Patent Description:
Laminate structures may be used for a wide range of applications in a variety of industries. For example, laminate structures may be used in architectural applications such as siding, decorative panels, cabinet installations, wall coverings, and the like. Laminate structures may also be used for furniture items and/or household appliances. For instance, laminate structures may be incorporated as outer panels for a cabinet, furniture item, and/or household appliance. Laminate structures can further serve as functional or decorative components in automobiles, e.g., windows, sunroofs, mirrors, and exterior or interior paneling.

Automotive, transportation, aviation, and architectural windows are often made from laminate structures comprising two glass sheets of similar thickness and composition. However, for various applications it may be desirable to provide laminate structures comprising dissimilar substrates, e.g., substrates of different composition and/or thickness. For instance, metal-glass laminates, plastic-glass laminates, glass-ceramic laminates, and other similar laminates may be desirable for aesthetic or structural qualities.

In addition, glass-glass laminates comprising dissimilar glass substrates may also be desirable for various applications, for example, laminates comprising glasses having different compositions, thicknesses, and/or other properties such as coefficient of thermal expansion (CTE). By way of a non-limiting example, a thin sheet of ion-exchanged glass may be laminated on a thicker soda lime glass sheet to provide enhanced damage resistance. Electrochromic windows and mirrors can comprise a thin, alkali-free glass substrate upon which an electrically active thin film is deposited, which can be laminated to a thicker soda lime glass substrate for enhanced structural rigidity.

Laminate structures comprising dissimilar substrates are referred to herein as "asymmetric" laminates. While asymmetric laminates may present one or more advantages as compared to symmetric laminates, these laminates can also present various challenges. For example, asymmetric laminates can comprise two or more substrates with different CTEs. During the lamination process, the substrates can be heated to a lamination temperature and subsequently cooled, e.g., to room temperature. When the laminate structure cools, the CTE mismatch between the substrates can lead to out-of-plane deflection (often referred to as "bow"). Bow in laminate structures can interfere with subsequent processing steps such as film deposition, can result in unwanted optical distortion in the final product, and/or can result in a product that is unsuitable for the intended application and/or does not meet the desired target shape.

Accordingly, it would be advantageous to provide asymmetric laminate structures with little or no out-of-plane deflection or bow. These and other aspects of the disclosure are discussed in further detail herein.

The invention relates to laminate structures comprising a first glass substrate having a thickness ranging from <NUM> to <NUM>, a second glass substrate having a thickness ranging from <NUM> to <NUM>, and an interlayer attaching the first and second glass substrates, wherein a CTE of the second glass substrate is at least about <NUM>% greater than a CTE of the first glass substrate, and wherein an out-of-plane deflection of the laminate structure is less than twice a thickness of the laminate structure.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the methods described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description present various embodiments of the disclosure, and are intended to provide an overview or framework for understanding the nature and character 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 various non-limiting embodiments and together with the description serve to explain the principles and operations of the disclosure.

Various features, aspects and advantages of the present disclosure are better understood when the following detailed description is read with reference to the accompanying drawings wherein like structures are indicated with like reference numerals when possible, in which:.

<FIG> illustrates a cross sectional view of a laminate structure <NUM> according to various embodiments of the disclosure. The laminate structure includes a first substrate <NUM>, a second substrate <NUM>, and an interlayer <NUM> attaching the first and second substrates. The first substrate <NUM> can have a first surface <NUM> and an opposing second surface <NUM>, with a thickness T1 between the two surfaces. Similarly, the second substrate can have a first surface <NUM> and an opposing second surface <NUM>, with a thickness T2 between the two surfaces. The interlayer <NUM> can also have a thickness T3.

