MICRO-PERFORATED GLASS LAMINATES WITH CONTROLLED HOLE SHAPE, APPLICATIONS THEREOF, AND METHODS OF MAKING MICRO-PERFORATED GLASS LAMINATES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application No. 62/928,694, filed October 31, 2019, the content of which is incorporated herein by reference in its entirety.

FIELD OF THE DISCLOSURE

[0002] The described embodiments relate generally to micro-perforated glass laminate systems, methods for noise abatement and methods of making micro-perforated glass laminate systems. In particular, embodiments relate to glass micro-perforated glass laminate systems with controlled hole shape through the laminate for improved noise abatement.

BACKGROUND

[0003] Glass is a highly desirable architectural product owing to its superior optical attributes, scratch and corrosion resistance, durability, waterproof, aesthetic quality, fire resistance, etc. For example, unlike polymeric materials such as polycarbonate, glass does not "yellow" over time, has high strength and scratch resistance, and may be cleaned using UV methods. However, the high density and acoustic impedance of glass leads to high acoustic reflections (e.g., echo), poor speech intelligibility, and a low noise reduction coefficient (NRC) which limits its widespread use in architectural applications particularly. Ordinary glass has nearly no sound absorption coefficient (NRC about 0.05) leading to undesirably long reverberation time and poor acoustic environment when used.

[0004] Establishing optimal room acoustics has been a growing need for many interior architectural applications including, for example, open office workspace, hospitals, classrooms, airports, automotive applications, and more. Not only can continuous exposure to sound levels greater than 85 decibels (dB) lead to hearing loss, but even noise at much lower level can be a significant distraction and lead to reduced productivity, reduced ability to concentrate or rest, and in general make a room acoustically unpleasant. Current approaches for sound absorbing include the use of acoustic foam, fibrous materials, and other nontransparent, non-glass materials.

[0005] A technical solution is desired to improve acoustic properties, including NRC rating, of glass to be used in various operative environments where noise control is desirable.

SUMMARY

[0006] In one embodiment, the present micro-perforated glass or glass-ceramics laminate, comprises a first substrate laminated to a second substrate by a first polymer interlayer, wherein the first and the second substrates are independently selected from one or more glass and glass-ceramics; and a plurality of micro-perforations, each of the plurality of microperforations extending through the first substrate, the first polymer interlayer, and the second substrate, wherein said micro-perforations have at least one diameter through each of the polymer layer, the first substrate and the second substrate, and the at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10%. For examples, the at least one diameter through the polymer layer can be at least about 10% larger than the at least one diameter through the first and/or second substrate. In another example, the at least one diameter through the polymer layer is at least about 10% smaller than the at least one diameter through the first and/or second substrate. The micro-perforations have a cross sectional shape through the first substrate, the first polymer interlayer, and the second substrate. Examples, of the cross- sectional shape of this embodiment include a muffler, hourglass with constricted waist, multiple angle, tapered, angled hourglass with constricted waist, torturous, tapered with open waist, stacked and combinations thereof. At least about 85% of the plurality of micro- perforations can have at least one diameter through the polymer layer that differs from the at least one diameter through the first and/or second substrate by at least about 10%.

[0007] In another embodiment, the micro-perforated glass or glass-ceramics laminate, comprises a first substrate laminated to a second substrate by a first polymer interlayer, wherein the first and the second substrates are independently selected from glass and glass- ceramics; and a plurality of micro-perforations, each of the plurality of micro-perforations extending through the first substrate, the first polymer interlayer, and the second substrate, wherein said micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate; and said inlet and outlet are offset from one another. The micro-perforations have a cross sectional shape through the first substrate, the first polymer interlayer, and the second substrate. Examples, of the cross-sectional shape of this embodiment include single angle, multiple angle, tapered, angled hourglass with constricted waist, torturous, and combinations thereof. At least about 85% of the plurality of micro-perforations can have the inlet and outlet offset from one another

[0008] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can have a Noise Reduction Coefficient (NRC) between about 0.5 and about 1.

[0009] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can have a largest diameter of the microperforations through the polymer layer, the first substrate and/or the second substrate ranges from about 20 um to about 1000 um.

[00010] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can have a ratio of thickness of the glass or glass- ceramics laminate to the largest diameter of said micro-perforations through the polymer layer, the first substrate and/or the second substrate is between about 0.1 and about 20.

[00011] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can have spacing between adjacent microperforations in the plane of the micro-perforated glass or glass-ceramics laminate ranges from about 40 um to about 5000 um.

[00012] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can have a porosity of the micro-perforations in the glass or glass-ceramics laminate ranges from about 0.5% to about 20%. [00013] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can have spacing between adjacent microperforations be uniform or non-uniform. For example, the micro-perforations can form decorative or regular patterns.

[00014] The first polymer interlayer for the micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can be, for example, polyvinyl butyral (PVB), ethylene-vinyl acetate, ionomers, polyurethanes, acrylics, silicones, and polycarbonates.

[00015] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can include strengthened glass or glass-ceramic that is strengthened by mechanical, thermal, chemical methods or combinations thereof.

[00016] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can include a coating, e.g., a photochromic, thermal control, electro-chromic, low emissivity, UV, anti-glare, hydrophilic, hydrophobic, anti-smudge, anti-fingerprint, anti-scratch, anti-reflective, ink-jet decorated, screen- printed, anti-splinter coating and combinations thereof.

[00017] The micro-perforated glass or glass-ceramics laminate according to one or more embodiments (e.g. all embodiments) above can have beneficial break characteristics, e.g. it does not shatter upon hole punch impact.

[00018] Acoustic micro-perforated panels comprising a micro-perforated glass or glass- ceramic laminate of any of the previous embodiments can be backed by a hard surface at a distance to generate a thin air gap.

[00019] According to an embodiment of the present technology, a method of forming a micro-perforated glass or glass-ceramics laminate comprises laminating a polymer interlayer between a first substrate and a second substrate, wherein the first and the second substrates are independently selected from glass or glass-ceramics, to form a glass or glass-ceramics laminate; forming a plurality of openings in the first substrate having a first set of diameters; forming a plurality of openings in the second substrate having a second set of diameters; and forming a plurality of openings in the polymer interlayer having a third set of diameters different than the first and second diameters with which they correspond, wherein at least one diameter of the openings through the polymer layer differs from at least one diameter of the openings through the first and/or second substrate by at least about 10%.

[00020] In some embodiments, the Noise Reduction Coefficient (NRC) of the micro- perforated glass or glass-ceramics laminate can be between 0.5 and 1.

[00021] The plurality of openings in the polymer interlayer and/or first and second substrates can by produced by solvent etching, laser drilling, thermal discharge, physical puncturing, mechanical drilling, and combinations thereof.

[00022] In some embodiments, laminating the polymer interlayer between the first substrate and the second substrate can be performed before forming the plurality of openings in the first substrate, the second substrate and the polymer interlayer. In other embodiments, laminating the polymer interlayer between the first substrate and the second substrate is performed after forming the plurality of openings in the first substrate, the second substrate and the polymer interlayer.

[00023] In some embodiments, forming the plurality of openings in the first and second substrates comprises: forming a plurality of damage tracks with a first laser beam; and etching the first and second substrates having the plurality of damage tracks in an acid solution. In some embodiments, the method comprises: laminating the polymer interlayer between the first substrate and the second substrate to form the glass or glass-ceramics laminate; forming the plurality of damage tracks in the first substrate and the second substrate with the first laser beam; after forming the plurality of damage tracks, etching the first and second substrates in the acid solution to form the plurality of openings in the first substrate and the second substrate from the plurality of damage tracks; and after forming the glass or glass-ceramics laminate and after forming the plurality of openings in the first and second substrates, removing a portion of the polymer interlayer to form the micro-perforated glass or glass-ceramics laminate. In other embodiments, the method comprises: forming the plurality of damage tracks in the first and second substrates with the first laser beam; forming the plurality of openings in the polymer interlayer with a second laser beam; etching the first and second substrates having the plurality of damage tracks in the acid solution to form the plurality of openings in the first and second substrates; and after etching, laminating the polymer interlayer between the first and second substrates while the plurality of openings in the first and second substrates and the plurality of openings in the polymer interlayer are positioned to create an open path through the laminate. In some embodiments, the plurality of openings in the first and second substrates and polymer layer are aligned. In other embodiments, the plurality of openings in the first and second substrates and polymer interlayer can be offset from each other while maintaining an open path, e.g. a torturous path.

[00024] In some embodiments, forming the plurality of openings in the polymer interlayer is performed by solvent etching for a sufficient time that the third set of diameters are smaller than the first and second diameters with which they correspond. In other embodiments, forming the plurality of openings in the polymer interlayer is performed by solvent etching for a sufficient time that the third set of diameters are greater than the first and second diameters with which they correspond. Variations in solvent, temperature, and/or sonication could also impact diameter and be varied to obtain different diameters of openings in the polymer interlayer (smaller or larger than the first and second openings). Moreover, where the diameter of the first or second openings in the glass substrates at the interface with the polymer is larger etching will occur more quickly.

