Cold formed laminate

Abstract

To provide a laminate that is more thin and intricately curved, and is used for window glass for automobiles or for construction application.SOLUTION: An intricately curved laminate, for example, window glass of an automobile, made from an intricately curved substrate and a flat substrate, and an intricately curved glass are cold molded from a curved substrate and a flat substrate. The laminate comprises a first intricately curved glass substrate having a first surface and a second surface opposite to the first surface, a second intricately curved glass substrate having a third surface and a fourth surface opposite to the third surface and a thickness between these, and a polymer intermediate layer fixed to the second and third surfaces, in which the compressive stress value of the fourth surface is greater than the compressive stress value of the third surface, and one of the first thickness or the second thickness is within the range of 0.1 mm to 1.4 mm, each of the first and second intricately curved glass substrates has a non planar shape having a curvature along two orthogonal axes different from each other.SELECTED DRAWING: Figure 2

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. §119 of U.S. Provisional Application No. 62 / 339,145, filed May 20, 2016, U.S. Provisional Application No. 62 / 281,301, filed January 21, 2016, and U.S. Provisional Application No. 62 / 190,828, filed July 10, 2015, the contents of which are hereby incorporated by reference in their entireties. [Technical field]

[0002] Principles and embodiments of the present disclosure relate generally to cold-formed complex curved laminates and methods of cold-forming such laminates. [Background technology]

[0003] Curved laminates are used in a variety of applications, including automotive glazing and architectural windows. For such applications, sheets of glass are precisely bent to a predetermined shape and / or curvature dictated by the construction and size of the opening, as well as the vehicle style or architectural aesthetics. Such curved laminates can be made by heating a flat glass sheet to a suitable temperature for shaping, applying forces to the sheet to deform it, and then laminating two curved sheets together. This process is typically called a "hot bending" process. In some known examples, the glass can be heated in a furnace and shaped while the sheet is still hot in the furnace (at or near the softening temperature of the glass). Glass sheets can also be bent by first heating the glass sheet in a furnace to a suitable temperature at or near the softening temperature of the glass, and then transferring the glass sheet to a glass bending device outside the furnace. Glass sheets that undergo such bending operations are typically 2.5 mm, 3 mm or more thick.

[0004] Curved laminates typically must meet stringent optical requirements, and the viewing area of ​​the closure, i.e., the window, must be free of surface defects and optical distortions that may impede a clear view through the curved laminate. Glass that is not at the proper temperature during the bending operation can exhibit optical distortions, such as roller waves (optical roll distortions), and / or discontinuity markings and / or defects that may render the bent sheet unsuitable for its intended purpose.

[0005] Existing methods for forming complex curved laminates currently require heating and bending two glass sheets at or near the softening point of the glass to form one laminate, and / or typically use very thick glass sheets to facilitate the bending operation, further increasing the overall weight of the laminate. Also, when the two glass sheets require different forming conditions or processes (e.g., due to different softening points and / or thicknesses), the two glass sheets are typically formed separately and then bonded together, often leading to shape mismatches and unnecessary processing steps and costs. Thus, such methods require complex manufacturing processes, long manufacturing times, and high costs. Summary of the Invention [Problem to be solved by the invention]

[0006] There is an increasing demand for thinner and more complex curved laminates in automotive glazing and architectural applications than are currently available, and therefore there is a need for such laminates that can be formed and laid to more precisely conform to shape using fewer processing steps. [Means for solving the problem]

[0007] A first aspect of the present disclosure relates to a laminate having a complex curved shape. In one or more embodiments, the laminate is cold formed by laminating a flat substrate to a curved substrate. As used herein, "cold forming" refers to a laminate formation process carried out at a temperature well below the softening temperature of either substrate. According to one or more embodiments, the laminate is cold formed at a temperature at least 200°C below the softening temperature of either substrate. In some embodiments, the cold formed complex curved laminate includes a thin substrate (e.g., having a thickness of less than about 1 mm), resulting in a laminate with reduced weight. The laminates described herein according to one or more embodiments exhibit the desired complex curved shape without the optical defects and distortions often found in known complex curved laminates (typically formed using a hot bending process).

[0008] In one embodiment, the laminate includes a first compound curved glass substrate including a first side, a second side opposite the first side, and a first thickness therebetween, a second compound curved glass substrate including a third side, a fourth side opposite the third side, and a second thickness therebetween, and a polymer interlayer secured to the second side and the third side.

[0009] In one or more embodiments, either or both of the first complexly curved glass substrate and the second complexly curved glass substrate have a thickness in the range of about 0.1 mm to about 1 mm, or about 0.2 mm to about 0.7 mm. In particular, in one or more embodiments, the second complexly curved glass substrate has a thickness less than that of the first complexly curved glass substrate. In one or more embodiments, the third surface and the fourth surface each have a compressive stress value such that the fourth surface has a compressive stress value greater than that of the third surface. In one or more embodiments, the first surface and the third surface form a convex surface, while the second surface and the fourth surface form a concave surface.

[0010] Another aspect of the present disclosure relates to a method for forming a laminate. In one embodiment, a method for manufacturing a complex curved laminate includes disposing a bonding layer between a complex curved substrate and a flat strengthened glass substrate to form a stack, applying pressure to the stack to press the strengthened glass substrate against the bonding layer and the bonding layer against the complex curved substrate, and heating the complex curved substrate, the bonding layer, and the complex curved strengthened glass substrate to a temperature below 400° C. to form a complex curved laminate in which the strengthened glass substrate conforms to the complex curved substrate.

[0011] The method described herein does not require heating and bending of both substrates, thus reducing manufacturing time and costs by avoiding both substrate heating and bending operations. In one or more embodiments, the method includes strengthening one substrate chemically, thermally, mechanically, or a combination thereof.

[0012] In another embodiment, a method for making a compound curved laminate includes forming a first glass substrate having two major surfaces and a thickness therebetween to provide a compound curved glass substrate having curvatures along two axes, and arranging the compound curved glass substrate in a stack with a bonding layer and a second glass substrate such that the bonding layer is between the compound curved glass substrate and the second glass substrate. In one or more embodiments, the second glass substrate has two major surfaces and a thickness therebetween and has curvatures along two axes, the curvature of the second glass substrate not matching the curvature of the first glass substrate. In one or more embodiments, the method includes applying pressure to the stack at room temperature to shape the second glass substrate to match the curvature of the compound curved glass substrate to form the compound curved laminate.

[0013] Additional features will be set forth in the following detailed description, and in part will be readily apparent to those skilled in the art from that description, or will be learned by practicing the embodiments described herein, including the following detailed description, the claims, and the accompanying drawings.

[0014] It should be understood that both the foregoing general description and the following detailed description are merely exemplary and are intended to provide an overview or framework for understanding the nature and nature of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated into and constitute a part of this specification. The drawings illustrate one or more embodiments, and together with the description, serve to explain the principles and operation of the various embodiments. [Brief description of the drawings]

[0015] [Figure 1] FIG. 1 shows a cross-sectional view of an exemplary embodiment of a laminate. [Diagram 2] FIG. 2 illustrates cross-sectional views of exemplary embodiments of a flat glass substrate, a curved glass substrate, and an intervening film layer prior to forming. [Diagram 3] FIG. 3 is a graph illustrating stack geometries of stacks according to embodiments of the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Reference will now be made in detail to various embodiments, examples of which are illustrated in the accompanying drawings.

[0017] Throughout this specification, the use of "one embodiment," "an embodiment," "various embodiments," "one or more embodiments," or "an embodiment" means that a particular feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of phrases such as "in one or more embodiments," "in an embodiment," "various embodiments," "in an embodiment," or "in an embodiment" in various places throughout this specification do not necessarily refer to the same embodiment of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0018] Automotive and architectural applications often require lightweight yet mechanically strong laminates for various applications. In the automotive field, there is a need to reduce the weight of the vehicle, thereby improving fuel efficiency. One approach to reduce the weight of the vehicle is to reduce the thickness of the laminate and / or the substrate used in the laminate. There is also a need for laminates with increasingly complex curved shapes that meet aesthetic requirements. For example, in the automotive field, windshields, backlights, sunroofs, fixedly mounted roof sheets, and sidelights utilize laminates with complex curved shapes. In architecture, such complex curved laminates can be used in various exterior and interior applications (e.g., walls, countertops, appliances, modular system furniture, etc.).

[0019] The bending requirements of inorganic materials often limit the thickness of the plies used in curved laminates. It has been found that thin glass substrates having a thickness of about 1.5 mm or 1.4 mm or less cool too quickly to be properly curved and shaped using known hot bending methods, which can result in unacceptable cracking or laminate breakage during the hot bending operation. Furthermore, thin glass substrates having a thickness of about 1.5 mm or less can be more prone to distortion if heated to higher temperatures to offset such cooling. The leading and trailing edges of each glass substrate form a cantilever if the substrate edges are not supported by a roller bending apparatus. When heated above a certain temperature, the glass substrate (regardless of thickness) can sag under the weight of the cantilever, but the thinner the substrate and the higher the temperature to which the substrate is heated, the greater such sagging can occur. Such sagging can also occur throughout the unsupported portion of the substrate between the support rollers. One or more of these challenges can be addressed by various embodiments described herein.