The first and second substrates <NUM>, <NUM> are glass substrates. In additional embodiments, both the first and second substrates comprise glass. Suitable glass substrates may comprise, for example, soda lime, aluminosilicate, alkali-aluminosilicate, borosilicate, alkali-borosilicate, aluminoborosilicate, and alkali-aluminoborosilicate glasses, or other suitable glass materials. The glass substrate can, in some embodiments, be treated, e.g., annealed or chemically or thermally tempered, to increase the strength of the glass and/or its resistance to breakage and/or scratching. In one embodiment, the glass sheet substrate can comprise chemically strengthened glass such as Corning® Gorilla® glass from Corning Incorporated. Such chemically strengthened glass, for example, may be provided in accordance with <CIT>, <CIT>, and/or <CIT>. Corning® Willow® glass, Corning® Lotus™ glass, Corning® EAGLE XG®, and Corning Iris™ glass from Corning Incorporated may also be suitable for use as a glass substrate in various embodiments.

According to further aspects, the first or second glass substrate can have a compressive stress (CS) greater than about <NUM> MPa and a depth of layer of compressive stress (DOL) greater than about <NUM> microns, for example, a compressive stress greater than about <NUM> MPa and a DOL greater than about <NUM> microns, or a compressive stress greater than about <NUM> MPa and a DOL greater than about <NUM> microns. For instance, a chemical strengthening process for making Corning® Gorilla® glass can impart a relatively high CS (e.g., from about <NUM> MPa to about <NUM> MPa, or even greater than about <NUM> MPa) at a relatively high DOL (e.g., about <NUM> microns, or even greater than about <NUM> microns).

According to further embodiments, the first or second glass substrate may be acid-etched to further strengthen the glass substrate. Acid etching of glass may enable use of even thinner substrates in the laminate structures of the disclosure without deterioration in structural integrity or impact performance. The acid etching step, in some examples, can remove a thin layer from one or more of the surfaces of the glass substrate. By removing the above-mentioned surface layer, it is believed that the acid etching can clear away a majority of surface flaws smaller than <NUM> micron and/or round the tips of larger flaws which could otherwise negatively impact the stress concentration factor. The improvement of the glass surface by acid etching (e.g., removal of small surface flaws and rounding the tips of larger flaws) can improve glass strength, such as impact resistance. Moreover, only a relatively small depth of glass may be removed, such that a significant CS drop in the glass sheet may not occur, as the glass can have a relatively high CS at a much larger depth, such as about <NUM> microns from the surface, or even greater than about <NUM> microns in some examples.

The first and second substrate <NUM>, <NUM> have a thickness T1, T2 extending between a first surface and an opposing second surface. The thickness of the first glass substrate ranges from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>. The second glass substrate has a thickness ranging from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

In some embodiments, the first and second substrate <NUM>, <NUM> can be glass substrates having a coefficient of thermal expansion (CTE) ranging, for example, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, such as from about <NUM> × <NUM>-<NUM>/°C to about <NUM> x <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, or from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C. In certain embodiments, the glass substrate can have a CTE ranging from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, for instance, ranging from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C. In other embodiments, the glass substrate can have a CTE ranging from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, such as from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C. According to non-limiting embodiments, the glass substrate can be Corning® Gorilla® glass having a CTE ranging from about <NUM> to about <NUM> × <NUM>-<NUM>/°C, Corning® EAGLE XG® glass having a CTE ranging from about <NUM> to about <NUM> × <NUM>-<NUM>/°C, Corning® Lotus™ glass having a CTE ranging from about <NUM> to about <NUM> × <NUM>-<NUM>/°C, or Corning® Willow® glass having a CTE ranging from about <NUM> to about <NUM> × <NUM>-<NUM>/°C. In additional embodiments, the glass substrate can be soda lime glass having a CTE ranging from about <NUM> to about <NUM> × <NUM>-<NUM>/°C.

It is to be understood that all CTE values disclosed herein are expressed as CTE measured over a temperature ranging from about <NUM> to about <NUM>. The CTEs of the first and second substrates, as provided herein, can thus independently range, by way of non-limiting example, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, such as from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, or from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C. The CTEs of the first and second substrates are mismatched, e.g., have values differing by at least <NUM>%, and may have values differing by at least about <NUM>%, and higher. Similarly, CTE mismatch may cause bowing in smaller parts, e.g., when CTE mismatch is greater than about <NUM>%. By way of a non-limiting example, the CTE of the second substrate can be as much as <NUM> times that of the first substrate, such as about <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM> times that of the CTE of the first substrate. In other non-limiting embodiments, the difference between the first and second CTEs (e.g., CTE<NUM>-CTE<NUM> or CTE<NUM>-CTE<NUM>) can range, for instance, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, such as from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, or from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C.