[00025] In some embodiments forming the plurality of openings in the polymer interlayer is performed by laser drilling such that the third set of diameters are smaller than the first and second diameters with which they correspond. In other embodiments, forming the plurality of openings in the polymer interlayer is performed by laser drilling such that the third set of diameters are greater than the first and second diameters with which they correspond

[00026] According to an embodiment of the present technology, a method of forming two micro-perforated glass or glass-ceramics sheets comprises laminating a first polymer interlayer between a first and a second glass or glass-ceramics sheet to form a glass or glass- ceramics laminate; forming a plurality of openings in the first glass or glass-ceramics sheet on the glass or glass-ceramics laminate; forming a plurality of openings in the second glass or glass-ceramics sheet on the glass or glass-ceramics laminate; and removing the first polymer interlayer to form two micro-perforated glass or glass-ceramics sheets. [00027] In an embodiment, forming the plurality of openings in the first and second glass or glass-ceramics sheets comprises: forming a plurality of damage tracks with a first laser beam; and etching the first and second glass or glass-ceramic sheets having the plurality of damage tracks in an acid solution. Removing the first polymer interlayer can be performed by a process of solvent etching. The micro-perforations can be conical.

[00028] According to an embodiment of the present technology, the two micro-perforated glass sheets produced as discussed above can be used in a method of forming a micro- perforated glass comprising: forming the plurality of openings in a second polymer interlayer with a second laser beam; and laminating the second polymer interlayer between the first and second glass or glass-ceramics sheets such that the plurality of openings in the first and second glass or glass-ceramic sheets and the plurality of openings in the second polymer interlayer are positioned to form a plurality of micro-perforations wherein at least one diameter of the openings through the second polymer layer differ from at least one diameter of the openings through the first and/or second glass or glass-ceramic sheets by at least 10%. In some embodiments, one or more of the glass sheets may be flipped to modify the shape of the micro-perforations through the glass or glass-ceramic laminate.

[00029] 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 the description or recognized by practicing the embodiments as described in the written description and claims hereof, as well as the appended drawings.

[00030] It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understand the nature and character of the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[00031] The accompanying figures, which are incorporated herein, form part of the specification and illustrate embodiments of the present disclosure. Together with the description, the figures further serve to explain the principles of and to enable a person skilled in the relevant art(s) to make and use the disclosed embodiments. These figures are intended to be illustrative, not limiting. Although the disclosure is generally described in the context of these embodiments, it should be understood that it is not intended to limit the scope of the disclosure to these particular embodiments. In the drawings, like reference numbers indicate identical or functionally similar elements.

[00032] FIG. 1 shows a perspective view of a micro-perforated glass or glass-ceramics laminate according to an embodiment.

[00033] FIG 2A shows a cross-section of a micro-perforated glass or glass-ceramics laminate along the plane 1-1’ shown in FIG. 1.

[00034] FIG. 2B shows an enlarged cross-section view of a portion of the micro-perforated glass or glass-ceramics laminate.

[00035] FIG. 3 shows examples of controlled micro-perforation shapes through the layers of a micro-perforated laminate according to an embodiment.

[00036] FIG. 4 shows process steps to form a micro-perforated glass or glass-ceramics laminate according to an embodiment.

[00037] FIG. 5 shows an exemplary process flowchart for forming a micro-perforated glass or glass-ceramics laminate according to an embodiment.

[00038] FIG. 6 shows an exemplary process flowchart for forming a micro-perforated glass or glass-ceramics laminate according to an embodiment.

[00039] FIG. 7 shows an exemplary process flowchart for forming a micro-perforated glass or glass-ceramics laminate according to an embodiment.

[00040] FIG. 8 shows exemplary process steps for forming a micro-perforated glass or glass- ceramics laminate according to an embodiment.

[00041] FIG. 9 shows exemplary process steps for forming a micro-perforated glass or glass- ceramics laminate according to an embodiment. [00042] FIG. 10 shows exemplary process steps for forming a micro-perforated glass or glass-ceramics laminate according to an embodiment.

[00043] FIG. 11 shows sound absorption profiles for laminates according to embodiments.

[00044] FIG. 12 shows testing of micro-perforation shape of an embodiment using a fluorescent dye.

DETAILED DESCRIPTION

[00045] Addressing room acoustics is challenging as it involves both architectural design and engineering in addition to acoustic science and principles. Micro-perforated glass laminates in general may form a resonant sound absorbing system, based on the Helmholtz resonance principle.

[00046] The present disclosure relates to the development of transparent, micro-perforated glass and glass-ceramic laminates with micro-perforations having a controlled shape through the laminate for enhanced safety while achieving higher acoustic absorption than prior laminates in the field. The combination of safety' and acoustic absorption (NRC > 0.5) is highly desirable by architects and acoustic consultants for several interior applications such as automotive interiors, office furniture etc. Applicable standards for acoustic properties include ASTM E1050 and ASTM C423.

[00047] In some embodiments, the present micro-perforated glass or glass-ceramics laminate of the presently described technology and claims comprises the first substrate, the first polymer interlayer, the second substrate, a second polymer interlayer, and a third substrate laminated to the second substrate by the second polymer interlayer, wherein the third substrate is selected from glass or glass-ceramics. In at least one embodiment, the microperforations can have at least one diameter through each of the polymer layer, the first substrate and the second substrate, and the at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10%. The at least one diameter through the polymer layer is at least about 10% larger or smaller than the at least one diameter through the first and/or second substrate. In another embodiment, the micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another. In yet another embodiment, the cross-sectional shape of the micro-perforations through the first substrate, the first polymer interlayer, and the second substrate is not cylindrical or not substantially cylindrical. Examples of a “substantially cylindrical” shapes include, for example, a slightly constricted waist, slight hourglass shape, or slight conical taper.

[00048] Some embodiments described herein have at least one of the many advantages listed below: i. High acoustic absorption - The NRC of the micro-perforated glass or glass- ceramics laminates with controlled micro-perforation shape is greater than about 0.5. In addition to developing micro-perforation features through the at least one glass or glass-ceramics laminate, polymer materials with high damping loss factor can be utilized to increase the acoustic absorption. ii. Tunable acoustic response based on micro-perforation shape, size, and porosity -

Adding shape options improves acoustic design flexibility. hi. Thinner installations - Acoustic micro-perforated panels are commonly backed by an additional piece of glass or suitable hard surface at a certain distance to generate an air gap. Utilizing a torturous path may allow this air gap distance to be minimized resulting in a slimmer installation, and therefore expanding to additional office interior applications with limited space, e.g. cubicle partitions. iv. Higher safety - In the glass or glass-ceramics laminate system, upon breakage, the glass would not shatter due to the presence of the polymer interlayer. v. Thin glass or glass-ceramics laminates - The ability to manufacture thin glass or glass- ceramics laminates while ensuring safety requirements. vi. Glass and other Glass compositions - Transparent, scratch-resistant materials are highly desirable for architectural and automotive interior applications. Various types of glasses and glass compositions can be processed including strengthened or treated glass. The glass substrates can be coated with different attributes such as thermal coating, photochromic, UV, eiectrochromic etc. v. Choice of polymer interlayers) - The poly vinyl butyral (PVB) polymer interlayer(s) can be of different colors or transparencies for enhanced aesthetic, decorative applications and/or privacy applications. The polymer interlayer can also be composed of multiple layers for aesthetic reasons or functional reasons such as stiffness and thickness. Alternatives to PVB such as ethylene-vinyl acetate (EVA) and ionomers may further extend applications and product lifespan. vii. Process flexibility - Not critical to chemically/thennally strengthening post etching. viii. Recyclability - The product may be recyclable. Equipment and processes exist to recycle windshields with PVB interlayers and may be similarly applied at the end of the product use or lifecycle. ix. Design flexibility - The micro-perforated glass or glass-ceramics laminates can be planar or could be curved for certain applications, as desired. The present methods disclosed allow forming micro-perforated laminated glass with decorative patterns such as logos, flower shapes etc. or regular patterns such as rectangular grid, square grid, etc. for functional or decorative applications.