[0020] A first aspect of the present disclosure relates to a cold-formed laminate having a complex curved shape. In one or more embodiments, the laminate can be obtained from a first substrate having a complex curved shape and a second substrate having a flat or planar shape. As used herein, "flat" and "planar" are used interchangeably and refer to a shape having a curvature less than that at which stacking faults would occur due to curvature mismatch when cold-forming such a flat substrate to another substrate (i.e., a radius of curvature of about 3 meters or more, about 4 meters or more, or about 5 meters or more) or a curvature (of any value) along only one axis. A flat substrate has said shape when placed on a surface. As used herein, "complex curve" and "complex curved" refer to a non-planar shape having a curvature along two different orthogonal axes. Examples of complex curved shapes include those having simple or compound curves, also referred to as non-developable shapes, including but not limited to spherical, non-spherical, and toroidal shapes. A complex curved laminate according to an embodiment may also include segments or portions of such surfaces, or may be composed of a combination of such curves and surfaces. In one or more embodiments, the laminate may have a compound curve including a major axis and a cross curvature. A complex curved laminate according to one or more embodiments may have different radii of curvature in two independent directions. According to one or more embodiments, a complex curved laminate may thus be characterized as having a "cross curvature" where the laminate is curved along an axis parallel to a given dimension (i.e., a first axis) and also curved along an axis perpendicular to the same dimension (i.e., a second axis). The curvature of the laminate may be even more complex when the effective minimum radius is combined with the effective cross curvature, and / or the bending depth. Some laminates may also include bending along axes that are not perpendicular to each other. As a non-limiting example, a complex curved laminate may have length and width dimensions of 0.5 m by 1.0 m, and a radius of curvature of 2 m to 2.5 m along the minor axis and 4 m to 5 m along the major axis. In one or more embodiments, the complex curved laminate may have a radius of curvature of 5 meters or less along at least one axis.In one or more embodiments, the complex curved laminate can have a radius of curvature of 5 m or less along at least a first axis and a second axis perpendicular to the first axis. In one or more embodiments, the complex curved laminate can have a radius of curvature of 5 m or less along at least a first axis and a second axis that is not perpendicular to the first axis.

[0021] FIG. 1 illustrates one embodiment of a laminate 100 including a first substrate 110 having a compound curved shape and at least one convex surface provided by a first surface 112 opposite at least one concave surface provided by a second surface 114, with a thickness therebetween. The laminate also includes a cold formed compound curved second substrate 130. The second substrate 130 includes at least one convex surface provided by a third surface 132 opposite at least one concave surface provided by a fourth surface 134, with a thickness therebetween. As shown in FIG. 1, an intermediate layer 120 can be disposed between the first substrate 110 and the second substrate 130. In one or more embodiments, the intermediate layer 120 is secured to at least the second surface 114 and the third surface 132 of the laminate. As used herein, the term "convex surface" refers to an outward bend or curvature, as indicated by reference numerals 112 and 132 in FIG. 1. The term "concave surface" refers to an inward bend or curvature, as indicated by reference numerals 114, 134 in FIG. 1.

[0022] In one or more embodiments, prior to the cold forming process, the respective compressive stresses at the third side 132 and the fourth side 134 are substantially equal. In embodiments in which the second substrate 130 is not reinforced (as defined herein), the third side 132 and the fourth side 134 exhibit no appreciable compressive stress prior to cold forming. In embodiments in which the second substrate 130 is reinforced (as described herein), the third side 132 and the fourth side 134 exhibit equal compressive stresses relative to one another prior to cold forming. In one or more embodiments, after cold forming, the compressive stress on the fourth side 134 increases (i.e., the compressive stress on the fourth side 134 is greater after cold forming than before cold forming). Without being bound by theory, the cold forming process increases the compressive stress of the substrate being formed (i.e., the second substrate) to offset the tensile stress imparted during the bending and / or forming operations. In one or more embodiments, the cold forming process places the third side of the substrate (ie, third side 132) under tensile stress, while the fourth side of the substrate (ie, fourth side 134) under compressive stress.

[0023] When utilizing a reinforced second substrate 130, the third and fourth sides (132, 134) of the second substrate are already under compressive stress, and thus the third side 132 may experience an even greater tensile stress. This allows the reinforced second substrate to conform more closely to the curved surface. Thus, for the laminate shown in FIG. 1, after formation of the laminate 100, the third side 132 has a compressive stress that is less than the compressive stress of the fourth side 134. In other words, the compressive stress of the fourth side 134 is greater than the compressive stress of the third side 132.

[0024] In one or more embodiments, the increased compressive stress at the fourth side 134 (relative to the third side) provides greater strength to the fourth side 134, which is the exposed surface after the laminate is formed.

[0025] In one or more embodiments, the second substrate 130 has a thinner thickness than the first substrate 110. This thickness difference means that the second substrate 130 requires less force and is more flexible to conform to the shape of the first substrate 110. Additionally, a thinner second substrate 130 can more easily deform to compensate for shape mismatches and gaps caused by the shape of the first substrate 110. In one or more embodiments, the thinner and stronger second substrate exhibits greater flexibility, especially during cold forming.

[0026] In one or more embodiments, the second substrate 130 conforms to the first substrate 110 to provide a substantially uniform distance between the second surface 114 and the third surface 132, which distance is filled by the intermediate layer.

[0027] In one or more embodiments, the laminate 100 may have a thickness of 6.85 mm or less, or 5.85 mm or less, where the thickness of the laminate 100 is the sum of the thicknesses of the first substrate 110, the second substrate 130, and the intermediate layer 120. In various embodiments, the laminate 100 can have a thickness in the range of about 1.8 mm to about 6.85 mm, or in the range of about 1.8 mm to about 5.85 mm, or in the range of about 1.8 mm to about 5.0 mm, or in the range of about 2.1 mm to about 6.85 mm, or in the range of about 2.1 mm to about 5.85 mm, or in the range of about 2.1 mm to about 5.0 mm, or in the range of about 2.4 mm to about 6.85 mm, or in the range of about 2.4 mm to about 5.85 mm, or in the range of about 2.4 mm to about 5.0 mm, or in the range of about 3.4 mm to about 6.85 mm, or in the range of about 3.4 mm to about 5.85 mm, or in the range of about 3.4 mm to about 5.0 mm.

[0028] In one or more embodiments, the laminate 100 exhibits a radius of curvature that is less than 1000 mm, or less than 750 mm, or less than 500 mm, or less than 300 mm. The laminate, the first substrate and / or the second substrate are substantially wrinkle-free.

[0029] In one or more embodiments, the second substrate 130 is relatively thin compared to the first substrate. In other words, the first substrate 110 has a greater thickness than the second substrate 130. In one or more embodiments, the first substrate 110 may have a thickness that is greater than twice the thickness of the second substrate 130. In one or more embodiments, the first substrate 110 may have a thickness within a range from about 1.5 times to about 2.5 times the thickness of the second substrate 130.

[0030] In one or more embodiments, the first substrate 110 and the second substrate 130 can have the same thickness, with the first substrate being harder or having greater rigidity than the second substrate, and in a particularly specific embodiment, both the first substrate and the second substrate have a thickness between 0.2 mm and 0.7 mm.

[0031] In one or more specific embodiments, the second substrate 130 has a thickness of 0.8 mm or less. In various embodiments, the second substrate 130 has a thickness within the range of about 0.1 mm to about 1.4 mm, or within the range of about 0.2 mm to about 1.4 mm, or within the range of about 0.3 mm to about 1.4 mm, or within the range of about 0.4 mm to about 1.4 mm, or within the range of about 0.5 mm to about 1.4 mm, or within the range of about 0.1 mm to about 1 mm, or within the range of about 0.2 mm to about 1 mm, or within the range of about 0.1 mm to about 0.7 mm, or within about 0.2 mm. The thickness may be in the range of about 0.2 mm to about 0.5 mm, or about 0.3 mm to about 0.5 mm, or about 0.2 mm to about 0.4 mm, or about 0.5 mm to about 0.6 mm, or about 0.3 mm to about 0.5 mm, or about 0.2 mm to about 0.4 mm.