As illustrated in <FIG>, the laminate structure further includes an interlayer <NUM> attaching the first substrate <NUM> to the second substrate <NUM>. The interlayer <NUM> can comprise a wide range of materials depending, e.g., on the application and the characteristics of the substrates. The interlayer can comprise various materials such as ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), polyvinyl butyral (PVB), and ionomers, such as SentryGlas® ionomer from Kuraray Co. , or any other suitable interlayer material. In certain embodiments, the interlayer may be chosen from EVA and PVB.

According to non-limiting embodiments, the interlayer <NUM> can be selected from those having a Young's modulus greater than or equal to <NUM> MPa, such as greater than or equal to about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, about <NUM> MPa, or about <NUM> MPa. PVB, for example, may have a Young's modulus greater than about <NUM> MPa, EVA can have a Young's modulus greater than about <NUM> MPa, and SentryGlas® ionomer can have a Young's modulus greater than about <NUM> MPa. In certain embodiments, the interlayer <NUM> may have a thickness T3 ranging from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

The interlayer <NUM> can be selected to improve the strength of the laminated structure and can further help retain pieces from the substrates, e.g., glass substrates, in the event that the laminate breaks or shatters. According to certain embodiments, an optically clear interlayer can be provided that is substantially transparent, although opaque and possibly colored interlayers may be provided in further examples. In other embodiments, desirable images can be printed, for example, by screen printing or digital scanning printing, onto the interlayer for aesthetic and/or functional purposes. Because these printed images can be arranged on the interface (e.g., on the interlayer and/or an interior surface of an optically clear substrate), they can be well preserved from scratch damages during the product lifetime.

According to various embodiments, when processed according to the methods disclosed herein, a laminate structure having little or no out-of-plane deflection (or bow) can be produced. Out-of-plane deflection can be measured as a distance between the lowest point on an edge of the laminate to the highest point in a central region of the laminate, or vice versa. In other words, out-of-plane deflection is the greatest distance between the lowest point (valley) in the laminate and the highest point (peak) in the laminate, e.g., the peak-to-valley bow (see, e.g., <FIG>). The out-of-plane deflection of the laminate structure is less than about <NUM> times, such as less than about <NUM> times the overall thickness. According to additional embodiments, the out-of-plane deflection of the laminate structure can be less than or equal to the overall thickness of the laminate structure, such as less than about half (<NUM>) the overall thickness, less than about a quarter (<NUM>) of the overall thickness, or less than about one tenth (<NUM>) of the overall thickness. By way of non-limiting example, the out-of plane deflection can be less than about <NUM>, such as less than about <NUM>, less than about <NUM>, less than about <NUM>, less than about <NUM>, less than about <NUM>, less than about <NUM>, less than about <NUM>, less than about <NUM>, or less than about <NUM>.

In certain non-limiting embodiments, the laminate structure can comprise first and second glass substrates and an interlayer disposed between the substrates, wherein a minimum radius of curvature of the laminate structure at a temperature ranging from about -<NUM> to about <NUM> is at least about <NUM> times greater than a maximum dimension of the laminate structure, and wherein a CTE of the second glass substrate is at least about <NUM>% greater than a CTE of the first glass substrate. For example, the CTE mismatch between the first and second glass substrates can be greater than about <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, or <NUM>%. In other embodiments, the difference in CTE between the first and second glass substrates (CTE<NUM>-CTE<NUM> or CTE<NUM>-CTE<NUM>) can range from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, such as from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, or from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C.

