirectly joins It is connected to the side of the glass plate.

22. window as claimed in claim 21, wherein the sandwich material includes the polymer selected from the group being made of following item Material：Polyvinyl butyral (PVB), polycarbonate, acoustics PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomer, thermoplastic material and combinations thereof.

23. a kind of window comprising：

First layer based on glass comprising the first main surface and the second main surface, formed by the first glass material it is first main Body and the first outer edge；

Second layer based on glass comprising the first main surface and the second main surface, formed by the second glass material it is second main Body and the second outer edge；

Described second based on glass layer with first distance with described first based on glass interlayer separate, and be arranged to One distance is arranged essentially parallel to the described first layer based on glass；

First main surface and second main surface of described second layer based on glass are separated by the thickness t, along First main surface of any 50mm or smaller profile of first main surface, the described second layer based on glass exist It is flat in the degree of 100 μm of total instruction bounce (TIR)；

Second glass material has the low-temperature linear CTE α indicated with 1/ DEG C^S _CTE, the linear CTE of high temperature that is indicated with 1/ DEG C α^L _CTE, by elastic modulus E that GPa is indicated, by DEG C as unit of the strain temperature T that indicates_StrainWith by DEG C as unit of the softening temperature that indicates Spend T_Softening；

First main surface of described second layer based on glass has a certain thermotropic bearing stress, the thermotropic surface pressure Stress is less than 600MPa and is greater than

As unit of MPa；

Wherein P₁It is provided by the following formula

P₂It is provided by the following formula

And h is greater than or equal to 0.020cal/scm²·℃。

24. window as claimed in claim 23, wherein the described second first main surface of layer and described based on glass The area of two main surfaces is at least 50cm²。

25. window as claimed in claim 23, wherein described second based on glass layer further include the length l indicated with millimeter and The width w indicated with millimeter, wherein t is less than l, and t is less than w.

26. the window as described in any one of claim 23-25, wherein the described second main table of the described second layer based on glass The surface roughness in face is between 0.2 and 1.5nm Ra roughness.

27. the window as described in any one of claim 23-26, wherein along described second based on glass layer described first The profile of the 50mm of main surface and second main surface, the described second first main surface of layer and described based on glass Second main surface is flat in the degree of at least 50 μm of total instruction bounce.

28. the window as described in any one of claim 23-27, wherein first glass material or second glass material Be soda-lime glass, alkali alumina silicate glass, containing alkali borosilicate glass, alkali aluminium phosphosilicate glass, alkali aluminium borosilicate glass, Photochromic glass, electrochomeric glass or thermochromism glass.

29. the window as described in any one of claim 23-28, wherein described first based on glass layer include hot-reinforced glass Layer, chemically strengthening glass layer, mechanical reinforcing glass layer, heat enhancing and chemically strengthening glass layer, heat enhancing and mechanical reinforcing glass Layer or Chemical enhancement and mechanical reinforcing glass layer.

30. the window as described in any one of claim 23-29, wherein first glass material and second glass material It is identical.

31. the window as described in any one of claim 23-30, wherein described first based on glass layer be based on described second The first distance between the layer of glass includes rare gas or air.

32. the window as described in any one of claim 23-30, further includes third layer based on glass, the third is based on The layer of glass has the first main surface and the second main surface, the main body formed by third glass material and third outer edge；

Wherein the third based on glass layer with described second based on glass the opposite side of layer be spaced apart with second Distance is arranged essentially parallel to described with the described first distance that interlayer separates, and is arranged to be spaced apart with second based on glass First layer based on glass.

33. window as claimed in claim 32, wherein the third glass material is soda-lime glass, alkali alumina silicate glass, contains Alkali borosilicate glass, alkali aluminium phosphosilicate glass, alkali aluminium borosilicate glass, photochromic glass, electrochomeric glass or Thermochromism glass.

34. the window as described in claim 32 or claim 33, wherein first glass material, second glass material It is identical with the third glass material.

35. the window as described in any one of claim 32-34, wherein layer includes hot-reinforced glass to the third based on glass Layer, chemically strengthening glass layer, mechanical reinforcing glass layer, heat enhancing and chemically strengthening glass layer, heat enhancing and mechanical reinforcing glass Layer or Chemical enhancement and mechanical reinforcing glass layer.

36. the window as described in any one of claim 23-30 and 32-35, wherein described first based on glass layer further include A projection of glass spacer more than first, a projection of glass spacer more than described first is by first main body from the described first main table A surface in face or second main surface is formed, and is made of first glass material, wherein the multiple glass Glass bump spacer contact described second based on glass layer to keep the first distance spaced apart；

First edge sealing is formed at least about first outer edge and the second outer peripheral corresponding portion, so as to described One based on glass layer and described second limit the first sealing between layer based on glass interior zone,

Wherein the interior zone of first sealing has the vacuum pressure less than atmospheric pressure.