[0032] In one or more embodiments, the first substrate 110 can have a thickness greater than the second substrate 130. In one or more embodiments, the first substrate 110 has a thickness of 4.0 mm or less, or 3.85 mm or less. In various embodiments, the first substrate 110 has a thickness within a range of about 1.4 mm to about 3.85 mm, or within a range of about 1.4 mm to about 3.5 mm, or within a range of about 1.4 mm to about 3.0 mm, or within a range of about 1.4 mm to about 2.8 mm, or within a range of about 1.4 mm to about 2.5 mm, or within a range of about 1.4 mm to about 2.0 mm, or within a range of about 1.5 mm to about 3.85 mm, or within a range of about 1.5 mm to about 3.5 mm, or within a range of about 1.5 mm to about 3.0 mm, or within a range of about 1.5 mm to about 2.8 mm. It may have a thickness within the range, or within the range of about 1.5 mm to about 2.5 mm, or within the range of about 1.5 mm to about 2.0 mm, or within the range of about 1.6 mm to about 3.85 mm, or within the range of about 1.6 mm to about 3.5 mm, or within the range of about 1.6 mm to about 3.0 mm, or within the range of about 1.6 mm to about 2.8 mm, or within the range of about 1.6 mm to about 2.5 mm, or within the range of about 1.6 mm to about 2.0 mm, or within the range of about 1.8 mm to about 3.5 mm, or within the range of about 2.0 mm to about 3.0 mm.

[0033] The materials of the first substrate 110 and the second substrate 130 may vary. According to one or more embodiments, the materials of the first substrate and the second substrate may be the same or different materials. In an exemplary embodiment, one or both of the first substrate and the second substrate may be a glass (e.g., soda-lime glass, alkali aluminosilicate glass, alkali-containing borosilicate glass, and / or alkali aluminoborosilicate glass) or a glass-ceramic. Examples of suitable glass-ceramics include Li2O-Al2O3-SiO2-based (i.e., LAS-based) glass ceramics, MgO-Al2O3-SiO2-based (i.e., MAS-based) glass ceramics, and glass ceramics including any one or more of the following crystalline phases: mullite, spinel, α-quartz, β-quartz solid solution, petalite, lithium disilicate, β-spodumene, nepheline, and alumina. Additionally, one or both of the first substrate and the second substrate may be chemically, thermally, mechanically, or a combination thereof. In one or more embodiments, the first substrate is unstrengthened (meaning not strengthened by a chemical, thermal or mechanical strengthening process, but may include an annealed substrate), while the second substrate is strengthened, hi one or more specific embodiments, the second glass substrate is chemically strengthened.

[0034] In one or more embodiments, the laminate may include one or both of the substrates made from glass or non-glass materials such as plastic, metal, ceramic, glass-ceramic, wood, and combinations thereof.

[0035] The substrate can be provided by a variety of different processes. For example, when the substrate comprises a glass substrate, exemplary glass substrate forming methods include float glass processes, and downdraw processes, such as fusion draw processes, and slot draw processes.

[0036] Glass substrates prepared by the float glass process can be characterized by a smooth surface, and uniform thickness is obtained by flattening the molten glass onto a bed of molten metal, typically tin. In an exemplary process, molten glass dispensed onto the surface of a molten tin bed forms a floating glass ribbon. As the glass ribbon flows along the tin bath, the temperature is gradually reduced until the glass ribbon solidifies into a solid glass substrate that can be lifted from the tin onto rollers. Upon exiting the bath, the glass substrate can be further cooled and annealed to reduce internal stresses.

[0037] The downdraw process produces glass substrates with a relatively unblemished surface and uniform thickness. Since the average bending strength of the glass substrate is controlled by the amount and size of surface cracks, an unblemished surface where contact has been minimal will have a higher initial strength. Downdrawn glass substrates can be stretched to a thickness of less than about 2 mm.

[0038] The fusion draw process, for example, uses a drawing tank having a channel for receiving molten glass raw material. The channel has weirs open at the top along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten glass spills over the weirs. Due to gravity, the molten glass flows down the outer surface of the drawing tank as two flowing glass films that extend downward and inward to meet at the lower edge of the drawing tank. The two flowing glass films meet and fuse at this edge to form one flowing glass substrate. The fusion draw process offers the advantage that the two glass films flowing on the channel fuse together and neither outer surface of the resulting glass substrate comes into contact with any part of the apparatus. Thus, the surface properties of the fusion drawn glass substrate are not affected by such contact.

[0039] The slot draw process differs from the fusion draw process. In the slot draw process, molten raw glass is provided to a drawing tank. The bottom of the drawing tank has an open slot with a nozzle that extends the length of the slot. The molten glass flows through the slot / nozzle and is drawn downward into an annealing region as a continuous substrate.

[0040] Once formed, either the first substrate or the second substrate can be strengthened to form a strengthened glass substrate. It is noted that glass-ceramic substrates can also be strengthened in the same manner as glass substrates. As used herein, the term "strengthened substrate" can refer to glass or glass-ceramic substrates that have been strengthened, for example, by chemical strengthening (e.g., ion exchange of large ions with small ions at the surface of the glass or glass-ceramic substrate), thermal strengthening, or mechanical strengthening. In some embodiments, the substrate can be strengthened using any one or more combinations of chemical, thermal, and mechanical strengthening processes.

[0041] In one or more embodiments, the strengthened substrates described herein can be chemically strengthened by an ion exchange process. In an ion exchange process, typically by immersing a glass or glass ceramic substrate in a molten salt bath for a predetermined time, ions at or near the surface of the glass or glass ceramic substrate are exchanged with larger metal ions from the salt bath. In one embodiment, the temperature of the molten salt bath is in the range of about 350° C. to about 430° C., and the predetermined time is about 2 hours to about 8 hours. The incorporation of larger ions into the glass or glass ceramic substrate strengthens the substrate by inducing compressive stresses (CS) in the near-surface region of the substrate, i.e., at the surface and adjacent to the surface. A corresponding tensile stress is induced in one or more central regions of the substrate some distance away from the surface to balance the compressive stress. The one or more central regions exhibiting tensile stress are referred to as central tension (CT) regions. Glass or glass ceramic substrates utilizing this strengthening process may be more specifically described as chemically strengthened glass or glass ceramic substrates or ion-exchanged glass or glass ceramic substrates.

[0042] In one example, sodium ions in the glass or glass ceramic substrate are replaced by potassium ions from a molten bath, such as a potassium nitrate salt bath, while other alkali metal ions with larger atomic radii, such as rubidium or cesium, can be substituted for the smaller alkali metal ions in the glass. According to a particular embodiment, the smaller alkali metal ions in the glass or glass ceramic are replaced by Ag. + Similarly, other alkali metal salts, such as, but not limited to, sulfates, phosphates, halides, etc., can be used in the ion exchange process.

[0043] The compressive stress is related to the central tension by the following equation (1):

[0044]

number

[0045] where t is the total thickness of the strengthened glass or glass-ceramic substrate and the compression depth of layer (DOL) is the depth of exchange. DOL refers to the depth into the glass or glass-ceramic substrate where the compressive stress switches to a tensile stress.

[0046] When using thermal strengthening, glass or glass-ceramic substrates can be made to exhibit very high heat transfer coefficients (h, in cal / cm) in a precise manner, with good physical control and gentle handling of the glass. 2 The glass substrate can be heated using a gas bearing (°C) and then cooled. In certain embodiments, the thermal strengthening process and system can utilize a small gap gas bearing in the cooling / quenching section, which allows the thin glass substrate to be processed at a higher relative temperature at the start of cooling, resulting in a higher thermal strengthening level. As described below, this small gap gas bearing cooling / quenching section achieves a very high heat transfer rate by conductive heat transfer to a heat sink across the gap, rather than using a large amount of airflow based on convection cooling. This high rate conductive heat transfer is achieved by supporting the glass substrate on a gas bearing in the gap, without the glass contacting any liquid or solid material.

[0047] In one or more embodiments, the resulting thermally strengthened glass or glass ceramic substrate exhibits a higher level 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 can be obtained for a number of reasons. The high uniformity of heat transfer in the process detailed herein reduces or eliminates physical and undesirable thermal stresses in the glass, allowing the glass substrate to be tempered at a higher rate of heat transfer without breaking. Furthermore, the method can be carried out at a lower glass substrate viscosity (higher initial temperature at the start of quenching) while preserving the desired glass flatness and shape, thereby providing a much larger temperature change in the cooling process and thus achieving an increased level of thermal strengthening.

[0048] In various embodiments, the thermally strengthened glass or glass ceramic substrate has both the stress profile described herein and low as-formed surface roughness. The processes and methods disclosed herein can thermally strengthen the substrate without increasing the surface roughness of the as-formed surface. For example, the incoming float glass air side surface and the incoming fusion formed glass surface were characterized by atomic force microscopy (AFM) before and after processing. a The surface roughness is less than 1 nm (0.6 nm to 0.7 nm) for the incoming 1.1 mm soda lime float glass, R a Surface roughness was not increased by thermal strengthening according to the process of the present invention. Similarly, R of less than 0.3 nm (0.2 nm to 0.3 nm) for a 1.1 mm sheet of fusion-formed glass. a The surface roughness was maintained by thermal strengthening according to the present disclosure. Thus, the thermally strengthened glass and glass ceramic substrates according to one or more embodiments have a roughness R of 0.2 nm to 1.5 nm on at least a first surface. a , 0.2 nm to 0.7 nm, 0.2 nm to 0.4 nm or even, for example, 0.2 nm to 0.3 nm; The surface roughness may be measured over an area of ​​10×10 μm in exemplary embodiments, or 15×15 μm in some embodiments.