The laminate structure can furthermore include a maximum dimension, e.g., length, width, diameter, etc., which is used herein to refer to the dimension of the substrate having the largest magnitude, e.g., as compared to other dimensions. For instance, for a rectangular sheet comprising two short sides and two long sides, the maximum dimension can correspond to a length of the long side. Non-rectangular, e.g., four-sided, glass sheets can similarly comprise a maximum dimension corresponding to the length of the longest side. Maximum dimension can likewise be determined for substrates having more or less than four sides, such as polygons, triangles, and circles, to name a few.

Radius of curvature is the inverse of curvature. Flatter substrates are defined by a higher radius of curvature and a completely flat substrate has an infinite radius of curvature. In certain embodiments, the radius of curvature of the laminate structure can be greater than the maximum dimension of the laminate structure. For example, the radius of curvature can be twice the maximum dimension, about <NUM> times, about <NUM> times, about <NUM> times, about <NUM> times, about <NUM> times, or about <NUM> times the maximum dimension of the laminate structure. According to various embodiments, the minimum radius of curvature of the laminate structure can be at least about <NUM> times, at least about <NUM> times, at least about <NUM> times, at least about <NUM> times, at least about <NUM> times, at least about <NUM> times, or at least about <NUM> times greater than the maximum dimension of the laminate structure. In further embodiments, the radius of curvature can be measured at a temperature ranging from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

In various embodiments, the laminate structure can have an overall thickness ranging from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>. Exemplary laminate structures may have at least one other dimension (e.g., length, width, diameter) ranging from about <NUM> to about <NUM> or greater, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>. These dimensions are, of course, exemplary only and other dimensions of the laminate thickness, length, width, diameter, etc. can be used depending on the particular application.

The laminate structure comprises a thin glass sheet and a thicker glass sheet. The first glass substrate has a thickness ranging from about <NUM> to about <NUM> and the second glass substrate has a thickness ranging from about <NUM> to about <NUM>. The CTE of the first glass substrate can range, for example, from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, and the CTE of the second glass substrate can range from about <NUM> × <NUM>-<NUM>/°C to about <NUM> × <NUM>-<NUM>/°C, or vice versa.

It is to be understood that the laminate structures in accordance with the disclosure are not limited to structures comprising two substrates and/or a single interlayer. For example, the laminate structure can also include additional substrates and/or interlayers, such as a second interlayer attaching a third substrate to the laminate. In certain embodiments, the laminate structure can include two glass substrates laminated to opposing surfaces of a plastic substrate. According to further aspects of the disclosure, the laminate structures can comprise one or more additional substrates or layers, such as a polymer film, an additional glass layer, a reflective layer, a photochromic layer, an electrochromic layer, an electrolytic layer, a photovoltaic layer, a sensor, indicator, or active device. For example, an electrochromic layer may include one or more electrically active thin films deposited on one or more surfaces of the substrates. Suitable electrochromic layers can include, but are not limited to, inorganic layers comprising tungsten trioxide WO<NUM>. Of course, other combinations of layers and their respective features can be used to provide a wide array of configurations which are intended to fall within the scope of the disclosure.

Methods for making laminate structures and reducing bow in laminate structures are also disclosed herein. The methods disclosed herein include a step of attaching the first substrate to the second substrate with an interlayer to produce, e.g., the three-layer laminate structure illustrated in <FIG>. The stack thus produced can then be heated to a lamination temperature using any suitable method or apparatus known in the art. By way of a non-limiting example, the stack can be placed in a vacuum chamber, such as in a vacuum or lamination bag. The stack may be wrapped or otherwise secured to prevent shifting of the stack. For example, the stack may be secured using high-temperature tape, such as polyester tape. A thin breather cloth can be wrapped around the stack.

The stack(s) may be processed one at a time, in a single layer within the chamber, or in multiple layers of stacks, depending on the desired throughput. The lamination bag can be heat sealed and a vacuum port can be attached thereto. The vacuum chamber can be at least partially evacuated and the stack(s) can be heated using a predetermined temperature and pressure profile. In some instances, the stack(s) can be placed between two plates which can be used to apply pressure to the stack and/or heat and/or cool the respective layers of the stack. For example, the lamination step may be carried out with specific temperature and pressure profiles used to achieve desired adhesion (bonding) quality of the laminated structure. Of course other apparatuses and methods for achieving the lamination temperature and/or pressure can be used and are envisioned as falling within the scope of the disclosure.