[00049] In some embodiments, the micro-perforated glass or glass-ceramic laminate is configured to decrease reverberation time of an operative environment. As used herein, "operative environment" may include an enclosed or semi-enclosed environment that requires a certain acoustic environment. For example, conference rooms, offices, schools, hospitals, manufacturing facilities, clean rooms (food, pharmaceutical), museums, historical buildings, restaurants, etc., may all be "operative environments". In some embodiments, the micro- perforated glass or glass-ceramic laminate is integrated in a lighting solution, for example, a lighting fixture in a ceiling or a wall. In this regard, the transparent, nature of the micro- perforated glass or glass-ceramic laminates is used to allow for light, while taking advantage of the noise reduction properties of the glass or glass-ceramic laminate as employed in the fixture. Natural air spacing behind the glass or glass-ceramic laminate (in the lighting fixture) may also be advantageous from a noise reduction perspective. [00050] In some embodiments, the micro-perforated glass or glass-ceramic laminate includes a strengthened glass or glass-ceramic. In further embodiments, for a strengthened glass, the surface compression is balanced by a tensile stress region in the interior of the glass. Surface compressive stress ("CS") greater than 750 MPa and compressive stress layer depths (also called depth of compression, or "DOC") greater than 40 microns are readily achieved in some glasses, for example, alkali aluminosilicate glasses, by chemically strengthening processes (e.g., by ion exchange processes). DOC represents the depth at. which the stress changes from compressive to tensile.

[00051] In still further embodiments, the micro-perforated glass or glass-ceramics laminate of the present technology includes a non-strengthened glass, for example, a soda-lime glass. In other embodiments, the micro-perforated glass or glass-ceramics laminate includes strengthened glass or glass-ceramic that is mechanically, thermally or chemically strengthened. In additional embodiments, the strengthened glass or glass-ceramic may be mechanically and thermally strengthened, mechanically and chemically strengthened or thermally and chemically strengthened. A mechanically-strengthened glass or glass-ceramic may include a compressive stress layer (and corresponding tensile stress region) generated by a mismatch of the coefficient of thermal expansion between portions of the glass or glass- ceramic. A chemically-strengthened glass or glass-ceramic may include a compressive stress layer (and corresponding tensile stress region generated by an ion exchange process), in such chemically strengthened glass and glass-ceramics, for example, the replacement of smaller ions by larger ions at a temperature below that at which the glass network can relax produces a distribution of ions across the surface of the glass that results in a stress profile. The larger volume of the incoming ion produces a CS on the surface portion of the substrate and tension in the center of the glass or glass-ceramic. In tiiermally-strengthened glass or glass-ceramics, the CS region is formed by heating the glass or glass-ceramic to an elevated temperature above the glass transition temperature, near the glass softening point, and then cooling the surface regions more rapidly than the inner regions of the glass or glass-ceramic. The differential cooling rates between the surface regions and the inner regions generates a residual surface CS, which in turn generates a corresponding tensile stress in the center region. In one or more embodiments, the glass substrates exclude annealed or heat strengthened soda lime glass. In one or more embodiments, the glass substrates include annealed or heat strengthened soda lime glass.

[00052] In some embodiments, the glass or glass-ceramic may have surface compressive stress of between about 100 MPa to about 1000 MPa, between about 100 MPa to about 800 MPa, between about 100 MPa to about 500 MPa, between about 100 MPa to about 300 MPa, or between about 100 MPa to about 150 MPa. In some embodiments, the DOC may be between 0.05*t to about 0.2 l*t (where t is cross-sectional thickness of the glass or glass- ceramic in micrometers), in some embodiments, DOC may be in the range from about 0.05*t to about 0.2*t, from about 0.05 *t to about 0.18*t, from about 0.05 *t to about 0.16*t, from about 0.05 *t to about 0.15 % from about 0.05 *t to about 0.12*t from about 0.05*t to about 0.1 *t, from about 0.075*t to about 0.2 1 *t, from about 0.1 *t to about 0.21 *t, from about 0.12*tto about 0.2 1 *t, from about 0.1.5 *tto about. 0.21 *t, from about 0.18 *t to about 0.21 *t, or from about 0.1 *t to about 0.18*t.

[00053] In at least some embodiments, the micro-perforated glass or glass-ceramics laminate of the present technology includes a strengthened glass substrate. In further embodiments, the micro-perforated glass or glass-ceramics laminate may have a particular- dicing pattern of the glass. In additional embodiments, the dicing pattern may be that of a safety glass. In other embodiments, the glass may be strengthened to have an optimum average size and size distribution of broken pieces, average angles of sharp point and distributions around those average angles, and distance of ejection upon breakage such that safety risks are reduced. Specifically, it may be desirable that the glass meet safe breaking requirements outlined in ANSI Z97.1, including that upon testing, e.g. hole punch impact testing, the total of the 10 largest crack-free pieces weighs no more than the weight of 10 square inches of the original test sample and no one piece is longer than 4 inches with minor exceptions.

[00054] In some embodiments, Noise Reduction Coefficient (NRC) is a metric used to evaluate the acoustic absorption effectiveness of a surface of an absorber, upon sound striking the surface of the absorber. It may be calculated by taking the arithmetic mean of the sound absorption coefficients at 250, 500, 1000 and/or 2000 Hz. In some embodiments, for example, a micro-perforated glass or glass-ceramics laminate has an NRC ranging between about 0.5 to about 1, or between about 0.5 to about 0.8. In some embodiments, the present micro-perforated glass or glass-ceramics laminate meet the requirements of ASTM El 050 and ASTM C423.

[00055] In various embodiments, a micro-perforated glass or glass-ceramics laminate has a predetermined sound absorption coefficient over a predetermined frequency band of between about 250 Hz to about 6000 Hz, or between 250 Hz to about 20,000 Hz. in some embodiments, the micro-perforated glass or glass-ceramics laminate is configured with a tailored location, frequency, size, or micro-perforation cross-sectional shapes such that the resuiting micro-perforated laminate selectively filters and/or is "tuned" to absorb particular frequencies of interest, for example, in a machinery- room or for a HVAC application, for example.

[00056] In some embodiments, the weighted sound absorption coefficient (a _w ) is a metric used to evaluate the acoustic absorption effectiveness of a surface of an absorber, upon sound striking the surface of the absorber. The weighted sound absorption coefficient (a _w ) is a result from comparison between the sound absorption coefficient values at standard frequencies and reference curve. The standard frequencies are 250, 500, 1000, 2000 and 4000 Hz, for example. In some embodiments, a micro-perforated glass or glass-ceramics laminate of the present technology has a weighted sound absorption coefficient (a _w ) between about 0.4 to about 1, or between about 0.4 to about 0.6.

[00057] In some embodiments, the micro-perforated glass or glass-ceramics laminate further includes a backing wall operatively connected to the micro-perforated glass or glass-ceramic laminate. As used herein, "operatively connected" may include a direct connection or indirect connection, or acoustic connection such that the micro-perforated glass or glass-ceramics laminate and backing wall work together to increase noise abatement. In some embodiments, the backing wall is an existing, substantially rigid structure in an operative environment (e.g., walls or ceiling in a room). In some embodiments, the backing wall may or may not contribute to acoustic echo. Advantageously, the backing wall may be a rigid or hard surface, so as to not change the acoustic performance of the micro-perforated glass or glass-ceramics laminate. In some embodiments, the micro-perforated glass or giass-ceramics laminates may be hung in front of the backing wall or placed in front of the back wall using fixtures, for example. [00058] In some embodiments, the micro-perforated glass or glass-ceramics laminate systems comprise a single laminate. A "cavity spacing”, as referred to herein, may be defined as the air spacing of the laminate from a backing w'all and is about 1 mm, about 3 mm, about 5 mm, about 10 mm, about 20 mm, about 25 mm, about 50 mm, about 100 mm, about 250 mm, about 500 mm, about 1000 mm, aboutZOOO mm, about 5000 mm, about 10000 mm, or any range having any of these two values as endpoints. For example, a cavity spacing of about 3 mm and about 25 mm may be used.

[00059] In some embodiments, the micro-perforated glass or glass-ceramics laminate systems comprise multiple laminates. In multiple -laminate systems, there may he two types of cavity spacing, namely, laminate-to-laminate cavity spacing (CSu) and laminate -to-backwal 1 cavity spacing (CSib). In some embodiments, laminate-to- laminate cavity spacing (CSu) may be defined as tire distance between the laminates in a direction perpendicular to the plane of the laminate, and laminate-to-backwall cavity spacing (CSu,) may be defined as the distance between the inner laminate and the backing wall, in a direction perpendicular to the plane of the laminate.

[00060] In some embodiments, laniinate-to-laniinate cavity spacing or the laminate-to- hackwali cavity spacing may be adjusted depending on the application or the frequency or a range of frequencies that the end-user desires to absorb, for example, in a given room or type of room. The laminate-to-laminate cavity' spacing and laminate-to-backwall cavity spacing may have similar or different values. In some embodiments, the cavity spacing has an effect on the peak absorption frequency.