[0049] In another embodiment, the thermally strengthened glass or glass ceramic substrates described herein have high flatness. In various embodiments, the strengthening systems discussed herein utilize controlled gas bearings to support the glass or glass ceramic substrate during transportation and heating, and in some embodiments can be used to help control and / or improve the flatness of the resulting thermally strengthened glass or glass ceramic substrate, resulting in a degree of flatness greater than previously obtainable, particularly for thin and / or highly strengthened glass or glass ceramic substrates. For example, glass or glass ceramic substrates in sheet form having a thickness of about 0.6 mm or greater can be strengthened to improve flatness after strengthening. The flatness of various embodiments of the thermally strengthened glass or glass ceramic substrate may include a maximum difference in reading (total indicator run-out, TIR) of 100 μm or less along any 50 mm length along one of its first or second sides, 300 μm TIR or less within 50 mm length along one of the first or second sides, or 200 μm TIR or less, 100 μm TIR or less, or 70 μm TIR or less within 50 mm length along one of the first or second sides. In exemplary embodiments, the flatness is measured along any 50 mm or less profile of the thermally strengthened glass or glass ceramic substrate. In contemplated embodiments, the thermally strengthened glass or glass ceramic substrate may be in sheet form, may have a thickness as disclosed herein, and have a flatness of 200 μm TIR or less (e.g., flatness of 100 μm TIR or less, flatness of 70 μm TIR or less, or flatness of 50 μm TIR or less) within 20 mm length along one of the first or second sides.

[0050] According to contemplated embodiments, a thermally strengthened glass or glass ceramic substrate according to one or more embodiments has a high degree of dimensional constancy, such that its thickness t along a length or width of 1 cm does not vary by more than 50 μm, e.g., does not vary by more than 10 μm, does not vary by more than 5 μm, or does not vary by more than 2 μm. Such dimensional constancy cannot be achieved by solid-state quenching as disclosed herein, for a given thickness, area, and / or magnitude of negative tensile stress, due to practical considerations such as cooling plate alignment and / or surface irregularities that may alter dimensions.

[0051] According to contemplated embodiments, a thermally strengthened glass or glass ceramic substrate according to one or more embodiments has at least one surface that is flat such that a 1 cm lengthwise profile there along remains within 50 μm, e.g., within 20 μm, 10 μm, 5 μm, 2 μm, linear, and / or a 1 cm widthwise profile there along remains within 50 μm, e.g., within 20 μm, 10 μm, 5 μm, 2 μm, linear. Such high flatness may not be achievable by liquid quenching as disclosed herein due to practical considerations such as warping or bending due to convection and associated liquid forces in glasses strengthened by these processes for a given thickness, area, and / or magnitude of negative tensile stress.

[0052] In various embodiments, the thermally strengthened glass or glass ceramic substrate according to one or more embodiments has a high fictive temperature. In various embodiments, the high fictive temperature is understood to be related to a high level of thermal strengthening, high central tensile stress and / or high compressive surface stress of the resulting glass or glass ceramic substrate. The surface fictive temperature can be determined by any suitable method, including differential scanning calorimetry, Brillouin spectroscopy, or Raman spectroscopy.

[0053] According to exemplary embodiments, a thermally strengthened glass or glass ceramic substrate according to one or more embodiments has a portion, such as at or near the surface, with a particularly high fictive temperature, such as at least 500° C., e.g., at least 600° C., or even at least 700° C. In some embodiments, a glass or glass ceramic substrate exhibiting such an activation temperature may include soda-lime glass. According to exemplary embodiments, a thermally strengthened glass or glass ceramic substrate according to one or more embodiments has a portion, such as at or near the surface, with a particularly high fictive temperature compared to an annealed glass of the same chemical composition. For example, in some embodiments, a thermally strengthened glass or glass ceramic substrate exhibits a fictive temperature that is at least 10° C. higher, at least 30° C. higher, at least 50° C. higher, at least 70° C. higher, or even at least 100° C. higher than the fictive temperature of an annealed glass of the same chemical composition (i.e., a glass that has not been or has not been thermally strengthened according to the processes described herein). A high fictive temperature can be achieved by a rapid transition from a hot zone to a cool zone in a thermally strengthened system. Without being bound by theory, it is believed that thermally strengthened glass or glass-ceramic substrates having high fictive temperatures exhibit increased damage resistance.

[0054] Some methods for measuring surface fictive temperature may require the thermally strengthened glass or glass-ceramic substrate to be fractured to relieve the "tempering stress" induced by the thermal strengthening process in order to measure the fictive temperature with reasonable accuracy. It is well known that the characteristic structural bands measured by Raman spectroscopy shift in a controlled manner in silicate glasses with respect to both fictive temperature and applied stress. This shift can be used to non-destructively measure fictive temperature if the tempering stress is known. A method for measuring fictive temperature is described in U.S. Provisional Patent Application No. 62236296, entitled "THERMALLY STRENGTHENED GLASS AND RELATED SYSTEMS AND METHODS," filed October 2, 2015, and incorporated herein by reference in its entirety.

[0055] The following dimensionless fictive temperature parameter θ can be used to compare the relative performance of thermal strengthening processes in terms of the resulting fictive temperature, where θs is the surface fictive temperature, expressed as:

[0056]

number

[0057] In the formula, T fs is the surface fictive temperature, T anneal (Viscosity η=10 13.2 (temperature of glass in poise) is the annealing temperature, T soft (Viscosity η=10 7.6 The softening point of the glass sheet is the temperature of the glass in poise. FIG. 10 is a plot of θ for the measured surface fictive temperature as a function of the heat transfer coefficient h applied during thermal strengthening for two different glasses. In one or more embodiments, the thermally strengthened glass or glass-ceramic has a softening temperature T soft , the annealing temperature T in °C anneal , T when expressed in °C fsand (T fs -T anneal ) / (T soft -T anneal ) where the parameter θs is in the range of 0.20 to 0.9. In embodiments, the parameter θs is in the range of about (e.g., ±10%) 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 0.30 to 0.09, or 0.40 to 0.09, or 0.5 to 0.9, or 0.51 to 0.9, or 0.52 to 0.9, or 0.53 to 0.9, or 0.54 to 0.9, or 0.54 to 0.9, or 0.55 to 0.9, or 0.6 to 0.9, or even 0.65 to 0.9.

[0058] However, even higher heat transfer rates (e.g., about 800 W / m 2 K and above), the high temperature or "liquid phase" CTE of the glass begins to affect tempering performance. Therefore, under such conditions, the temperability parameter Ψ, which is based on an approximation of the integral for the CTE values ​​varying across the viscosity curve, has proven useful.

[0059]

number

[0060] In the formula, α S CTE is 1 / ℃(℃ -1 ), where α is the low-temperature linear CTE (for glass, it is equal to the average linear expansion coefficient from 0°C to 300°C) and L CTE is 1 / ℃(℃ -1), E is the high temperature linear CTE in GPa (not MPa) (which allows the value of the (dimensionless) parameter Ψ to range generally between 0 and 1), and T strain is the temperature of the strain point of the glass in °C (viscosity η = 10 14.7 (temperature of glass in poise), and T soft is the softening point of the glass in °C (viscosity η = 10 7.6 (temperature of glass in poise).

[0061] The thermal strengthening process and the resulting surface CS values ​​were modeled for glasses with various properties to determine the tempering parameter Ψ. 8.2 The glasses were modeled with the same starting viscosity in poise and various heat transfer coefficients. The properties of the various glasses are listed in Table 1. 8.2 The temperature of each glass in poise is given along with the calculated temperability parameter Ψ for each.

[0062] [Table 1]

[0063] The results in Table 1 show that Ψ is proportional to the thermal strengthening performance of the glass. In another aspect, for any glass, any given heat transfer coefficient value h (cal / cm 2 s °C), and the curve of the surface CS (σ CS It was found that the linear relationship between the thickness (t, mm) and the compressive strength (MPa) can be fitted by a hyperbola (over the range of t from 0 mm to 6 mm), where P1 and P2 are functions of h, so that

[0064]

number

[0065] Or, substituting the expression for Ψ into this, we get CSσ CSThe curve for (glass, h, t) is

[0066]

number

[0067] The constants P1 and P2 in either formula (4) or (5) are respectively represented by:

[0068]

number

[0069] and

[0070]

number

[0071] is a continuous function of the heat transfer value h, expressed as

[0072] In some embodiments, a similar formula can be used to predict the CT of thermally strengthened glass sheets, particularly for thicknesses of 6 mm or less and 800 W / m 2 The heat transfer coefficient above K can be predicted simply by dividing the predicted CS under the same conductance by 2. Thus, the predicted CT is

[0073]

number

[0074] In the formula, P 1CT and P 2CT is expressed as follows:

[0075]

number

[0076] and

[0077]

number

[0078] In some embodiments, h and h CT may have the same value for a given physical example of thermal strengthening, however in some embodiments they may be varied, providing additional variables and allowing for their variability to capture cases where the typical CS / CT ratio of 2:1 is not maintained within the descriptive performance curve.