The average lamination temperature can range from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>. For example, the lamination step can comprise ramping to the lamination temperature at a ramp rate ranging from about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min, from about <NUM>/min to about <NUM>/min , from about <NUM>/min to about <NUM>/min, or from about <NUM>/min to about <NUM>/min. The lamination pressure can range from about <NUM> MPa to about <NUM> MPa, such as from about <NUM> MPa to about <NUM> MPa, from about <NUM> MPa to about <NUM> MPa, from about <NUM> MPa to about <NUM> MPa, from about <NUM> MPa to about <NUM> MPa, from about <NUM> MPa to about <NUM> MPa, or from about <NUM> MPa to about <NUM> MPa. Pressure, if applied, may be applied gradually during temperature ramping or upon reaching the lamination temperature. Pressure may be gradually applied, e.g., at a ramp rate ranging from about <NUM> Pa/min to about <NUM> Pa/min, such as from about <NUM> Pa/min to about <NUM> Pa/min, from about <NUM> Pa/min to about <NUM> Pa/min, or from about <NUM> Pa/min to about <NUM> Pa/min. The laminate structure may be held at the lamination temperature and pressure for a residence time ranging from about <NUM> minutes to about <NUM> minutes, such as from about <NUM> minutes to about <NUM> minutes, from about <NUM> minutes to about <NUM> minutes, or from about <NUM> minutes to about <NUM> minutes.

After the desired residence time, the temperature can be ramped down, e.g., to room temperature at a rate ranging from about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min, from about <NUM>/min to about <NUM>/min, from about <NUM>/min to about <NUM>/min, or from about <NUM>/min to about <NUM>/min. The temperature can be ramped down while maintaining the lamination pressure which can reduce the formation of bubbles in the interlayer. Alternatively, the pressure can be reduced before or during temperature ramping. A gradual pressure reduction can be used for instance, at a ramp rate ranging from about <NUM> Pa/min to about <NUM> Pa/min, such as from about <NUM> Pa/min to about <NUM> Pa/min, from about <NUM> Pa/min to about <NUM> Pa/min, or from about <NUM> Pa/min to about <NUM> Pa/min.

The interlayer may be conditioned prior to lamination, for example, to control the moisture content of the interlayer, to soften the interlayer, and/or to remove any residual air between the interlayer and the substrates. In one example, the step of conditioning can adjust the moisture content of the interlayer to less than about <NUM>%, such as less than or equal to about <NUM>%, such as less than or equal to about <NUM>%, less than or equal to about <NUM>%, or less than or equal to about <NUM>%. Controlling the moisture content of the interlayer may be beneficial to improve bonding quality of the interlayer during the lamination procedure. A conditioning step may be used to soften a PVB interlayer prior to lamination.

Conditioning can be carried out according to any method known in the art. For example, the interlayer may be placed in a controlled environment where the temperature and/or humidity can be adjusted to achieve the desired moisture content of the interlayer. Conditioning can take place before the interlayer is positioned between the two substrates and/or after the stack is formed. For instance, prior to lamination, the stack may be pre-heated to a conditioning temperature ranging from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

Before and/or after lamination, the methods disclosed herein can further include optional processing steps that may provide additional beneficial features to the laminate structure. For instance, additional processing steps for exemplary glass substrates can include chemical strengthening (e.g., ion exchange), thermal tempering, acid etching, anti-glare processing, mechanical roughening, sol-gel processing, film deposition, or anti-microbial coating.