[00061] In some embodiments, the micro-perforated glass or glass-ceramics laminate of present disclosure can include a coating, such as a photochromie, thermal control, electro- chromic, low emissivity, UV coatings, anti-glare, hydrophilic, hydrophobic, anti-smudge, anti-fingerprint, anti-scratch, anti-reflective, ink-jet decorated, screen- printed, anti-splinter, etc. In some embodiments, the micro-perforations are not blocked by the coating. In some embodiments, the interior of the micro-perforations is not coated. In some embodiments, a portion of the micro-perforations are blocked by the coating. In some embodiments, the glass or glass-ceram ic laminate includes an anti-microbial component. [00062] In some embodiments, the micro-perforated glass or glass-ceramics laminate of the present disclosure may be of uniform thickness, or non-uniform thickness. In some embodiments, the micro-perforated glass or glass-ceramics laminate may be substantially planar. In some embodiments, the micro-perforated glass or glass- ceramics laminate may be curved, for example, or have a complex shape. In some embodiments, the micro-perforated glass or glass-ceramics laminate may be a shape, for example, rectangular, round, etc. in some embodiments, the micro-perforated glass or glass-ceramics laminate may be flexible, in some embodiments, the micro-perforated glass or glass-ceramics laminate may be substantially rigid, in some embodiments, the geometric attributes of the micro-perforated glass or glass-ceramics laminate (e.g., micro-perforation diameter, micro-perforation shape, pitch, thickness, etc.) and the sound absorption coefficient of the micro-perforated glass or glass- ceramics laminate may be tuned to achieve desired room acoustics.

[00063] FIC3. 1 shows a perspective view 100 of a micro-perforated glass or glass- ceramics laminate 110, including a plurality of micro-perforations 120, each of the plurality of micro- perforations extending through the thickness of the glass or glass- ceramics laminate. FIG. 1 shows the micro-perforations having at least one diameter through each of the polymer layer, the first substrate and the second substrate, where the at least one diameter through the polymer layer greater than at least one diameter through the first and second substrates. FIG. 1 show's micro-perforations having a cross-sectional shape that is not cylindrical or not substantially cylindrical. Examples of a “substantially cylindrical ^' '’ shapes include a slightly constricted waist, slight homglass shape, or slight conical taper.

[00064] In some embodiments, the micro-perforated glass or glass-ceramics laminate 110 comprises the first substrate, the first polymer interlayer, the second substrate, a second polymer interlayer, and a third substrate laminated to the second substrate by the second polymer interlayer, wherein the third substrate is selected from glass or glass-ceramics. In an embodiment, the micro-perforations can have at least one diameter through each of the polymer layer, the first substrate and the second substrate, and the at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10%. The at least one diameter through the polymer layer is at least about 10% larger or smaller than the at least one diameter through the first and/or second substrate. In another embodiment, the micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another.

[00065] As discussed above, at least one diameter through the polymer layer can be at least about 10% larger or smaller than at least one diameter through the first and/or second substrate. Alternatively, at least one diameter through the polymer layer can be at least about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45% larger or smaller than at least one diameter through the first and/or second substrate. Alternatively at least one diameter through the polymer layer can be between about 10 to about 50%, about 20 to about 40% or about 30 to about 35% larger or smaller than at least one diameter through the first and/or second substrate. In some embodiments, the diameter through the polymer layer can be larger or smaller than both the first and second substrate. In some embodiments, the diameter through the polymer layer can be larger or smaller than one of the first and second substrate.

[00066] In some embodiments, all or substantially all of the micro-perforations have at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10%. In some embodiments, at least about 85%, at least about 86%, at least about 87%, at least about 88%, at least about 89%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94% or at least about 95% of the micro-perforations have at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10%.

[00067] In another embodiment, the micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another. In some embodiments, the inlet and outlet are offset from one another by an angle of at least about 10° (angle is drawn from a perpendicular line through the laminate). Alternatively, the inlet and outlet are offset from one another by an angle of about 10 to about 60°, about 10 to about 45°, about 10 to about 25°, about 10 to about 20°, about 10 to about 15°, about 15 to about 45°, about 15 to about 30°, about 15 to about

25°. [00068] In some embodiments, all or substantially all of the micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another. In some embodiments, at least about 85%, at least about 86%, at least about 87%, at least about 88%, at least about 89%, at least about 90%, at least about 91%, at least about 92%, at least about 93%, at least about 94% or at least about 95% of the micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another.

[00069] FIG. 3 shows examples of potential shapes of micro-perforations extending through the thickness of the glass or glass-ceramics laminate. FIG. 3 shows examples of microperforations having at least one diameter through each of the polymer layer, the first substrate and the second substrate, where at least one diameter through the polymer layer is greater than at least one diameter through the first and/or second substrates (e.g., 310, 340, 350, 370, 380, 311, 312, 390). It also shows examples of micro-perforations having at least one diameter through each of the polymer layer, the first substrate and the second substrate, where at least one diameter through the polymer layer is at smaller than at least one diameter through the first and/or second substrates (e.g., 320, 360, 321). It also shows examples of micro-perforations having an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another (e.g., 330, 340, 360, 370). It also shows examples of micro-perforations having a cross- sectional shape that is not cylindrical or not substantially cylindrical (e.g., 310, 320, 330, 340, 350, 360, 370, 380, 311, 321, 312, 390). Examples of potential cross-sectional shapes include, but are not limited to muffler 310, 311 and 312, hourglass (with constricted waist) 320 and 321, single angle 330, multiple angle 340, tapered 350, angled hourglass (with constricted waist) 360, torturous 370, tapered with open waist 380, and stacked 390. The shapes show in FIG. 3 are generally shown with straight lines and angles. However, they could be curved irregular lines forming similar general shapes (e.g., 311).

[00070] Applicant determined that laminates with micro-perforations having one of the described traits (e.g., (1) having at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10%, (2) having an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another or (3) having a cross-sectional shape of the micro-perforations through the laminate layers are not cylindrical or not substantially cylindrical) have advantages over previously known laminates lacking such features. For example, they can provide higher acoustic absorption. The NRC of the micro-perforated glass or glass-ceramics laminates with micro-perforations having controlled shapes, differing diameters and/or offset inlets/outlets is greater than 0.5. In addition to developing micro-perforation features through the glass or glass-ceramics laminate, polymer materials with high damping loss factor can be utilized to increase the acoustic absorption. As another example, the described traits of the micro-perforations improve acoustic design flexibility by allowing for tunable acoustic response based on micro-perforation shape, size, and porosity. As another example, they can allow for thinner installations. Acoustic micro- perforated panels are commonly backed by an additional piece of glass or suitable hard surface at a certain distance to generate an air gap. Utilizing a torturous path (as described herein) may allow this air gap distance to be minimized resulting in a slimmer installation, and therefore expanding to additional office interior applications with limited space, e.g. cubicle partitions.

[00071] In some embodiments, the micro-perforated glass or glass-ceramics laminate 110 may be planar. In some embodiments, the micro-perforated glass or glass-ceramics laminate 110 may be non-planar. When a dimension, for example the diameter of a circular micro- perforation, is measured relative to the "plane" of a non-planar surface, the dimension should be measured relative to the plane tangent to the surface of the non-planar micro-perforated glass or glass-ceramics laminate where the measurement is taken.

[00072] in some embodiments, tire micro-perforated glass or glass-ceramics laminate 110 comprises the first substrate, the first polymer interlayer, the second substrate, a second polymer interlayer, and a third substrate laminated to the second substrate by the second polymer interlayer, wherein the third substrate is selected from glass or glass-ceramics. In an embodiment, the micro-perforations can have at least one diameter through each of the polymer layers, the first substrate, second substrate, and third substrates and the at least one diameter through the polymer layer differs from the at least one diameter through the first, second and/or third substrate by at least about 10%. The at least one diameter through the polymer layer is at least about 10% larger or smaller than the at least one diameter through the first, second and/or third substrate, in another embodiment, the micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said third substrate and said inlet and outlet are offset from one another. In another embodiment, the shape of the micro-perforations through the first substrate, the tirat polymer interlayer, and the second substrate is not cylindrical or not substantially cylindrical.

[00073] In some embodiments, the type of glass or glass-ceramics and thickness may be allowed to vary in combination with the thickness of the polymer interlayer to obtain the desired rigidity and safety ratings. For example, using photo structurabie glass and UV processing followed by etching to generate openings in the glass.

[00074] In some embodiments, each of the plurality of micro-perforations 120 have a largest diameter. As referred to herein, "largest diameter" is the length of the longest straight line that may be drawn across a micro-perforation 120 in the plane of a surface of the laminate. For a square or rectangle, the "largest diameter" is the length of a diagonal line connecting two opposite comers. For an ellipse, the "largest diameter" is the length of the major axis.

[00075] In some embodiments, the "thickness” of the micro-perforated glass or glass- ceramics laminate 110, as referred to herein, may be defined as the dimension of the glass or glass-ceramics laminate perpendicular to the plane of the laminate.