37. window as claimed in claim 36, wherein a projection of glass spacer more than described first is irradiated by laser beam in institute First is stated to be formed in first main surface or second main surface of layer based on glass.

38. the window as described in any one of claim 32-37 further includes a projection of glass spacer more than second, and described A projection of glass spacer more than two is integrally formed in described first based on glass in layer, be located at with more than described first a glass In the opposite main surface of the main surface of glass bump spacer, a projection of glass spacer is by first glass more than described second Glass material form and contact the third based on glass layer to keep the second distance spaced apart；And

(i) the second edge sealing is at least about first outer edge and the outer peripheral corresponding portion of the third, described first Layer and the third limit second sealing with the vacuum pressure less than atmospheric pressure between layer based on glass based on glass Interior zone, or (ii) described first edge sealing is further around the outer peripheral at least part of the third, with further Described first, layer and the third limit the vacuum pressure having less than atmospheric pressure between layer based on glass based on glass Second sealing interior zone.

39. window as claimed in claim 38, wherein a projection of glass spacer more than described second is irradiated by laser beam in institute First is stated to be formed in first main surface or second main surface of layer based on glass.

40. the window as described in any one of claim 32-37 further includes a projection of glass spacer more than second, and described A projection of glass spacer more than two is integrally formed in first main surface or described second of third layer based on glass In main surface, the neighbouring described first layer based on glass is opposite with more than described second a projection of glass spacers, and by described Third glass material form and contact described first based on glass layer to keep the second distance spaced apart；And

I) the second edge sealing is at least about first outer edge and the outer peripheral corresponding portion of the third, in first base Second sealing with the vacuum pressure less than atmospheric pressure is limited between the layer of glass and the third based on glass layer Interior zone or ii) first edge sealing is further around the outer peripheral at least part of the third, further in institute Stating first, layer and the third limit between layer have the of the vacuum pressure less than atmospheric pressure based on glass based on glass The interior zone of two sealings.

41. window as claimed in claim 40, wherein a projection of glass spacer more than described second is irradiated by laser beam in institute Third is stated to be formed in first main surface or second main surface of layer based on glass.

42. the window as described in any one of claim 23-31, wherein the first layer or the second layer based on glass based on glass At least one of further include Low emissivity layer.

43. the window as described in any one of claim 32-42, wherein layer further includes Low emissivity to the third based on glass Layer.

44. the window as described in any one of claim 23-43, wherein described second based on glass layer pass through at least one and press from both sides Be pressed onto glass plate layer by layer, the interlayer with described second layer is at least partly coextensive based on glass and directly or indirectly joins It is connected to the side of the glass plate.

45. window as claimed in claim 44, wherein the sandwich material includes the polymer selected from the group being made of following item Material：Polyvinyl butyral (PVB), polycarbonate, acoustics PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomer, thermoplastic material and combinations thereof.

46. a kind of window comprising：

First glass plate comprising the first main surface and the second main surface, the first main body formed by the first glass material and First outer edge；

Second glass plate comprising the first main surface and the second main surface, the second main body formed by the second glass material and Second outer edge；

Second glass plate is spaced apart with first distance with first glass plate, and is arranged to first distance substantially It is parallel to first glass plate；

Along any 50mm or smaller profile of first main surface of second glass plate, second glass plate First main surface is flat in the degree of 100 μm of total instruction bounce (TIR)；

Second glass plate includes glass, the glass have by DEG C as unit of the softening temperature T that indicates_SofteningWith DEG C to be single The annealing temperature T that position indicates_AnnealingWith measure in first main surface of second glass plate by DEG C as unit of indicate When by Tfs indicate surface fictive temperature；

Second glass plate has by (Tfs-T_Annealing)/(T_Softening-T_Annealing) the dimensionless surface fictive temperature parameter θ s that provides；And And

Wherein the parameter θ s is in the range of 0.20 to 0.9.

47. window as claimed in claim 46, wherein the stress in second glass plate is depended on relative to described the First main surface of two glass plates and the position of second main surface and change, wherein the institute in second glass plate State stress has at least slope of 200MPa in the distance of the thickness of second glass plate less than 500 μm.

48. the window as described in claim 46 or claim 47, wherein second main surface of second glass plate Surface roughness is between 0.2 and 1.5nm Ra roughness.

49. the window as described in any one of claim 46-48, wherein along first main surface of second glass plate With the profile of the 50mm of second main surface, first main surface and second main surface of second glass plate exist At least it is flat in the degree of 50 μm of total instruction bounce.

50. the window as described in any one of claim 46-49, wherein first main surface of second glass plate and institute The area for stating the second main surface is at least 50cm²。

51. the window as described in any one of claim 46-50, wherein first glass material or second glass material Be soda-lime glass, alkali alumina silicate glass, containing alkali borosilicate glass, alkali aluminium phosphosilicate glass, alkali aluminium borosilicate glass, Photochromic glass, electrochomeric glass or thermochromism glass.

52. the window as described in any one of claim 46-51, wherein first glass material and second glass material It is identical.

53. the window as described in any one of claim 46-52, wherein between first glass plate and second glass plate The first distance include rare gas or air.

54. the window as described in any one of claim 46-53 further includes third glass plate, the third glass plate has First main surface and the second main surface, the main body formed by third glass material and third outer edge；

Wherein the third glass plate in the side opposite with second glass plate towards first glass plate, between second The distance separated is spaced apart with first glass plate, and is arranged to be arranged essentially parallel to the second distance spaced apart described First glass plate.

55. window as claimed in claim 54, wherein first glass material, second glass material and the third glass Glass material is identical.

56. the window as described in any one of claim 46-55, wherein first glass plate includes hot-reinforced glass layer, changes Learn reinforcing glass layer, mechanical reinforcing glass layer, heat enhancing and chemically strengthening glass layer, heat enhancing and mechanical reinforcing glass layer or change Learn enhancing and mechanical reinforcing glass layer.

57. the window as described in any one of claim 54-56, wherein the third glass material is soda-lime glass, alkali aluminium silicon Silicate glass, containing alkali borosilicate glass, alkali aluminium phosphosilicate glass, alkali aluminium borosilicate glass, photochromic glass, electroluminescent Photo chromic glass or thermochromism glass.

58. the window as described in any one of claim 54-57, wherein the third glass plate includes hot-reinforced glass layer, changes Learn reinforcing glass layer, mechanical reinforcing glass layer, heat enhancing and chemically strengthening glass layer, heat enhancing and mechanical reinforcing glass layer or change Learn enhancing and mechanical reinforcing glass layer.

59. the window as described in any one of claim 46-52 and 54-58, wherein first glass plate further includes more than first A projection of glass spacer, a projection of glass spacer more than described first is by first main body from first main surface or institute It states in the second main surface surface to be formed, and is made of first glass material, wherein the multiple projection of glass Spacer contacts second glass plate to keep the first distance spaced apart；

First edge sealing is formed at least about first outer edge and the second outer peripheral corresponding portion, so as to described The interior zone of the first sealing is limited between one glass plate and second glass plate,

Wherein the interior zone of first sealing has the vacuum pressure less than atmospheric pressure.

60. window as claimed in claim 59, wherein a projection of glass spacer more than described first is irradiated by laser beam in institute It states and is formed in first main surface or second main surface of the first glass plate.

61. the window as described in any one of claim 59-60 further includes a projection of glass spacer more than second, and described A projection of glass spacer is integrally formed in first glass plate more than two, be located at with more than described first a projection of glass In the opposite main surface of the main surface of spacer, a projection of glass spacer is by first glass material more than described second It forms and contacts the third glass plate to keep the second distance spaced apart；And

(i) the second edge sealing is at least about first outer edge and the outer peripheral corresponding portion of the third, described first The interior zone with the second sealing of the vacuum pressure less than atmospheric pressure is limited between glass plate and the third glass plate, or Person (ii) first edge sealing is further around the outer peripheral at least part of the third, further in first glass The interior zone with the second sealing of the vacuum pressure less than atmospheric pressure is limited between plate and the third glass plate.

62. window as claimed in claim 61, wherein a projection of glass spacer more than described second is irradiated by laser beam in institute It states and is formed in first main surface or second main surface of the first glass plate.

63. the window as described in any one of claim 59-60 further includes a projection of glass spacer more than second, and described A projection of glass spacer more than two is integrally formed in first main surface or second main surface of the third glass plate In, neighbouring first glass plate is opposite with more than described second a projection of glass spacers, and by the third glass material It forms and contacts first glass plate to keep the second distance spaced apart；And

I) the second edge sealing is at least about first outer edge and the outer peripheral corresponding portion of the third, in first glass The interior zone with the second sealing of the vacuum pressure less than atmospheric pressure is limited between glass plate and the third glass plate, or Ii) first edge sealing is further around the outer peripheral at least part of the third, further in first glass plate The interior zone with the second sealing of the vacuum pressure less than atmospheric pressure is limited between the third glass plate.

64. the window as described in claim 63, wherein a projection of glass spacer more than described second is irradiated by laser beam in institute It states and is formed in first main surface or second main surface of third glass plate.

65. the window as described in any one of claim 46-64, wherein at least one of the first glass plate or the second glass plate It further include Low emissivity layer.

66. the window as described in any one of claim 54-65, wherein the third glass plate further includes Low emissivity layer.

67. the window as described in any one of claim 46-66, wherein second glass plate is laminated by least one interlayer To the 4th glass plate, the interlayer is at least partly coextensive with second glass plate and is directly or indirectly coupled to described The side of 4th glass plate.

68. the window as described in claim 67, wherein the sandwich material includes the polymer selected from the group being made of following item Material：Polyvinyl butyral (PVB), polycarbonate, acoustics PVB, ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), ionomer, thermoplastic material and combinations thereof.