At least one of the substrates may be an asymmetrically annealed or tempered glass substrate. For example, one or more glass substrates in a laminate structure can be chemically tempered, thermally tempered, and/or annealed to provide added durability and/or safety. Chemical tempering can include, for example, ion exchange processes in which metal ions within the glass substrate at or near the surface can be exchanged for larger metal ions. Incorporation of the larger ions into the glass can create a compressive stress in a near surface region and induce a corresponding tensile stress within a central region of the glass sheet to balance the compressive stress. Thus, the degree of surface compression may be related to the degree of ion exchange for chemical tempering. Thermal tempering can be achieved by heating the glass above its transition temperature (Tg) and rapidly quenching the glass surfaces, e.g., by forced air convection. Annealing can be carried out by heating the glass to an annealing temperature (or stress-relief point) and slowly cooling the glass to below its strain point. For both thermal tempering and annealing, the degree of surface compression may be related to the rate of cooling.

Such tempering and annealing processes are often carried out symmetrically, such that both major surfaces of the glass sheet are evenly ion exchanged and/or heated or cooled at equal temperatures and/or rates. A method for manufacturing a laminate structure using a symmetrically tempered glass substrate is shown in <FIG>. The second substrate <NUM> can be tempered (or annealed) by a symmetric process TS to create symmetric substrate <NUM>. This symmetric substrate can then be arranged in step A with a first substrate <NUM> and an interlayer (not shown) to produce stack <NUM>. A symmetric or isothermal lamination process LI can then be used to produce laminate <NUM>. Noticeably, when the CTE of the second substrate <NUM> is different from the CTE of the first substrate <NUM> (as depicted), the resulting laminate <NUM> can become undesirably bowed while the laminate structure cools due to the CTE mismatch.

However, by replacing one or more of the symmetric tempering and/or lamination steps (TS or LI) with an asymmetric process (TA or LD) as shown in <FIG>, it may be possible to reduce or eliminate the out-of-plane deflection in the resulting laminate. For example, it may be desirable to thermally temper or anneal one or both of the substrates, such that one surface has a higher CS than the other. Due to the imbalanced internal stresses, the resulting asymmetric substrate may be bowed. As shown in <FIG>, the second substrate <NUM> can be tempered (or annealed) by an asymmetric process TA to create asymmetric substrate 307a with first surface <NUM> and second surface <NUM> having different CS. The asymmetric substrate can then be arranged in step A with a first substrate <NUM> and an interlayer (not shown) to produce stack <NUM>. An isothermal (symmetric) lamination process LI can then be used to produce laminate <NUM>. Alternatively, a differential (asymmetric) lamination process (not shown) can be used. Without wishing to be bound by theory, it is believed that the bow in the asymmetric substrate 307a may counterbalance the bow that would otherwise occur when laminating flat, e.g., symmetrically tempered (or annealed) substrates (see, e.g., <FIG>). In other words, the thermal stresses due to CTE mismatch may be balanced by the internal stresses in the asymmetric substrate, thus reducing or eliminating the out-of-plane bow of the resulting laminate.

Asymmetric chemical tempering can be carried out, for instance, by applying a coating to one surface to prevent ion exchange while leaving the opposite surface exposed and/or by applying an electrical field during the tempering step. Asymmetric thermal tempering and/or annealing can be carried out by cooling one surface of the substrate at a different rate (e.g., faster or slower) than the opposite surface. Using such asymmetric processes it may be possible to produce a glass substrate that is bowed out of plane, e.g., in a substantially spherical shape. By way of non-limiting example, the shape and/or magnitude of the bow of the asymmetric glass substrate may be comparable to the bow that would be present in a laminate produced by symmetrical processing (see, e.g., laminate <NUM> in <FIG>).

The asymmetric substrate 307a can be oriented in stack <NUM> such that the bow in the substrate counterbalances the potential bow in the laminate. For example, as depicted in <FIG>, an asymmetric substrate 307a may have a first surface <NUM> with a CS less than a CS of the second surface <NUM>. Alternatively, the asymmetric substrate 307a may have a first surface <NUM> with a CS greater than a CS of the second surface <NUM> (not depicted). The CS of the first and second surfaces may differ, e.g., may have values differing by at least about <NUM>%, such as at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, and higher. For instance, a difference between the CS of the first and second surfaces (CS<NUM>-CS<NUM> or CS<NUM>-CS<NUM>) may be greater than about <NUM> MPa, such as greater than about <NUM> MPa, greater than about <NUM> MPa, greater than about <NUM> MPa, greater than about <NUM> MPa, greater than about <NUM> MPa, greater than about <NUM> MPa, greater than about <NUM> MPa, greater than about <NUM> MPa, or greater.