[00076] in some embodiments, the "spacing" between adjacent micro-perforations 12.0, as referred to herein, may be defined as the shortest distance between the geometrical centers of adjacent micro-perforations along a plane of the micro-perforated glass or glass-ceramics laminate. In some embodiments, the spacing between adjacent micro-perforations 120 is uniform in each predetermined direction. For example, a square or rectangular array of micro-perforations exhibits such uniformity, because the spacing in any given direction is uniform, even though the spacing in different directions (such as the side and diagonal of a square) may be different. In some embodiments, the spacing between adjacent microperforations 120 may be non-uniform. [00077] In some embodiments, the "aspect ratio” may be defined as the ratio of the thickness of the micro-perforated glass or glass-ceramics laminate 110 to the largest dimension of each of plurality of the micro-perforations 120 in a plane of the micro-perforated glass or glass- ceramics laminate 110. In some embodiments, the aspect ratio is less than about 25, or is between about 0.05 to about 25, between about 0.1 to about 20, between about 1 to about 15, between about 1 to about 10, between about 5 to about 20, between about 5 to about 15, between about. 5 to about 10, between about 10 to about 20, or between about 10 to about 15, or about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25, or any range having any of these two values as endpoints. Other aspect ratios may be used.

[00078] In some embodiments, the thickness of the micro-perforated glass or glass- ceramics laminate 110 is between about 0.1 mm to about 6 mm, between about 0.2 mm to about 3 mm, between about 0.2 mm to about 2 mm, between about 0.3 mm to about 3 mm, between about 0.3 mm to about 2 mm, between about 0.3 mm to about about 1 mm. in some embodiments, the thickness of the micro-perforated glass or glass-ceramics laminate 110 may be 0.1 nun, 0.5 mm, 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 8 mm, or 10 mm, or any range having any of these two values as endpoints. Other thicknesses may be used.

[00079] In some embodiments, the largest diameter of the micro-perforations .120 may be 20 um, 40 inn, 60 um, 80 um, 100 um, 150 um, 200 um, 250 um, 300 um, 350 um, 400 um, 450 urn, 500 um, 550 um, 600 um, 700 um, 800 um, 900 um, or 1000 um, or any range having any of these two values as endpoints. For example, the largest diameter of the microperforations 120 in a plane of the micro-perforated glass or glass-ceramics laminate 110 may be between about 20 um to about 1000 urn, between about 20 um to about 800 um, between about 20 um to about 500 um, between about 20 um to about 100 um, and between about 20 um to about 50 um.

[00080] In some embodiments, the spacing between adjacent micro-perforations in the plane of the micro-perforated glass or glass-ceramics laminate 110 is 40 am , 60 um, 80 um, 100 urn, 200 um, 400 um, 600 um, 800 um, 1000 um, 2000 um, 3000 um, 4000 um, or 5000 um, or any range having any of these two values as endpoints. For example, the spacing between adjacent micro-perforations in the plane of the micro-perforated glass or glass-ceramics laminate 110 may be between about 40 um to about 5000 um, between about 80 urn to about 5000 um, between about 200 um to about 5000 urn, between about 500 um to about 5000 um.

[00081] in some embodiments, the "porosity" of the micro-perforated glass or glass- ceramics laminate 110, as referred to herein, may be defined as the ratio of the cumulative surface area of each of tire plurality ⁷ of micro-perforations in the glass or glass- ceramics laminate to the total surface area, including micro-perforations, of the micro-perforated glass or glass-ceramics laminate 110. In some embodiments, the porosity of the micro-perforations in the micro-perforated glass or glass-ceramics laminate 1.10 may be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18%, 20%, or 25%, or any range having any of these two values as endpoints. For example, the porosity of the micro-perforations in the micro-perforated glass or glass-ceramics laminate 110 may range from about 0.5% to about 20%, from about 0.5% to about 15%, and from about 0.5% to about 10%.

[00082] in some embodiments, the micro-perforations 120 are positioned at uniform intervals along the glass or glass-ceramics laminate. In some embodiments, the micro-perforations are distributed with uniform density along the glass or glass-ceramics laminate. In some embodiments, the spacing may be of non-uniform intervals. In some embodiments, the micro-perforations 120 are distributed with non-uniform density ⁷ , in some embodiments, non- uniform density or spacing may decrease optical distortion, or be used in decorative applications, for example. In some embodiments, acoustic performance may be controlled through the mean distance between micro-perforations to be substantially uniform to maximize sound absorption at a certain frequency. In some embodiments, spacing may be varied across the glass or glass- ceramics laminate, for example, to achieve broader absorption spectrum. In some embodiments, the micro-perforations are distributed with non- uniform densities, which can find various applications, for example, logos, text, flower patterns, etc.

[00083] FIG. 2A shows cross-section view 200 of a micro-perforated glass or glass- ceramics laminate 110 along the plane 1-F shown in FIG. 1. As viewed along the 1-1’, the micro- perforated glass or glass-ceramics laminate 110 includes a first substrate 210, a first polymer interlayer 230, and a second substrate 220. in some embodiments, the micro-perforated glass or glass-ceramics laminate 110 comprises a first substrate 210 laminated to a second substrate 220 by a first polymer interlayer 230, wherein the first and the second substrates are independently selected from glass or glass- ceramics, and a plurality of micro-perforations 120, each of the plurality of micro-perforations 120 extending through the first substrate 210, the first polymer interlayer 230, and the second substrate 220. FIG. 2B shows an enlarged view of a portion of the micro-perforated glass or glass-ceramics laminate 110 along the plane 1-1.

[00084] In some embodiments, each of the plurality of micro-perforations 120 comprise an opening 215 through the first substrate 210, an opening 225 through the second substrate 22.0 and an opening 235 through the first polymer interlayer 230, as shown in FIG. 2B. FIG. 2B shows at least one diameter through the polymer layer is at least greater than at least one diameter through the fust and second substrates. The shape of the micro-perforations 120 through tire layers of the laminate is not cylindrical or not substantially cylindrical. A muffler shape is shown as a non-limiting example. By way of non-limiting example, any of the shapes shown in FIG. 3 could also be used.

[00085] In some embodiments, polymer interlayer thickness may be varied to accommodate fee desired rigidity and safety ratings as well as acoustic design requirements. The polymer interlayer may be a single layer or multiple layers.

[00086] In some embodiments, the polymer interlayer(s) may be selected from the group consisting of polyvinyl butyral (PVB), ethylene-vinyl acetate (EVA), ionomers, acrylics, silicones, or polycarbonate-thermoplastic polyurethanes. These polymers may or may not be soluble in a solvent. Product lifespan and appearance may be impacted by the choice of the polymer interlayer. In some embodiments, the polymer interiayer(s) may be optically transparent, colored, frosted, or translucent. The polymer interlayers) could be in the form of pressure sensitive adhesives or liquid optically clear adhesives.

[00087] Some embodiments of the present disclosure are directed to a method of forming a micro-perforated glass or glass-ceramics laminate where at least one diameter through the polymer layer differs from the at. least one diameter through the first and/or second substrate by at least about 10%. The at least one diameter through the polymer layer is at least about 10% larger or smaller than the at least one diameter through fee first and/or second substrate. In other embodiments, the present disclosure is directed to a method of fonning a micro- perforated glass or glass-ceramics laminate the micro-perforations have an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another. The method comprises laminating a polymer interlayer 230 between a first substrate 210 and a second substrate 220, wherein the first and the second substrates are independently selected from glass or glass-ceramics. The method further comprises forming a plurality of openings 215 in the first substrate 210 having a first set of diameters, forming a plurality of openings 225 in the second substrate 220 having a second set of diameters, and forming a plurality of openings 235 in the polymer interlayer 230 having a third set of diameters, wherein the plurality of openings in each of the first substrate, the polymer interlayer and the second substrate are positioned to form a plurality of micro-perforations where the at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10% or where an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another. The third diameters are different than the first and second diameters with which they correspond. This results in micro-perforation shapes through the laminate layers such as those in FIG. 3, e.g. muffler 310, 311 and 312, hourglass (with constricted waist) 320 and 321, tapered with open waist 380, etc. These method steps may be performed in any order, as illustrated in various exemplary embodiments described herein with different ordering of the steps. And, various techniques may be used to form the openings. The NRC of the micro-perforated glass or glass-ceramics laminate formed is between 0.5 and 1.

[00088] The method is generally illustrated in FIG. 4. In some embodiments, the method of forming a micro-perforated glass or glass-ceramics laminate 110 comprises the following steps, in no specific order:

Step 410: forming a plurality of openings in the first substrate having a first set of diameters;

Step 420: forming a plurality of openings in the second substrate having a second set of diameters; Step 430: forming a plurality of openings in the polymer interlayer having a third set of diameters different than the first and second diameters with which they correspond;

Step 440: laminating the polymer interlayer between the first substrate and the second substrate.

[00089] In some embodiments, steps 410-440 may be performed in any order. For example, a plurality ⁷ of openings 215 in the first substrate 210 may be formed simultaneously, before, or after forming a plurality of openings 225 in the second substrate 220. The steps can be done contemporaneously, sequentially, serially, etc. Laminating the polymer interlayer between the first and second substrates may be performed before or after forming the plurality of openings in the first substrate or the second substrate. In some embodiments, tire plurality of openings in the first and second substrates 210 and 220 are formed simultaneously, before, or after forming the plurality of openings 235 in the polymer interlayer 230.

