US20140162036A1

US20140162036A1 - Thin glass/metal laminate with anti-glare surface

Info

Publication number: US20140162036A1
Application number: US14/183,135
Authority: US
Inventors: Brenna Elizabeth Marcellus; Paul George Rickerl; May Yanmei Xun; Chunhe Zhang
Original assignee: Corning Inc
Current assignee: Corning Inc
Priority date: 2012-10-05
Filing date: 2014-02-18
Publication date: 2014-06-12
Also published as: EP2903820A1; US10864707B2; JP6495991B2; KR20150064192A; CN105102217A; JP6228217B2; US20190091973A1; CN110435253A; US20150246507A1; KR102162896B1; WO2014055583A1; US10166744B2; JP2015535763A; JP2018039726A

Abstract

Disclosed herein are laminated structures comprising a metal sheet including a first face and a second face with a thickness of from about 0.5 mm to about 2 mm extending between the first face and the second face. The laminated structure further includes a first chemically strengthened or non-chemically strengthened glass sheet including a thickness of less than or equal to about 2 mm and a first interlayer attaching the first glass sheet to the first face of the metal sheet. Also disclosed herein are methods of manufacturing a laminated structure comprising the steps of laminating a metal sheet and a first glass sheet together with an interlayer.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of International Patent Application No. PCT/US2013/062956, filed on Oct. 2, 2013, which claims the benefit of priority to U.S. Provisional Application No. 61/710,287 filed on Oct. 5, 2012, the contents of which are incorporated herein by reference in their entireties.

FIELD OF THE DISCLOSURE

Disclosed herein are glass/metal laminated structures and methods of manufacturing laminated structures and, more particularly, glass/metal laminated structures including a chemically strengthened or non-chemically strengthened glass sheet and methods of manufacturing laminated structures including a chemically strengthened or non-chemically strengthened glass sheet.

BACKGROUND

A variety of apparatuses, such as appliances, may comprise an outer housing including a metal sheet. For example, relatively thin metal sheets can be used as an outer housing surface for an appliance such as a refrigerator and/or freezer. As such, the metal sheet may protect the appliance while also maintaining the outer appearance of the appliance. However, it has been observed that the metal outer housing sheet may lose its aesthetic appearance over time due to poor scratch resistance and/or cleaning difficulties, for example, with respect to fingerprints and/or oil smudges. Accordingly, it would be advantageous to provide a metal sheet with a protective skin, such as a thin glass/metal laminated structure, which can be more easily cleaned and/or which may have increased scratch resistance. It would also be advantageous to provide such laminated structures with improved aesthetic properties, such as an anti-glare and/or antimicrobial surface.

SUMMARY

The disclosure relates, in various embodiments, to a laminated structure comprising a metal sheet including a first face and a second face with a thickness ranging from about 0.1 mm to about 5 mm extending between the first face and the second face. The laminated structure further includes a first chemically strengthened or non-chemically strengthened glass sheet including a thickness ranging from about 0.3 mm to about 2 mm and a first interlayer attaching the first glass sheet to the first face of the metal sheet.
In certain embodiments, the first interlayer may comprise polyvinyl butyral or an ionomer. The first interlayer may, in various embodiments, have a thickness ranging from about 0.1 mm to about 2 mm, such as from about 0.1 mm to about 0.8 mm. In further embodiments, the first interlayer may have a Young's modulus of greater than or equal to 15 MPa, such as greater than or equal to 275 MPa.
According to other non-limiting embodiments, the first glass sheet may have a thickness ranging from about 0.5 mm to about 1.1 mm. The first glass sheet may, in various embodiments, be chemically strengthened and may comprise a glass selected from the group consisting of aluminosilicate glass and alkali-aluminoborosilicate glass. The first glass sheet may also comprise, by way of non-limiting example, an anti-glare surface which may be obtained, for instance, by etching-based and/or sol gel processes.
The disclosure also relates to a method of manufacturing a laminated structure comprising: (i) providing a metal sheet including a first face and a second face having a thickness ranging from about 0.1 mm to about 5 mm extending between the first face and the second face, (ii) providing a chemically strengthened or non-chemically strengthened glass sheet having a thickness of less than or equal to about 2 mm and at least one anti-glare surface, and (iii) attaching the glass sheet to the first face of the metal sheet with a first interlayer.
The disclosure further relates to a method of manufacturing a laminated structure comprising: (i) providing a metal sheet including a first face and a second face having a thickness ranging from about 0.1 mm to about 5 mm extending between the first face and the second face, (ii) providing a glass sheet having a thickness of less than or equal to about 2 mm, (iii) treating the glass sheet to produce at least one anti-glare surface, (iv) optionally chemically strengthening the glass sheet, (v) optionally acid etching the glass sheet, and (vi) attaching the glass sheet to the first face of the metal sheet with a first interlayer. In certain embodiments, the anti-glare treatment step may be chosen from acid etching, creamy etching, masked acid etching, sol gel processing, mechanical roughening, and combinations thereof. According to other non-limiting embodiments, the chemical strengthening step may comprise an ion exchange process.
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.

BRIEF DESCRIPTION OF THE DRAWINGS

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. 1 is a schematic view of a cabinet incorporating a laminated structure in accordance with aspects of the disclosure;

FIG. 2 is a partial cross sectional view of the cabinet along line 2-2 of FIG. 1 illustrating a laminated structure in accordance with aspects of the disclosure;

FIG. 3 is another cross sectional view illustrating another example laminated structure in accordance with further aspects of the disclosure;

FIG. 4 is a flow chart illustrating exemplary steps of manufacturing laminated structures in accordance with aspects of the disclosure;

FIG. 5 is a schematic view illustrating the optional step of placing a stack within a vacuum chamber and heating the stack to a lamination temperature to produce the laminated structure in accordance with aspects of the disclosure;

FIG. 6 is a Weibull plot demonstrating impact energy at breakage for six groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, 16 Gauge (1.59 mm) stainless steel, and various types of interlayers;

FIG. 7 is a Weibull plot demonstrating impact energy at breakage for five groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, a layer of 0.38 mm polyvinyl butyral, and various thicknesses of stainless steel;

FIG. 8 is a Weibull plot demonstrating impact energy at breakage for three groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, a layer of 0.89 mm SentryGlas® ionomer, and various thicknesses of stainless steel;

FIG. 9 is a Weibull plot demonstrating impact energy at breakage for three groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass compared to two groups of fully tempered 4 mm Soda Lime glass;

FIG. 10 is a Weibull plot demonstrating impact energy at breakage for two groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, 0.38 mm polyvinyl butyral together with two alternative stainless steel sheets [i.e., 16 Gauge (1.59 mm) and 24 Gauge (0.64 mm)] compared to another two groups of laminated structures in accordance with aspects of the disclosure including acid-etched 1 mm Corning® Gorilla® glass, 0.38 mm polyvinyl butyral together with two alternative stainless steel sheets [i.e., 16 Gauge (1.59 mm) and 24 Gauge (0.64 mm)];

FIG. 11 is a Weibull plot demonstrating impact energy at breakage for two groups of laminated structures in accordance with aspects of the disclosure including acid-etched 0.7 mm Corning® Gorilla® glass, a layer of 0.89 mm SentryGlas® ionomer together with two alternative stainless steel sheets [i.e., 16 Gauge (1.59 mm) and 24 Gauge (0.64 mm)];

FIG. 12 is a Weibull plot demonstrating impact resistance for 1 mm creamy etched anti-glare Corning® Gorilla® glass sheets at 10% and 40% haze levels under tension or compression as compared to 1 mm Corning® Gorilla® glass without anti-glare treatment; and

FIG. 13 is a Weibull plot demonstrating impact resistance for 1 mm sol gel treated anti-glare Corning® Gorilla® glass sheets with 10% haze under tension or compression as compared to 1 mm Corning® Gorilla® glass without anti-glare treatment.