[0079] One or more embodiments of the processes and systems of the present disclosure provide heat transfer coefficient values ​​(h and h) shown in Table 2. CT ) were used to produce thermally strengthened SLG sheets.

[0080] [Table 2]

[0081] In some embodiments, the heat transfer coefficient values ​​(h and h CT ) is approximately 0.024 cal / s cm 2 / ℃ to about 0.15cal / s cm 2 / ℃ (approx. 1004 to approx. 6280 W / m 2 K), approximately 0.026 cal / s cm 2 / ℃ to about 0.10 cal / s cm 2 / ℃ (approx. 1089 to approx. 4187 W / m 2 K), or approximately 0.026 cal / s cm 2 / ℃ to approximately 0.075cal / s cm 2 / ℃ (approx. 1089 to approx. 3140 W / m 2 K).

[0082] In one or more embodiments, a strengthened glass or glass ceramic substrate can be mechanically strengthened by taking advantage of the mismatch in thermal expansion coefficients between portions of the substrate to create compressive stresses and form a central elongated region.

[0083] In one embodiment, the strengthened glass or glass ceramic substrate can have a surface CS of 300 MPa or more, e.g., 400 MPa or more, 450 MPa or more, 500 MPa or more, 550 MPa or more, 600 MPa or more, 650 MPa or more, 700 MPa or more, 750 MPa or more, or 800 MPa or more. In one or more embodiments, the surface CS is the maximum CS in the strengthened glass or glass ceramic substrate.

[0084] The strengthened glass or glass ceramic substrate may have a DOL of about 15 μm or more, 20 μm or more (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or more). In one or more embodiments, the strengthened glass or glass ceramic substrate may exhibit a maximum CT value that is 10 MPa or more, 20 MPa or more, 30 MPa or more, 40 MPa or more (e.g., 42 MPa, 45 MPa, or 50 MPa or more), but less than 100 MPa (e.g., 95 MPa, 90 MPa, 85 MPa, 80 MPa, 75 MPa, 70 MPa, 65 MPa, 60 MPa, 55 MPa or less).

[0085] In one or more specific embodiments, the strengthened glass or glass ceramic substrate has one or more of a surface compressive stress greater than 300 MPa, a compressive layer depth greater than 15 μm, and a central tension greater than 18 MPa.

[0086] Examples of glasses that can be used in the substrate can include alkali aluminosilicate glass compositions or alkali aluminoborosilicate glass compositions, although other glass compositions are contemplated. One example of a glass composition includes SiO2, B2O3, and Na2O, where (SiO2+B2O3)>66 mol% and Na2O>9 mol%. In an embodiment, the glass composition includes at least 6 wt% aluminum oxide. In a further embodiment, the substrate includes a glass composition having one or more alkaline earth oxides such that the alkaline earth oxide content is at least 5 wt%. Suitable glass compositions further include at least one of K2O, MgO, and CaO in some embodiments. In certain embodiments, the glass composition used in the substrate can include 61-75 mol% SiO2, 7-15 mol% Al2O3, 0-12 mol% B2O3, 9-21 mol% Na2O, 0-4 mol% K2O, 0-7 mol% MgO, and 0-3 mol% CaO.

[0087] Further examples of glass compositions suitable for the substrate include 60-70 mol% SiO2, 6-14 mol% Al2O3, 0-15 mol% B2O3, 0-15 mol% Li2O, 0-20 mol% Na2O, 0-10 mol% K2O, 0-8 mol% MgO, 0-10 mol% CaO, 0-5 mol% ZrO2, 0-1 mol% SnO2, 0-1 mol% CeO2, less than 50 ppm As2O3, and less than 50 ppm Sb2O3, where 12 mol%≦(Li2O+Na2O+K2O)≦20 mol% and 0 mol%≦(MgO+CaO)≦10 mol%.

[0088] Further examples of glass compositions suitable for the substrate include 63.5-66.5 mol% SiO2, 8-12 mol% Al2O3, 0-3 mol% B2O3, 0-5 mol% Li2O, 8-18 mol% Na2O, 0-5 mol% K2O, 1-7 mol% MgO, 0-2.5 mol% CaO, 0-3 mol% ZrO2, 0.05-0.25 mol% SnO2, 0.05-0.5 mol% CeO2, less than 50 ppm As2O3, and less than 50 ppm Sb2O3, where 14 mol%≦(Li2O+Na2O+K2O)≦18 mol% and 2 mol%≦(MgO+CaO)≦7 mol%.

[0089] In certain embodiments, an alkali aluminosilicate glass composition suitable for the substrate comprises alumina, at least one alkali metal, and in some embodiments greater than 50 mol% SiO2, in other embodiments at least 58 mol% SiO2, and in yet other embodiments at least 60 mol% SiO2, with a ratio ((Al2O3+B2O3) / Σmodifier)>1, where the components are expressed in mol% and the modifier is an alkali metal oxide. In certain embodiments, the glass composition comprises 58-72 mol% SiO2, 9-17 mol% Al2O3, 2-12 mol% B2O3, 8-16 mol% Na2O, and 0-4 mol% K2O, with a ratio ((Al2O3+B2O3) / Σmodifier)>1.

[0090] In yet another embodiment, the substrate may comprise an alkali aluminosilicate glass composition including 64-68 mol% SiO2, 12-16 mol% Na2O, 8-12 mol% Al2O3, 0-3 mol% B2O3, 2-5 mol% K2O, 4-6 mol% MgO, and 0-5 mol% CaO, where 66 mol%≦SiO2+B2O3+CaO≦69 mol%, Na2O+K2O+B2O3+MgO+CaO+SrO>10 mol%, 5 mol%≦MgO+CaO+SrO≦8 mol%, (Na2O+B2O3)-Al2O3≦2 mol%, 2 mol%≦Na2O-Al2O3≦6 mol%, and 4 mol%≦(Na2O+K2O)-Al2O3≦10 mol%.

[0091] In another embodiment, the substrate may include an alkali aluminosilicate glass composition including 2 mol % or more of Al2O3 and / or ZrO2, or 4 mol % or more of Al2O3 and / or ZrO2.

[0092] In some embodiments, the composition for use with a glass substrate can be combined with 0-2 mol % of at least one fining agent selected from the group including Na2SO4, NaCl, NaF, NaBr, K2SO4, KCl, KF, KBr, and SnO2.

[0093] In one or more embodiments, the intermediate layer 120 comprises a material selected from the group consisting of polyvinyl butyral (PVB) resin, ethylene vinyl acetate copolymer (EVA), ionomer, polyvinyl chloride copolymer, and thermoplastic polyurethane (TPU). The thickness of the intermediate layer can be in the range of about 0.3 mm to about 2 mm.

[0094] In one or more embodiments, the laminate may have a length and width within the range of 30.5 cm by about 30.5 cm (12 inches by 12 inches) to about 50.8 cm by 101.6 cm (20 inches by 40 inches), or 30.5 cm by about 30.5 cm (12 inches by 12 inches) to about 121.9 cm by 127 cm (48 inches by 50 inches), or 30.5 cm by about 30.5 cm (12 inches by 12 inches) to about 127 cm by 183 cm (50 inches by 72 inches). Although the stack has been described in two dimensions, the stack may have a variety of shapes including quadrilateral (e.g., rectangular, square, trapezoid, etc.), triangular, having dimensions in two directions, e.g., along two different sides or axes in a plane, or non-rectangular (e.g., circular, elliptical, oval, polygonal, etc.) that can be described in terms of radius and / or major and minor axis lengths, where a non-rectangular may relate to a rectangle, e.g., corresponding to two largest perpendicular dimensions as measured when cut from a rectangular substrate. The substrate may be of any suitable configuration and dimensions to provide the stack of the intended size.

[0095] In one or more embodiments, the laminate may have additional coatings or layers applied to the exposed surfaces, including, but not limited to, tint, anti-reflective coatings, anti-glare coatings, scratch resistant coatings, and the like. In one or more embodiments, the polymer interlayer may be modified to have one or more of the following properties: ultraviolet (UV) absorption, infrared (IR) absorption, IR reflection, and tint. The polymer interlayer may be modified with suitable additives, such as dyes, pigments, dopants, and the like, to impart desired properties.