Process Order Variations

Laminating before Forming Openings

[00090] In some embodiments, as shown in the process flowchart in FIG. 5, laminating the polymer interlayer 230 between the first substrate 210 and the second substrate 220 is performed before forming the plurality of openings 215 having a first set of diameters in the first substrate 210, plurality of openings 225 having a second set of diameters in the second substrate 220, and the plurality of openings 235 having a third set of diameters different from the first and second diameters with which they correspond in the polymer interlayer 235 so as to produce micro-perforated glass or glass-ceramics laminate having micro-perforations through the layers of the laminate w'here at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10% or having an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another.

Laminating after Forming Openings [00091] In some embodiments, forming the plurality of openings 235 in the polymer interlayer 230 is performed after laminating the polymer interlayer between the first and second substrates. Where a laser is used to form the opening or create damage tracks, this order of steps may require the use of a laser beam or laser energy different from that used to form openings or damage tracks before lamination, such that the laser beam reaches and is absorbed by each of the first and second substrates and the polymer layer where the laser is used with sufficient intensity to achieve the desired damage.

[00092] In some embodiments, as shown in the process fiow'chart in FIG. 6, laminating the polymer interlayer 230 between the first substrate 210 and the second substrate 220 is performed after forming the plurality of openings 215 having a first set of diameters in the first substrate 210, plurality of openings 225 having a second set of diameters in the second substrate 220, and the plurality of openings 235 having a third set of diameters different than the first and second diameters with which they correspond in tire polymer interlayer 235 so as to produce micro-perforated glass or glass-ceramics laminate having micro-perforations through the layers of the laminate where the at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10% or having an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another. The plurality of openings in the first substrate 210, polymer interlayer 230 and the second substrate 220 may be positioned during laminating the polymer interlayer between the first substrate 210 and the second substrate 220 such that the openings are properly positioned to create an open path through the laminate where at least one diameter through the polymer layer differs from the at least one diameter through the first and/or second substrate by at least about 10% or having an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another.

[00093] In some embodiments, the plurality of openings in the first and second substrates and polymer layer are aligned. In other embodiments, the plurality of openings in the first and second substrates and polymer interlayer can be offset from each other w'hile maintaining an open path, e.g. a torturous path.

Laminating before Forming Openings and Etching [00094] In some embodiments, as shown in the process flowchart in FIG. 7, a micro- perforated glass or glass-ceramics laminate may be formed by performing the following steps in order:

Step 710: laminating a polymer interlayer between the first substrate and the second substrate to form the glass or glass-ceramics laminate;

Step 720: forming a plurality' of damage tracks in the glass or glass-ceramics laminate with a laser beam;

Step 730: etching the glass or glass-ceram ics laminate in acid to form a plurality of openings in the first and second substrates having first and second sets of diameters respectively;

Step 740: removing a portion of the polymer interlayer.

[00095] In some embodiments, the method of forming a micro-perforated glass or glass- ceramics laminate comprises laminating the polymer interlayer 230 between the first substrate 210 and the second substrate 220 to form the glass or glass-ceramics laminate, forming the plurality of damage tracks in the first substrate and the second substrate with the laser beam. After forming the plurality' of damage tracks, etching the first and second substrates in an acid solution to fonn the plurality of openings 215 in the first substrate 210 and the second substrate 220 from the plurality' of damage tracks. After forming the glass or glass-ceramics laminate and after forming the plurality' of openings in the first and second substrates, removing a portion of the polymer interlayer 230 to form the micro-perforated glass or glass-ceramics laminate 110.

[00096] In some embodiments, the plurality of openings 215 in the first substrate 210, plurality of openings 225 in the second substrate 220, and the plurality of openings 235 having a third set of diameters different from the first and second diameters with which they correspond in the polymer interlayer 235, are positioned to form a plurality' of microperforations 120 through the thickness of the glass or glass-ceramics laminate at least one diameter through the polymer layer differs fiom the at least one diameter through the first and/or second substrate by at least about 10% or having an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another.

[00097] In some embodiments, forming the plurality of openings in the first and second substrates comprises forming a plurality of damage tracks with a laser beam and etching the first and second substrates having the plurality of damage tracks in an acid solution.

[00098] When single glass panels are laser damaged and etched, e g., with hydrofluoric acid (HF), they typically result in micro-perforations that are roughly cylindrical or have a slight hourglass shape because the acid is able to penetrate towards the middle from both sides of the single piece of glass. FIG. 8 illustrates acidic etching, e.g., HF etching, of a glass or glass-ceramics laminate with a polymer interlayer, e.g., PVB, between glass or glass- ceramics substrates. The far left image of FIG. 8 shows that etching such a glass or glass- ceramics laminate with a PVB polymer interlayer results in constriction near the PVB as HF can only penetrate each glass substrate from one side. PVB is resistant to HF and therefore does not etch through. The PVB serves as an etch stop. Each of the two glass sheets of the laminate will therefore have holes that are shaped like a cone or a cone frustum. It is also possible to laminate a polymer layer to a single glass sheet or to coat one side of the glass with an acid resistant ink or tape. In this way one glass sheet may be etched to form conical holes rather than etching two sheets simultaneously.

[00099] In order to form a micro-perforated laminate, the PVB is subsequently etched by solvent or ablated by a laser process. However, the PVB can be dissolved away and form two separate sheets of glass with cone shaped holes as shown in the second figure from the left in FIG. 8. In an analogous manner an acid-resistant (e.g., HF resistant) polymer (e.g., PVB) could be laminated to a single sheet of glass and create a similar conical hole shape. The three pictures on the right in FIG. 8 show that the two sheets can then be flipped and positioned to form various micro-perforation shapes through a glass or glass-ceramic laminate. The glass sheets could then be bonded to each other using another polymer layer which could have a plurality of openings according to the present invention or other methods of bonding known to those in the technology. [000100] In some embodiments, forming the plurality of openings in the polymer interlayer is performed by solvent etching for a sufficient time that the third set of diameters are smaller than the first and second diameters with which they correspond. In other embodiments, forming the plurality of openings in the polymer interlayer is performed by solvent etching for a sufficient time that the third set of diameters are greater than the first and second diameters with which they correspond. Variations in solvent, temperature, and/or sonication could also impact diameter and be varied to obtain different diameters of openings in the polymer interlayer (smaller or larger than the first and second openings). Moreover, where the diameter of the first or second openings in the glass substrates at the interface with the polymer is larger etching will occur more quickly.

[000101] FIG. 9 illustrates process steps for forming a micro-perforated glass or glass- ceramics laminate according to an embodiment. The process includes the following steps, in order:

Step 910: laminating the polymer interlayer between the first and second substrates to form a glass or glass-ceramics laminate;

Step 920: forming a plurality of damage tracks in the glass or glass-ceramics laminate with a laser beam;

Step 930: etching the glass or glass-ceramics laminate in an acid solution to form a plurality of openings in the first and second substrates;

Step 940: removing a portion of the polymer interlayer by solvent etching. The polymer, e.g., PVB may be removed leaving a diameter smaller than the conic shapes of the etched glass, which preserves the constricted waist (e.g., as shown in FIG. 3 at 320, 321), or through a longer etch time forming a much larger open waist (e.g., as shown in FIG. 3 at 380).

[000102] In some embodiments, the first laser beam configured to form a plurali ty of damage tracks in the first and second substrates may be different than the second laser beam configured to form openings 235 in the polymer interlayer 230. In some embodiments, the first and the second laser beam are the same. In some embodiments, the laser energy', focus line, laser exposure time, and combinations thereof may be the same or different for forming the plurality of openings in tire first and second substrates and the polymer interlayer.

Laminating after Forming Openings and Etching

[000103] In some embodiments, the method for forming a micro-perforated glass or glass- ceramics laminate further comprises forming die plurality of damage tracks in the first and second substrates with the first laser beam, forming the plurality' of openings in the polymer interlayer with a second laser beam, etching the first and second substrates having the plurality of damage tracks in the acid solution to form the plurality of openings in the first and second substrates, and after etching, laminating the polymer interlayer between the first and second substrates while the plurality' of openings in the first and second substrates and the plurality of openings in the polymer interlayer are positioned to create an open path through the laminate the at least one diameter through the polymer layer differs front the at least one diameter through the first and/or second substrate by at. least about 10% or having an inlet on a top surface of said first substrate and an outlet on a bottom surface of said second substrate and said inlet and outlet are offset from one another.

[000104] In some embodiments, forming the plurality of openings in the polymer interlayer is performed by a process selected from the group consisting of solvent etching, laser drilling, thermal discharge, physical puncturing, mechanical drilling, and combinations thereof. Other- suitable methods may be used. Where the laminate is formed and openings are formed in the first and/or second substrates before openings are formed in the polymer interlayer, the openings in the first and / or second substrate may be used as a guide or mask when forming openings in the polymer interlayer.