DETAILED DESCRIPTION

Laminated structures may be used in a wide range of applications in accordance with aspects of the disclosure. For example, laminated structures may be used in various architectural applications such as siding, decorative panels, cabinet installations, wall coverings or other architectural applications. In further examples, the laminated structures may be used for furniture items and/or household appliances. For instance, the laminated structures may be incorporated as outer panels of a cabinet or other furniture and/or household appliance. FIG. 1 illustrates a schematic view of a cabinet 101 incorporating a laminated structure 103 in accordance with aspects of the disclosure. In one non-limiting embodiment, the cabinet 101 can be incorporated in a wall unit for storage. In another embodiment, the cabinet can be refrigerated. For instance, the cabinet 101 can comprise a refrigerator and/or a freezer although various other non-refrigerated examples may be alternatively provided.
FIG. 2 illustrates an exemplary partial cross section along line 2-2 of FIG. 1 wherein the laminated structure has been incorporated as an outer skin layer of a refrigerated cabinet (e.g., refrigerator and/or freezer). The laminated structure 103 may comprise the entire construction in use although the laminated structure 103 may be combined with other elements of the panel, such as an insulating layer and/or inner skin depending on the particular application.
As shown in FIG. 2, the laminated structure can include a metal sheet 201 that can comprise a wide range of metal types and/or a wide range of thicknesses and configurations. For instance, the metal sheet 201 can comprise steel, cold rolled steel, aluminum or any other suitable metal. In one non-limiting example, the metal sheet comprises stainless steel. Stainless steel may have suitable application for outer panel constructions providing desired protection, resisting corrosion over time and/or providing a desired outer appearance, such as a brushed stainless steel appearance.
The metal sheet 201 can include a first face 203 and a second face 205 with a thickness T1 extending between the first face 203 and the second face 205. The thickness T1 of the metal sheet 201 may vary depending on the particular application. Relatively thin metal sheets may be used in applications to reduce material costs and/or weight of the laminated structure while still providing sufficient resistance to deformation. In further embodiments, relatively thick metal sheets may be used in applications where further support is required to maintain the mechanical integrity of the laminated structure. In some embodiments, the thicknesses may range from a 25 Gauge metal sheet (e.g., about 0.5 mm) up to a 12 Gauge metal sheet (e.g., about 2 mm). In further embodiments, the thicknesses may range from a 24 Gauge metal sheet (e.g., about 0.64 mm thick stainless steel) up to a 16 Gauge metal sheet (e.g., about 1.59 mm thick stainless steel). As such, referring to FIG. 2, the thickness T1 of the metal sheet 201 may range from about 0.1 mm to about 5 mm, such as from about 0.5 mm to about 2 mm, or from about 0.6 mm to about 1.6 mm, although other thicknesses may be provided depending on the particular application.
As illustrated in FIG. 2, the laminated structure 103 can further include a chemically strengthened or non-chemically strengthened glass sheet 207 including a thickness T2 extending between a first face 209 and a second face 211 of less than or equal to about 2 mm, such as less than or equal to 1.5 mm, such as from about 0.1 mm to about 1.1 mm, or from about 0.3 mm to about 1 mm. In one non-limiting embodiment, the glass sheet 207 has a thickness T2 of about 0.7 mm. In another embodiment, the glass sheet 207 has a thickness T2 of about 1 mm. In a further embodiment, the glass sheet 207 has a thickness T2 of about 0.3 mm. According to still further embodiments, the glass sheet 207 has a thickness T2 ranging from about 0.3 mm to about 0.5 mm, or from about 0.5 mm to about 1 mm. The glass sheet 207 may comprise, according to various embodiments, a glass such as an aluminosilicate glass, and alkali-aluminoborosilicate glass, or other glass material.
Various glass forming techniques may be used to produce glass sheets 207 that may be incorporated within the laminated structure 103. For instance, fusion down draw techniques, fusion updraw techniques, slot draw techniques or other processes may be used to provide a glass ribbon that may be processed into glass sheets having the desired dimensional configuration. For example, a fusion draw process can be provided to obtain a substantially pristine surface. In some embodiments, display quality glass sheets 207 may be used to provide a transparent covering over the first face 203 of the metal sheets 201. Providing display quality glass can allow the aesthetic appearance of the first face 203 of the metal sheets 201 to be preserved. At the same time, the glass sheet 207 can help maintain the pristine surface quality of the first face 203 of the metal sheet 201. Indeed, scratches, smudging and/or other imperfections may be avoided by covering the metal sheet 201 with the protective glass sheet 207.
In one embodiment, the glass sheets 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 U.S. Pat. Nos. 7,666,511, 4,483,700, and 5,674,790, which are incorporated herein by reference in their entireties. Corning® Willow™ glass and Corning® EAGLE XG® glass from Corning Incorporated may also be suitable for use as the glass sheet in various embodiments.
Chemical strengthening may be carried out by an ion exchange process. For instance, a glass sheet (e.g., aluminosilicate glass, alkali-aluminoborosilicate glass) may be made by fusion drawing and then chemically strengthening by immersing the glass sheet in a molten salt bath for a predetermined period of time. Ions within the glass sheet at or near the surface of the glass sheet are exchanged for larger metal ions, for example, from the salt bath. The temperature of the molten salt bath and treatment time period will vary; however, it is within the ability of one skilled in the art to determine the time and temperature according to the desired application. By way of non-limiting example, the temperature of the molten salt bath may range from about 430° C. to about 450° C. and the predetermined time period may range from about 4 to about 8 hours.
Without wishing to be bound by theory, it is believed that the incorporation of the larger ions into the glass strengthens the sheet by creating a compressive stress in a near surface region. A corresponding tensile stress is induced within a central region of the glass sheet to balance the compressive stress. The chemical strengthening process of Corning® Gorilla® glass can have a relatively high compressive stress (e.g., from about 700 MPa to about 730 MPa; and even capable of greater than 800 MPa) at a relatively deep depth from the surface (e.g., about 40 microns; and even capable of greater than 100 microns). Such glass can have a high retained strength and high resistance to scratch damage, high impact resistance, and/or high flexural strength as well as a substantially pristine surface. One exemplary glass composition may comprise SiO₂, B₂O₃and Na₂O, wherein (SiO₂+B₂O₃)≧66 mol. %, and Na₂O≧9 mol. %.
In further embodiments, the chemically strengthened or non-chemically strengthened glass sheet 207 may be acid-etched to further strengthen the glass sheet. The introduction of acid etching may enable use of even thinner metal in the laminated structure of the disclosure without deterioration in impact performance. The acid etching step, in some examples, can remove from about 1.5 to about 1.7 microns from the surfaces of the glass sheet 207.
Acid etching addresses the fact that glass strength is extremely sensitive to the size and the tip shape of surface flaws. By removing the above-mentioned surface layer, it is believed that the acid etching can clear away a majority of surface flaws smaller than 1 micron. While acid etching may not remove larger flaws, the acid etching procedure will tend to round the flaw tip which would otherwise dramatically decrease the stress concentration factor. The improvement in glass surface (e.g., removal of small surface flaws and rounding the tips of larger flaws) can dramatically increase glass strength, such as impact resistance. Moreover, only a relatively small depth of glass is removed, that will not result in significant compressive stress drop in the glass sheet which has relatively high compressive stress at a much larger depth into the glass sheet such as 40 microns from the surface, or even greater than 100 microns in some examples.
In one embodiment, the acid etching step can be conducted on a horizontal spray etching system, with a chemical solution of about 1.5M HF/0.9M H₂SO₄. The other process parameters can include a process temperature of about 90° F. (32.2° C.), process time of about 40 seconds, spray pressure of about 20 psi, spray oscillation of about 15 cycles per minute, and using approximately 0.48 gallon-per-minute conical spray nozzles. However, it is possible to vary one or more of the above process parameters depending on the particular application and such variations are within the ability of one skilled in the art. After acid etching, the processed glass sheets may be cleaned with a rinse step, e.g., using water. For example, approximately 0.3 gallon-per-minute fanjet pattern nozzles may be used at a spray pressure of about 20 psi. The acid-etched glass sheets may then be dried. For instance, an air flow dryer system may be employed, such as an air turbine operating at approximately 5 hp.