The CTE of the second substrate <NUM> is greater than that of the first substrate <NUM> and the first surface <NUM> (lower CS) of the asymmetric substrate may be oriented towards the first substrate <NUM> in the stack <NUM>, e.g., the first surface may be in contact with the interlayer. Both the first and second substrates may be asymmetrically tempered or annealed. Of course, any other arrangements and/or orientations of the substrates are possible and envisioned as falling within the scope of the disclosure.

As shown in <FIG>, the second substrate <NUM> can be tempered (or annealed) by a symmetric process TS to create symmetric substrate <NUM> with first surface <NUM> and second surface <NUM> having substantially the same CS. Alternatively, an asymmetric tempering process (not shown) can be used. The symmetric substrate <NUM> can then be arranged in step A with a first substrate <NUM> and an interlayer (not shown) to produce stack <NUM>. A differential (asymmetric) lamination process LD can then be used to produce laminate <NUM>. Without wishing to be bound by theory, it is believed that the thermal stresses due to CTE mismatch may be reduced by asymmetrically or differentially heating and/or cooling the substrates during lamination, thus reducing or eliminating the out-of-plane bow of the resulting laminate.

For example, for a laminate comprising a second substrate with a CTE higher than that of the first substrate, out-of-plane deflection of a laminate may be reduced by differentially heating the stack during lamination such that the first substrate is heated at a faster rate and/or by differentially cooling the laminate after lamination such that the first substrate is cooled at a slower rate than the second substrate. For instance, the heating and/or cooling rate of the first and second surfaces may differ, e.g., may have values differing by at least about <NUM>%, such as at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, at least about <NUM>%, and higher. A difference between the heating and/or cooling rate of the first and second surfaces may be greater than about <NUM>/min, such as greater than about <NUM>/min, greater than about <NUM>/min, greater than about <NUM>/min, greater than about <NUM>/min, greater than about <NUM>/min, greater than about <NUM>/min, greater than about <NUM>/min, greater than about <NUM>/min, greater than about <NUM>/min, or greater.

In the case of differential heating, the lamination can take place at an average lamination temperature as described above. The average lamination temperature can thus range from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>. A differential heating profile can include holding one substrate at a higher (or lower) lamination temperature. For example, the first substrate may be held at a first lamination temperature that is at least <NUM> greater than a second lamination temperature at which the second substrate is held, or vice versa. Suitable hold (or residence) times are described above. A differential between the first and second lamination temperatures (TL1-TL2 or TL2-TL1) can range from about <NUM> to about <NUM>, from about <NUM> to about <NUM>, or from about <NUM> to about <NUM>.

It is to be understood that the various asymmetric processing methods disclosed herein can be combined with one another in any desired arrangement to produce a substantially flat laminate having the desired degree of out-of-plane deflection. In some embodiments, the first and second substrates may both be asymmetrically tempered or annealed and the resulting stack may be isothermally heated during lamination and/or isothermally cooled after lamination. In other embodiments, the second substrate may be asymmetrically tempered or annealed and the resulting stack may be differentially heated during lamination and/or differentially cooled after lamination. In further embodiments, the first substrate may be asymmetrically tempered or annealed and the resulting stack may be differentially heated during lamination and/or differentially cooled after lamination. Accordingly, the methods disclosed herein can comprise one or more asymmetric processing steps which can counterbalance the bow that might otherwise result from laminating symmetric substrates using symmetric processing steps.

The methods disclosed herein can be used to produce asymmetric laminate structures with one or more advantages as compared to conventional lamination methods. For example, the ability to reduce the impact of CTE mismatch on laminate deflection (or bow) may allow for a wider choice of substrate materials, interlayers, and/or laminate geometries. Further, the instant methods may provide a wider selection of deflection-free laminates, such as larger laminate structures and/or laminate structures comprising unconventional combinations of substrates. Because laminate structures manufactured according to the instant methods may have little or no deflection, e.g., bow, the optical performance of such laminates may also be improved. Finally the methods disclosed herein may be less complex than other methods for manufacturing asymmetric laminates, such as laminating under pressure and/or using asymmetric heating. Of course, it is to be understood that the laminate structures and methods disclosed herein may not have one or more of the above advantages, but are intended to fall within the scope of the appended claims.

It will be appreciated that the various disclosed embodiments may involve particular features, elements or steps that are described in connection with that particular embodiment. It will also be appreciated that a particular feature, element or step, although described in relation to one particular embodiment, may be interchanged or combined with alternate embodiments in various non-illustrated combinations or permutations.

It is also to be understood that, as used herein the terms "the," "a," or "an," mean "at least one," and should not be limited to "only one" unless explicitly indicated to the contrary. Thus, for example, reference to "a glass substrate" includes examples having two or more such glass substrates unless the context clearly indicates otherwise.

When such a range is expressed, examples include from the one particular value and/or to the other particular value.

Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is no way intended that any particular order be inferred.

While various features, elements or steps of particular embodiments may be disclosed using the transitional phrase "comprising," it is to be understood that alternative embodiments, including those that may be described using the transitional phrases "consisting" or "consisting essentially of," are implied. Thus, for example, implied alternative embodiments to a structure that comprises A+B+C include embodiments where a structure consists of A+B+C and embodiments where a structure consists essentially of A+B+C.

The following Examples are intended to be non-restrictive and illustrative only, with the scope of the invention being defined by the claims.

An asymmetric laminate structure having dimensions <NUM> x <NUM> (<NUM>" x <NUM>") was prepared using <NUM> thick Corning® EAGLE XG® glass, <NUM> thick soda lime glass (SLG), and a <NUM> thick EVA interlayer. The Corning EAGLE XG® substrate had a CTE of approximately <NUM> × <NUM>-<NUM>/°C, while soda lime glass has a CTE of approximately <NUM>-<NUM> × <NUM>-<NUM>/°C. The three layers were placed in contact with each other at room temperature and, heated to a lamination temperature of <NUM>-<NUM> at a pressure of about <NUM> MPa (<NUM> psi), and subsequently cooled back down to room temperature.

The glass substrates naturally contracted when cooled down from the lamination temperature to room temperature. Due to the differing CTEs, the two substrates contracted to varying degrees, resulting in uniform biaxial stress and thus spherical out-of-plane bow, which is depicted in <FIG>. The out-of-plane bow (center-to-corner or peak-to-valley) for this part was <NUM> (<NUM> - (-<NUM>)).

Three asymmetric laminate structures having dimensions <NUM> × <NUM> (<NUM>' × <NUM>') were prepared using <NUM> thick Corning® EAGLE XG® glass, <NUM> thick soda lime glass, and a <NUM> PVB interlayer. The rate of heating or cooling of both glass substrates was varied by using insulating blankets during lamination. In Example 2A, the soda lime glass was cooled faster than the EAGLE XG® glass; in Example 2B, the soda lime glass was heated faster than the EAGLE XG® glass; and in Example 2C, the soda lime glass was cooled slower than the EAGLE XG® glass. The resulting out-of-plane bow (mm) for each laminate is shown in Table I below.

Claim 1:
A laminate structure comprising a first glass substrate having a thickness ranging from <NUM> to <NUM>, a second glass substrate having a thickness ranging from <NUM> to <NUM>, and an interlayer attaching the first and second glass substrates,
wherein a coefficient of thermal expansion of the second glass substrate is at least <NUM>% greater than a coefficient of thermal expansion of the first glass substrate; and
wherein an out-of-plane deflection of the laminate structure is less than twice a thickness of the laminate structure.