[000105] FIG. 10 illustrates process steps for forming a micro-perforated glass or glass- ceramics laminate. The process includes the following steps, in order:

Step 1010: forming a plurality of damage tracks in the first and second substrates (210 and 220) with a laser beam;

Step 1020: forming a plurality of openings in the polymer interlayer 230 by a laser beam; Step 1030: etching the first and second substrates in an acid solution to form a plurality of openings in the first and second substrates from the damage tracks formed in step 910;

Step 1040: laminating the polymer interlayer 230 with a plurality of openings 235 between the first substrate 210 with a plurality of openings 215 and the second substrate 220 with a plurality of openings 225 while positioned to form a micro-perforated glass or glass-ceramics laminate 110. A non-cylindrical micro-perforation through the glass laminate with a larger waist (e.g., as shown in FIG. 3 at 310 and 311) may be obtained by laminating drilled and/or etched glass with laser drilled polymer having larger diameter holes.

[000106] In some embodiments, the openings in the substrates and the polymer interlayer may be uniquely tailored and/or configured with positions targeted to obtain improved sound absorption and a higher Noise Reduction Coefficient.

[000107] Various process orders are described above in description of FIGS. 4-10. Any sui table process order may be used. Exemplars' details of each process are described below. Any suitable combination of process details and process order may be used to form the micro-perforated glass or glass-ceramic laminate.

Process Details

Laminating the polymer interlayer

[000108] In some embodiments, laminating the polymer interlayer may be performed by any suitable method for laminating glass and polymers including, but not limited to, use of rollers, vacuum bags, autoclaves etc. and combinations of time, temperature, pressure, and combinations thereof. Other suitable methods may be used.

Laser drilling the substrates

[000109] In some embodiments, forming the plurality of openings in the first and second substrates is performed by a process selected from the group consisting of acid etching, laser drilling, laser drilling followed by acid etching, mechanical drilling, and combinations thereof. Other suitable methods may be used. [000110] In some embodiments, a laser beam is a pulsed laser beam having a focal line oriented along a beam propagation direction and directing the laser beam focal line into a glass substrate, a polymer interlayer, or a glass or glass-ceramics laminate.

[000111] In some embodiments, the laser beam may be a Gauss-Bessel laser beam followed by chemical etching. In some embodiments, the method may be configured as a large scale process, with high throughput. In some embodiments, the method may be used to manufacture micro-perforated glass or glass-ceramics laminates of large size. The method is a high speed process for manufacturing high density array of micro-perforations, and affords flexibility to manufacture various micro-perforation shapes, sizes, micro-perforation locations and density to time and achieve the desired acoustic performance. Further, the micro- perforated glass or glass-ceramics laminates may be thermally or chemically strengthened post etching to achieve superior strength, as described herein.

Laser drilling the Polymer Interlayer

[000112] In some embodiments, removing a portion of the polymer interlayer may comprise forming a plurality of openings in the polymer interlayer by a laser beam, followed by solvent etching. In some embodiments, removing a portion of the polymer interlayer may comprise forming plurality of openings in the polymer interlayer by solvent etching, followed by a laser drilling method. In some embodiments, the plurality of openings in the polymer interlayer may be formed by laser drilling or ablation of the polymer interlayer.

[000113] in some embodiments, the laser configured to remove portions of the polymer interlayer may be a carbon dioxide laser. Other suitable lasers and laser energies may be used. The diameter of the openings may be adjusted by changing the laser parameters such as, but not limited to, laser energy, exposure time, frequency, etc.

Solvent Etching the Polymer Interlayer

[000114] In some embodiments, removing a portion of the polymer interlayer may be performed by etching the polymer interlayer in a solvent. The polymer etching solvent may be selected from a group consisting of methanol, toluene, butyl glycol, butyl diglycol, and combinations thereof. For example, about 40 to about 60% methanol with the balance toluene may be used for dissolving the polymer interlayer. Other suitable solvents may be used. For example, a non-limiting list of potential other solvents includes xylene, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methylene chloride, n-butanoi, ethyl acetate, acetone, naphtha, xylene, nitric acid, sulfuric acid, dimethyl formamide, dimethyl sulfoxide, chloroform, or combinations thereof.

[000115] In some embodiments, a portion of the polymer interlayer may be removed using any suitable solvent or solvent blend, including the use of any suitable solvent temperature, agitation, sonication, and exposure time. Other suitable methods may be used.

[000116] In some embodiments, unless protected, portions of the polymer interlayer around the edges of the glass or glass-ceramics laminate may be exposed to solvents during removal of a portion of the polymer interlayer by solvent etching. Edges of the glass or glass-ceramics laminate wherein the polymer interlayer is exposed to the solvent may be sealed with a sealant, resistant to the solvent or solvent mixture used for removing a portion of the polymer interlayer. For example, a sealant may be used to prevent undesirable etching of the polymer interlayer from the edges of the glass or glass-ceramics laminate during solvent etching. In some embodiments the edges may be sealed by a tape, or temporarily sealed to a fixture by an o-ring or other compliant material.

Excess solvent removal

[000117] In some embodiments, removal of excess or residual solvent is desirable from a quality ⁷ standpoint. Excess solvent may be removed under atmospheric gas pressure, humidity, pressure, temperature, and a combination thereof. For example, excess solvent may be removed following etching by placing the parts in a vacuum oven at about 20 to about 40 °C. Other suitable methods may be used.

Acid Etching the Substrates

[000118] In some embodiments, the laser damaged glass or glass-ceramics laminate is then acid etched to open the damage tracks to the desired diameter and shape. The acid etching processing of the first and second substrates may be performed by using a hydrofluoric acid (HF) based solution, for example, to chemically attack and remove material from the preferential damage track created by the laser. In some embodiments, while this reaction is occurring, byproducts such as alkali or aluminofluorates are generated depending on the glass composition. These byproducts are relatively insoluble in HF. In some embodiments, a secondary' mineral acid is added, for example, nitric acid (HNO3). The addition of the nitric acid increases the solubility of these etchant byproducts as well as the overall etch rate to prevent clogging of the etch openings and lengthen bath life.

[000119] In some embodiments, the shape of the etched micro-perforation may depend on the ratio of reaction rate to diffusion rate. The reaction rate directly effects the etch rate of the bulk glass on the surface while the diffusion rate drives the etch rate of the opening. The reaction rate or effective etch rate is driven by kinetics and can be controlled by the etchant chemistry, glass composition, and temperature. For example, using a more concentrated HF solution, a glass of weaker bonding network, or an increased bath temperature can all increase the reac tion rate of the system by introducing more available hydronium and fluorine ions and adding energy to allow them to react at a higher rate. The diffusion rate is the rate at which these active ions are introduced to the bulk or inside the glass part to react with new' glass molecules. Diffusion may be affected by many factors such as agitation (e.g., ultrasonics and recirculation), wettability of the part, and temperature. By adjusting these parameters the shape of the micro-perforation may be tailored.

[000120] In some embodiments, the acid etchant used is about 1.5 M Hydrofluoric and about 1.6 M Nitric acid. The glass substrates or glass or glass-ceramics laminates may be etched in a JST etching system equipped with a directly coupled, base ultrasonic transducer with an output frequency of about 40 kHz. In some embodiments, the glass substrates or glass or glass-ceramics laminates are vertically agitated at about 300 mm/s while the etchant is recirculated bottom to top within the bath. This agitation increases diffusion into the openings and helps to homogenize the ultrasonic waves that meet the glass surface. In some embodiments, the bath temperature is maintained at about 20.3 C° (within about +·/- 0.1 C°) by pumping cooler etchant from the bottom. Warmer etchant, which is heated by the ultrasonics, overflow's and is routed back through a chiller. This configuration of etching process allows for the appropriate amount of diffusion of acid into the damage tracks so that the resulting micro-perforations are open and may be substantially cylindrical. To attain a more hourglass shape in the openings, the ultrasonics in the system may be turned off to decrease the diffusion into the openings which in turn decreases the etch rate of the openings interior. The shape of the openings can be tailored by adjusting the ratio of diffusion rate to reaction rate by tuning parameters such as concentration, temperature, agitation, etc.

[000121] After etching, in some embodiments, the glass or glass-ceramic may be tempered, or chemically treated (e.g., an ion-exchanging operation) to strengthen the micro-perforated glass or glass-ceramic layers prior to lamination with the polymer interlayer forming laminate

110.

[000122] In some embodiments a single laser may be used to create the damage tracks. In some embodiments, multiple lasers may be used to create the damage tracks.