[0096] A second aspect of the present disclosure relates to a method for cold forming the laminates described herein. Figure 2 shows a cross-sectional view of an exemplary embodiment of a first substrate 110, an intermediate layer 120, and a second substrate 130 prior to cold forming.

[0097] The first substrate 110 is arranged in a stack with the intermediate layer 120 and the second substrate 130. As shown in FIG. 2, the second substrate 130 is flat prior to the forming process. In various embodiments, during the cold forming process, pressure is applied to the stack as shown by the arrow "P" in FIG. 2, such that the second substrate 130, the intermediate layer 120, and the first substrate 110 are pressed together. In one or more embodiments, the pressure may be about 1 atmosphere or more. In one or more other embodiments, the pressure applied may be about 1 atmosphere or less. As further described below, heat may be applied at a temperature lower than the forming temperature of the second substrate 130. The second substrate 130 deforms to take the shape of the first substrate 110, and the first substrate 110 and the second substrate are bonded together by the intermediate layer 120. Thus, as shown in FIG. 1, the second substrate 130, the first substrate 110 having a complex curved shape, and the intermediate layer 120 are laminated together by the cold forming process to form the laminate 100. In one or more embodiments, the first glass substrate 110 can also be annealed or thermally tempered.

[0098] In one or more embodiments, the first and second substrates can be stacked, aligned, and introduced simultaneously into a cold forming apparatus, and multiple substrates can then be formed and cold formed together at once by a bending apparatus.

[0099] In one or more embodiments, the method includes hot forming the first substrate into a complex curved shape, followed by cold forming the first substrate and the second substrate into one or more embodiments of a laminate described herein. In one or more embodiments, hot forming the first substrate can include heating the first substrate to a temperature near the softening point of the substrate, and then bending the heated first substrate into the complex curved shape. In one or more embodiments, the first substrate is a glass substrate, and hot forming the first substrate can include heating the first substrate to a temperature near the softening point, for example, greater than 400° C.

[0100] In one or more embodiments, the complex curved first substrate and the flat second substrate are cold-formed into a laminate at a temperature well below the softening point of the second substrate. In one or more embodiments, the cold-forming process is performed at a temperature 200° C. or more below the softening point of the substrate. The softening point refers to the temperature at which glass deforms under its own weight. In one or more specific embodiments, the temperature during the cold-forming process is less than about 400° C., less than about 350° C., less than about 300° C., less than about 200° C., less than about 175° C., or less than about 150° C. In one particular embodiment, the cold-forming process is within the range of room temperature to about 140° C. Room temperature can be considered to be the ambient temperature of the manufacturing facility (e.g., 16° C. to about 35° C.).

[0101] In one or more embodiments, the method includes placing an interlayer between a first, compound curved substrate and a second, flat substrate, and cold forming the substrates so that the flat substrate is compound curved while simultaneously bonding the two substrates together through the interlayer. In one or more embodiments, the method includes bonding the first and second substrates together through the interlayer in a step separate from the cold forming step in which the flat second substrate is formed to conform to the first substrate. In various embodiments, the bonding step includes heating the stack of the first substrate, the interlayer, and the second substrate to a temperature in the range of about 100° C. to about 140° C. to form a bond between the substrates and the interlayer. In one or more embodiments, the method includes bonding the substrates together using an adhesive in addition to or instead of the interlayer.

[0102] In one or more embodiments, the method does not include bonding a first substrate and a second substrate. In such embodiments, the first complex curved substrate and the second flat substrate are stacked, aligned together, and pressed together to form the second substrate into a complex curved shape that matches the shape of the first substrate. The two substrates are then separated and used individually.

[0103] In one or more embodiments, during the cold forming process, the periphery of the second substrate exerts a compressive force on the intermediate layer (if present) and the first substrate as it is desired that the second substrate deform and conform to the second surface 114 of the first substrate and bend back to a flatter state, and the central portion of the second substrate exerts a tensile force on the intermediate layer (if present) and the first substrate as it attempts to bend back to a flatter state away from the intermediate layer, relieving at least a portion of the tensile stress.

[0104] The method embodiments described herein allow for higher manufacturing yields because the second substrate can have a wide range of shapes and still be successfully cold formed into the first substrate. According to one or more embodiments in which the second substrate is glass, the method described herein overcomes shape mismatches that can occur during glass forming, resulting in a laminate with a desirable and reproducible shape even when the second substrate lacks shape uniformity.

[0105] In one or more embodiments, the cold forming process can be performed in a press bending apparatus that includes a male form and a female form. In various embodiments, the second substrate can be supported by the female form and provide a cavity at least in the middle to receive a portion of the second substrate during the forming operation. In various embodiments, the female form and the male form are configured to engage with each other to cold form the second substrate and the first substrate into a laminate.

[0106] In various embodiments, a vacuum technique can be used to cold-form the first and second substrates into a laminate as described herein. Suitable vacuum techniques include vacuum bag techniques or vacuum rings, which can also be used. In another embodiment, a flatbed clamshell type laminator can be used.

[0107] In the vacuum bag technique, the first substrate, the second substrate, and optionally an intermediate layer can be stacked, aligned, and placed in a suitable bag. The air is removed from the bag until the air pressure surrounding the bag exerts a force of about 1 atmosphere (i.e., taking into account altitude / geographical location, the limitations of the vacuum equipment to evacuate all air, etc.). In various embodiments, the applied force causes the second substrate to cold-form the first substrate with a complex curve.

[0108] A third aspect of the present disclosure relates to a vehicle including a body having an opening and one or more embodiments of a laminate disclosed herein disposed in the opening. The vehicle may include an automobile, a large truck, an ocean-going vessel, a rail car, an aircraft, etc. The laminate may be movable relative to the opening.

[0109] A fourth aspect of the present disclosure relates to a vehicle having a body defining an interior cabin, the interior cabin comprising a surface formed from one or more laminates described herein, in one or more embodiments, the surface forms at least a portion of a dashboard, a floor, a door panel, a center console, an instrument panel, a display panel, a headrest, a pillar, or the like. EXAMPLES

[0110] The principles and embodiments of the present disclosure are illustrated by the following non-limiting examples.

[0111] Examples using the methods described herein were prepared by laminating flat, chemically strengthened substrates (formed from alkali aluminosilicate glass) to form complex curved, unstrengthened substrates (formed from soda-lime glass (SLG)) having a thickness greater than that of the flat, chemically strengthened substrates. The resulting laminates included a three-layer acoustic polyvinyl butyrate interlayer between the substrates. Laminates were also formed using vacuum techniques using either vacuum bag or vacuum channel degassing, and standard autoclave processes.

[0112] Example 1 A glass substrate having a diameter of 355.6 mm and a thickness of 0.7 mm (labeled "GG") formed from an aluminosilicate glass composition was assembled into a stack with a glass substrate having the same diameter and a thickness of 1.6 mm (labeled "SLG") formed from SLG. The 1.6 mm thick substrate had a spherical and therefore complex curved shape. The stack was placed in a vacuum bag, which was then placed in an autoclave to cold-form the 0.7 mm thick substrate into a 1.6 mm thick substrate. The shape of the substrate and the resulting stack was measured by a confocal sensor available from Micro-Epsilon used in conjunction with a common motion platform. In each case, the substrate (before lamination) or stack was placed on a common motion platform. The platform controls and monitors the xy position. The confocal sensor measures the displacement of the substrate (before lamination) or stack from the plane of the platform. A map of the displacement from the platform versus the xy position defines the shape of the substrate (before lamination) or stack. Figure 3 is a graph of the measurement results. After lamination, both substrates had the same shape, indicating that the initially flat substrate was able to conform to the spherical shape of the thicker, more rigid substrate.

[0113] Example 2 A flat substrate having length, width and thickness dimensions of 237 mm x 318 mm x 0.7 mm containing an aluminosilicate glass composition was assembled with a complex curved substrate into a stack. The complex curved substrate had the same length and width dimensions as the flat substrate, but had a thickness of 2.1 mm and contained an SLG composition. The 2.1 mm thick substrate exhibited a central sag depth (total depth of curvature from edge to center) of 6.75 mm. The stack was vacuum bagged and the flat substrate was cold formed into the complex curved shape of the SLG substrate. The optical properties of the resulting laminate were measured using transmitted optics according to ASTM standard C1036-06 looking at a "zebra board" through the laminate at various angles. The zebra board consisted of a series of black and white diagonal stripes (i.e., 25 mm wide black stripes separated by 25 mm wide white stripes). The quality of the transmission optics is evaluated by observing the degree of distortion of the stripes when viewed through the laminate. The transmission optical distortion of the central clear portion showed no signs of degradation due to the cold forming process. A low level of distortion was detected at the periphery of the laminate, but was not visible to the naked eye due to the cosmetic band on the periphery.

[0114] Example 3 A flat substrate having length, width and thickness dimensions of 237 mm x 318 mm x 0.55 mm and comprising an aluminosilicate glass composition was assembled with a complex curved substrate. The complex curved substrate had the same length and width dimensions as the flat substrate, but had a thickness of 1.6 mm and comprised an SLG composition. The 1.6 mm thick substrate exhibited a central sag depth (total depth of curvature from edge to center) of 6.75 mm. The stack was placed in a vacuum bag, thus cold forming the flat substrate into the complex curved shape of the SLG substrate. The optical properties of the resulting laminate were measured using transmission optics as in Example 2. The transmission optical distortion of the central transparent portion showed no signs of degradation due to the cold forming process. A low level of distortion was detected at the periphery of the laminate, but was not visible to the naked eye due to the decorative band on the periphery.

[0115] Example 4 A flat substrate having dimensions of 1350 mm x 472 mm x 0.7 mm length, width and thickness and comprising an aluminosilicate glass composition was assembled with a complex curved substrate having the same length and width dimensions as the flat substrate but a thickness of 3.85 mm and comprising an SLG composition. The stack was placed in a vacuum bag and the flat substrate was cold formed into the complex curved shape of the SLG substrate. The optical properties of the resulting stack were measured using transmission optics in the same manner as in Example 2. No signs of degradation due to the cold forming process were observed.

[0116] In a first embodiment, the present disclosure provides a laminate including a first compound curved glass substrate having a first side and a second side opposite the first side and a first thickness therebetween, a second compound curved glass substrate having a third side and a fourth side opposite the third side and a second thickness therebetween, and a polymer interlayer secured to the second side and the third side, wherein one of the first thickness and the second thickness is in the range of about 0.2 mm to about 0.7 mm, and the third side and the fourth side each have a compressive stress value such that the fourth side has a compressive stress value greater than the compressive stress value of the third side.

[0117] In a second embodiment, the present disclosure provides the laminate of the first embodiment, wherein the complex curved glass substrate having a thickness in the range of about 0.2 mm to about 0.7 mm is a chemically strengthened glass.

[0118] In a third embodiment, the present disclosure provides a laminate of either or both of the first and second embodiments, wherein the first compound curved glass substrate has a thickness in the range of about 1.4 mm to about 3.85 mm, and the second compound curved glass substrate has a thickness in the range of about 0.2 mm to about 0.7 mm.

[0119] In a fourth embodiment, the present disclosure provides a laminate of any of the first to third embodiments, wherein the first complex curved glass substrate is made of soda-lime glass.

[0120] In a fifth embodiment, the present disclosure provides a laminate of any of the first to fourth embodiments, wherein the intervening polymer interlayer is selected from the group consisting of polyvinyl butyral, ethylene vinyl acetate, ionomers, polyvinyl chloride copolymers, and thermoplastic polyurethanes.

[0121] In a sixth embodiment, the present disclosure provides a laminate of any of the first to fifth embodiments, wherein a peripheral portion of the second compound curved glass substrate applies a compressive force to the polymer interlayer and a central portion of the second compound curved glass substrate applies a tensile force to the polymer interlayer.

[0122] In a seventh embodiment, the present disclosure provides the laminate of any of the first to sixth embodiments, further comprising a uniform distance between the second side and the third side.

[0123] In an eighth embodiment, the present disclosure provides a laminate of any of the first to seventh embodiments, wherein the laminate exhibits a radius of curvature, the radius of curvature being less than 1000 mm.

[0124] In a ninth embodiment, the present disclosure provides a vehicle including a vehicle body, an opening in the vehicle body, and a laminate disposed in the opening, the laminate including a first compound curved glass substrate having a first side, a second side opposite the first side, and a first thickness therebetween, a second compound curved glass substrate having a third side, a fourth side opposite the third side, and a second thickness therebetween, and a polymer interlayer secured to the second side and the third side, one of the first thickness and the second thickness being in the range of about 0.2 mm to about 0.7 mm, and the third side and the fourth side each have a compressive stress value such that the fourth side has a compressive stress value greater than the compressive stress value of the third side.

[0125] In a tenth embodiment, the present disclosure provides the vehicle of the ninth embodiment, wherein the laminate is moveable relative to the opening.

[0126] In an eleventh embodiment, the present disclosure provides the vehicle of either or both of the ninth and tenth embodiments, wherein the first compound curved substrate has a soda-lime glass composition and a thickness greater than about 0.7 mm, and the second compound curved substrate has a tempered glass composition and a thickness in the range of about 0.2 mm to about 0.7 mm.

[0127] In a twelfth embodiment, the present disclosure provides a method of manufacturing a complex curved laminate, the method comprising: disposing an interlayer between a first complex curved substrate and a flat second glass substrate to form a stack; applying pressure to the stack to press the second glass substrate against the interlayer and the first complex curved substrate to form the complex curved laminate; and heating the complex curved laminate to a temperature below 400°C.

[0128] In a thirteenth embodiment, the present disclosure provides the method of the twelfth embodiment, wherein the first complex curved substrate is made of metal, ceramic, plastic or glass.

[0129] In a fourteenth embodiment, the present disclosure provides the method of one or both of the twelfth and thirteenth embodiments, wherein the flat second glass substrate has a thickness in the range of about 0.2 mm to about 0.7 mm, and the first complex curved substrate has a thickness greater than 0.7 mm.

[0130] In a fifteenth embodiment, the present disclosure provides the method of any one of the twelfth to fourteenth embodiments, wherein the pressure is about 1 atmosphere or greater.

[0131] In a sixteenth embodiment, the present disclosure provides the method of any one of the twelfth to fifteenth embodiments, wherein pressure is applied to the stack using vacuum techniques.

[0132] In a seventeenth embodiment, the present disclosure provides the method of any one of the twelfth to sixteenth embodiments, wherein pressure is applied to the stack at room temperature.

[0133] In an eighteenth embodiment, the present disclosure provides the method of any one of the twelfth to seventeenth embodiments, wherein the laminate is heated to a temperature in the range of about 100° C. to about 140° C. to form an intact bond between the bonding layer and the complex curved glass substrate.

[0134] In a nineteenth embodiment, the present disclosure provides a complex curved laminate formed by the method of any one of the twelfth to eighteenth embodiments.

[0135] In a twentieth embodiment, the present disclosure provides a method of manufacturing a compound curved laminate, the method comprising: shaping a first glass substrate having two major surfaces and a thickness therebetween to provide a compound curved glass substrate having curvatures along two axes; arranging the compound curved glass substrate with an interlayer and a second glass substrate in a stack, such that the interlayer is between the compound curved glass substrate and the second glass substrate, the second glass substrate having two major surfaces and a thickness therebetween and having curvatures along two axes, the curvature of the second glass substrate not matching the curvature of the first glass substrate; and applying pressure to the stack at room temperature, whereby the curvature of the second glass substrate matches the curvature of the first glass substrate to form a compound curved laminate.

[0136] In a twenty-first embodiment, the present disclosure provides the method of the twentieth embodiment, further comprising heating the stack to a temperature in the range of about 100° C. to about 140° C. to form bonds between the intermediate layer and the first and second glass substrates.

[0137] In a twenty-second embodiment, the present disclosure provides the method of either or both of the twentieth and twenty-first embodiments, wherein the second glass substrate is a chemically strengthened glass having a thickness in the range of about 0.2 mm to about 0.7 mm, and the first glass substrate is a soda-lime glass having a thickness in the range of about 1.4 mm to about 3.85 mm.

[0138] In a twenty-third embodiment, the present disclosure provides a complex curved laminate formed by the method of any one of the twentieth to twenty-second embodiments.

[0139] Although the disclosure herein has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed method and apparatus without departing from the spirit and scope of the disclosure. Thus, the disclosure is intended to cover modifications and alterations that come within the scope of the appended claims and their equivalents.

[0140] Preferred embodiments of the present invention will be described below in detail.

[0141] EMBODIMENT 1 a first compound curved glass substrate having a first surface, a second surface opposite the first surface, and a first thickness therebetween; a second compound curved glass substrate having a third side and a fourth side opposite the third side and a second thickness therebetween; and a polymeric interlayer secured to said second surface and said third surface; A laminate comprising: one of the first thickness and the second thickness is within a range of about 0.2 mm to about 0.7 mm, and the third side and the fourth side each have a compressive stress value such that the fourth side has a compressive stress value that is greater than a compressive stress value of the third side. Laminate.

[0142] EMBODIMENT 2 2. The laminate of embodiment 1, wherein the compound curved glass substrate having a thickness in the range of about 0.2 mm to about 0.7 mm is chemically strengthened glass.

[0143] EMBODIMENT 3 3. The laminate of claim 1 or claim 2, wherein the first compound curved glass substrate has a thickness in the range of about 1.4 mm to about 3.85 mm, and the second compound curved glass substrate has a thickness in the range of about 0.2 mm to about 0.7 mm.

[0144] EMBODIMENT 4 4. The laminate of any one of the preceding claims, wherein the first complex curved glass substrate is made of soda-lime glass.

[0145] EMBODIMENT 5 5. The laminate of any one of the preceding claims, wherein the intervening polymer interlayer is selected from the group consisting of polyvinyl butyral, ethylene vinyl acetate, ionomers, polyvinyl chloride copolymers, and thermoplastic polyurethanes.

[0146] EMBODIMENT 6 6. The laminate of any one of claims 1 to 5, wherein a peripheral portion of the second compound curved glass substrate exerts a compressive force on the polymer interlayer and a central portion of the second compound curved glass substrate exerts a tensile force on the polymer interlayer.

[0147] EMBODIMENT 7 7. The laminate of any one of the preceding claims, further comprising a uniform distance between the second side and the third side.

[0148] EMBODIMENT 8 8. The laminate of any one of the preceding claims, wherein the laminate exhibits a radius of curvature, the radius of curvature being less than 1000 mm.

[0149] EMBODIMENT 9 A vehicle comprising a vehicle body, an opening in the vehicle body, and a laminate disposed in the opening, the laminate comprising: a first compound curved glass substrate having a first surface, a second surface opposite the first surface, and a first thickness therebetween; a second compound curved glass substrate having a third side, a fourth side opposite the third side, and a second thickness therebetween; and a polymeric interlayer secured to said second surface and said third surface; Including, one of the first thickness and the second thickness is within a range of about 0.2 mm to about 0.7 mm, and the third side and fourth side each have a compressive stress value such that the fourth side has a compressive stress value that exceeds the compressive stress value of the third side.

[0150] EMBODIMENT 10 10. The vehicle of embodiment 9, wherein the laminate is movable relative to the opening.

[0151] EMBODIMENT 11 11. The vehicle of claim 9 or 10, wherein the first compound curved substrate has a soda-lime glass composition and a thickness greater than about 0.7 mm, and the second compound curved substrate comprises tempered glass and has a thickness in the range of about 0.2 mm to about 0.7 mm.

[0152] EMBODIMENT 12 A method for manufacturing a complex curved laminate, comprising the steps of: disposing an intermediate layer between a first complex curved substrate and a second flat glass substrate to form a stack; applying pressure to the stack to press the second glass substrate against the interlayer and the first compound curved substrate to form the compound curved laminate; heating the complex curved laminate to a temperature below 400°C; A method comprising:

[0153] EMBODIMENT 13 The method of claim 12, wherein the first complex curved substrate is made of metal, ceramic, plastic or glass.

[0154] EMBODIMENT 14 14. The method of claim 12 or 13, wherein the second flat glass substrate has a thickness in the range of about 0.2 mm to about 0.7 mm, and the first complex curved substrate has a thickness greater than 0.7 mm.

[0155] EMBODIMENT 15 15. The method of any one of embodiments 12-14, wherein the pressure is about 1 atmosphere or greater.

[0156] EMBODIMENT 16 16. The method of any one of embodiments 12 to 15, wherein pressure is applied to the stack using vacuum techniques.

[0157] EMBODIMENT 17 17. The method of any one of embodiments 12 to 16, wherein the pressure is applied to the stack at room temperature.

[0158] EMBODIMENT 18 18. The method of any one of claims 12 to 17, wherein the laminate is heated to a temperature in the range of about 100°C to about 140°C to form a complete bond between the bonding layer and the complex curved glass substrate.

[0159] EMBODIMENT 19 19. A complex curved laminate formed by the method according to any one of embodiments 12 to 18.

[0160] EMBODIMENT 20 A method for manufacturing a complex curved laminate, comprising the steps of: shaping a first glass substrate having two major surfaces and a thickness therebetween to provide a compound curved glass substrate having curvatures along two axes; arranging the compound curved glass substrate together with an intermediate layer and a second glass substrate in a stack such that the intermediate layer is between the compound curved glass substrate and the second glass substrate, the second glass substrate having two major surfaces and a thickness therebetween, and having a curvature along two axes, the curvature of the second glass substrate not matching the curvature of the first glass substrate; applying pressure to the stack at room temperature such that the curvature of the second glass substrate matches the curvature of the first glass substrate to form a complex curved laminate; A method comprising:

[0161] EMBODIMENT 21 21. The method of claim 20, further comprising heating the stack to a temperature in the range of about 100° C. to about 140° C. to form bonds between the intermediate layer and the first and second glass substrates.

[0162] EMBODIMENT 22 22. The method of claim 20 or 21, wherein the second glass substrate is a chemically strengthened glass having a thickness in the range of about 0.2 mm to about 0.7 mm, and the first glass substrate is a soda-lime glass having a thickness in the range of about 1.4 mm to about 3.85 mm.

[0163] EMBODIMENT 23 23. A complex curved laminate formed by the method of any one of claims 20 to 22. [Explanation of symbols]

[0164] 100 Laminate 110 First board 112 Front page 114 Second side 120 Middle Class 130 Second board 132 Third side 134 Fourth side

Claims

1. a first compound curved glass substrate having a first surface, a second surface opposite the first surface, and a first thickness therebetween; a second compound curved glass substrate having a third side, a fourth side opposite the third side, and a second thickness therebetween; and a polymeric interlayer secured to said second surface and said third surface; A laminate comprising: the second thickness is within a range of 0.1 mm to 1.4 mm, the compressive stress value of the fourth surface is greater than the compressive stress value of the third surface; each of the first and second complex curved glass substrates has a non-planar shape with curvatures along two mutually different orthogonal axes; the laminate has a radius of curvature along each axis of 5 meters or less, the second compound curved glass substrate is transformed from an initial planar shape to the non-planar shape via the non-planar shape of the first compound curved glass substrate, and the polymer interlayer prevents the second compound curved glass substrate from returning to its original initial planar shape; and the laminate has at least one of the following characteristics: (A) the second complex curved glass substrate is a chemically strengthened glass having a surface compressive stress of 300 MPa or more, the chemical strengthening being by immersion in a molten salt bath having a temperature in the range of 350° C. to 450° C. for a time period in the range of 2 hours to 8 hours; and (B) the second compound curved glass substrate is a thermally strengthened glass having a fictive temperature of at least 500° C., and the thermal strengthening is less than 0.024 cal / cm ２ s °C to 0.15 cal / cm ２ Heating and cooling are achieved with heat transfer coefficients in the range of .s.°C.

2. 2. The laminate of claim 1, wherein when the second complex curved glass substrate is a chemically strengthened glass, the DOL of the glass substrate is 15 μm or more.

3. 3. The laminate of claim 1 or 2, wherein the first compound curved glass substrate is unstrengthened glass.

4. 4. The laminate of claim 1, wherein the first thickness is 4.0 mm or less.

5. 5. The laminate of claim 4, wherein the first thickness is within the range of 1.4 mm to 3.85 mm.

6. 6. The laminate of claim 1 , wherein a peripheral portion of the second compound curved glass substrate exerts a compressive force on the polymer interlayer and a central portion of the second compound curved glass substrate exerts a tensile force on the polymer interlayer.

7. 7. The laminate of claim 1, wherein the laminate exhibits a radius of curvature, the radius of curvature being less than 1000 mm.

8. A vehicle comprising a vehicle body, an opening in the vehicle body, and a laminate disposed in the opening, the laminate comprising: a first compound curved glass substrate having a first surface, a second surface opposite the first surface, and a first thickness therebetween; a second compound curved glass substrate having a third side, a fourth side opposite the third side, and a second thickness therebetween; and a polymeric interlayer secured to said second and third surfaces; Including, the second thickness is within a range of 0.1 mm to 1.4 mm, the compressive stress value of the fourth surface is greater than the compressive stress value of the third surface; each of the first and second complex curved glass substrates has a non-planar shape with curvatures along two mutually different orthogonal axes; a vehicle, the laminate having a radius of curvature along each axis of 5 meters or less, the second compound curved glass substrate being transformed from an initial planar shape to the non-planar shape via the non-planar shape of the first compound curved glass substrate, the polymer interlayer preventing the second compound curved glass substrate from returning to its original initial planar shape, the vehicle having at least one of the following characteristics: (A) the second complex curved glass substrate is a chemically strengthened glass having a surface compressive stress of 300 MPa or more, the chemical strengthening being by immersion in a molten salt bath having a temperature in the range of 350° C. to 450° C. for a time period in the range of 2 hours to 8 hours; and (B) the second compound curved glass substrate is a thermally strengthened glass having a fictive temperature of at least 500° C., and the thermal strengthening is less than 0.024 cal / cm ２ s °C to 0.15 cal / cm ２ Heating and cooling are achieved with heat transfer coefficients in the range of .s.°C.

9. The vehicle of claim 8 , wherein the laminate is moveable relative to the opening.

10. 10. The vehicle of claim 8 or 9, wherein the first thickness is less than 4.0 mm.

11. 11. The vehicle of claim 8, wherein the first complex curved substrate is an unstrengthened glass substrate.

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