As still further illustrated in FIG. 2, the laminated structure 103 can further include an interlayer 213 attaching the first glass sheet 207 to the first face 203 of the metal sheet 201. The interlayer 213 can be formed from a wide range of materials depending on the application and characteristics of the glass sheet and metal sheet. 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 further embodiments, desirable images can be printed, with either screen printing or digital scanning printing, onto the glass side for aesthetic purposes or onto the interlayer. Because these printed images can be arranged on the interface (e.g., on the interlayer), they can be well preserved from scratch damages during the product lifetime. In addition or alternatively, the interlayer may comprise a transparent layer to allow clear viewing of the outer surface of the metal sheets. Indeed, the interlayer 213 can comprise a transparent interlayer 213 that provides an excellent optical interface between the glass sheet 207 and metal sheet 201. In some embodiments a display-quality glass sheet 207 may be laminated to the metal sheet 201 by the transparent interlayer 213 so that the outer appearance of the first face 203 of the metal sheet 201 may be easily viewed and preserved over time.
Still further, the interlayer 213 can be selected to help strengthen the laminated structure 103 and can further help arrest glass pieces from the glass sheet 207 in the event that the glass sheet 207 shatters. The interlayer can comprise various materials such as ethylene vinyl acetate (EVA), thermoplastic polyurethane (TPU), Polyester (PET), acrylic (e.g., acrylic pressure sensitive adhesive tape), polyvinyl butyral (PVB), SentryGlas® ionomer, or any other suitable interlayer material. If PET is used, in one embodiment, the PET material can be sandwiched between two layers of acrylic adhesive material. In another non-limiting embodiment, the interlayer 213 can be selected to provide a Young's modulus greater than or equal to 15 MPa. For instance, the interlayer 213 may comprise polyvinyl butyral having a thickness ranging from about 0.1 mm to about 0.8 mm, such as from about 0.3 mm to about 0.76 mm, such as about 0.38 mm.
In a further embodiment, the interlayer 213 can comprise a Young's modulus of greater than or equal to 275 MPa. For example, the first interlayer can include an ionomer with a Young's modulus of greater than or equal to 275 MPa, such as about 300 MPa. In various embodiments, the ionomer can comprise SentryGlas® ionomer available from DuPont. In such embodiments, the thickness of the interlayer 213 can range, for example, from about 0.1 mm to about 2 mm, such as from about 0.5 mm to about 1.5 mm, such as about 0.89 mm.
FIG. 3 illustrates another exemplary laminated structure 301 in accordance with various aspects of the disclosure. The laminated structure 301 includes the interlayer 213 attaching the glass sheet 207 to the first face 203 of the metal sheet 201. As shown, the laminated structure 301 can also include a second interlayer 303 attaching a second glass sheet 305 to the second face 205 of the metal sheet 201. The second glass sheet 305 may, in certain embodiments, be a chemically strengthened glass sheet. The second interlayer 303 can, in certain embodiments, comprise the same material and have the same thickness T3 as the first interlayer 213. Likewise, the second glass sheet 305, in some embodiments, can be identical to the first glass sheet 207 including having the same thickness T2 and other features. Providing the laminated structure 301 with a second glass sheet 305 can protect the second face of the metal sheet 201 in the same way the first glass sheet 207 protects the first face 203 of the metal sheet 201.
With reference to FIG. 4, exemplary methods of manufacturing the laminated structures 103 will now be described with the understanding that similar or identical procedures maybe used to produce the laminated structures 301. The method begins with step 401 including providing and/or preparing the chemically strengthened or non-chemically strengthened glass sheet 207 (see column A), interlayer 213 (column B), and the metal sheet 201 (Column C). As described below, the method concludes with step 403 wherein the interlayer 213 attaches the glass sheet 207 to the first face 203 of the metal sheet 201.
As shown in FIG. 4, column A demonstrates optional steps that may be carried out during a step of providing the chemically strengthened or non-chemically strengthened glass sheet 207. The method of providing and/or preparing the glass sheet 207 can include the step 405 of providing a glass sheet with a desired thickness (e.g., see T2 in FIG. 2). As mentioned previously, the thickness T2 of the glass sheet 207 can be less than equal to about 2 mm, such as less than or equal to 1.5 mm, such as from about 0.3 mm to about 1.1 mm, such as from about 0.5 mm to about 1 mm. In one embodiment, the glass sheet 207 has a thickness T2 of about 0.7 mm. In another embodiment, the glass sheet 207 has a thickness T2 of about 1 mm. In a further embodiment, the glass sheet 207 has a thickness T2 of about 0.3 mm. The glass sheet 207 can comprise a glass such as an aluminosilicate glass, and alkali-aluminoborosilicate glass, or any other suitable glass material. The glass sheet 207 can be provided by various techniques such as fusion down draw, fusion updraw, slot draw or other processes known in the art.
The glass sheet 207 may be optionally processed in step 406 so as to provide the glass sheet 207 with at least one anti-glare surface. Anti-glare processing may take place before (step 406) or after (step 412) the chemical strengthening step 411. For example, if the glass sheet 207 undergoes anti-glare processing before the chemical strengthening step 411, etching-based anti-glare processes can be used. Non-limiting processes are described, for example, in European Patent Application Publication No. 2563733 A1 and International Application Publication No. WO 2012/0749343 A1, which are incorporated herein by reference in their entireties. Suitable etching-based anti-glare processes include, but are not limited to, acid etching, creamy etching, masked acid etching, mechanical roughening (e.g., sand blasting), and combinations thereof. In some non-limiting embodiments a combination of mechanical roughening and acid etching is employed, although other combinations are envisioned. According to various embodiments, the anti-glare processing may take place before and/or after the shaping/sizing step 407.
The method can then optionally proceed from step 405 or 406 to step 407 of separating a plurality of glass sheets from a source glass sheet. For example, a glass ribbon of aluminosilicate glass or alkali-aluminoborosilicate glass may be formed from a fusion down draw process with the desired thickness. Then a plurality of glass sheets may be cut from the glass ribbon and optionally further separated into a subset of glass sheets having the overall desired dimensions for the particular application. Separating a plurality of glass sheets can be carried out with a wide range of techniques. For example, processing can be selected to minimize adverse effects to glass strength due to its risk in introducing extra flaws, especially for thin glass. In one example, an approximately 3 mm diameter scoring wheel with a tip angle of about 110°, e.g., including diamond, may be used for the scoring operation. Meanwhile, the applied force of approximately 0.8 kgf may be used for the scoring force.
The glass sheet having the desired size from step 407 may then be further optionally processed during step 409. For instance, it may be desirable to machine or otherwise finish at least one edge of the glass sheet 207 prior to the step of chemically strengthening the glass sheet 207. For example, step 409 may include the step of edge grinding and finishing to round or bevel the edge to the required profile to reduce sharp edges, improve aesthetics and edge strength. In one embodiment, a profiled diamond wheel of 400# (mesh size of diamond abrasive) may be used in a wide variety of applications. Other processing parameters can include a grinding speed ranging from about 10 m/sec to about 30 m/sec, a feed rate of about 0.5 m/min, and a grinding depth ranging from about 0.1 mm to about 0.2 mm. If a higher edge strength is required, a subsequent grinding step may be carried out, for example, with an 800# diamond wheel. Such optional subsequent grinding step can include similar processing parameters, for example a grinding speed ranging from about 10 m/sec to about 30 m/sec, a feed rate of about 0.5 m/min, and a grinding depth ranging from about 0.05 mm to about 0.1 mm.
Once the desired size and properties are obtained and any edges are machined or otherwise finished (e.g., during steps 406, 407, and/or 409), the glass sheet may be chemically strengthened during step 411. For example, as discussed above, the chemical strengthening step may comprise an ion exchange chemical strengthening technique used to generate Corning® Gorilla® glass. Still further, the glass sheet 207 may be optionally acid etched during step 413. Acid etching may be carried out with exemplary procedures discussed above to further strengthen the glass sheets as desired for particular applications.
As discussed above, anti-glare processing may also be carried out subsequent to the chemical strengthening step 411. For example, in step 412, the strengthened glass sheet 207 may be subjected to sol gel processing to produce at least one anti-glare surface. Non-limiting sol gel processes are described, for example, in European Patent No. 1802557 B1, which is incorporated herein by reference in its entirety. Suitable sol gel-based anti-glare processes may also include, for example, coating the glass sheet 207 with an anti-glare sol gel composition and baking the sheet at relatively low temperature (e.g., less than about 350° C.). According to various embodiments, subsequent to sol gel anti-glare processing, the glass sheet 207 can then be further processed by acid etching in step 413.
Optionally, before entering the lamination block 403 of the method for manufacturing, the glass sheet may be cleaned during step 415. Cleaning may be designed to remove surface dirt, stains, and other residues. The glass cleaning step can be conducted with an industrial ultrasonic cleaner, a horizontal spray system or other cleaning technique.
Many of the steps of column A are optional and may be even excluded altogether. For instance the chemically strengthened or non-chemically strengthened glass sheet may simply be provided for the process of laminating. Moreover, various steps are optional and may be excluded altogether. For example, after the step 405, the glass sheet may already include the desired thickness as well as the desired dimensions. In such an example, the method may proceed directly from step 405 to step 409 or may even proceed directly to step 411. If the provided glass sheet already exhibits the desired strength properties, the chemical strengthening step 411 and/or the acid etching step 413 may be skipped. Moreover, if the glass sheet is sized during step 407, the edge characteristics may be sufficient for the particular application, wherein the method may proceed directly to step 411 without machining the edges during step 409. As further illustrated in column A, the step of cleaning 415 can also be skipped depending on the particular application. Finally, if the glass sheet is processed in step 406 to produce at least one anti-glare surface, then step 412 can be skipped, or vice versa.
The providing and/or preparing block 401 can further include providing and/or preparing the interlayer 213 (column B). For instance, the method can include the step 417 of providing the interlayer. The interlayer can be provided, by way of non-limiting example, as polyvinyl butyral (PVB) or a SentryGlas® ionomer interlayer although other interlayer types may be provided in further examples as discussed above. In one embodiment, the interlayer 213 can comprise PVB with a thickness ranging from about 0.1 mm to about 0.8 mm, such as from about 0.3 mm to about 0.76 mm, such as about 0.38 mm. In another embodiment, the interlayer 213 can comprise SentryGlas® ionomer with a thickness ranging from about 0.1 mm to about 2 mm, such as from about 0.5 mm to about 1.5 mm, such as about 0.89 mm.
In various embodiments, the method can continue to step 419 of cutting the interlayer to the appropriate size for the laminated structure. Still further, the interlayer may be conditioned, for example, to control the moisture content of the interlayer. In one example, the step 421 of conditioning adjusts the moisture content of the interlayer to less than about 1%, such as less than or equal to about 0.65%, such as less than or equal to about 0.2%. Controlling the moisture content of the interlayer may be beneficial to help achieve excellent bonding quality of the interlayer during the lamination procedure. In other embodiments, if the interlayer comprises PVB, the moisture content may be controlled to be less than or equal to about 0.65%. If SentryGlas® ionomer is used, the moisture content may be controlled to be less than or equal to about 0.2% according to certain embodiments. Controlling the moisture content can be carried out in various ways known in the art. For example, the interlayer may be placed in a controlled environment where the temperature and/or humidity are adjusted to achieve the desired moisture content of the interlayer.
As shown in column B, steps of providing and/or preparing the interlayer 213 may be carried out in different orders and/or certain steps may be omitted altogether. For example, the interlayer may be provided with the appropriate size. In such examples, the step 419 of cutting may be omitted. Furthermore, the step of conditioning may be omitted in further examples or may be carried out without the step of cutting or prior to the step of cutting as shown in FIG. 4.
The providing and/or preparing block 401 can further include providing and/or preparing the metal sheet 201 (column C). The method can begin with step 423 of providing the metal sheet 201 including a first face 203 and a second face 205 with the desired thickness extending between the first face 203 and the second face 205. In one embodiment, the metal sheet 201 can be provided as a stainless steel metal sheet 201 although other materials can be used in further embodiments. In another embodiment, the stainless steel metal sheet 201 may range from a 25 Gauge metal sheet (e.g., about 0.5 mm) up to a 12 Gauge metal sheet (e.g., about 2 mm). In further examples, the thicknesses may range from a 24 Gauge metal sheet (e.g., about 0.64 mm thick stainless steel) up to a 16 Gauge metal sheet (e.g., about 1.59 mm thick stainless steel). As such, the thickness T1 of the metal sheet 201 can range from about 0.1 mm to about 5 mm, such as from about 0.5 mm to about 2 mm, or from about 0.64 mm to about 1.59 mm, although other thicknesses may be provided depending on the particular application.
The method can further proceed from the step 423 of providing the metal sheet 201 to the step 425 of cutting or otherwise shaping the metal sheet 201 to including the appropriate dimensions. In one example, laser cutting may be employed to minimize edge deformation that would otherwise affect bonding quality of the interlay and glass sheet at the edge of the metal sheet 201.
After step 425, the method can optionally proceed to step 427 of edge trimming and cleaning. For example, after the cut, the edge of the stainless steel sheet may be trimmed by a mechanical milling or broaching method, and cleaned with a clean wiper and/or isopropanol or other suitable solvent. The steel surface can also be cleaned with a Teknek (or equivalent) tacky roller to remove surface dust and particulates. The method can then proceed to step 429 of removing any protective film from the steel sheet. For example, the front and back protective films can be removed prior to lamination. As shown, steps 425, 427 and 429 are optional wherein any one of the steps may be omitted and/or the steps may be carried out in various orders as illustrated.
After the glass sheet 207, interlayer 213 and metal sheet 201 are provided and/or prepared under the providing/preparing block 401, the method can then proceed to the lamination block 403 including the step of attaching the glass sheet 207 to the first face 203 of the metal sheet 201 with a first interlayer 213 to provide the laminated structure 103 illustrated in FIG. 2. Likewise, the lamination block 403 may also include the step of attaching a second glass sheet 305 to the second face 205 of the metal sheet 201 with a second interlayer 303 to provide the laminated structure 301 shown in FIG. 3.
Under the lamination block 403, the method can begin by step 431 of building a stack with the interlayer 213 placed between the glass sheet 207 and the first face 203 of the metal sheet 201 to provide a 3-layer stack (e.g., see FIG. 2). In addition, if desired, the method can continue to build the stack with the second interlayer 303 placed between the second glass sheet 305 and the second face 205 of the metal sheet 201 to provide a 5-layer stack (e.g., see FIG. 3). The stack 501 can then be optionally secured to prevent shifting, for example, by placing pieces of high-temperature polyester tape on at least two edges.
The glass sheet 207 may be attached to the metal sheet 201 using the interlayer 213 by any means known in the art. For instance, as shown in FIG. 5, the stack 501 can then be placed within a vacuum chamber, such as a vacuum bag 503. In the step of vacuum bagging, these assembled parts may be wrapped in thin breather cloth which is secured by tape (e.g., polyester tape), then wrapped in looser breather material and placed within a plastic film lamination bag. The parts may be arranged in a single layer within the bag, or multiple stacks may be processed at one time for higher throughput. The bag can be heat sealed with a vacuum port attached. The port of the vacuum bag may be attached to a vacuum hose within an autoclave chamber 505 and vacuum may be applied with the chamber still open to check for leaks. Other bagged parts may be loaded as well, up to the part capacity of the autoclave 505.
As shown in step 433, the vacuum chamber 503 can then be at least partially evacuated and the stack can be heated with a predetermined temperature and pressure profile. For example, the thermal processing step may be carried out with an autoclave wherein specific temperature and pressure profiles are used in order to achieve preferred adhesion (bonding) quality of the laminated structure.
For laminated structures with a PVB interlayer, the parts are placed under vacuum within the sealed bag and subjected to an appropriate temperature and pressure profile. For instance, the temperature may be ramped to the soak temperature of about 130° C. (266° F.) at a rate of approximately 3° F./minute. When the temperature setpoint is reached, a pressure ramp of about 5 psi/minute is initiated until the pressure setpoint of about 80 psi is reached. After a soak time of about 30 minutes, the temperature is ramped back down at a rate of approximately 3° F./minute. Pressure is held at about 80 psi until the temperature reaches about 50° C. (122° F.) to minimize bubble formation in the PVB, at which point the pressure is also ramped down at a rate of about 5 psi/minute. After the chamber has cooled and pressure equilibrium is established, the parts are removed from the autoclave, the bagging, breather cloth, and tape is removed, and the parts cleaned of lamination residues.
For glass/steel laminates with a SentryGlas® ionomer interlayer, a cycle similar to that detailed above for PVB may be used. For instance, the temperature may be ramped to about 133° C. (272° F.) at a ramp rate of about 4° F./minute. After a soak time of about 60 minutes, the ramp rate can be ramped down at a rate of about 4° F./minute until the temperature reaches 210° F. to minimize haze formation in the film. The laminated structure 103, 301 is then provided at the end of the process designated by 435 in FIG. 4.
Still further aspects of the disclosure can include optional processing techniques for use during a method of manufacturing the laminated structure that may provide further beneficial features to the laminated structure. For example, processing techniques can optionally include preparation steps for the glass sheet including a scoring and breaking step, edge finishing, ion exchange to apply the compressive surface layer and acid etching to further reduce glass surface flaws. In further embodiments, optional processing techniques can include decoration of the glass or other components to provide the glass with a decorated appearance. For the interlayer, processing techniques can optionally include proper conditioning of the interlayer (e.g., PVB or SentryGlas® ionomer) interlayer to improve bonding strength. For the steel layer, processing techniques can optionally include laser cutting so as to avoid the edge deformation caused by mechanical methods. During the step of lamination, the present disclosure can further include the step of vacuum applied thermal processing with the specific thermal cycling profiles that may be customized for various interlayers (e.g., PVB and SentryGlas® ionomer interlayers), for the purpose of improved bonding strength and reduced air bubbles.
Further optional processing steps may include providing the laminated structures with integrated mounting features, such as holes and/or hooks, which may facilitate installation during end product use. For instance, mounting brackets may be attached to the metal sheet or otherwise provided on the laminated structure. In certain embodiments, the metal sheet may be machined so as to incorporate the holes and/or hooks or any other suitable mounting features.
In another embodiment, the laminated structures may be manufactured so as to reduce or eliminate the occurrence of glass edge contact. Edge contact, especially during the process of handling glass panels, is one of the main causes of glass panel breakage either during installation or use of the laminated structure. In certain cases, edge contact may induce latent defects and/or edge chipping and/or edge cracks on the glass layer. Thus, according to various embodiments disclosed herein, the laminated substrate may be assembled so as to protect the glass edges, e.g., by providing a metal sheet which wraps around the outer edges of the glass sheet. In some embodiments, the glass sheet may be nested inside the recess created by the metal sheet. Other configurations are also envisioned which can reduce the potential for contact with the outer edges of the glass sheet and therefore reduce or avoid the mechanical degradation of the laminated structure.
In various embodiments, an anti-microbial coating can be applied to the surface of the glass sheet. In other embodiments, the glass sheet can include a composition having anti-microbial characteristics. For example, the glass sheet can be a glass or glass ceramic material containing silver, copper or a combination of silver and copper. Exemplary compositions include, but are not limited to, silver and copper, or mixture thereof, which may be zero valent existing in the glass or glass ceramic as Ag⁰or Cu⁰, which is the metallic form; can be ionic and exist in the glass or glass ceramic as Ag⁺¹, Cu⁺¹or Cu⁺²; or can be in the glass or glass ceramic as a mixture of the zero valent and ionic forms of one or both agents, for example, Ag⁰and Cu⁺¹and/or Cu⁺², Ag⁺¹and Cu⁰, and other combination of the zero valent and ionic species. The antimicrobial agent can be incorporated into the glass or glass ceramic by either (1) ion-exchange of a preformed GC using an ion-exchange bath containing one or both of the foregoing antimicrobial agents, or (2) by including one or both of the foregoing antimicrobial agents into batched materials used to prepare a glass that is then cerammed to form a glass or glass ceramic. In (1), the antimicrobial agent will be present in the glass or glass ceramic in ionic form, as the oxide, since nitrates of the antimicrobial agent can be used for the ion-exchange and because the nitrate species on the glass or glass ceramic are easily decomposed during the ion-exchange process. Additional anti-microbial coatings and compositions are described in WO2013/036746, entitled, “Antimicrobial Composite Material,” U.S. application Ser. No. 13/649,499, entitled “Antimicrobial Glass-Ceramics,” U.S. application Ser. No. 13/197,312, entitled “Coated, Antimicrobial, Chemically Strengthened Glass and Method of Making,” and U.S. application Ser. No. 14/176,470 entitled, “Antimicrobial Glass Articles and Methods of Making and Using Same,” the entirety of each being incorporated herein by reference.
As described above, laminated structures can comprise a metal sheet including a first face and a second face with a thickness ranging from about 0.1 mm to about 5 mm extending between the first face and the second face. The laminated structures can further include a first chemically strengthened or non-chemically strengthened glass sheet including a thickness of less than or equal to about 2 mm. The laminated structures can still further include a first interlayer attaching the first glass sheet to the first face of the metal sheet. In illustrative examples, the laminated structures can comprise: 1) at least one layer of thin Corning® Gorilla® glass (e.g., with a thickness of about 0.7 mm or about 1.0 mm) or Corning® Willow™ glass (e.g., with a thickness of about 0.3 mm or less) as the outermost surface, 2) at least one layer of polymer interlayer (0.38 mm Polyvinyl butyral (PVB) or 0.89 mm SentryGlas® ionomer), and 3) a layer of stainless steel (e.g., ranging from 24 Gauge to 16 Gauge, about 0.635 mm to 1.59 mm).
Laminated structures of the present disclosure may have a number of advantages over fully tempered soda lime and stainless steel. For example, laminated structures of the present disclosure may exhibit either comparable or superior performance in terms of impact resistance over the fully tempered soda lime mono-layers (as thick as 4 mm). In addition, the laminated structures of the present disclosure may be able to retain glass fragments in place if they break, as compared to fully tempered soda lime which releases glass chips to the surrounding environment if broken. Compared to stainless steel monolithic structures, the presence of a glass layer in the laminated structures of the present disclosure may enable higher structure hardness and therefore higher scratch resistance, and may help maintain the fresh aesthetic look of the steel surface over a longer period of time.
Advantages of some exemplary embodiments of the disclosure can produce high quality laminated structures with one or two layers of relatively thin glass (e.g., less than or equal to 2 mm). Moreover, by use of various processing techniques for stainless steel laminated applications, the laminated structures may have the ability to maintain the aesthetic look of brushed stainless steel during a longer service time. Moreover, laminated structures of the present disclosure may circumvent typical issues of low impact resistance caused by “localized deformation” that might otherwise occur with other laminate structures with a relatively thin glass layer. In addition, exemplary laminated structures strengthened by acid etching may enable the use of thinner steel like 24 Gauge (0.635 mm) for glass/steel laminates without a substantial adverse effect on impact resistance.
As such, the disclosure further presents laminated structures that protect a metal sheet with a glass sheet to avoid scratching of the metal sheet and soiling the surface of the glass sheet. Indeed, smudges or dirt may be easily removed from the surface of the glass sheet in a convenient manner that may be more difficult to remove from an unprotected metal surface. In some examples, the glass sheet can be laminated to a stainless steel metal sheet to provide an attractive surface that has enhanced scratch resistance, and is relatively easy to clean, for example, with respect to fingerprints, oil smudges, microbial contaminants, etc. According to various embodiments, the glass sheet may also be treated to provide an anti-glare surface to provide the laminated structure with further aesthetic benefits. The glass sheet can thereby help preserve the aesthetic look of the stainless steel and can help facilitate cleaning and maintenance of the surface of the laminated structure.
Moreover, the glass sheet of the laminated structure can provide the stainless steel metal sheet with increased resistance to plastic deformation under sharp impact. As such, the glass sheet may help to shield the metal sheet from impacts that may otherwise dent or damage the metal sheet. The glass sheet may also increase the chemical/electrochemical stability when compared to a stainless steel metal sheet, thereby preserving the surface characteristics of the stainless steel.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present disclosure without departing from the spirit and scope of the disclosure. Since modifications combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the disclosure may occur to persons skilled in the art, the disclosure should be construed to include everything within the scope of the appended claims and their equivalents.
The following Examples are intended to be non-restrictive and illustrative only, with the scope of the invention being defined by the claims.

Examples

Laminated Glass/Metal Structures

FIGS. 6-11 show test results performed on various laminated structures to illustrate performance characteristics. In each test, a four inch square laminated structure was placed on a 1 inch thick flexible foam support with the glass sheet facing upwards. A 535 gram ball was then dropped at varying heights from the glass sheet. Once breakage was noted, the energy corresponding to the height of the ball was recorded. The Weibull plots illustrated in FIGS. 6-11 were created by plotting the percent failure vs. the energy at failure. As such, in each plot, the Y-axis (i.e., vertical axis) has the units of percent (%) while the X-axis (i.e., horizontal axis) has the units of Joules (i.e., the energy at failure).
FIG. 6 is a Weibull plot demonstrating impact energy at breakage for six groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, 16 Gauge (1.59 mm) stainless steel, and various types of interlayers. Data set 601 represents a laminated structure including an interlayer comprising SentryGlas® ionomer with a thickness of 0.89 mm. Data set 603 represents a laminated structure with an interlayer comprising polyvinyl butyral (PVB) with a thickness of 0.38 mm. Data set 605 represents a laminated structure with an interlayer comprising SentryGlas® ionomer with a thickness of 1.5 mm. Data set 607 represents a laminated structure with an interlayer comprising thermoplastic polyurethane (TPU) with a thickness of 0.34 mm. Data set 609 represents a laminated structure with an interlayer comprising acrylic pressure sensitive adhesive tape (hereinafter “APSAT”) with a thickness of 0.05 mm. Data set 611 represents a laminated structure with an interlayer comprising APSAT+PET+APSAT with a thickness of 0.17 mm. The APSAT+PET+APSAT interlayer comprises a PET film in the middle of the laminate that is sandwiched between two layers of APSAT. Data set 613 is a comparative sample for comparison purposes with the six other groups 601, 603, 605, 607, 609, and 611 of laminated structures in accordance with aspects of the disclosure. Data set 613 comprises a fully tempered soda lime glass sheet with a thickness of 4 mm. The data represented by the data sets shown in FIG. 6 is reproduced in Table 1 below wherein the samples in each set are sorted in ascending order of impact energy:

TABLE 1

					609	611
	601	603	605	607	APSAT	APSAT + PET +	613
Sample	SG0.89	PVB0.38	SG1.5	TPU0.34	0.05	APSAT	SL4 mm

1	2.24	3.03	2.24	2.24	2.25	1.98	3.28
2	4.87	3.56	2.50	2.24	2.25	1.98	3.54
3	4.87	3.56	2.76	2.24	2.25	2.25	3.54
4	5.39	3.82	2.76	2.51	2.51	2.25	3.81
5	5.39	3.82	2.76	2.77	2.77	2.25	3.81
6	5.91	4.08	2.76	2.77	2.77	2.51	3.81
7	6.18	4.08	2.76	2.77	2.77	2.77	4.07
8	6.44	4.08	2.76	2.77	2.77	2.77	4.07
9	6.70	4.08	3.29	3.03	2.77	2.77	4.33
10	7.23	4.08	3.55	3.03	2.77	3.30	4.33
11	7.23	4.08	3.55	3.03	3.03	3.30	4.59
12	7.49	4.08	3.55	3.03	3.03	3.56	4.59
13	7.49	4.08	3.81	3.29	3.03	3.82	4.86
14	7.49	4.08	3.81	3.29	3.03	4.61	4.86
15	7.49	4.08	4.07	3.29	3.30		4.86
16	7.49	4.34	4.34	3.29	3.30		4.86
17	7.49	4.34	4.34	3.29	3.30		4.86
18	7.49	4.34	4.34	3.29	3.30		5.12
19	7.49	4.34	4.60	3.29	3.30		5.12
20	7.49	4.34	5.12	3.29	3.30		5.38
21		4.60	5.12	3.29	3.30		5.38
22		4.60	5.12	3.56	3.56		5.38
23		4.60	5.65	3.56	3.56		5.64
24		4.60	5.91	3.56	3.56		5.90
25		4.60	6.17	3.82	3.56		5.90
26		4.87	6.70	4.08	3.82
27		5.13	6.70	4.08	3.82
28		5.65	6.70	4.34	3.82
29		6.18	6.96	4.60	3.82
30			7.48	4.60	3.82

Data sets 605, 607, 609, and 611 of the Weibull plot of FIG. 6 show that the laminated structures with APSAT, TPU, and 1.5 mm SentryGlas® ionomer do not have comparable impact resistance with a 4 mm sheet of fully tempered soda lime glass represented by data set 613. On the other hand, the laminated structures with 0.38 mm PVB represented by data set 603 is comparably impact-resistant, and the group with 0.89 SentryGlas® ionomer represented by data set 601 has a superior impact resistance, which is much higher than all other data sets 603, 605, 607, 609, and 611 and the soda lime 613. Comparing data sets 601 and 605, it is recognized that impact resistance increased with decreased thickness of the SentryGlas Plus® ionomer interlayer.
FIG. 7 is a Weibull plot demonstrating impact energy at breakage for five groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, a layer of 0.38 mm polyvinyl butyral (PVB), and various thicknesses of stainless steel sheets. Data set 701 represents a laminated structure including a 16 Gauge stainless steel sheet (i.e., 1.59 mm thick). Data set 703 represents a laminated structure including an 18 Gauge stainless steel sheet (i.e., 1.27 mm thick). Data set 705 represents a laminated structure including a 20 Gauge stainless steel sheet (i.e., 0.95 mm thick). Data set 707 represents a laminated structure including a 22 Gauge stainless steel sheet (i.e., 0.79 mm thick). Data set 709 represents a laminated structure including a 24 Gauge stainless steel (i.e., 0.64 mm thick). The data represented by the data sets shown in FIG. 7 is reproduced in Table 2 below wherein the samples in each set are sorted in ascending order of impact energy:

TABLE 2

	701	703	705	707	709
	Gauge	Gauge	Gauge	Gauge	Gauge
Sample	16	18	20	22	24

1	3.03	2.25	1.992	1.73	1.99
2	3.56	2.78	1.992	1.99	2.26
3	3.56	3.30	2.254	2.25	2.52
4	3.82	3.56	2.254	2.25	2.52
5	3.82	3.82	2.516	2.25	2.52
6	4.08	3.82	2.516	2.25	2.52
7	4.08	4.09	2.516	2.52	2.52
8	4.08	4.09	2.778	2.52	2.52
9	4.08	4.09	3.040	2.52	2.78
10	4.08	4.35	3.040	2.78	3.04
11	4.08	4.61	3.302	3.04	3.04
12	4.08	4.61	3.564	3.04	3.30
13	4.08	4.87	3.564	3.30	3.30
14	4.08	5.14	3.827	3.57	3.83
15	4.08	5.40	4.875	3.57	4.09
16	4.34
17	4.34
18	4.34
19	4.34
20	4.34
21	4.60
22	4.60
23	4.60
24	4.60
25	4.60
26	4.87
27	5.13
28	5.65
29	6.18

As noted, the three groups of laminates with thinner stainless steel sheet thicknesses (i.e., Gauge 20, Gauge 22, and Gauge 24 thicknesses) cannot achieve as high impact resistance as the two groups with thicker stainless steel sheet thicknesses (i.e., Gauge 16 and Gauge 18 thicknesses).
FIG. 8 is a Weibull plot demonstrating impact energy at breakage for three groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, a layer of 0.89 mm SentryGlas® ionomer, and various thicknesses of stainless steel sheets. Data set 801 represents a laminated structure including a 16 Gauge stainless steel sheet (i.e., 1.59 mm thick). Data set 803 represents a laminated structure including a 22 Gauge stainless steel sheet (i.e., 0.79 mm thick). Data set 805 represents a laminated structure including a 24 Gauge stainless steel (i.e., 0.64 mm thick). The data represented by the data sets shown in FIG. 8 is reproduced in Table 3 below wherein the samples in each set are sorted in ascending order of impact energy:

TABLE 3

	801	803	805
Sample	Gauge 16	Gauge 22	Gauge 24

1	2.24	2.77	1.73
2	4.87	3.04	2.25
3	4.87	3.30	2.78
4	5.39	3.30	3.30
5	5.39	4.35	3.30
6	5.91	4.35	3.30
7	6.18	4.61	3.56
8	6.44	4.87	3.56
9	6.70	5.13	3.56
10	7.23	5.40	3.56
11	7.23	5.66	3.82
12	7.49	5.92	4.09
13	7.49	6.44	4.09
14	7.49	6.71	4.35
15	7.49	7.49	4.61
16	7.49
17	7.49
18	7.49
19	7.49
20	7.49

As these data show, the presence of 0.89 mm SentryGlas® ionomer provides impressive impact resistance. Indeed, as shown by data set 803, even the laminated structures with a thinner steel layer (as thin as 0.79 mm) reaches a comparable impact resistance with the fully tempered 4 mm Soda Lime (see data set 613 in FIG. 6) or the laminated structures with 1 mm Gorilla glass plus 0.38 PVB plus 1.59 mm steel (see data set 603 in FIG. 6). As shown by data set 801, laminate structures with 1.59 mm stainless steel and 0.89 mm SentryGlas® ionomer has the highest impact resistance.
FIG. 9 is a Weibull plot demonstrating impact energy at breakage for three groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass compared to two groups of fully tempered 4 mm Soda Lime glass. Data set 901 represents a laminated structure including a 16 Gauge stainless steel sheet (i.e., 1.59 mm thick) with a PVB interlayer having a thickness of 0.38 mm. Data set 903 represents a laminated structure including a 16 Gauge stainless steel sheet (i.e., 1.59 mm thick) with a 0.89 mm SentryGlas® ionomer as the interlayer. Data set 905 represents a laminated structure including a 22 Gauge stainless steel sheet (i.e., 0.79 mm thick) with a 0.89 mm SentryGlas® ionomer as the interlayer. For comparison purposes, two sets of soda lime glass where added. Data set 907 represents fully tempered soda lime glass with a thickness of 4 mm. Data set 909 represents fully tempered soda lime glass with a thickness of 4 mm with a black frit coating added. The data represented by the data sets shown in FIG. 9 is reproduced in Table 4 below wherein the samples in each set are sorted in ascending order of impact energy:

TABLE 4

	901	903	905		909
	PVB0.38	SG0.89	SG0.89	907	FT SL4
	Steel	Steel	Steel	SL4	mm
Sample	1.59	1.59	0.79	mm	w/Frit

1	3.03	2.24	2.77	3.28	1.45
2	3.56	4.87	3.04	3.54	1.71
3	3.56	4.87	3.30	3.54	1.71
4	3.82	5.39	3.30	3.81	1.71
5	3.82	5.39	4.35	3.81	1.71
6	4.08	5.91	4.35	3.81	1.97
7	4.08	6.18	4.61	4.07	1.97
8	4.08	6.44	4.87	4.07	1.97
9	4.08	6.70	5.13	4.33	1.97
10	4.08	7.23	5.40	4.33	1.97
11	4.08	7.23	5.66	4.59	1.97
12	4.08	7.49	5.92	4.59	1.97
13	4.08	7.49	6.44	4.86	1.97
14	4.08	7.49	6.71	4.86	1.97
15	4.08	7.49	7.49	4.86	2.23
16	4.34	7.49		4.86	2.23
17	4.34	7.49		4.86	2.23
18	4.34	7.49		5.12	2.23
19	4.34	7.49		5.12	2.50
20	4.34	7.49		5.38	2.76
21	4.60			5.38
22	4.60			5.38
23	4.60			5.64
24	4.60			5.90
25	4.60			5.90
26	4.87
27	5.13
28	5.65
29	6.18

FIG. 10 is a Weibull plot demonstrating impact energy at breakage for two groups of laminated structures in accordance with aspects of the disclosure including 1 mm Corning® Gorilla® glass, 0.38 mm polyvinyl butyral (PVB) together with two alternative stainless steel sheets. Data set 1005 represents 16 Gauge (1.59 mm) stainless steel sheet and data set 1007 represents 24 Gauge (0.64 mm) stainless steel sheet. FIG. 10 further shows impact energy at breakage for two groups of laminated structures in accordance with aspects of the disclosure including acid-etched 1 mm Corning® Gorilla® glass, 0.38 mm polyvinyl butyral (PVB) together with two alternative stainless steel sheets. Data set 1003 represents 16 Gauge (1.59 mm) stainless steel sheet and data set 1001 represents 24 Gauge (0.64 mm) stainless steel sheet. For comparative purposes, data set 1009 represents fully tempered soda lime glass sheet with a thickness of 4 mm. The data represented by the data sets shown in FIG. 10 is reproduced in Tables 5a and 5b below wherein the samples in each set are sorted in ascending order of impact energy:

TABLE 5a

	1001	1003	1005	1007
	F_GG1	F_GG1	IOXed_GG1	IOXed_GG1		1009
	Gauge	Gauge	Gauge	Gauge	SL4
Sample	24	16	16	24	mm

1	4.34	4.34	2.51	1.99	3.28
2	4.60	5.39	2.77	2.26	3.54
3	5.65	5.91	2.77	2.52	3.54
4	5.65	6.70	3.03	2.52	3.81
5	6.96	6.96	3.56	2.52	3.81
6	7.23	7.49	3.56	2.52	3.81
7	7.49	7.49	3.82	2.52	4.07
8	7.49	7.49	3.82	2.52	4.07
9	7.49	7.49	3.82	2.78	4.33
10	7.49	7.49	3.82	3.04	4.33
11	7.49	7.49	3.82	3.04	4.59
12	7.49	7.49	3.82	3.30	4.59
13	7.49	7.49	4.08	3.30	4.86
14	7.49	7.49	4.08	3.83	4.86
15	7.49	7.49	4.08	4.09	4.86
16	7.49	7.49	4.08		4.86
17	7.49	7.49	4.08		4.86
18			4.08		5.12
19			4.08		5.12
20			4.08		5.38

TABLE 5b

	1001	1003	1005	1007
	F_GG1	F_GG1	IOXed_GG1	IOXed_GG1		1009
	Gauge	Gauge	Gauge	Gauge	SL4
Sample	24	16	16	24	mm

21			4.08		5.38
22			4.08		5.38
23			4.08		5.64
24			4.08		5.90
25			4.34		5.90
26			4.34
27			4.34
28			4.34
29			4.34
30			4.60
31			4.60
32			4.60
33			4.60
34			4.60
35			4.60
36			4.60
37			4.87
38			5.13
39			5.39
40			5.65
41			5.65
42			5.91
43			6.18
44			7.23

As demonstrated by data sets 1001 and 1003, both acid-etched Corning® Gorilla® glass laminated structures have superior impact performance when compared to non-acid treated chemically strengthened glass laminated structures and when compared to 4 mm soda lime glass.
FIG. 11 is a Weibull plot demonstrating impact energy at breakage for two groups of laminated structures in accordance with aspects of the disclosure including acid-etched 0.7 mm Corning® Gorilla® glass, a layer of 0.89 mm SentryGlas® ionomer together with two alternative stainless steel sheets. Data set 1103 represents 16 Gauge (1.59 mm) stainless steel sheet. Data set 1101 represents 24 Gauge (0.64 mm) stainless steel sheet. For comparative purposes, data set 1105 represents fully tempered soda lime glass sheet with a thickness of 4 mm. The data represented by the data sets shown in FIG. 11 is reproduced in Table 6 below wherein the samples in each set are sorted in ascending order of impact energy:

TABLE 6

	1101	1103	1105
	F_GG07	F_GG07	SL4
Sample	Gauge 24	Gauge 16	mm

1	4.60	5.91	3.28
2	5.91	7.49	3.54
3	6.18	7.49	3.54
4	7.49	7.49	3.81
5	7.49	7.49	3.81
6	7.49	7.49	3.81
7	7.49	7.49	4.07
8	7.49	7.49	4.07
9	7.49	7.49	4.33
10	7.49	7.49	4.33
11	7.49	7.49	4.59
12	7.49	7.49	4.59
13	7.49	7.49	4.86
14	7.49	7.49	4.86
15	7.49	7.49	4.86
16	7.49	7.49	4.86
17	7.49		4.86
18			5.12
19			5.12
20			5.38
21			5.38
22			5.38
23			5.64
24			5.90
25			5.90

FIG. 11 demonstrates that thinner sheets of glass comprising acid-etched 0.7 mm Corning® Gorilla® glass used in a laminated structure can be used with thin sheets of steel (e.g., 24 Gauge—0.64 mm thick stainless steel) with a layer of 0.89 mm SentryGlas® ionomer and still achieve superior impact performance when compared to 4 mm soda lime glass. As such, the experimental results demonstrate that acid-etched Corning® Gorilla® glass indeed has the ability to enable the use of thinner steel (like 24 Gauge) for the construction of highly impact resistant glass/steel laminates, even with 0.7 mm Gorilla® glass.
Glass Sheets with Anti-Glare Function
FIGS. 12 and 13 show test results performed on various glass sheets to illustrate strength performance characteristics. In each test, a four inch square glass sheet having a thickness of 1 mm was placed on a 1 inch thick flexible foam support. A 128 gram ball was then dropped at varying heights from the glass sheet. Once breakage was noted, the height of the ball was recorded. The Weibull plots illustrated in FIGS. 12 and 13 were created by plotting the percent failure vs. the height of the ball at failure. As such, in both plots, the Y-axis (i.e., vertical axis) is expressed in units of (%) while the X-axis (i.e., horizontal axis) is expressed in units of (cm).
FIG. 12 is a Weibull plot demonstrating impact resistance for creamy etched anti-glare glass sheets at 10% and 40% haze levels under tension or compression as compared to Corning® Gorilla® glass without anti-glare treatment. Data set 1201 represents a 1 mm thick creamy etched anti-glare Corning® Gorilla® glass sheet with 10% transmission haze under tension. Data set 1203 represents a 1 mm thick creamy etched anti-glare Corning® Gorilla® glass sheet with 10% transmission haze under compression. Data set 1205 represents a 1 mm thick creamy etched anti-glare Corning® Gorilla® glass sheet with 40% transmission haze under tension. Data set 1207 represents a 1 mm thick creamy etched anti-glare Corning® Gorilla® glass sheet with 40% transmission haze under compression. Data set 1209 represents a 1 mm thick Corning® Gorilla® glass sheet without anti-glare treatment as a control. As shown in FIG. 12, the creamy etched anti-glare glass sheets have comparable impact resistance as compared to the control, i.e., standard Corning® Gorilla® glass without anti-glare treatment, both under tension and compression. It is therefore believed that etched anti-glare glass sheets can be used in the laminated structures disclosed herein without a substantial adverse effect on the structure's resistance to impact.
FIG. 13 is a Weibull plot demonstrating impact resistance for sol gel treated anti-glare glass sheets with 10% haze under tension or compression as compared to Corning® Gorilla® glass without anti-glare treatment. Data set 1301 represents a 1 mm thick sol gel treated anti-glare Corning® Gorilla® glass sheet with 10% transmission haze under tension. Data set 1303 represents a 1 mm thick sol gel treated anti-glare Corning® Gorilla® glass sheet with 10% transmission haze under compression. Data set 1305 represents a 1 mm thick Corning® Gorilla® glass sheet without anti-glare treatment as a control. As shown in FIG. 13, the sol gel anti-glare glass sheets under tension have a lower impact resistance as compared to the control, i.e., standard Corning® Gorilla® glass without anti-glare treatment. However, the sol gel treated anti-glare glass sheets under compression exhibit comparable impact resistance as compared to the control. In a large majority of applications it is believed that the laminated structure will be under compression (rather than tension) when the structures are loaded. It is therefore believed that sol gel treated anti-glare glass sheets can be used in the laminated structures disclosed herein without a substantial adverse effect on the structure's resistance to impact.

Claims

What is claimed is:

1. A laminated structure comprising:

a metal sheet including a first face and a second face with a thickness of from about 0.1 mm to about 5 mm extending between the first face and the second face;

a first chemically strengthened or non-chemically strengthened glass sheet having a thickness ranging from about 0.3 mm to about 2 mm; and

a first interlayer attaching the first glass sheet to the first face of the metal sheet.

2. The laminated structure of claim 1, wherein the first interlayer comprises a layer of polyvinyl butyral or an ionomer.

3. The laminated structure of claim 2, wherein the layer of polyvinyl butyral has a thickness ranging from about 0.1 mm to about 0.8 mm.

4. The laminated structure of claim 2, wherein the layer of ionomer has a thickness ranging from about 0.1 mm to about 2 mm.

5. The laminated structure of claim 1, wherein the first glass sheet comprises a glass or glass ceramic containing silver, copper or a combination of silver and copper or comprises a glass or glass ceramic having a coating thereon, said coating containing silver, copper or a combination of silver and copper.

6. The laminated structure of claim 1, wherein the Young's modulus of the first interlayer is greater than or equal to 15 MPa.

7. The laminated structure of claim 6, wherein the Young's modulus of the first interlayer is greater than or equal to 275 MPa.

8. The laminated structure of claim 1, wherein the first glass sheet comprises an acid-etched glass sheet.

9. The laminated structure of claim 1, wherein the first glass sheet has a thickness ranging from about 0.5 mm to about 1.1 mm.

10. The laminated structure of claim 1, wherein the first glass sheet is chemically strengthened and comprises a glass selected from the group consisting of aluminosilicate glass and alkali-aluminoborosilicate glass.

11. The laminated structure of claim 1, wherein the first glass sheet comprises at least one anti-glare surface and/or at least one anti-microbial surface.

12. The laminated structure of claim 1, further comprising:

a second glass sheet including a thickness of less than or equal to about 2 mm; and

a second interlayer attaching the second glass sheet to the second face of the metal sheet,

wherein the second glass sheet is chemically strengthened.

13. A method of manufacturing a laminated structure comprising:

(i) providing a metal sheet including a first face and a second face with a thickness ranging from about 0.1 mm to about 5 mm extending between the first face and the second face;

(ii) providing a chemically strengthened or non-chemically strengthened glass sheet having a thickness of less than or equal to about 2 mm and at least one anti-glare surface;

(iii) attaching the glass sheet to the first face of the metal sheet with a first interlayer.

14. The method of claim 13, wherein the glass sheet has a thickness ranging from about 0.3 mm to about 1 mm.

15. The method of claim 13, wherein the glass sheet is chemically strengthened and is selected from the group consisting of aluminosilicate glass and alkali-aluminoborosilicate glass.

16. The method of claim 13, further comprising the step of treating the glass sheet to produce the at least one anti-glare surface, wherein the treating step is chosen from acid etching, creamy etching, masked acid etching, sol gel processing, mechanical roughening, and combinations thereof.

17. The method of claim 13, further comprising a step of further strengthening the glass sheet, wherein the further strengthening step is chosen from acid etching.

18. A method of manufacturing a laminated structure comprising:

(i) providing a metal sheet including a first face and a second face with a thickness of from about 0.1 mm to about 5 mm extending between the first face and the second face;

(ii) providing a glass sheet having a thickness of less than or equal to about 2 mm;

(iii) treating the glass sheet to produce at least one anti-glare surface;

(iv) optionally chemically strengthening the glass sheet;

(v) optionally acid etching the glass sheet; and

(vi) attaching the glass sheet to the first face of the metal sheet with a first interlayer.

19. The method of claim 18, wherein the treating step (iii) is chosen from acid etching, creamy etching, masked acid etching, sol gel processing, mechanical roughening, and combinations thereof.

20. The method of claim 18, wherein the chemical strengthening step (iv) is chosen from ion exchange processes.