[000123] In some embodiments, the laser can be programmed to create single or multiple tiny adjacent damage tracks to form a plurality of damage tracks close to each other through control of the buret or pulse pattern or location. In some embodiments, the spacing between the adjacent damage tracks can be tailored to the desired perforation shape or perforation size on the glass or glass-ceramic substrate. For example, to create an elliptical micro-perforation shape, the laser can be programmed to create more adjacent damage tracks along a center line and less damage tracks above and below the center line. Upon etching in an acid solution this pattern will result in an elliptical shape as opposed to creating a circular micro-perforation shape with a single laser damage track.

[000124] In some embodiments, the laser can be programmed to strike the glass with multiple damage tracks on a particular section of the glass and also strike it to create less damage tracks on other sections. In some embodiments, the laser can be programmed to strike the glass substrate in the same location multiple times. Upon etching, this will result in a glass substrate or glass or glass-ceramics laminate with different micro-perforation sizes along the glass or glass-ceramics laminate, which allows for control of micro-perforation size or the largest dimension along the surface of the glass or glass-ceramics laminate.

[000125] Advantageously, in some embodiments, this particular method results in a high speed micro-perforation process. By using multiple laser pulses or bursts to create a plurality of damage tracks adjacent to one another, and followed by a chemical etching process to connect the damage tracks to form a larger perforation or opening, this process increases speed for creating such perforations/openings. In turn, the micro-perforations or openings may be applied in use for acoustic applications or other applications, for example, for decorative purposes.

[000126] Compared to a process in which a single laser pulse or burst is used to create a single preferential damage track for each micro-perforation, followed by the chemical etching to enlarge the perforations to the desired size or shape, a process utilizing multiple laser pulses or bursts to create adjacent damage tracks that merge into a single micro-perforation reduces the chemical etching time significantly, resulting in a process that is at least about 1.5 times greater than the speed of a single laser pulse method. Advantageously, the method employing multiple damage tracks per micro-perforation enhances the ease of manufacturing high aspect ratio micro-perforations in thick glass, achieving lower glass thickness reduction. In turn, these advantages reduce cost of manufacturing (in part to reduced etching time), and allow for high density micro-perforations to be formed relatively quickly, increasing manufacturing throughput of micro-perforated glass panels. The current cost driver for this process is the etching process, and utilizing a process that decreases etching time, hazardous waste, safety hazards, etc., is advantageous. Further, this process utilizing multiple damage tracks per micro-perforation results in decreased thickness reduction of the glass or glass- ceramics laminates during etching and therefore improves surface quality' through reduced roughness, waviness, or surface imperfections from the etching process. Additionally, the process results in reduced distortions and increased optical quality.

[000127] Further, utilizing several damage tracks per micro-perforation is particularly advantageous when micro-perforations of high aspect ratio need to be created (e.g., in perforated sound absorption glass using relatively thick glass, such as in architectural or automotive applications), because etching time is reduced significantly.

[000128] Additionally, utilizing several damage tracks per micro-perforation is particularly advantageous when it is necessary to create micro-perforations/openings of varying sizes and shapes on a single substrate. For example, micro-perforations may be formed in various shapes, as previously described. Different sizes, shapes, densities of perforations may be formed on a single substrate using a single process utilizing different numbers of laser- created damage tracks in various patterns, without the need for several separate drilling and etching steps. The cross-section of the perforations may also be controlled, for example, providing control over whether a cross section is generally circularly cylindrical or an “hour glass" shape. For example, in shapes 330 and 340 of FIG. 3 an angle of perforation may be used. The damage track does not need to be normal to the glass surface.

[000129] Finally, for the methods utilizing multiple damage tracks per micro-perforation, acceptable process tolerances may be greater for both the laser drilling and etching, reducing risk and improving yield, especially for large substrate sizes. This is due to the resulting multiple laser drilled openings rendering the etching process relatively less critical, in addition to the laser drilling process being rendered relatively less critical because individual opening quality will have less impact when several laser drilled micro-perforations are merged into one micro-perforation after etching.

[000130] in some embodiments, the removal of the polymer interlayer may be performed by laser drilling using a laser beam suitably adjusted to drill openings in polymer layers.

[000131] in some embodiments, the diameter of a plurality ⁷ of laser drilled openings in the polymer interlayer may be uniform or may be non-uniform. The diameter of the laser drilled openings in the polymer interlayer of the laminate may be about 20 um, about 50 urn, 100 urn, 150 um, 200 um, 250 urn, 300 um, 350 um, 400 um, 500 urn, 1000 urn, or any range having any of these two values as endpoints. In some embodiments the diameter of laser drilled openings in the polymer interlayer may he different from the diameter of openings in the glass or glass-ceramics layers to accommodate changes in the polymer opening diameter during lamination. For example, the diameter of the laser drilled opening in the polymer interlayer may be about 250 um, about 300 um, or about 340 um.

[000132] The openings can he intentionally designed to have uniform opening size through the entire laminate or intentionally designed to be different in the glass or glass-ceramic substrates and polymer interlayer or even different between different glass or glass-ceramic substrates. For instance, the openings in the first glass or glass-ceramic substrate can be the same as the opening in the polymer interlayer, but the opening in the second glass or glass- ceramic substrate can have a different opening size. Similarly, the openings in two glass or glass-ceramic substrates can be the same, but the polymer opening size can be different. Finally, each of the glass or glass-ceramic substrates and the polymer interlayer can have the same opening size.

[000133} FIG. 11 show sound absorption coefficients across a range of acoustic frequencies (Hz) tor laminate systems with cylindrical, hourglass and tapered micro-perforations through the laminate. The sound absorption coefficient is the ratio of the absorbed sound intensity to the incident sound intensity on a surface of the absorber. The targeted acoustic frequencies in the interior architectural spaces are linked to the speech frequencies which may lie in the range of 500-5000 Hz. In the figures, an absorption coefficient of "1" indicates complete absorption. It can be observed that the laminates with non-cylindrical micro-perforations through the layers of the glass or glass-ceramics laminate showed improved sound absorption over much of the relevant range. Without, wishing to be bound by theory, it is believed that increased friction through micro-perforation constriction in the shapes that are not cylindrical ornot substantially cylindrical provided performance benefits.

[000134} FIG. 12 demonstrates the constricted waist hourglass micro-perforation shape in the present embodiments using a fluorescent dye. Micro-perforated laminate samples exhibit through holes to the naked eye. In order to confirm that the holes are truly through holes, a fluorescent dye in oil was allowed to soak into a laminate. The dye was excited using a laser confbcal microscope and imaged in three dimensions. Only the areas with dye present exhibit fluorescence, which demonstrates that the holes are open and accessible to the liquid oil. Note the hourglass shape, with the waist narrower than the outer openings. A similar geometry- can be ob tained wi th single sheets of glass or glass ceramic.

[000135] Embodiments of the present disclosure are described in detail herein with reference to embodiments thereof as illustrated in the accompanying drawings, in which like reference numerals are used to indicate identical or functionally similar elements. References to "one embodiment," "an embodiment," "some embodiments," "in certain embodiments," etc., indicate that the embodiment described may include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.

[000136} Where a range of numerical values is recited herein, comprising upper and lower values, unless otherwise stated in specific circumstances, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the claims be limited to the specific values recited when defining a range. Further, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed . Finally, when the term "about" is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end- point referred to. Whether or not a numerical value or end-point of a range recites "about," the numerical value or end-point of a range is intended to include two embodiments: one modified by "about," and one not modified by "about."

[000.137} As used herein, the term "about" means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off ^" measurement error and the like, and other factors known to those of skill in the art.

[000.138} As used herein, "comprising" is an open-ended transitional phrase. A list of elements following the transitional phrase "comprising” is a non-exclusive list, such that elements in addition to those specifically recited in the list may also be present.

[000139} The term "or," as used herein, is inclusive; more specifically, the phrase "A or B" means "A, B, or both A and B." Exclusive "or" is designated herein by terms such as "either A or B" and "one of A or B," for example.

[000140] The indefinite articles "a" and "an" to describe an element or component means that one or at least one of these elements or components is present. Although these articles are conventionally employed to signify that the modified noun is a singular noun, as used herein the articles "a" and "an" also include the plural, unless otherwise stated in specific instances. Similarly, the definite article “the," as used herein, also signifies that the modified noun may be singular or plural, again unless otherwise stated in specific instances.

[000141J The term “wherein" is used as an open-ended transitional phrase, to introduce a recitation of a series of characteristics of the structure.

[000142] The examples are illustrative, but not limiting, of the present disclosure. Other sui table modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which would be apparent to those skilled in the art, are within the spirit, and scope of the disclosure.

[000143] While various embodiments have been described herein, they have been presented by way of example only, and not limitation. It should be apparent that adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. It therefore will be apparent to one skilled in the art that various changes in form and detail can be made to the embodiments disclosed herein without departing from the spirit and scope of the present disclosure. The elements of the embodiments presented herein are not necessarily mutually exclusive, but may be interchanged to meet various needs as would be appreciated by one of skill in the art.

[000.144] It is to be understood that the phraseology or terminology used herein is for the purpose of description and not of limitation. The breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents.