Glass-based articles having a hard coating and crack mitigation composite structure for maintaining article strength and scratch resistance

Abstract

An article comprising: a glass-based substrate comprising opposing major surfaces; a crack mitigating composite over one of the major surfaces, the composite comprising an inorganic component and a polymeric component; and a hard film disposed on the crack mitigating composite, the hard film comprising an elastic modulus greater than or equal to the elastic modulus of the glass-based substrate. The crack mitigating composite is characterized by an elastic modulus greater than about 30 GPa. Further, the hard film comprises at least one of: a metal-containing oxide, a metal-containing oxynitride, a metal-containing nitride, a metal-containing carbide, a silicon-containing polymer, carbon, a semiconductor, and combinations thereof.

Description

[0001] This invention patent application is a divisional application of the invention patent application with international application number PCT / US2018 / 023974, international application date March 23, 2018, application number 201880035192.6 entering the Chinese national phase, and invention name “Glass-based products with a hard film and crack mitigation composite structure for maintaining product strength and scratch resistance”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of priority under 35 U.S.C. §119 to U.S. Provisional Application Serial No. 62 / 477,708, filed on March 28, 2017, upon which this application is based and which is incorporated herein by reference in its entirety. Background Art

[0004] The present disclosure relates to articles having a glass-based substrate having a scratch-resistant film deposited on its surface and display device applications thereof.

[0005] Recently, articles comprising glass-based substrates (which may be strengthened or otherwise toughened, as described herein) have found widespread use as protective cover glasses for displays, particularly in touch screen applications, and have potential use in many other applications, such as automotive or architectural windows, glass for photovoltaic systems, and glass-based substrates used in other electronic device applications. Furthermore, these articles are often used in consumer electronic products to protect devices within the product, to provide user interfaces for input and / or display, and / or to provide numerous other functionalities. Such consumer electronic products include mobile devices such as smartphones, MP3 players, and tablet computers.

[0006] When these products are used in cover substrates and some household substrate applications, strong optical performance, in terms of maximum light transmittance and minimum reflectivity, is beneficial in many of these products. Furthermore, in cover substrate applications, it is desirable that the color displayed or perceived in reflection and / or transmission does not change significantly with changes in viewing angle (or incident illumination angle). In other words, if the color, reflection, or transmission changes to a perceptible degree with changes in viewing angle, users of products containing cover glass would perceive a change in the color or brightness of the display, which would degrade the perceived quality of the display. Of these changes, color changes are often the most noticeable and the most objectionable to users.

[0007] In many of these applications, it can be advantageous to apply the scratch resistant film to a glass-based substrate. The scratch resistant film may also include other functional films and / or layers disposed between the exterior scratch resistant film and the substrate. Thus, exemplary scratch resistant films may include one or more layers or one or more films of the following materials: indium tin oxide (ITO) or other transparent conductive oxides (e.g., aluminum or gallium doped zinc oxide and fluorine doped tin oxide), various types of hard coatings (e.g., diamond-like carbon, Al2O3, AlN, AlO x N y 、Si3N4、SiO x N y 、Si u Al x O y N z , TiN, TiC), IR or UV reflecting layers, conductive or semiconductive layers, electronic device layers, thin film transistor layers or antireflective (AR) films (e.g., SiO2, Nb2O5 and TiO2 layered structures). These scratch-resistant films, whether stand-alone or multi-layered, are expected to have high scratch resistance and are often hard and / or have a high elastic modulus, otherwise their other functional properties or the functional properties of the underlying substrate (e.g., mechanical properties, durability, conductivity and / or optical properties) will be compromised. In most cases, these scratch-resistant films are thin films, and therefore, their thickness is generally in the range of 0.005 μm to 10 μm (e.g., 5 nm to 10,000 nm).

[0008] When a scratch-resistant film is applied to the surface of a glass-based substrate (which may be strengthened or characterized as tough), the average flexural strength of the glass-based substrate may be reduced, for example, when evaluated using a ring-on-ring strength test. The property is not affected by temperature (i.e., the property is not due to any heating that results in significant or measurable surface compressive stresses in the strengthened glass-based substrate). The reduction in average flexural strength is also apparently unaffected by any damage or corrosion to the glass surface during processing and is apparently an inherent mechanical property of the article, even when a scratch-resistant film having a thickness of about 5 nm to about 10 μm is applied to the article. Without being bound by theory, it is believed that this reduction in average flexural strength is related to the adhesion of the scratch-resistant film to the strengthened or toughened glass-based substrate, the high average flexural strength (or high average strain at break) of the selected strengthened or toughened glass-based substrate relative to the selected scratch-resistant film, and crack bridging between the film and the glass-based substrate.

[0009] When these articles employing glass-based substrates are used in certain electronic device applications, for example, they may undergo additional high-temperature processing during manufacturing. More specifically, the articles may undergo additional high-temperature processing after the scratch-resistant film is deposited on the glass-based substrate. These additional high-temperature treatments are often required to develop additional structures and features on the substrate and / or film of the article for specific applications. Furthermore, the scratch-resistant film itself may be deposited on the substrate at relatively high temperatures.

[0010] In light of these new insights, there is a need to prevent the scratch-resistant film from reducing the average flexural strength of the glass-based substrate in these articles. There is also a need to ensure that the average flexural strength of the glass-based substrate is substantially maintained even after heat treatment, as applied during additional, application-specific heat treatments during the scratch-resistant film deposition process. Furthermore, there is a need to preserve the scratch resistance and optical properties of both the substrate and the scratch-resistant film, given additional design, construction, and / or processing of the interface between the substrate and the scratch-resistant film. That is, when introducing additional interface features designed to preserve article strength, such as those required for a specific application, there is a need to preserve or otherwise balance the scratch resistance and optical properties of the article. Summary of the Invention

[0011] A first aspect of the present disclosure relates to an article comprising: a glass-based substrate comprising opposing major surfaces; a crack mitigation composite over one of the major surfaces, the composite comprising an inorganic component and a polymeric component; and a hard film disposed on the crack mitigation composite, the film comprising an elastic modulus greater than or equal to the elastic modulus of the glass-based substrate. The crack mitigation composite is characterized by an elastic modulus greater than about 30 GPa. Further, the hard film comprises at least one of the following: a metal-containing oxide, a metal-containing oxynitride, a metal-containing nitride, a metal-containing carbide, a silicon-containing polymer, carbon, a semiconductor, and combinations thereof.

[0012] According to a second aspect, there is provided an article as described in aspect 1, wherein the article is characterized in that: when measured by a ring-on-ring (ROR) test, using an average of five (5) or more samples, the average flexural strength of the article is greater than or equal to about 50% of the average flexural strength of the substrate.

[0013] According to a third aspect, there is provided an article as described in aspect 1 or aspect 2, wherein the hard film is further characterized by an indentation hardness greater than or equal to about 8 GPa.

[0014] According to a fourth aspect, there is provided an article as described in any one of aspects 1-3, wherein the inorganic component comprises an oxide, a nitride, or an oxynitride, and the polymeric component comprises at least one of a polyimide, a polycarbonate, a polyurethane, a polyester, and a fluorinated polymer.

[0015] According to a fifth aspect, there is provided an article as described in any one of aspects 1-4, wherein the article is further characterized in that: the light transmittance in the visible spectrum from about 400 nm to about 800 nm is greater than or equal to 50%.

[0016] According to a sixth aspect, there is provided an article as described in any one of aspects 1 to 5, wherein the article is further characterized in that: the pencil hardness is 9H or greater.

[0017] According to a seventh aspect, there is provided an article as described in any one of aspects 1-6, wherein the article is further characterized in that: when the hard film is subjected to a Berkovich Ramped Scratch Test, a delamination threshold is 150 mN or greater.

[0018] According to an eighth aspect, there is provided an article as described in any one of aspects 1-7, wherein the hardcoat comprises a multi-layer antireflective coating, and further wherein the crack mitigating composite and the hardcoat together comprise an average single-sided illumination reflectance of less than about 2%.

[0019] A ninth aspect of the present disclosure relates to an article comprising: a glass-based substrate comprising opposing major surfaces; a crack mitigation composite over one of the major surfaces, the composite comprising an inorganic component and a polymeric component; and a hard film disposed on the crack mitigation composite, the film comprising an elastic modulus greater than or equal to the elastic modulus of the glass-based substrate. The crack mitigation composite is characterized in that the ratio of the elastic moduli between the inorganic component and the polymeric component is greater than 10:1. Further, the hard film comprises at least one of the following: a metal-containing oxide, a metal-containing oxynitride, a metal-containing nitride, a metal-containing carbide, a silicon-containing polymer, carbon, a semiconductor, and combinations thereof.

[0020] According to aspect 10, there is provided an article as described in aspect 9, wherein the article is characterized in that: when measured by a ring-on-ring (ROR) test using an average of five (5) or more samples, the average flexural strength of the article is greater than or equal to about 50% of the average flexural strength of the substrate.

[0021] According to an eleventh aspect, there is provided the article of aspect 9 or aspect 10, wherein the hard film is further characterized by an indentation hardness greater than or equal to about 8 GPa.

[0022] According to a twelfth aspect, there is provided an article as described in any one of aspects 9-11, wherein the inorganic component comprises an oxide, a nitride, or an oxynitride, and the polymeric component comprises at least one of a polyimide, a polycarbonate, a polyurethane, a polyester, and a fluorinated polymer.

[0023] According to a 13th aspect, there is provided the article of any one of aspects 9-12, wherein the article is further characterized in that: the light transmittance in the visible spectrum from about 400 nm to about 800 nm is greater than or equal to 50%.

[0024] According to a 14th aspect, there is provided the article of any one of aspects 9-13, wherein the article is further characterized by a pencil hardness of 9H or higher.

[0025] According to a fifteenth aspect, there is provided an article as described in any one of aspects 9-14, wherein the article is further characterized in that: when the hard film is subjected to a Brinell ramp load scratch test, a delamination threshold is 150 mN or greater.

[0026] According to a 16th aspect, there is provided an article as described in any of aspects 9-15, wherein the hardcoat comprises a multi-layer antireflective coating, and further wherein the crack mitigating composite and the hardcoat together comprise an average single-sided illumination reflectance of less than about 2%.

[0027] A seventeenth aspect of the present disclosure relates to an article comprising: a glass-based substrate comprising opposing major surfaces; a crack mitigation composite over one of the major surfaces, the composite comprising an inorganic component and a polymeric component; and a hard film disposed on the crack mitigation composite, the film comprising an elastic modulus greater than or equal to the elastic modulus of the glass-based substrate. The inorganic layer comprises an oxide, a nitride, or an oxynitride, and the polymeric layer comprises at least one of a polyimide, a polycarbonate, a polyurethane, a polyester, and a fluorinated polymer. Further, the hard film comprises at least one of a metal-containing oxide, a metal-containing oxynitride, a metal-containing nitride, a metal-containing carbide, a silicon-containing polymer, carbon, a semiconductor, and combinations thereof.

[0028] According to aspect 18, there is provided an article as described in aspect 17, wherein the article is characterized in that: when measured by ROR testing, using an average of five (5) or more samples, the average flexural strength of the article is greater than or equal to about 50% of the average flexural strength of the substrate.

[0029] According to a 19th aspect, there is provided the article of aspect 17 or aspect 18, wherein the hard film is further characterized by an indentation hardness greater than or equal to about 8 GPa.

[0030] According to a twentieth aspect, there is provided the article of any one of aspects 17-19, wherein at least one polymeric layer is a polyimide comprising PMDA-ODA, ODPA-ODA, BPDA-ODA, or a fluorinated polyimide.

[0031] According to the 21st aspect, there is provided an article as described in any one of aspects 17-20, wherein at least one inorganic layer comprises: SiO2, Al2O3, ZrO2, CaO, CaCO3, SnO, ZnO, SiN x 、AlN x 、AlO x N y 、Si u Al v O x N y or SiO x N y .

[0032] According to a twenty-second aspect, there is provided the article of any one of aspects 17-21, wherein the article is further characterized in that: in the visible spectrum from about 400 nm to about 800 nm, the light transmittance is greater than or equal to 50%.

[0033] According to a twenty-third aspect, there is provided the article of any one of aspects 17-22, wherein the article is further characterized by a pencil hardness of 9H or greater.

[0034] According to a twenty-fourth aspect, there is provided the article of any one of aspects 17-23, wherein the article is further characterized in that when the film is subjected to a Brinell ramp load scratch test, a delamination threshold is 150 mN or greater.

[0035] According to aspect 25, there is provided an article as described in any of aspects 17-24, wherein the crack mitigation composite comprises two or more inorganic layers and at least one polymeric layer, wherein one of the two or more inorganic layers is in contact with the substrate and another of the two or more inorganic layers is in contact with the hardcoat.

[0036] According to aspect 26, an article as described in any of aspects 17-25 is provided, wherein each of the at least one inorganic layer comprises an inorganic layer thickness, and each of the at least one polymeric layer comprises a polymeric layer thickness, and further, wherein the ratio of the polymeric layer thickness to the inorganic layer thickness is about 0.1:1 to about 5:1.

[0037] According to aspect 27, there is provided an article as described in any of aspects 17-26, wherein the hardcoat comprises a multi-layer antireflective coating, and further wherein the crack mitigating composite and the hardcoat together comprise an average single-sided illumination reflectance of less than about 2%.

[0038] According to a 28th aspect of the present disclosure, a consumer electronic product is provided, comprising: a housing having a front surface, a rear surface, and side surfaces; electronic components at least partially located within the housing, the electronic components including at least a controller, a memory, and a display, the display being located at or adjacent to the front surface of the housing; and a cover glass disposed above the display. Furthermore, at least one of a portion of the housing or the cover glass comprises the article of any one of aspects 1-27.

[0039] According to the 29th aspect of the present disclosure, there is provided an article as described in any one of aspects 1-27, wherein during a cube corner indentation test, when the hard film is subjected to indentation from a diamond indenter at a load level of 250 mN, the length of any cracked, damaged, or delaminated area associated with at least one of the hard film and the crack mitigating composite is less than 15 microns. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1A is a schematic diagram of an article comprising a glass-based substrate, a hardcoat, and a crack mitigation composite according to one or more embodiments.

[0041] Figure 1B is a schematic diagram of an article comprising a glass-based substrate, a hardcoat, and a crack mitigating composite comprising a polymeric layer and two inorganic layers, according to one or more embodiments.

[0042] Figure 1C is a schematic diagram of an article comprising a glass-based substrate, a hardcoat, and a crack mitigating composite comprising three inorganic layers and two polymeric layers, according to one or more embodiments.

[0043] Figure 2 Schematic diagram of crack development in a film or layer and its possible bridging modes.

[0044] Figure 3 Schematic diagram of a theoretical model of cracks in a film or layer and their possible bridging paths.

[0045] Figure 4 This is an example of the energy release ratio G d / G p Picture.

[0046] Figure 5A is a schematic diagram of cohesive failure in a crack mitigation composite between a hardcoat and a glass-based substrate, according to some embodiments of the present disclosure.

[0047] Figure 6Ais a graph of the elastic modulus of a crack mitigating composite disposed on a glass-based substrate as a function of the ratio of the thickness of the polymer layer in the composite to the thickness of the entire crack mitigating composite, as measured by nanoindentation, according to some embodiments of the present disclosure.

[0048] Figure 6B is a graph showing the hardness of a crack mitigating composite disposed on a glass-based substrate as a function of the ratio of the thickness of the polymer layer in the composite to the thickness of the entire crack mitigating composite, as measured by nanoindentation, according to some embodiments of the present disclosure.

[0049] Figure 7 is a scanning electron microscope (SEM) image from a cross section of an article comprising a glass-based substrate, a hardcoat, and a crack mitigating composite comprising two inorganic layers and two polymeric layers, according to some embodiments of the present disclosure.

[0050] Figure 8 is a graph showing the ring-on-ring load failure performance of the following objects, according to aspects of the present disclosure, the objects being a glass-based substrate control (Example 1C); articles comprising glass-based substrates (1 mm and 0.7 mm thick) with a silicon nitride hard film (440 μm thick) (Examples 1A and 1A1, respectively); and articles comprising glass-based substrates (1 mm and 0.7 mm thick) with a silicon nitride hard film (440 μm) and a five-layer crack mitigation composite (Examples 1B and 1B1, respectively).

[0051] Figures 9A-9D are optical micrographs from respective articles comprising a glass-based substrate having a hardcoat comprising a silicon nitride layer and a fluorosilane layer, and respective articles having no crack mitigating composite ( Figure 9A ), having a crack mitigation composite comprising three thick aluminum oxide layers and two thin polyimide layers ( Figure 9B ), and a crack mitigation composite comprising three thin aluminum oxide layers and two thick polyimide layers ( Figure 9C ), or having a crack mitigating composite comprising polyimide ( Figure 9D ).

[0052] Figure 10 is a graph showing optical transmittance data as a function of wavelength in the visible spectrum for articles including a glass-based substrate and a silicon nitride hardcoat, according to some embodiments of the present disclosure, and wherein the articles have no crack mitigating composite (Example 2C), have a crack mitigating composite including polyimide (Examples 2B1, 2B2), and have a crack mitigating composite including aluminum oxide and polyimide layers (Example 2A).

[0053] Figure 11Aand 11B is an atomic force microscope (AFM) image of an article comprising a glass-based substrate, a silicon nitride hard film, and a crack mitigation composite comprising aluminum oxide and a polyimide layer according to some embodiments of the present disclosure ( Figure 11A ), and atomic force microscopy (AFM) images of articles comprising a glass-based substrate, a silicon nitride hard film, and no crack mitigation composite ( Figure 11B ).

[0054] Figure 12A are optical microscope images from an article comprising a glass-based substrate, a silicon nitride hard film, and a barium fluoride crack mitigating composite when subjected to a Brinell ramp load scratch test (0 to 150 mN).

[0055] Figure 12B is an optical microscope image of an article from an embodiment of the present disclosure comprising a glass-based substrate, a silicon nitride hard film, and a crack mitigation composite comprising aluminum oxide and polyimide layers when subjected to a Brinell ramp load scratch test (0 to 150 mN).

[0056] Figure 13A and 13B According to an embodiment of the present disclosure, there are provided a plurality of crack mitigation composites having five layers of Al2O3 / polyimide and SiO2 / AlO x N y Optical data were modeled for dual surface transmittance (ie, encompassing both sides of the coated laminate) and first surface reflectance (ie, considering only the coated side of the laminate) generated on the laminate of the scratch resistant film.

[0057] Figure 14A and 14B According to an embodiment of the present disclosure, there is provided a structure having five layers of Al2O3 / polyimide crack mitigation composite and SiO2 / AlO x N y The color of the dual surface transmission and the color of the first surface reflection formed on the scratch-resistant film laminate are modeled optical data.

[0058] Figure 15 According to an embodiment of the present disclosure, there is provided a method for fabricating a crack mitigation composite having five layers of Al2O3 / polyimide crack mitigation composite and SiO2 / AlO x N y Modeled optical data of the light reflectance of the first surface formed on the scratch-resistant film laminate. DETAILED DESCRIPTION

[0059] In the following detailed description, in order to provide a thorough understanding of the embodiments of the present disclosure, many specific details may be set forth. However, it will be apparent to those skilled in the art that the embodiments of the present disclosure may be practiced without some or all of these specific details. In other cases, well-known features or processes may not be described in detail to avoid unnecessarily obscuring the present invention. In addition, similar or identical figure numbers may be used to identify identical or similar elements.

[0060] As used herein, the term "about" refers to amounts, dimensions, formulas, parameters, and other quantities and features that are not exact and need not be exact, but may be approximate and / or larger or smaller as required, such as reflective tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. When the term "about" is used to describe a value or endpoint of a range, it should be understood that the disclosure includes the specific value or endpoint referenced. Regardless of whether the numerical value or endpoint of a range in the specification is listed using "about," the numerical value or endpoint of the range is intended to include two embodiments: one modified with "about" and the other not modified with "about." It should also be understood that the endpoint of each range is important both in relation to and independently of the other endpoint.

[0061] As used herein, the terms "substantially," "substantially," and variations thereof are intended to mean that the characteristic being described is equal to or approximately equal to a value or description (except when used with respect to "substantially no delamination," which is defined elsewhere). For example, "substantially flat surface" is intended to mean a flat or approximately flat surface. Furthermore, as defined above, "substantially similar" is intended to mean that two values ​​are equal or approximately equal. In some embodiments, "substantially similar" can mean values ​​that are within about 10% of each other, such as within about 5% of each other, or within about 2% of each other.

[0062] Directional terms used herein, such as up, down, right, left, front, back, top, and bottom, are only used with reference to the drawings and are not intended to indicate absolute orientations.

[0063] As used herein, the articles "the," "a," or "an" mean "at least one" and should not be limited to "only one" unless expressly specified to the contrary. Thus, for example, reference to "a component" includes embodiments having two or more such components unless the context clearly indicates otherwise.

[0064] As used herein, the term "glass-based" is meant to include any material made at least in part of glass (including glass and glass ceramics) and sapphire. "Glass ceramics" include materials produced by controlled crystallization of glass. In an embodiment, the glass ceramic has a crystallinity of about 1% to about 99%. Non-limiting examples of glass ceramic systems that can be used include: Li2O×Al2O3×nSiO2 (i.e., LAS system), MgO×Al2O3×nSiO2 (i.e., MAS system) and ZnO×Al2O3×nSiO2 (i.e., ZAS system).

[0065] refer to Figure 1A Aspects of the present disclosure include a laminated article 100a having a total stack thickness of 10a. Article 100a also includes a hardcoat 110 having a thickness of 11, a glass-based substrate 120 having a thickness of 12, and a crack mitigation composite 130a having a thickness of 13a, the crack mitigation composite 130a comprising an inorganic element 33 and a polymeric element 35. In these aspects, crack mitigation composite 130a includes inorganic element 33 and polymeric element 35, one or both of which are in the form of one or more layers, films, or other structures (e.g., particles, fibers, and / or whiskers). Further, crack mitigation composite 130a (including its inorganic element 33 and polymeric element 35) is characterized by an elastic modulus greater than 30 GPa. For example, the crack mitigating composite 130a can be characterized by an elastic modulus of 30.5 GPa, 31 GPa, 32 GPa, 33 GPa, 34 GPa, 35 GPa, 40 GPa, 45 GPa, 50 GPa, etc., including all elastic modulus values ​​between these levels, contemplated to be up to 80 GPa, and in some cases even approaching 120 GPa.

[0066] According to some embodiments of laminate 100a, crack mitigation composite 130a includes inorganic component 33 and polymeric component 35, with greater than about 20% by volume of material associated with inorganic component 33 and greater than about 0.5% by volume or more of material associated with polymeric component 35. For example, the amount of material associated with inorganic component 35 can be greater than about 20% by volume, 30% by volume, 40% by volume, 50% by volume, 60% by volume, and any amount between these volume levels. Preferably, polymeric component 35 comprises a polymeric material having C-C, C-N, C-O, and / or C=C bonds as polymer chain-forming bonds. Further, in some embodiments, crack mitigation composite 130a can have a composite crack initiation strain (COS) value greater than about 0.8%, greater than 1%, greater than about 1.5%, and any COS values ​​between or above these levels.

[0067] The COS on the glass substrate is measured in a ring-on-ring setup connected to a camera system. More specifically, to determine the fracture strain of the coated article 100, a force is applied downward to the top ring 304 and / or upward to the bottom ring in a ring-on-ring mechanical testing setup. The article 100 is positioned between a bottom ring and a top ring according to the ring-on-ring tensile testing procedure. The top and bottom rings have different diameters. As used herein, the diameter of the top ring is 12.7 mm, and the diameter of the bottom ring is 25.4 mm. The cross-section of the portions of the top and bottom rings contacting the article is circular, each with a radius of 1.6 mm. The top and bottom rings are made of steel. Testing is conducted in an environment of approximately 22°C and a relative humidity of 45%-55%. The article used for testing is a 50 mm x 50 mm square. The force on the top and / or bottom rings is increased to strain the article 100 until catastrophic failure of one or both of the substrate and any optical coatings occurs. Light and a camera are provided below the bottom ring to record catastrophic failure during testing. An electronic controller, such as a Dewetron acquisition system, is provided to coordinate the camera image with the applied load to determine the load at which the camera observes the destructive image. To determine the fracture strain, the camera image is synchronized with the load signal by the Dewetron system, so that the load at which the coating and / or its material exhibits failure can be determined. Finite element analysis is then used to analyze the strain level of the sample when it is subjected to the load. The element size can be selected to be fine enough to represent the stress concentration under the load loop. The strain level is averaged over 30 or more nodes under the load loop. In addition, a test technique for determining load failure can be found in "Dynamic fracturing of strengthened glass under biaxial tensile loading by Hu, G. et al. Journal of Non-Crystalline Solids, 2014. 405(0): pp. 153-158".

[0068] Furthermore, in some embodiments of the laminate 100a, the crack mitigating composite 103a can be characterized by an elastic modulus ratio between the inorganic component 33 and the polymeric component 35 that is greater than 10:1 (e.g., an inorganic component 33 having an elastic modulus of 150 GPa and a polymeric component having an elastic modulus of 10 GPa would result in an elastic modulus ratio of 15:1). For example, the crack mitigating composite 130a can have an elastic modulus ratio of 11:1, 12:1, 13:1, 14:1, 15:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and all elastic modulus ratios between or above these ratios. According to some embodiments, for certain very low elastic modulus (e.g., <1 GPa) polymeric components 35 included in the crack mitigating composite 130a along with relatively high elastic modulus (e.g., >75 GPa) inorganic components 33, the practical elastic modulus ratio limit of the crack mitigating composite 130a is about 500:1.

[0069] Furthermore, the hard film 110 of the laminated product 100a comprises at least one of the following: a metal-containing oxide, a metal-containing oxynitride, a metal-containing nitride, a metal-containing carbide, a silicon-containing polymer, carbon, a semiconductor, and combinations thereof. In some embodiments of the laminated product 100a, the hard film 110 comprises silicon nitride or silicon dioxide. In certain aspects, the hard film 110 may also be characterized by an indentation hardness greater than or equal to approximately 8 GPa. In other embodiments, the hard film 110 may be characterized by an indentation hardness greater than or equal to approximately 12 GPa. Thus, the hard film 110 may be characterized by an indentation hardness of 8 GPa, 9 GPa, 10 GPa, 11 GPa, 12 GPa, 13 GPa, 14 GPa, 15 GPa, 20 GPa, 25 GPa, 30 GPa, and all indentation hardness values ​​between or above these levels. According to some embodiments, the practical limit of the indentation hardness of the hard film 110 is approximately 50 GPa.

[0070] In the article 100a, the interfacial properties at the effective interface 140 between the hard film 110 and the crack mitigating composite 130a, or between the crack mitigating composite 130a and the substrate 120, are modified, typically by the crack mitigating composite 130a, such that the article 100a substantially retains its average flexural strength and the film 110 retains the functional properties for its application, particularly scratch resistance. For example, in some embodiments of the laminated article 100a, the article is characterized by an average flexural strength that is greater than or equal to about 50% of the average flexural strength of a glass substrate (i.e., a glass substrate tested without the crack mitigating composite 130a and hard film 110 structure disposed thereon). In other embodiments, the flexural strength of the article 100a comprising the crack mitigating composite 130a can be characterized by comparison with a similar article comprising the same hard film 110 and the same substrate 120, but without the crack mitigating composite structure. In these embodiments, the average or characteristic flexural strength of the article 100a including the crack mitigating composite 130a may be 25% greater, or 50% greater than the same article without the crack mitigating composite (ie, a comparative article having the hardcoat 110 deposited directly over the substrate 120).

[0071] Now refer to Figure 1B , aspects of the present disclosure include a laminated article 100b having a total stack thickness of 10b. Article 100b also includes a hardcoat 110, a glass-based substrate 120, and a crack mitigation composite 130b having a total thickness of 13b and comprising an inorganic element 33 and a polymeric element 35. Laminated article 100b is similar to laminate 100a; therefore, like reference numerals have the same or similar structure and function (e.g., hardcoat 110). Further, as Figure 1B As shown, the crack mitigation composite 130b may include one or more layers of inorganic elements 33 and one or more layers of polymeric elements 35. Figure 1B As shown in the exemplary form of FIG, the laminate 100b has: an inorganic element 33 having two layers and a polymer element 35 interposed between the two layers of inorganic elements 33. Figure 1B As shown, one of the layers of the inorganic element 33 is in contact with the glass-based substrate 120, and another layer of the inorganic element 33 is in contact with the hard film 110. Figure 1B As shown, each layer of inorganic element 33 has a thickness 63, and each layer of polymeric element 35 has a thickness 65. Furthermore, the thickness of each layer may be the same as the other layers, or may be different from the other layers.

[0072] Furthermore, the crack mitigating composite 130b (including the inorganic element 33 and the polymer element 35 in the form of its layers) is characterized by an elastic modulus greater than 30 GPa. For example, the crack mitigating composite 130b may be characterized by an elastic modulus of 30.5 GPa, 31 GPa, 32 GPa, 33 GPa, 34 GPa, 35 GPa, 40 GPa, 45 GPa, 50 GPa, etc., including all elastic modulus values ​​between these levels, and contemplatedly up to 80 GPa, and in some cases even approaching 120 GPa. As described herein, the "elastic modulus" or "average elastic modulus" of the crack mitigating composite 130b (including the inorganic element 33 and the polymer element 35 in the form of its layers) is calculated by obtaining a measured value for each layer of the inorganic element 33 and the polymer element 35 based on a single film having a thickness of approximately 100 nm to 1000 nm, and then calculating the bulk average elastic modulus of the crack mitigating composite 130b. Furthermore, the volume average elastic modulus may be calculated as understood by one of ordinary skill in the art of the present disclosure, for example, given an estimate of the volume or actual volume measurement of the various layers of the inorganic element 33 and the polymeric element 35. Furthermore, the modulus of the crack mitigating composite (which may include various layers) may be an effective or empirical modulus measured directly on the composite using known nanoindentation methods that sample the volume of the composite structure, which averages the moduli of the organic and inorganic layer components.

[0073] According to some embodiments of laminate 100a, crack mitigation composite 130b includes an inorganic component 33 comprising one or more layers and a polymeric component 35 comprising one or more layers, with greater than approximately 20% by volume of material associated with inorganic component 33 and greater than approximately 0.5% by volume or more of material associated with polymeric component 35. For example, the amount of material associated with inorganic component 35 may be greater than approximately 20% by volume, 30% by volume, 40% by volume, 50% by volume, 60% by volume, and any amount in between. Preferably, polymeric component 35 comprises a polymeric material having C-C, C-N, C-O, and / or C=C bonds as bonds forming the polymeric chain. Further, in some embodiments, crack mitigation composite 130b may have a composite crack initiation strain (COS) value greater than approximately 0.8%, greater than 1%, greater than approximately 1.5%, and any COS values ​​in between or above these levels.

[0074] Furthermore, in some embodiments of the laminate 100b, the crack mitigating composite 103b can be characterized by an elastic modulus ratio between the inorganic component 33 and the polymeric component 35 (i.e., including their respective layers) that is greater than 10:1 (e.g., an inorganic component 33 having two layers, each with an elastic modulus of 150 GPa, and a polymeric component having one layer with an elastic modulus of 10 GPa would result in an elastic modulus ratio of 15:1). For example, the crack mitigating composite 130b can have an elastic modulus ratio of 11:1, 12:1, 13:1, 14:1, 15:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and all elastic modulus ratios between or above these ratios. According to some embodiments, for certain very low elastic modulus (e.g., <1 GPa) polymeric components 35 included in the crack mitigating composite 130b along with relatively high elastic modulus (e.g., >75 GPa) inorganic components 33, the practical elastic modulus ratio limit of the crack mitigating composite 130b is about 500:1.

[0075] Reference again Figure 1B , the crack mitigation composite 130b of the laminate 100b includes an inorganic element 33 having one or more layers having a thickness 63. In some aspects, the thickness 63 of each layer of the inorganic element 33 can be in the range of about 1 nm to about 200 nm, preferably about 5 nm to about 150 nm. Further, in some aspects, the thickness 65 of each layer of the polymeric element 35 can be in the range of about 1 nm to about 500 nm, preferably about 5 nm to about 300 nm. According to another embodiment, the total thickness 13b of the crack mitigation composite 130b can be in the range of about 10 nm to about 1000 nm. In a preferred aspect, the total thickness 13b of the crack mitigation composite 130b can be in the range of about 50 nm to about 750 nm.

[0076] In some embodiments, the laminate 100b may include a crack mitigating composite 130b that is controlled by the thickness ratio of its inorganic component 33 and polymeric component 35 layers. For example, the ratio between the total thickness of the polymeric component 35 (i.e., the sum of the thickness 65 values ​​of each layer therein) and the total thickness of the inorganic component 33 (i.e., the sum of the thickness 63 values ​​of each layer therein) may be from about 0.1:1 to about 5:1. In other embodiments, the thickness ratio may be from about 0.2:1 to about 3:1. As further understood herein, embodiments of the laminate 100b and crack mitigating composite 130b controlled by the thickness ratio are configured such that the thickness ratio is calculated independent of any additional layers of the crack mitigating composite 130b added to one or both of the hardcoat 110 and / or the glass-based substrate 120. As described herein, such layers are referred to as "tie layers," which are typically thinner by half to one (or more) orders of magnitude than the other layers in the inorganic component 33 and polymeric component 35.

[0077] In the article 100b, the interfacial properties at the effective interface 140 between the hard film 110 and the crack mitigating composite 130b, or between the crack mitigating composite 130b and the substrate 120, are modified, typically by the crack mitigating composite 130b, such that the article 100b substantially retains its average flexural strength and the film 110 retains the functional properties for its application, particularly scratch resistance. For example, in some embodiments of the laminated article 100b, the article is characterized by an average flexural strength that is greater than or equal to about 70% of the average flexural strength of a glass substrate (i.e., a glass substrate tested without the crack mitigating composite 130b and the hard film 110 structure disposed thereon).

[0078] As understood in this disclosure, the terms "hard film," "scratch-resistant film," and "hard film 110" may refer to one or more films, layers, structures, and combinations thereof. Furthermore, in some embodiments, the hard film 110 may include additional functional films, including but not limited to anti-fingerprint coatings, anti-fouling coatings, easy-to-clean coatings, coatings with low surface energy, and fluorosilane-based coatings. It should also be understood that for a "film" comprising more than one film, layer, structure, etc., the refractive index associated with the "film" is the total or combined refractive index of the individual films, layers, structures, etc., comprising the "film."

[0079] Now refer to Figure 1C, aspects of the present disclosure include a laminated article 100c having a total stack thickness of 10c. Article 100c also includes a hardcoat 110, a glass-based substrate 120, and a crack mitigation composite 130c having a total thickness of 13c and comprising an inorganic element 33 and a polymeric element 35. Laminated article 100c is similar to laminate 100b; therefore, like reference numerals have the same or similar structure and function (e.g., hardcoat 110). Further, as Figure 1C As shown, the crack mitigation composite 130c of the laminate 100c is shown in an exemplary preferred form. Specifically, the crack mitigation composite 130c includes an inorganic component 33 in the form of three layers, which preferably contains Al2O3; and a polymer component 35 in the form of two layers, which preferably contains polyimide. Figure 1C As shown, one of the layers of the inorganic element 33 is in contact with the glass-based substrate 120, and another layer of the inorganic element 33 is in contact with the hard film 110. Figure 1C As shown, each layer of inorganic element 33 has a thickness 62 , which is preferably from about 1 nm to about 200 nm, and each layer of polymeric element 35 has a thickness 65 , which is preferably from about 1 nm to about 500 nm.

[0080] Reference again Figures 1A-1C Aspects of the present disclosure include laminated articles 100a, 100b, 100c comprising a glass-based substrate 120 and a crack mitigating composite 130a, 130b, 130c. In the articles 100a, 100b, 100c, the interfacial properties at an effective interface 140 between the crack mitigating composite 130a, 130b, 130c and the substrate 120 are modified such that the articles 100a, 100b, 100c substantially retain their average flexural strength. In other embodiments, the interfacial properties at the effective interface 140 between the crack mitigating composite 130a, 130b, 130c and the substrate 120 are modified such that the articles 100a, 100b, 100c substantially retain 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 95% or more of their average flexural strength. In other embodiments, the interfacial properties at the effective interface 140 are modified such that the article 100a , 100b , 100c substantially retains its scratch resistance, particularly the scratch resistance associated with the hardcoat 110 .

[0081] In one or more embodiments, the laminated articles 100a, 100b, 100c exhibit functional properties, such as scratch resistance, retained after the interface modification. The functional properties of the hard film 100 and / or articles 100a, 100b, 100c may include optical, electrical, and / or mechanical properties, such as hardness, elastic modulus, fracture strain, wear resistance, scratch resistance, mechanical durability, coefficient of friction, electrical conductivity, resistivity, electron mobility, electron or hole carrier doping, optical refractive index, density, opacity, transparency, reflectivity, absorptivity, transmittance, and the like.

[0082] In one or more embodiments, the refractive index can be measured using a Model 1512-RT analyzer provided by n&k Technology, Inc., located in San Jose, California, or by spectroscopic ellipsometry as is known in the art. The elastic modulus can be measured by nanoindentation using methods known in the art according to one skilled in the art in light of the present disclosure. In certain embodiments, the optical properties of the articles 100a, 100b, 100c are preserved independent of the properties and / or processing of the crack mitigating composites 130a, 130b, 130c. In certain aspects, the optical transmittance of the glass-based substrate 120 and the crack mitigating composites 130a, 130b, 130c can differ from the optical transmittance of the substrate 120 by 1% or less (e.g., optical transmittance from wavelengths of 400 nm to 800 nm). In other aspects, the optical properties of the laminated articles 100a, 100b, 100c can be characterized by a light transmission greater than or equal to 50% in the visible spectrum from about 400 nm to about 800 nm or from about 450 nm to about 650 nm. In other aspects, the optical properties of the laminated articles 100a, 100b, 100c can be characterized by a light transmission greater than or equal to 20%, 50%, or 80% in the visible spectrum. As described herein, these functional properties of the articles 100a, 100b, 100c can be retained after combination with the crack mitigating composite 130a, 130b, 130c and before any separation of the crack mitigating composite 130a, 130b, 130c from the glass-based substrate 120.

[0083] The advantageous properties of the articles 100a-100c can also be characterized by cube corner indentation testing. Specifically, the cube corner indentation test uses a diamond indenter tip shaped like the corner of a cube, which is pushed down into the surface of the film, structure, or other feature to be measured. For the articles 100a-c of the present disclosure, it is beneficial to quantify the delamination and cracking thresholds, which are related to the scratch performance of the articles in real-world applications. These properties can be quantified by the severity and / or area of ​​the damaged surface after loading and unloading by the cube corner indenter during the cube corner indentation test. These properties related to scratch resistance can also be quantified by monitoring the load versus displacement curve during the loading phase of the cube corner indentation test for discontinuous jumps, which are indicative of crack initiation points under certain loading conditions. Both methods can be used to quantify the thresholds for cracking or delamination events. For example, in embodiments of articles 100a-c, after cube corner indentation, cracked, delaminated, and / or chipped regions (i.e., associated with the hard film and / or crack mitigation composite) may be less than 15 microns in length from the center of the indentation at a load level of 250 mN and less than 30 microns in length from the center of the indentation at a load level of 400 mN. Furthermore, during cube corner indentation testing, discontinuities in the load versus displacement curve obtained from the cube corner indentation test may occur during loading with the indenter at loads greater than 200 mN (no significant discontinuities were observed at loads less than 200 mN).

[0084] In one or more embodiments, the laminates 100a, 100b, 100c comprising the crack mitigating composite 130a, 130b, 130c and the hard film 110 can exhibit substantially preserved scratch resistance as judged relative to the scratch resistance of an identical film 110 disposed directly on a glass-based substrate 120 but without a comparable crack mitigating composite. For example, when the laminates 100a, 100b, 100c are subjected to a Brinell ramp load test and the scratch load on each sample is increased from 0 mN up to 150 mN as the stylus moves from left to right (or vice versa), the laminates 100a, 100b, 100c can exhibit no signs of delamination. Specifically, in a Brinell ramp load scratch test, a Brinell diamond indenter was scratched on the surface of the laminates 100a, 100b, 100c (with a load at the corner of the indenter tip) with a load increasing linearly from 0 mN to 150 mN over a length of 1500 microns and at a rate of 15 microns / second (1.5 mN / second). The onset of delamination (e.g., delamination between the hardcoat and the underlying crack mitigation composite and / or glass-based substrate) was determined using an optical microscope, and the scratch location where delamination began was correlated with the indenter load level at which delamination began.

[0085] As another example, laminates 100a, 100b, 100c comprising crack mitigating composites 130a, 130b, 130c and hard film 110 can exhibit substantially retained scratch resistance, as determined by pencil hardness measurements, as compared to the scratch resistance of an identical film 110 disposed directly on a glass-based substrate 120, but without a comparable crack mitigating composite. Specifically, laminates 100a-c can be subjected to pencil hardness testing according to the ASTM D3363 test method. A pencil is placed in an angled holder and scratched against the surface of laminates 100a-c on the side of hard film 110 using a force sufficient to crush the pencil graphite. Thus, the maximum pencil hardness value in the ASTM D3363 test is associated with the hardest common pencil (a 9H pencil). In some embodiments, laminates 100a-c are further characterized by a pencil hardness of 9H or greater.

[0086] In one or more embodiments of the laminated articles 100a, 100b, 100c, modifying the effective interface 140 between the hard film 110 and the glass-based substrate 120 includes preventing one or more cracks from bridging from one of the film 110 or the glass-based substrate 120 to the other of the film 110 or the glass-based substrate 120 while preserving other functional properties of the film 110 and / or the article. Figure 1A 、 1B In the specific embodiments shown in FIG and 1C , the modification of interface properties includes disposing crack mitigating compounds 130a, 130b, 130c between the glass-based substrate 120 and the hard film 110. In one or more embodiments, the crack mitigating compounds 130a, 130b, 130c are disposed on the glass-based substrate 120 to form a first interface 150, and the film 110 is disposed on the crack mitigating compounds 130a, 130b, 130c to form a second interface 160. The effective interface 140 includes the first interface 150, the second interface 160, and / or the crack mitigating compounds 130a, 130b, 130c.

[0087] for Figures 1A-1C The laminated products 100a-c shown, the term "hard film" applied to the hard film 110 and / or other films incorporated into the products 100a, 100b, 100c, includes one or more layers formed by methods known in the art, including discrete deposition or continuous deposition processes. These layers of the hard film may be in direct contact with each other. Each layer may be formed of the same material or more than one different material. In one or more alternative embodiments, intervening layers of different materials may be provided between these layers. In one or more embodiments, the hard film 110 may include one or more continuous and uninterrupted layers and / or one or more discontinuous and intermittent layers (i.e., layers formed by different materials adjacent to each other).

[0088] As used herein (e.g., with respect to laminates 100a, 100b, 100c), the term "disposed" includes coating, depositing, and / or forming a material onto a surface using any method known in the art. The disposed material may constitute a layer or film as defined herein. The term "disposed on" includes forming a material onto a surface so that the material is in direct contact with the surface, as well as forming a material onto a surface with one or more intervening materials between the disposed material and the surface. The intervening materials may constitute a layer or film as defined herein.

[0089] As used herein, the term "average flexural strength" refers to the flexural strength of a glass-containing material (e.g., an article and / or a glass-based substrate), as measured by a ring-on-ring (also referred to herein as "ROR") test. When used in conjunction with average flexural strength or any other property, the term "average" is the mathematical mean of the values ​​measured for that property over five or more samples. Average flexural strength can refer to the scale parameter of the two-parameter Weibull statistic of the load to failure under the ring-on-ring test. This scale parameter is also known as the Weibull characteristic strength, where the probability of failure of the material is 63.2%. More broadly, average flexural strength can also be defined by other tests, such as a ball drop test, in which the flexural strength of a glass surface is characterized by the height of the ball drop that can be tolerated without failure. Glass surface strength can also be tested in an apparatus configuration in which an apparatus or device containing a glass-containing material (e.g., an article and / or a glass-based substrate) article is dropped in different orientations that produce surface flexural stresses. In some cases, the average flexural strength may also include strength tested by other methods known in the art, such as three-point bend or four-point bend tests. In some cases, these test methods may be significantly affected by the edge strength of the article.

[0090] As used herein, the terms "bridging" or "bridging" are interchangeable and refer to the formation of a crack, flaw or defect and the increase in size and / or propagation of the crack, flaw or defect from one material, layer or film into another material, layer or film. For example, bridging includes the case where a crack present in the hard film 110 propagates into another material, layer or film (e.g., a glass-based substrate 120). The term "bridging" or "bridging" also includes the case where a crack passes through an interface between different materials, different layers and / or different films. For a crack to bridge between materials, layers and / or films, the materials, layers and / or films do not need to be in direct contact with each other. For example, a crack can bridge from a first material to a second material that is not in contact with the first material by bridging through an intermediate material disposed between the first and second materials. The same can be applied to layers and films and combinations of materials, layers and films. In the laminates 100a, 100b, 100c, as described herein (see Figures 1A-1C ), a crack can initiate in one of the hard film 110 or the glass-based substrate 120 and bridge across the effective interface 140 (specifically, across the first interface 150 and the second interface 160) to the other of the hard film 110 and the glass-based substrate 120.

[0091] As will be described herein with respect to the laminates 100a, 100b, 100c, regardless of where the crack originates (i.e., the film 110 or the glass-based substrate 120), the crack mitigating composites 130a, 130b, 130c can deflect the crack by bridging the gap between the hard film 110 and the glass-based substrate 120. Similarly, the crack mitigating composites 130a, 130b, 130c of the laminates 100a, 100b, 100c can deflect the crack by bridging the gap between the crack mitigating composites 130a, 130b, 130c and the glass-based substrate 120. As described herein, crack deflection can include at least partial delamination of the crack mitigating composites 130a, 130b, 130c from the film 110 and / or glass-based substrate 120 as the crack bridges from one material (e.g., the film 110, the glass-based substrate 120, or the crack mitigating composites 130a, 130b, 130c) to another material (e.g., the film 110, the glass-based substrate 120, or the crack mitigating composites 130a, 130b, 130c). Crack deflection can also include propagation of the crack through the crack mitigating composites 130a-c but not into the film 110 and / or glass-based substrate 120. In these cases, the crack mitigating composites 130a-c can form a low-toughness interface at the effective interface 140 that promotes crack propagation through the crack mitigating composite but not into the glass-based substrate or film. This type of mechanism can be described as crack deflection along the effective interface 140.

[0092] The following theoretical fracture mechanism analysis illustrates how cracks can form in laminates [e.g., laminates 100a, 100b, 100c (see Figures 1A-1C )] in which bridging or selective methods can be mitigated. Figure 2 is a schematic diagram illustrating the presence of cracks and their possible bridging or mitigation modes in a film disposed on a glass-based substrate. Figure 2 The numbered elements in the FIG are: glass-based substrate 40 (e.g., Figures 1A-1C 120 in FIG. 1 ), a film 42 (e.g., which may be comparable to the hard film 110) on top of a surface (not numbered) of the glass-based substrate 40, a double-sided deflection crack 44 that enters the interface between the glass-based substrate 40 and the film 42, an arrest crack 46 (which is a crack that starts to form in the film 42 but does not completely penetrate through the film 42), a "torsion crack" 48 (which forms in the surface of the film 42 but does not penetrate directly into the glass-based substrate when it reaches the surface of the glass-based substrate 40, but instead penetrates in a direction similar to the direction of the film 42). Figure 2 , and then penetrates the surface of the glass-based substrate 40 at another location), a penetration crack 41 that develops in the film 42 and penetrates into the glass-based substrate 40, and a single-sided deflection crack 43. Figure 2 Also shown is a plot of tension versus compression (i.e., element 47) in a glass-based substrate relative to the zero axis (i.e., element 45), which may be induced by chemical and / or thermal tempering of the glass-based substrate 40, wherein the surface of the glass-based substrate is in compression (including compressive stress) while the central portion is in tension (including tensile stress). Thus, the portion of element 47 to the right of the zero axis (i.e., element 45) indicates compressive stress, while the portion of element 47 to the left of the zero axis indicates tensile stress. As shown in the figure, when an external load is applied (in these cases, a tensile load is the least favorable), flaws in the film are preferentially stimulated to form cracks (e.g., deflection cracks 44) before cracks develop in the residually compressed or strengthened glass-based substrate 40. Figure 2In the illustrated case, as the external load continues to increase, the cracks will bridge until they encounter the glass-based substrate. Once a crack initiates in the film 42 and reaches the surface of the glass-based substrate 40, the crack's possible bridging modes are: (a) penetrating into the glass-based substrate without changing its path, as indicated by reference numeral 41; (b) deflecting to one side along the interface between the film and the glass-based substrate, as indicated by reference numeral 43; (c) deflecting to both sides along the interface, as indicated by reference numeral 44; (d) first deflecting along the interface and then twisting into the glass-based substrate, as indicated by reference numeral 48; or (e) terminating due to a microscopic deformation mechanism (e.g., plasticity at the crack tip, nanoscale blunting, or nanoscale deflection), as indicated by reference numeral 46. A crack can originate in the film and can bridge into the glass-based substrate. The above-described bridging mode may also apply to situations where cracks originate in a glass-based substrate and bridge into the film, for example, a pre-existing crack or flaw in the glass-based substrate may induce or nucleate a crack or flaw in the film, thereby causing the crack to grow or propagate from the glass-based substrate into the film, resulting in crack bridging.

[0093] Cracks penetrating into the glass-based substrate 120 and / or the hardcoat 110 reduce the average flexural strength of the laminated articles 100a, 100b, 100c and the glass-based substrate 120 compared to the glass-based substrate 120 alone (i.e., without the hardcoat 110 and / or the crack mitigation composites 130a-c), while crack deflection, crack blunting, or crack arrest (collectively referred to herein as crack mitigation) helps preserve the average flexural strength of the articles. "Crack blunting" and "crack arrest" can be different from one another. "Crack blunting" can include an increased crack tip radius, such as through plastic deformation or yielding mechanisms. "Crack arrest," on the other hand, can include a variety of different mechanisms, such as encountering high compressive stress at the crack tip; a reduction in the stress intensity factor at the crack tip due to the presence of a low elastic modulus interlayer or a low to high elastic modulus interface transition; nanoscale crack deflection or crack bending, as in some polycrystalline or composite materials; and strain hardening at the crack tip. This article will describe the various modes of crack deflection.

[0094] Without being bound by theory, some possible crack bridging paths can be analyzed in the context of linear elastic fracture mechanisms. In the following paragraphs, a crack path is used as an example, and fracture mechanism concepts are applied to this crack path to analyze the problem and illustrate the required material parameters to help preserve the average flexural strength performance of the article for a specific range of material properties.

[0095] Figure 3An illustration of the theoretical model framework is shown. The figure is a simplified schematic diagram of the interface region between a film 52 (e.g., film 52 can be comparable to hard film 110 in laminates 100a-100c) and a glass-based substrate 50 (e.g., substrate 40 can be comparable to glass-based substrate 120 in laminates 100a-100c). The terms μ1, E1, ν1 and μ2, E2, ν2 are the shear modulus (in Pa), Young's modulus (elastic modulus) (in Pa), Poisson's ratio (unitless), and and are the critical energy release rates of the glass-based substrate and the interface between the substrate and the film, respectively, in J / m 2 .

[0096] Common parameters that characterize the elastic mismatch between a film and a substrate are the Dundurs parameters α and β, which are defined as follows:

[0097]

[0098] in is the plane strain, and

[0099]

[0100] It is worth noting that the critical energy release rate is closely related to the fracture toughness of the material through the relationship defined by:

[0101]

[0102] Assuming there is a pre-existing flaw in the film, when a tensile load is applied, the crack will Figure 3 As shown, it extends vertically downward. If equation (4) is satisfied, then at the interface, the crack tends to deflect along the interface.

[0103]

[0104] If equation (5) is satisfied, the crack will penetrate into the glass-based substrate.

[0105]

[0106] Among them G d and G p are the energy release rates of cracks deflecting along the interface and cracks penetrating into the glass-based substrate, respectively. On the left side of equations (4) and (5), the ratio G d / G p is a strong function of the elastic misfit parameter α and weakly depends on β, while on the right, the toughness ratio Γ c IT / Γ c玻璃 is a material parameter.

[0107] Figure 4 The figure shows the G of the double deflection crack reproduction d / G p [See Ming-Yuan, H. and JW Hutchinson, "Crack deflection at an interface between dissimilarelastic materials", International Journal of Solids and Structures, 1989, 25(9): 1053-1067].

[0108] In G d / G p There is a strong dependence on α, where a negative α means the film is tougher than the glass-based substrate, and a positive α means the film is softer than the glass-based substrate. c IT / Γ c 玻璃 It has nothing to do with α. Figure 4 is a horizontal line. If Figure 4 If the criterion in equation (4) is satisfied in the region above the horizontal line in , the crack tends to deflect along the interface, which may be beneficial to the preservation of the average flexural strength of the substrate. On the other hand, if Figure 4 If the criterion of equation (5) is satisfied in the area below the horizontal line in , the cracks tend to penetrate into the glass-based substrate, which results in a decrease in the average flexural strength of the article, especially those articles using strengthened or toughened glass-based substrates as described elsewhere in this article.

[0109] According to the above concept, an indium tin oxide (ITO) film (e.g., as the hard film 110 including ITO) is used as an illustrative example according to the following analysis. For a glass-based substrate, E1=72 GPa, v1=0.22, and K 1c =0.7MPa·m 1 / 2For ITO, E2 = 99.8 GPa and v2 = 0.25. [Zeng, K. et al., "Investigation of mechanical properties of transparent conducting oxide thin films." Thin Solid Films, 2003(1–2): 60–65.] Depending on the deposition conditions, the interface toughness between an ITO film and a glass-based substrate can be about Γ in =5J / m 2 [Cotterell, B. and Z. Chen, “Buckling and cracking of thin films on compliant substrates under compression” International Journal of Fracture, 2000(2): 169-179.] This yields an elastic mismatch α = -0.17 and Γ c IT / Γ c 玻璃 =0.77. Figure 4 These values ​​are plotted. This crack analysis predicts that for ITO films, cracks favor penetration into the glass-based substrate, which results in a decrease in the average flexural strength of the glass-based substrate, especially if the glass-based substrate is reinforced or solid. This is believed to be one of the underlying mechanisms observed in various hard coatings disposed on glass-based substrates (including reinforced or solid glass-based substrates), including those containing indium tin oxide or other transparent conductive oxides, silicon nitride, and other hard coatings. Figure 4 As shown, one way to slow down the decrease in average flexural strength may be to select appropriate materials to change the elastic mismatch α (i.e., “Option 1,” which involves shifting the elastic mismatch value α to the right), or to adjust the interface toughness (i.e., “Option 2,” which involves shifting the value of Gd / Gp downward).

[0110] The theoretical analysis outlined above suggests that crack mitigating compounds 130a, 130b, and 130c can be used to better retain the strength of laminated articles 100a, 100b, and 100c, respectively. Specifically, inserting crack mitigating compounds 130a, 130b, and 130c between glass-based substrate 120 and hardcoat film 110 allows crack mitigation, as described herein, to become a more preferred path, and thus, the articles can better retain their strength. In some embodiments, crack mitigating compounds 130a, 130b, and 130c promote crack deflection, as described in greater detail below.

[0111] Glass-based substrates

[0112] refer to Figures 1A-1C Laminates 100a, 100b, 100c include a glass-based substrate 120, which may be strengthened or toughened, as described herein, having opposing major surfaces 122, 124. Laminates 100a, 100b, 100c also include a hardcoat 110 disposed on at least one opposing major surface (122 or 124) of the substrate. Furthermore, laminates 100a, 100b, 100c include a crack mitigation composite 130a, 130b, 130c. For laminates 100a, 100b, 100c, the crack mitigation composite 130a, 130b, 130c is disposed between the hardcoat 110 and the glass-based substrate 120. In one or more alternative embodiments, the crack mitigating composite 130a, 130b, 130c and / or hard film 110 may be disposed on one or more minor surfaces of the glass-based substrate 120 (e.g., edges of the substrate perpendicular to the opposing major surfaces 122, 124) in addition to or as an alternative to being disposed on at least one major surface (e.g., surface 122 or 124) or on both major surfaces.

[0113] As used herein, the glass-based substrate 120 can be a substantially planar sheet, but other embodiments may employ curved or otherwise shaped or contoured glass-based substrates. The glass-based substrate 120 can be substantially clear, transparent, and non-light scattering. The refractive index of the glass-based substrate can be in the range of about 1.45 to about 1.55. As will be described in greater detail herein, in one or more embodiments, the glass-based substrate 120 can be strengthened or characterized as being strong. The glass-based substrate 120 can be relatively pristine and flawless (e.g., having a small number of surface flaws or an average surface flaw size of less than about 1 micron) prior to strengthening. If a strengthened or strong glass-based substrate 120 is used, the substrate can be characterized as having a high average flexural strength (when compared to a glass-based substrate that has not been strengthened or is not strong) or having a high surface fracture strain (when compared to a glass-based substrate that has not been strengthened or is not strong).

[0114] Additionally or alternatively, the thickness 12 of the glass-based substrate 120 may vary along one or more dimensions thereof for aesthetic and / or functional reasons. For example, the edges of the glass-based substrate 120 may be thicker than more central regions of the glass-based substrate 120. The length, width, and thickness dimensions of the glass-based substrate 120 may also vary depending on the application or use of the articles 100a, 100b, 100c.

[0115] According to one or more embodiments, the glass-based substrate 120 includes an average flexural strength, which can be measured before or after combining the glass-based substrate 120 with the hardcoat 110, the crack mitigating composite 130a, 130b, 130c, and / or other films or layers. In one or more embodiments described herein, the laminated articles 100a, 100b, 100c retain their average flexural strength after combining the glass-based substrate 120 with the hardcoat 110, the crack mitigating composite 130a, 130b, 130c, and / or other films, layers, or materials, as compared to the average flexural strength of the glass-based substrate 120 before combining the glass-based substrate 120 with the hardcoat 110, the crack mitigating composite 130a, 130b, 130c, and / or other films, layers, or materials. In other words, the average flexural strength of the articles 100a, 100b, 100c is substantially the same before and after disposing the hardcoat 110, the crack mitigating composite 130a, 130b, 130c, and / or other films or layers on the glass-based substrate 120. In one or more embodiments, the average flexural strength of the articles 100a, 100b, 100c is significantly greater than the average flexural strength of a similar article that does not include the crack mitigating composite 130a, 130b, 130c (e.g., greater strength than an article that includes the film 110 and the glass-based substrate 120 in direct contact, but does not include the intervening crack mitigating composite 130a, 130b, 130c). In other embodiments, the average flexural strength of the articles 100a, 100b, 100c is 50% or greater greater than that of a similar article that includes only the glass-based substrate (i.e., without other coatings or films).

[0116] According to one or more embodiments, the glass-based substrate 120 has an average strain at break, which can be measured before or after the glass-based substrate 120 is combined with the hardcoat 110, the crack mitigation composites 130a, 130b, 130c, and / or other films or layers. The term "average strain at break" refers to the strain at which a crack will propagate without the application of additional load, typically leading to catastrophic failure in a given material, layer, or film, and possibly even bridging to other materials, layers, or films as described herein. The average strain at break can be measured, for example, using a ball-on-ring test. Without being bound by theory, the average strain at break can be directly related to the average flexural strength using appropriate mathematical transformations. In specific embodiments, the average fracture strain of the glass-based substrate 120, which may be strengthened or toughened as described herein, is 0.5% or more, 0.6% or more, 0.7% or more, 0.8% or more, 0.9% or more, 1% or more, 1.1% or more, 1.2% or more, 1.3% or more, 1.4% or more, 1.5% or more, or even 2% or more, and all ranges and subranges therebetween. Unless otherwise specified, the average fracture strain values ​​supported herein are determined by the Ring-on-Ring test. In specific embodiments, the average fracture strain of the glass-based substrate 120 is 1.2%, 1.4%, 1.6%, 1.8%, 2.2%, 2.4%, 2.6%, 2.8%, or 3% or more, and all ranges and subranges therebetween. The average fracture strain of the film 110 may be less than the average fracture strain of the glass-based substrate 120 and / or the average fracture strain of the crack mitigating composites 130a-c. Without being bound by theory, it is believed that the average fracture strain of the glass-based substrate 120 or any other material depends on the surface quality of these materials. For glass-based substrates (such as substrate 120), in addition to or instead of depending on the surface quality of the glass-based substrate, the average fracture strain of the specific glass-based substrate also depends on the conditions of the ion exchange or strengthening process used. In some embodiments, the elastic modulus of the glass-based substrate can be from about 55 GPa to about 100 GPa, and all ranges and sub-ranges between the aforementioned values. In other embodiments, the elastic modulus of the glass-based substrate can be from about 55 GPa to about 80 GPa. Further, other embodiments utilize glass-based substrates with an elastic modulus of 60 GPa to 90 GPa. The elastic modulus of the glass-based substrates described in the present disclosure is measured using resonant ultrasonic spectroscopy.

[0117] In one or more embodiments, the glass-based substrate 120 retains its average fracture strain after being combined with the hard film 110, the crack mitigating composites 130a, 130b, 130c, and / or other films or layers. In other words, the average fracture strain of the glass-based substrate 120 is substantially the same before and after the hard film 110, the crack mitigating composites 130a, 130b, 130c, and / or other films or layers are disposed on the glass-based substrate 120. In one or more embodiments, the average fracture strain of the articles 100a, 100b, 100c is significantly greater than the average fracture strain of similar articles that do not include the crack mitigating composites 130a-c (e.g., has a higher fracture strain than an article that includes the film 110 and the glass-based substrate 120 in direct contact, but does not include an intervening crack mitigating composite). For example, the articles 100a, 100b, 100c can exhibit an average strain at break that is 10% or greater, 25% greater, 50% greater, 100% greater, 200% greater, or 300% greater than the average strain at break of a similar article not containing the crack mitigating composite 130a, 130b, 130c, and all ranges and subranges therebetween. Similarly, the laminated articles 100a, 100b, 100c can be characterized by an average strain at break of greater than about 0.5%, greater than about 0.8%, greater than about 1%, greater than about 1.2%, greater than about 1.4%, and all average strain at break thresholds between these levels.

[0118] The glass-based substrate 120 can be provided using a variety of different processes. For example, methods for forming the glass-based substrate include the float glass process, the press roller process, the tube forming process, and up-draw and down-draw processes, such as fusion drawing and slot drawing. In the float glass process, a glass-based substrate characterized by a smooth surface and uniform thickness is produced by floating molten glass on a bed of molten metal (usually tin). In one exemplary process, molten glass is fed onto the surface of the molten tin bed to form a floating glass ribbon. As the glass ribbon flows through the tin bath, the temperature gradually decreases until the glass ribbon solidifies into a solid glass-based substrate, which can be lifted from the tin onto rollers. Once out of the tin bath, the glass-based substrate can be further cooled and annealed to reduce internal stresses.

[0119] The down-draw process produces a glass-based substrate of uniform thickness having a relatively pristine surface. Because the average flexural strength of a glass-based substrate is controlled by the frequency, number, and / or size of surface defects, a pristine surface with minimal contact has a higher initial strength. When this high-strength glass-based substrate is subsequently further strengthened (e.g., chemically or thermally), the resulting strength can be higher than that of a glass-based substrate whose surface has been ground and polished. The down-drawn glass-based substrate can be drawn to a thickness of less than about 2 mm. In addition, the down-drawn glass-based substrate has a very flat, smooth surface that can be used in its final application form without the need for expensive grinding and polishing processes.

[0120] The fusion draw process, for example, uses a drawing trough having a channel for receiving molten feedstock. The channel has weirs that are open at the top along the length of the channel on both sides of the channel. When the channel is filled with molten material, the molten material overflows the weirs. Under the action of gravity, the molten material flows downward from the outer surfaces of the drawing trough as two flowing films. The outer surfaces of these drawing troughs extend downward and inward so that they converge at an edge below the drawing trough. The two flowing films converge at this edge to fuse and form a single flowing substrate. An advantage of the fusion draw method is that because the two films overflowing from the channel fuse together, neither outer surface of the resulting substrate comes into contact with any part of the equipment. Therefore, the surface properties of the fusion drawn glass substrate are not affected by this contact.

[0121] The slot draw process differs from the fusion draw method. In the slot draw method, molten raw glass is supplied to a drawing tank. The bottom of the drawing tank has an open slot with a nozzle extending along the length of the slot. The molten material flows through the slot / nozzle and is drawn downward as a continuous substrate and into the annealing zone.

[0122] Once formed, the glass-based substrate 120 may be strengthened to form a strengthened glass-based substrate for use in the laminates 100a-c. As used herein, the term "strengthened glass-based substrate" may refer to a glass-based substrate that has been chemically strengthened, such as by ion exchange to exchange smaller ions in the surface of the glass-based substrate for larger ions. However, other strengthening methods known in the art, such as thermal tempering, may also be used to form a strengthened glass-based substrate. As will be explained, a strengthened glass-based substrate may include a glass-based substrate having surface compressive stresses in its surface, thereby contributing to the strength retention of the glass-based substrate. As also used herein, a "strong" glass-based substrate is within the scope of the present disclosure and includes glass substrates that may not have undergone a specific strengthening process and may not have surface compressive stresses, but are still strong, as understood by those of ordinary skill in the art. Such strong glass-based substrate articles can be defined as glass sheet articles or glass-based substrates having an average fracture strain greater than about 0.5%, 0.7%, 1%, 1.5%, or even greater than 2% (and all ranges and subranges therebetween). Strong glass-based substrates can be made, for example, by protecting the pristine glass surface after melting and forming the glass-based substrate. One example of such protection occurs in a fusion draw process, where, after forming, the surface of the glass film does not come into contact with any part of the apparatus or other surfaces. Glass-based substrates formed by the fusion draw process derive their strength from their pristine surface quality. Pristine surface quality can also be obtained by etching or polishing and then protecting the surface of a glass-based substrate, as well as by other methods known in the art. In one or more embodiments, both the strengthened glass-based substrate and the toughened glass-based substrate may comprise a glass sheet article having an average fracture strain greater than about 0.5%, 0.7%, 1%, 1.5%, or even greater than 2% (and all ranges and sub-ranges therebetween), for example, when measured using the Ring-on-Ring or Ball-on-Ring Flexure Test.

[0123] As described above, the glass-based substrates described herein can be chemically strengthened via an ion exchange process to provide a strengthened glass-based substrate 120. The glass-based substrates can also be strengthened by other methods known in the art, such as thermal tempering. During the ion exchange process, ions at or near the surface of the glass-based substrate are exchanged with larger metal ions from the salt bath, typically by immersing the glass-based substrate in a molten salt bath for a predetermined period of time. In some embodiments, the temperature of the molten salt bath is between about 350° C. and 450° C., and the predetermined period of time is between about 2 hours and about 8 hours. The inclusion of larger ions into the glass-based substrate strengthens the glass-based substrate by creating compressive stress in one or more near-surface regions at or near the surface of the glass-based substrate. A corresponding tensile stress is induced in one or more central regions at a distance from the surface of the glass-based substrate to balance the compressive stress. Glass-based substrates using this strengthening process can be more specifically described as chemically strengthened glass-based substrates 120 or ion-exchanged glass-based substrates 120. Glass-based substrates that are used in laminates 100a-100c and that are not strengthened may be referred to herein as non-strengthened glass-based substrates.

[0124] In one example, sodium ions in the strengthened glass-based substrate 120 are replaced by potassium ions from a molten bath (e.g., a potassium nitrate bath), but other alkali ions with larger atomic radii (e.g., rubidium or cesium) may also replace smaller alkali ions in the glass. Depending on the embodiment, smaller alkali ions in the glass may be replaced by Ag. + Ion exchange. Similarly, other alkali metal salts, such as sulfates, phosphates, halides, etc., can be used in the ion exchange process.

[0125] At temperatures below the temperature at which the glass network relaxes, the replacement of smaller ions with larger ions creates an ion distribution, and thus a stress distribution, across the surface of the strengthened glass-based substrate 120. The larger volume of the incoming ions creates a compressive stress (CS) on the surface of the strengthened glass-based substrate 120 and a tensile stress (central tension, or CT) in the center of the strengthened glass-based substrate 120. The exchange depth can be described as the depth within the strengthened glass-based substrate 120 (i.e., the distance from the surface of the glass-based substrate to the central region of the glass-based substrate) at which ion exchange facilitated by the ion exchange process occurs.

[0126] Compressive stress (at the surface of the glass) is measured by a surface stress meter (FSM), using a commercially available instrument such as the FSM-6000 manufactured by Orihara Industrial Co., Ltd., Japan. Surface stress measurement relies on accurate measurement of the stress-optical coefficient (SOC), which is related to the birefringence of the glass. SOC is measured according to Protocol C (Glass Disc Method) as described in ASTM Standard C770-16, entitled "Standard Test Method for Measurement of Glass Stress-Optical Coefficient," which is incorporated herein by reference in its entirety.

[0127] As used herein, depth of compression (DOC) means the depth at which the stress in the strengthened alkali aluminosilicate glass-based substrate described herein changes from compressive stress to tensile stress. When chemically induced, the DOC can be measured by FSM or scattered light polariscope (SCALP), depending on the ion exchange treatment. If the stress in the glass article is generated by exchanging potassium ions into the glass article, the DOC is measured using FSM. If the stress is generated by exchanging sodium ions into the glass article, the DOC is measured using SCALP. If the stress in the glass article is generated by exchanging both potassium and sodium ions into the glass, the DOC is measured by SCALP, because the depth of exchange of sodium is considered to represent the DOC, while the depth of exchange of potassium ions represents the magnitude of the change in compressive stress (but not the change in stress from compressive stress to tensile stress); the depth of exchange of potassium ions in such glass articles is measured by FSM.

[0128] In some embodiments, the surface CA of the strengthened glass-based substrate 120 used in the laminates 100a-c can be 300 MPa or greater, e.g., 400 MPa or greater, 450 MPa or greater, 500 MPa or greater, 550 MPa or greater, 600 MPa or greater, 650 MPa or greater, 700 MPa or greater, 750 MPa or greater, or 800 MPa or greater, and all ranges and sub-ranges therebetween. The strengthened glass-based substrate 120 may have a DOC of 15 μm or greater, 20 μm or greater (e.g., 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or greater), and / or a central tension of 10 MPa or greater, 20 MPa or greater, 30 MPa or greater, 40 MPa or greater (e.g., 42 MPa, 45 MPa, or 50 MPa or greater) but less than 100 MPa (e.g., 95 MPa, 90 MPa, 85 MPa, 80 MPa, 75 MPa, 70 MPa, 65 MPa, 60 MPa, 55 MPa or less), and all ranges and sub-ranges therebetween. In one or more specific embodiments, the strengthened glass-based substrate 120 has one or more of the following: a surface CS greater than 500 MPa, a compressive layer depth greater than 15 μm, and a central tension greater than 18 MPa.

[0129] Without being bound by theory, it is believed that strengthened glass-based substrates 120 having a surface CS greater than 500 MPa and a DOC greater than about 15 μm generally have a greater fracture strain than non-strengthened glass-based substrates (or in other words, glass-based substrates that have not been ion-exchanged or otherwise strengthened). In some aspects, the benefits of one or more embodiments described herein may not be as significant as compared to non-strengthened or weakly strengthened glass-based substrates that do not meet these CS or DOC requirements due to handling or common glass surface damage events in many typical applications. However, as previously discussed, in specific applications where the surface of the glass-based substrate can be adequately protected from scratching or surface damage (e.g., by a protective coating or other layer), strong glass-based substrates with relatively high fracture strains can also be produced, for example, by forming and preserving the original glass surface quality using fusion forming methods. In these alternative applications, the benefits of one or more embodiments described herein can be similarly achieved.

[0130] Exemplary ion-exchangeable glasses that can be used in the strengthened glass-based substrate 120 of the laminates 100a-100c can include an alkali aluminosilicate glass composition or an alkali aluminoborosilicate glass composition, although other glass compositions are also contemplated. As used herein, "ion-exchangeable" means that the glass-based substrate is capable of exchanging cations located at or near the surface of the glass-based substrate with cations of the same valence, either larger or smaller in size. An exemplary glass composition comprises SiO2, B2O3, and Na2O, wherein (SiO2 + B2O3) is ≥ 66 mol% and Na2O is ≥ 9 mol%. In some embodiments, the glass-based substrate 120 comprises a glass composition having an aluminum oxide content of 6 wt% or greater. In some embodiments, the glass-based substrate 120 comprises a glass composition having one or more alkaline earth metal oxides, such that the alkaline earth metal oxide content is 5 wt% or greater. In some embodiments, suitable glass compositions further comprise at least one of KO, MgO, and CaO. In some embodiments, the glass composition used in the glass-based substrate 120 may include: 61-75 mol% SiO2; 7-15 mol% Al2O3; 0-12 mol% B2O3; 9-21 mol% Na2O; 0-4 mol% K2O; 0-7 mol% MgO; and 0-3 mol% CaO.

[0131] Another exemplary glass composition suitable for a glass-based substrate 120 (which may optionally be strengthened or otherwise hardened) comprises: 60-70 mol% SiO2; 6-14 mol% Al2O3; 0-15 mol% B2O3; 0-15 mol% Li2O; 0-20 mol% Na2O; 0-10 mol% KO; 0-8 mol% MgO; 0-10 mol% CaO; 0-5 mol% ZrO2; 0-1 mol% SnO2; 0-1 mol% CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3; wherein 12 mol% ≤ (Li2O + Na2O + KO) ≤ 20 mol% and 0 mol% ≤ (MgO + CaO) ≤ 10 mol%.

[0132] Another exemplary glass composition suitable for a glass-based substrate 120 (which may optionally be strengthened or otherwise solidified) comprises: 63.5-66.5 mol% SiO2; 8-12 mol% Al2O3; 0-3 mol% B2O3; 0-5 mol% Li2O; 8-18 mol% Na2O; 0-5 mol% KO; 1-7 mol% MgO; 0-2.5 mol% CaO; 0-3 mol% ZrO2; 0.05-0.25 mol% SnO2; 0.05-0.5 mol% CeO2; less than 50 ppm As2O3; and less than 50 ppm Sb2O3; wherein 14 mol% ≤ (Li2O + Na2O + KO) ≤ 18 mol% and 2 mol% ≤ (MgO + CaO) ≤ 7 mol%.

[0133] In some embodiments, alkali aluminosilicate glass compositions suitable for glass-based substrates 120 (which may optionally be strengthened or otherwise hardened) comprise aluminum oxide, at least one alkali metal, and in some embodiments, greater than 50 mol% SiO2, in other embodiments, 58 mol% or more SiO2, and in other embodiments, 60 mol% or more SiO2, all as further defined by the ratios given by Equation (6):

[0134]

[0135] The components are expressed in mole % and the modifier is an alkali metal oxide.

[0136] In a specific embodiment, the glass composition comprises: 58-72 mol% SiO2; 9-17 mol% Al2O3; 2-12 mol% B2O3; 8-16 mol% Na2O; 0-4 mol% K2O, and is further defined as above in equation (6).

[0137] In some embodiments, the optionally strengthened or toughened glass-based substrate 120 may comprise an alkali aluminosilicate glass composition comprising: 64-68 mol% SiO2; 12-16 mol% Na2O; 8-12 mol% Al2O3; 0-3 mol% B2O3; 2-5 mol% KO; 4-6 mol% MgO; and 0-5 mol% CaO, wherein: 66 mol% ≤ SiO2 + B2O3 + CaO ≤ 69 mol%; Na2O + KO + B2O3 + MgO + CaO + SrO > 10 mol%; 5 mol% ≤ MgO + CaO + SrO ≤ 8 mol%; (Na2O + BO)-Al2O3 ≤ 2 mol%; 2 mol% ≤ Na2O-Al2O3 ≤ 6 mol%; and 4 mol% ≤ (Na2O + KO)-Al2O3 ≤ 10 mol%.

[0138] In some embodiments, the optionally strengthened or toughened glass-based substrate 120 may include an alkali silicate glass composition comprising: 2 mol% or more of Al2O3 and / or ZrO2, or 4 mol% or more of Al2O3 and / or ZrO2.

[0139] In some embodiments, the glass-based substrate used in the glass-based substrate 120 of the laminates 100a-100c may be formulated with 0-2 mol% of at least one fining agent selected from the group consisting of: Na2SO4, NaCl, NaF, NaBr, K2SO4, KCl, KF, KBr, and SnO2.

[0140] The thickness 12 of the glass-based substrate 120 according to one or more embodiments may be in the range of about 50 μm to about 5 mm. Exemplary thicknesses of the glass-based substrate 120 may be 100 μm to 500 μm, such as 100 μm, 200 μm, 300 μm, 400 μm, or 500 μm. Other exemplary thicknesses 12 are 500 μm to 1000 μm, such as 500 μm, 600 μm, 700 μm, 800 μm, 900 μm, or 1000 μm. The thickness 12 of the glass-based substrate 120 may be greater than 1 mm, such as about 2 mm, 3 mm, 4 mm, or 5 mm. In one or more embodiments, the thickness 12 of the glass-based substrate 120 may be 2 mm or less, or less than 1 mm. The glass-based substrate 120 may be acid polished or treated in any other manner to remove or reduce the effects of surface imperfections.

[0141] dura mater

[0142] Laminated products 100a, 100b, 100c (see Figures 1A-1C ) includes a film 110 disposed on a surface of a glass-based substrate 120, specifically on crack mitigation composites 130a, 130b, 130c. The hard film 110 may be disposed on one or both major surfaces 122, 124 of the glass-based substrate 120. In one or more embodiments, in addition to or as an alternative to being disposed on one or both major surfaces 122, 124, the film 110 may be disposed on one or more minor surfaces (not shown) of the glass-based substrate 120. In one or more embodiments, the hard film 110 is free of macroscopic scratches or defects that are readily visible to the eye. Further, as Figures 1A-1C As shown, the film 110 forms an effective interface 140 with the glass-based substrate 120 .

[0143] In one or more embodiments, the hard film 110 can reduce the average flexural strength of the laminated articles 100a, 100b, 100c (e.g., such as articles comprising the film and a glass-based substrate 120) through the mechanisms described herein. In one or more embodiments, the mechanisms include the case where the film 110 can reduce the average flexural strength of the article due to cracks developed in the film 110 bridging into the glass-based substrate 120. In other embodiments, the mechanisms include the case where the film can reduce the average flexural strength of the article due to cracks developed in the glass-based substrate bridging into the film. The film 110 of one or more embodiments can exhibit a fracture strain of 2% or less, or a fracture strain less than the fracture strain of the glass-based substrate described herein. Further, the film 110 of one or more embodiments can exhibit an elastic modulus greater than or equal to the elastic modulus of the glass-based substrate 120. Films comprising one or more of these properties can be characterized as "brittle" in the present disclosure.

[0144] According to one or more embodiments of the laminates 100a-c, the fracture strain (or crack initiation strain level) of the hard film 110 can be lower than the fracture strain of the glass-based substrate 120. For example, the fracture strain of the film 110 can be about 2% or less, about 1.8% or less, about 1.6% or less, about 1.5% or less, about 1.4% or less, about 1.2% or less, about 1% or less, about 0.8% or less, about 0.6% or less, about 0.5% or less, about 0.4% or less, or about 0.2% or less, and all ranges and sub-ranges therebetween. In some embodiments, the fracture strain of the film 110 can be lower than the fracture strain of a strengthened glass-based substrate 120 having a surface CS greater than 500 MPa and a DOC greater than about 15 μm. In one or more embodiments, the fracture strain of the film 110 can be 0.1% (or more) lower or less than the fracture strain of the glass-based substrate 120, or in some cases, 0.5% (or more) lower or less, and all ranges and sub-ranges therebetween. In one or more embodiments, the fracture strain of the film 110 can be about 0.15% (or more) lower or less than the fracture strain of the glass-based substrate 120, for example, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.50%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9%, 0.95%, or 1% lower or less, and all ranges and sub-ranges therebetween. These fracture strain values ​​can be measured, for example, using ball-on-ring or ring-on-ring flexure testing methods combined with optional microscopic or high-speed video analysis. Unless otherwise stated, the fracture strain properties and measurements of films (e.g., film 110) on substrates (e.g., substrate 120) in the present disclosure are performed using a microscope camera attached in situ to a ring-on-ring flexure test apparatus (same as that used to measure COS as described above) to measure displacement and other relevant data, thereby calculating fracture strain values ​​according to equations understood by those skilled in the art. As also understood by those skilled in the art, these assessments can be performed during the application of a load or stress, or in some cases, after the application of a load or stress by inspection. In the case where the film (e.g., film 110) is conductive or coated with a thin conductive layer, those skilled in the art also understand that the onset of film cracking can be measured by analyzing the resistivity of the conductive film.

[0145] Exemplary films 110 for laminates 100a-c may have an elastic modulus of at least 25 GPa and / or a hardness of at least 1.75 GPa, but some combinations outside of this range are possible. However, in general, the hard films 110 for laminates 100a-c are "hard" in the sense that they exhibit an elastic modulus of at least 25 GPa and / or a hardness of at least 1.75 GPa. In some embodiments, the elastic modulus of the hard film 110 can be 50 GPa or greater, or even 70 GPa or greater, and all ranges and subranges between the aforementioned values. For example, the elastic modulus of the film can be 55 GPa, 60 GPa, 65 GPa, 75 GPa, 80 GPa, 85 GPa, and all ranges and subranges between the aforementioned values. In one or more embodiments, the hardness value of the measured film 110 is higher than 3.0 GPa. For example, the hardness of the film 110 can be 5 GPa, 5.5 GPa, 6 GPa, 6.5 GPa, 7 GPa, 7.5 GPa, 8 GPa, 8.5 GPa, 9 GPa, 9.5 GPa, 10 GPa, 11 GPa, 12 GPa, 13 GPa, 14 GPa, 15 GPa, 16 GPa or more, as well as all indentation hardness values ​​between or above these levels. According to another embodiment, the hard film 110 for the laminated products 100a-c can exhibit a hardness greater than or equal to 8 GPa, or greater than or equal to 12 GPa. These elastic modulus and hardness values ​​of the film 110 can be measured using known diamond nanoindentation methods commonly used by those of ordinary skill in the art to determine the elastic modulus and hardness of films. An exemplary diamond nanoindentation method can use a Berkovich diamond indenter. Widely accepted nanoindentation practices were used to determine the hardness and Young's modulus of thin film coatings, such as the films and layers of the present disclosure (eg, film 110 and crack mitigating composites 130a, 130b, 130c).[See Fischer-Cripps, A.C., “Critical Review of Analysis and Interpretation of Nanoindentation Test Data,” Surface & Coatings Technology, Vol. 200, pp. 4153-4165, 2006 (hereinafter “Fischer-Cripps”); and Hay, J. et al., “Continuous Stiffness measurement During Instrumented Indentation Testing,” Experimental Techniques, 34(3), pp. 86-94, 2010 (hereinafter referred to as "Hay"). For coatings, hardness and modulus are usually measured as a function of indentation depth. As long as the coating is thick enough, the coating properties can be isolated from the resulting response distribution. It should be recognized that if the coating is too thin (e.g., less than ~500nm), the coating properties may not be completely isolated because they may be affected by the presence of a nearby substrate with different mechanical properties. (See Hay). The method used to report the properties herein represents the coating itself. The process is to measure the hardness and modulus as a function of indentation depth until the depth approaches 1000nm. In the case of a hard coating on softer glass, the response curve will reveal maximum levels of hardness and modulus at relatively small indentation depths (≤ about 200nm). At deeper indentation depths, both hardness and modulus will gradually disappear. Loss because the response is affected by the softer glass substrate. In this case, the coating hardness and modulus selected are those associated with the areas exhibiting the maximum hardness and modulus. In the case of a soft coating on a harder glass, the coating properties will be represented by the lowest hardness and modulus levels that appear at relatively small indentation depths. At deeper indentation depths, the hardness and modulus will gradually increase due to the influence of the harder glass. These hardness and modulus versus depth distribution curves can be obtained using the traditional Oliver and Pharr method (as described in Fischer-Cripps) or the more effective continuous stiffness method (see Hay). The acquisition of reliable nanoindentation data requires following recognized protocols. Otherwise, these measurements may suffer from significant errors. Using the known diamond nanoindentation method as described above, these elastic modulus and hardness values ​​of the film were measured with a Brinell diamond indenter tip.Further, without being bound by theory, the hardness value exhibited by the hard film 110 is indicative of the hardness of the laminate 100a-c, provided that the hardness measurement of the film is performed with all aspects of the laminate 100a-c, including the crack mitigating composites 130a-c and the glass-based substrate 120, in place.

[0146] The hard film 110 described herein for use in the laminates 100a-c may also exhibit a fracture toughness of less than about 10 MPa·m 1 / 2 , or in some cases less than 5 MPa·m 1 / 2 , or in some cases less than 1 MPa·m 1 / 2 For example, the fracture toughness of the film may be 4.5 MPa·m 1 / 2 , 4MPa·m 1 / 2 , 3.5MPa·m 1 / 2 , 3MPa·m 1 / 2 , 2.5MPa·m 1 / 2 , 2MPa·m 1 / 2 , 1.5MPa·m 1 / 2 , 1.4MPa·m 1 / 2 , 1.3MPa·m 1 / 2 , 1.2MPa·m 1 / 2 , 1.1MPa·m 1 / 2 , 0.9MPa·m 1 / 2 , 0.8MPa·m 1 / 2 , 0.7MPa·m 1 / 2 , 0.6MPa·m 1 / 2 , 0.5MPa·m 1 / 2 , 0.4MPa·m 1 / 2 , 0.3MPa·m 1 / 2 , 0.2MPa·m 1 / 2 , 0.1MPa·m 1 / 2 or less, and all ranges and subranges therebetween. The fracture toughness as reported herein was measured as described in DS Harding, W COliver and GM Pharr, Cracking During Indentation and its use in the Measurement of Fracture Toughness, Mat. Res. Soc. Symp. Proc., Vol. 356, 1995, 663-668.

[0147] The hard film 110 described herein for use in the laminates 100a-c may also have a critical strain energy release rate (G IC =KIC 2 / E), which is less than about 0.1 kJ / m 2 , or in some cases less than 0.01 kJ / m 2 In one or more embodiments, the critical strain energy release rate of the film 110 may be 0.09 kJ / m 2 , 0.08kJ / m 2 , 0.07kJ / m 2 , 0.06kJ / m 2 , 0.05kJ / m 2 , 0.04kJ / m 2 , 0.03kJ / m 2 , 0.02kJ / m 2 , 0.01kJ / m 2 、0.0075kJ / m 2 , 0.005kJ / m 2 , 0.0025kJ / m 2 or less, and all ranges and subranges therebetween. The critical strain energy release rate is calculated using the values ​​of fracture toughness and modulus measured as described above.

[0148] In one or more embodiments, the hard film 110 may include multiple layers, each having the same or different thicknesses. In some aspects, the composition of one or more layers in the film 110 may be different from the other layers in the film 110. Certain aspects of the present disclosure also contemplate various orders of the layers that make up the film 110. In one or more embodiments, each layer of the film may be characterized as brittle based on the effect of one or more layers on the average flexural strength of the laminate 100a, 100b, 100c and / or the fracture strain, fracture toughness, elastic modulus, or critical strain energy release rate values ​​of one or more layers as described elsewhere herein. In one variation, the layers in the hard film 110 do not need to have the same properties, such as elastic modulus and / or fracture toughness. In another variation, the layers of the film 110 may include materials that are different from each other, for example, as alternating thin layers having different compositions. In some embodiments, the hard film 110 includes one or more outermost layers with high scratch resistance (e.g., one or more silicon nitride and / or silicon dioxide layers) and one or more innermost layers with other functional properties (e.g., a conductive film including a transparent conductive oxide such as ITO).

[0149] From the perspective that the bulk of the hard film 110, or at least one or more outermost layers thereof, should exhibit scratch resistance that is beneficial for the desired application of the laminated products 100a, 100b, 100c, in certain embodiments, the composition or material of the hard film 110 may be limited. According to some embodiments of the laminated products 100a, 100b, 100c, the hard film 110 may include at least one of the following: a metal-containing oxide, a metal-containing oxynitride, a metal-containing nitride, a metal-containing carbide, a silicon-containing polymer, carbon, a semiconductor, and combinations thereof. Some additional examples of the material of the hard film 110 include: oxides such as SiO2, Al2O3, TiO2, Nb2O5, Ta2O5; oxynitrides such as SiO x N y 、Si u Al v O x N y and AlO x N y ; Nitrides, such as SiN x 、AlN x , cubic boron nitride and TiN x ; Carbides such as SiC, TiC and WC; Combinations of the above, such as carbon oxides and oxycarbonitrides (such as SiC x O y and SiC x O y N z ); semiconductor materials such as Si and Ge; transparent conductors such as indium tin oxide (ITO), tin oxide, fluorinated tin oxide, aluminum zinc oxide, or zinc oxide; carbon nanotubes or graphene-doped oxides; oxides doped with silver or other metals; highly siliceous polymers such as highly cured siloxanes and silsesquioxanes; diamond or diamond-like carbon materials; or selected metal films that can exhibit fracture properties. Further, for those hard films 110 that contain one or more layers of materials not typically associated with high scratch resistance (e.g., semiconductor materials, cubic boron nitride, etc.), the outermost layer or layers of the hard film may contain: metal-containing oxides, metal-containing oxynitrides, metal-containing nitrides, metal-containing carbides, silicon-containing polymers, diamond-like carbon materials, and combinations thereof. Furthermore, the various multi-layer hard coating designs described in US Patent Nos. 9,079,802, 9,355,444, 9,359,261, and 9,366,784, which are incorporated herein by reference, may also be used in laminates and thereby gain the benefits of the crack mitigating composite approach of the present disclosure.

[0150] Solids are often described using an "integer formula" (e.g. Al2O3). Equivalent "atomic fraction formulas" are also often used (e.g. Al 0.4 O0.6 ) to describe solids, Al 0.4 O 0.6 Equivalent to Al2O3. In the atomic fraction formula, the sum of all atoms in the formula is 0.4 + 0.6 = 1, and the atomic fractions of Al and O in the formula are 0.4 and 0.6, respectively. Atomic fraction expressions are described in many general textbooks and are often used to describe alloys. See also, for example: (i) Charles Kittel, Introduction to Solid State Physics, 7th ed., John Wiley & Sons, Inc., New York, 1996, pp. 611-627; (ii) Smart and Moore, Solid State Chemistry, An introduction, Chapman & Hall University and Professional Division, London, 1992, pp. 136-151; (iii) James F. Shackelford, Introduction to Materials Science for Engineers, 6th ed., Pearson Prentice Hall, New Jersey, 2005, pp. 404-418.

[0151] In short, regarding alloys, such as aluminum oxide, without specifying a specific subscript value, it can be said that it is Al v O x .Al v O x The expression can represent Al2O3 or Al 0.4 O 0.6 If the sum of v+x is chosen to be 1 (i.e., v+x=1), the formula will be expressed in terms of atomic fractions. Similarly, more complex mixtures can be described, such as Si u Al v O x N y , where similarly, if the sum of u+v+x+y is equal to 1, then this is the atomic fraction representation case.

[0152] The atomic fraction formula is sometimes easier to use for comparison. For example, (Al2O3) 0.3 (AlN) 0.7 An exemplary alloy of composition is represented by the following formula: Al 0.448 O 0.31 N 0.241 and Al 367 O 254 N198 Very similar. Made of (Al2O3) 0.4 (AlN) 0.6 Another exemplary alloy of composition is represented by the following formula: 0.438 O 0.375 N 0.188 and Al 37 O 32 N 16 Very similar. Atomic fraction formula Al 0.448 O 0.31 N 0.241 and Al 0.438 O 0.375 N 0.188 are relatively easy to compare with each other; for example, it is found that the atomic fraction of Al decreases by 0.01, the atomic fraction of O increases by 0.065, and the atomic fraction of N decreases by 0.053. 367 O 254 N 198 and Al 37 O 32 N 16 More detailed calculations and considerations are required. Therefore, it is sometimes preferable to use the atomic fraction expression for the solid. However, Al v O x N y , as it captures any alloy containing Al, O and N atoms.

[0153] The hard film 110 can be provided on the glass-based substrate 120 by vacuum deposition techniques such as chemical vapor deposition (e.g., plasma-enhanced chemical vapor deposition, atmospheric pressure chemical vapor deposition, or plasma-enhanced atmospheric pressure chemical vapor deposition), physical vapor deposition (e.g., reactive or non-reactive sputtering or laser ablation), thermal evaporation, resistive heating, or electron beam evaporation, or atomic layer deposition. The hard film 110 can also be deposited on one or more surfaces 122, 124 of the glass-based substrate 120 using liquid-based techniques such as sol-gel coating or polymer coating methods, such as, among others, spin coating, spray coating, slot coating, slide coating, wound rod coating, doctor blade / knife coating, air knife coating, curtain coating, gravure coating, and roller coating. In some embodiments, it may be desirable to use an adhesion promoter, such as a silane-based material, between the hardcoat 110 and the glass-based substrate 120, between the glass-based substrate 120 and the crack mitigating composites 130a, 130b, 130c, between the layers (if any) of the crack mitigating composites 130a, 130b, 130c, between the layers (if any) of the film 110, and / or between the film 110 and the crack mitigating composites 130a, 130b, 130c.

[0154] The thickness 11 of the hard film 110 (see Figures 1A-1C ) may vary depending on the intended use of the laminates 100a, 100b, 100c. In some embodiments, the thickness 11 of the hard film 110 may be in the range of about 0.005 μm to about 5 μm, about 0.2 μm to about 5 μm, or about 0.2 μm to about 0.5 μm. In some embodiments, the thickness 11 of the hard film 110 may be in the range of about 0.005 μm to about 10 μm, about 0.05 μm to about 0.5 μm, about 0.01 μm to about 0.15 μm, or about 0.015 μm to about 0.2 μm, and all ranges and sub-ranges therebetween.

[0155] In some embodiments of the laminates 100a, 100b, 100c, it can be advantageous to include a material (or multiple materials) in the hard film 110 (e.g., as comprising a single layer, dual layer, or multilayer structure) that has: (1) a refractive index that is similar to (or greater than) the refractive index of the glass-based substrate 120, the crack mitigation composite 130a, 130b, 130c, and / or other films or layers to minimize optical interference effects; (2) a refractive index (real and / or imaginary) that is adjusted to achieve an anti-reflective interference effect; and / or (3) a refractive index (real and / or imaginary) that is adjusted to achieve a wavelength-selective reflection effect or a wavelength-selective absorption effect, for example, to achieve a UV or IR blocking or reflection effect, or to achieve a coloring / tinting effect. In some embodiments of laminates 100a-c, for example, hardcoat 110 may comprise a multi-layer antireflective coating, wherein the crack mitigation composites 130a-c and hardcoat 110 together comprise an average single-sided illumination reflectance of less than about 2%. Single-sided reflectance values, as referred to herein, are measured by optically coupling the back surface of a glass-based substrate to a strong light absorber to effectively remove reflections from the back surface of the substrate from the measurement. Furthermore, the illumination average is obtained by weighting the measured reflectances according to the sensitivity of the human eye and averaging the results using methods readily understood by those of ordinary skill in the art.

[0156] In one or more embodiments, the refractive index of the hard film 110 can be greater than the refractive index of the glass-based substrate 120 and / or greater than the refractive index of the crack mitigation composites 130a, 130b, 130c. In one or more embodiments, the refractive index of the film 110 can be in the range of about 1.7 to about 2.2, or in the range of about 1.4 to about 1.6, or in the range of about 1.6 to about 1.9, and all ranges and subranges therebetween. Some embodiments may employ a film 110 having one or more layers whose refractive index is comparable to that of the substrate, even if the total refractive index of the film exceeds that of the substrate (e.g., a film 110 having one or more silicon dioxide layers and the remainder being silicon nitride layers disposed on a substrate 120 having a silicate glass composition).

[0157] The hard film 110 can also be used for a variety of functions, including scratch resistance, or can be integrated with additional films or layers described herein that are used for functions other than the scratch resistance associated with the hard film 110. For example, the hard film 110 can include a UV or IR light reflecting or absorbing layer, an anti-reflective layer, an anti-glare layer, an anti-fouling layer, a self-cleaning layer, a scratch-resistant layer, a barrier layer, a passivation layer, an airtight layer, a diffusion barrier layer, an anti-fingerprint layer, and the like. In addition, the film 110 can include a conductive or semiconductor layer, a thin-film transistor layer, an EMI shielding layer, a damage sensor, an alarm sensor, an electrochromic material, a photochromic material, a touch sensing layer, or an information display layer. The film 110 and / or any of the aforementioned layers can contain a colorant or tinting agent. When an information display layer is integrated into the laminated products 100a, 100b, 100c, the product can form a component of a touch-sensitive display, a transparent display, or a head-up display. In these cases, it may be desirable for the hardcoat 110 to perform an interferometric function that selectively transmits, reflects, or absorbs light of different wavelengths or colors. For example, in a head-up display application, the hardcoat 110 may selectively reflect a target wavelength.

[0158] In addition to scratch resistance, other functional properties of the hard film 110 include optical, electrical, and / or mechanical properties, such as hardness, elastic modulus, fracture strain, abrasion resistance, mechanical durability, coefficient of friction, conductivity, resistivity, electron mobility, electron or hole carrier doping, optical refractive index, density, opacity, transparency, reflectivity, absorptivity, transmittance, etc. These functional properties are substantially maintained or even improved after the hard film 110 is combined with the glass-based substrate 120, the crack mitigation composites 130a, 130b, 130c, and / or other films included in the laminates 100a, 100b, 100c.

[0159] Crack mitigation compounds

[0160] As described herein, the crack mitigating composites 130a, 130b, 130c (see Figures 1A-1C ) inhibit crack growth through the effective interface 140 in the laminates 100a, 100b, 100c. The crack mitigating composites 130a-c can inhibit crack growth by one or more of the following mechanisms: 1) reducing the stress intensity at the crack tip due to changing the elastic modulus in the composite structure; 2) blunting the crack through plastic deformation in the composite structure; and 3) deflecting the crack by providing a preferred path for crack growth that is tortuous and dissipates fracture energy in the crack mitigating composite / stack rather than in the hard film 110 or the glass-based substrate 120.

[0161] For the laminates 100a-c, the crack mitigation composites 130a-c comprise an inorganic element 33 and a polymeric element 35. In these aspects, the crack mitigation composites 130a-c include the inorganic element 33 and the polymeric element 35, one or both of which are in the form of one or more layers, films, or other structures (e.g., particles, fibers, and / or whiskers). In some embodiments, the inorganic element 33 may comprise an oxide, a nitride, or an oxynitride, and the polymeric element 35 may comprise at least one of a polyimide, a polycarbonate, a polyurethane, a polyester, and a fluorinated polymer. In some embodiments, the inorganic element 33 may comprise SiO2, Al2O3, ZrO2, CaO, CaCO3, SnO, ZnO, SiN x 、AlN x 、AlO x N y or SiO x N y and / or the polymeric element 35 of the crack mitigating composite 130a-c may comprise a polyimide derived from or otherwise comprise one or more of: poly(pyromellitic dianhydride-co-4,4'-oxydianiline) (PMDA-ODA); 4,4'-oxydiphthalic anhydride and 4,4'-diaminodiphenyl ether monomer (ODPA-ODA); biphenyltetracarboxylic dianhydride-4,4'-oxydianiline (BPDA-ODA); and a fluorinated polyimide. In some cases, the polymer component or the entire composite may exhibit high temperature tolerance, which can be characterized in a variety of ways, including one or more of the following: 1) a change in mass of 2% or less for a layer or the entire crack mitigating composite; and 2) a change in optical reflectance or transmittance of 2% or less after heating the article to 200° C. for 30 minutes, or in some cases, to 250° C. for 30 minutes.

[0162] According to some embodiments of laminated articles 100a-c, crack mitigating composites 130a-c include an inorganic component 33 and a polymeric component 35, with greater than about 20% by volume of material associated with the inorganic component 33 and greater than about 0.5% by volume or more of material associated with the polymeric component 35. For example, the amount of material associated with the inorganic component 35 may be greater than about 20%, 30%, 40%, 50%, 60%, and any amount in between. Preferably, the polymeric component 35 comprises a polymeric material having C-C, C-N, C-O, and / or C=C bonds as bonds forming the polymeric chain. Further, in some embodiments, the crack mitigating composites 130a-c may have a composite crack initiation strain (COS) value greater than about 0.8%, greater than 1%, greater than about 1.5%, and any COS values ​​between or above these levels. Furthermore, the crack mitigating composites 130a-c (including their inorganic component 33 and polymeric component 35) may be characterized by an elastic modulus greater than 30 GPa. For example, the crack mitigating composites 130a-c may be characterized by an elastic modulus of 30.5 GPa, 31 GPa, 32 GPa, 33 GPa, 34 GPa, 35 GPa, 40 GPa, 45 GPa, 50 GPa, etc., including all elastic modulus values ​​between these levels, contemplated up to 80 GPa, and in some cases even approaching 120 GPa.

[0163] Further, in some embodiments of the laminates 100a-c, the crack mitigating composites 103a-c can be characterized by an elastic modulus ratio between the inorganic component 33 and the polymeric component 35 that is greater than 10:1 (e.g., an inorganic component 33 having an elastic modulus of 150 GPa and a polymeric component having an elastic modulus of 10 GPa would result in an elastic modulus ratio of 15:1). For example, the crack mitigating composite 130a can have an elastic modulus ratio of 11:1, 12:1, 13:1, 14:1, 15:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, and all elastic modulus ratios between or above these ratios. According to some embodiments, for certain very low elastic modulus (e.g., <1 GPa) polymeric components 35 included in crack mitigating composites 130a-c along with relatively high elastic modulus (e.g., >75 GPa) inorganic components 33, the practical elastic modulus ratio limit for crack mitigating composites 130a-c is about 500:1.

[0164] Furthermore, if Figures 1B-1CAs shown, the crack mitigating composite 130b, 130c of the laminates 100b, 100c can include one or more layered inorganic elements 33 and one or more layered polymeric elements 35. Without being bound by theory, the retained strength, optical properties, and scratch resistance values ​​of the laminates 100b-c can be achieved for various qualities, combinations, thicknesses, and / or compositions of the one or more layers comprising each of the inorganic elements 33 and the polymeric elements 35. Preferably, laminates (e.g., laminates 100b, 100c) that utilize one or more layered inorganic elements 33 and polymeric elements 35, respectively, are such that the layers of inorganic elements 33 and polymeric elements 35 alternate. In some embodiments, the laminates 100b, 100c include the crack mitigating composite 130b, 130c such that a layer of the inorganic element 33 is in contact with at least one of the glass-based substrate 120 and the hardcoat 110. In the event that one layer of inorganic element 33 contacts both glass-based substrate 120 and hard film 110, the various layers of inorganic element 33 will serve this purpose, as at least one layer of polymeric element 35 will be disposed between these layers.

[0165] As described herein or previously, the "elastic modulus" or "average elastic modulus" of the crack mitigating composites 130b, 130c (including the inorganic and polymeric elements 33, 35 in their layered form) can be calculated by obtaining measurements of each layer of the inorganic and polymeric elements 33, 35 based on measurements of a single film having a thickness of approximately 100 nm to 1000 nm, and then calculating the bulk average elastic modulus of the crack mitigating composite 130b. Furthermore, the bulk average elastic modulus can be calculated as understood by one of ordinary skill in the art, for example, based on estimated or actual volume measurements of the various layers of the inorganic and polymeric elements 33, 35. Furthermore, these methods of calculating the average elastic modulus of the crack mitigating composite closely align with measurements of elasticity made directly on the crack mitigating composite by nanoindentation methods, also as described herein.

[0166] like Figure 1B and 1CAs shown, the crack mitigation composite 130b, 130c of the laminates 100b, 100c includes an inorganic element 33 having one or more layers having a thickness 63. In some aspects, the thickness 63 of each layer of the inorganic element 33 can be in the range of about 1 nm to about 200 nm, preferably about 5 nm to about 150 nm. Additionally, in some aspects, the thickness 65 of each layer of the polymeric element 35 can be in the range of about 1 nm to about 500 nm, preferably about 5 nm to about 300 nm. According to another embodiment, the total thickness 13b of the crack mitigation composite 130b can be in the range of about 10 nm to about 1000 nm. In another aspect, the total thickness 13b of the crack mitigation composite 130b is in the range of about 50 nm to about 750 nm. In further embodiments, the crack mitigating composite 130b has a total thickness 13b in the range of about 25 nm to about 1000 nm, about 50 nm to about 800 nm, about 50 nm to about 700 nm, about 50 nm to about 600 nm, about 50 nm to about 500 nm, and all total thickness ranges and sub-ranges within these ranges.

[0167] In some embodiments, the laminated articles 100b, 100c may include a crack mitigating composite 130b, 100c that is controlled by the thickness ratio of its inorganic component 33 and polymeric component 35 layers. For example, the ratio of the total thickness of the polymeric component 35 (i.e., the sum of the values ​​of the thickness 65 of each layer therein) to the total thickness of the inorganic component 33 (i.e., the sum of the values ​​of the thickness 63 of each layer therein) may be from about 0.1:1 to about 5:1. In other embodiments, the thickness ratio may be from about 0.2:1 to about 3:1. As further understood herein, the embodiments of the laminated articles 100b, 100c and crack mitigating composites 130b, 130c controlled by the thickness ratio are configured such that the thickness ratio is calculated independent of any additional layers of the crack mitigating composite 130b, 130c added to one or both of the hardcoat 110 and / or the glass-based substrate 120. As described herein, such a layer is referred to as a “connecting layer,” which is typically one-half to one (or more) orders of magnitude thinner than the other layers in the inorganic element 33 and the organic element 35 .

[0168] According to other embodiments of the laminates 100b, 100c, the crack mitigating composite 130b, 130c comprises a hardness sufficient to preserve the scratch resistance of the film 110 while also exhibiting a toughness sufficient to improve or otherwise preserve the flexural strength of the glass-based substrate 120 and the hard film 110. To find a favorable balance between hardness and toughness, the elastic modulus E and the hardness H of the crack mitigating composite 130b, 130c can be adjusted by controlling the thickness ratio between the thickness of the individual layers of the polymeric element 35 (e.g., the sum of the individual thicknesses 63) and the total thickness 13b, 13c of the composite. Figure 6A and 6B , which is a graph showing the elastic modulus (GPa) and hardness (GPa) of a crack mitigating composite disposed on a glass-based substrate as a function of the ratio of the thickness of the polymer layer in the composite to the thickness of the entire crack mitigating composite, as measured by nanoindentation. Figure 6A and 6B It is evident that an increase in the thickness ratio of the total thickness of the polymeric elements to the total thickness of the crack mitigating composite (i.e., about 400 nm for the data point) more than reduces the elastic modulus and hardness levels of the laminate. Figure 6A and 6B The fitted lines for the data shown have R values ​​of 0.93 and 0.91, respectively. 2 , indicating a strong correlation between the thickness ratio and the elastic modulus or hardness of the crack mitigating composite.

[0169] With more particular reference to laminated articles 100a-c, the interfacial properties at the effective interface 140 between the hardcoat 110 and the crack mitigating composite 130a-c, or between the crack mitigating composite 130a-c and the substrate 120, are modified, generally by the crack mitigating composite 130a-c, such that the articles 100a-c substantially retain their average flexural strength and the hardcoat 110 retains its functional properties for its application, particularly scratch resistance. For example, in some embodiments of the laminated articles 100a-c, the articles are characterized by an average flexural strength that is greater than or equal to about 50% of the average flexural strength of a glass substrate (i.e., a glass substrate tested without the crack mitigating composite 130c and the hardcoat 110 structure disposed thereon).

[0170] exist Figures 1A-1CIn one or more embodiments of the illustrated laminates 100a-c, the crack mitigating composites 130a-c can form a preferred crack propagation path without bridging between the hard film 110 and the glass-based substrate 120. In other words, the crack mitigating composites 130a-c can deflect a crack that forms in one of the film 110 and the glass-based substrate 120 and propagates toward the other of the film 110 and the glass-based substrate 120 into the crack mitigating composites 130a-c. In such embodiments, the crack can propagate through the crack mitigating composites 130a-c in a direction substantially parallel to at least one of the first interface 150 or the second interface 160 of the laminates 100a-c. Figure 5A As shown, when the crack is confined within the crack mitigating composite 130a-c, the crack becomes a cohesive failure 180. As used herein, the term "cohesive failure" relates to crack propagation being substantially confined within the crack mitigating composite 130a-c.

[0171] When the crack mitigating composites 130a-c are configured to produce Figure 5AWhen cohesive failure 180 is shown, in such embodiments, the crack mitigating compounds 130a-c provide a preferred crack propagation path. The crack mitigating compounds 130a-c can cause cracks to initiate in either the hard film 110 or the glass-based substrate 120 and propagate into the crack mitigating compounds 130a-c, thereby being retained within the crack mitigating compounds. Alternatively or additionally, the crack mitigating compounds 130a-c of the laminates 100a-c effectively confine cracks originating in one of the hard film 110 and the glass-based substrate 120 from propagating into the other of the film and the glass-based substrate. Similarly, the crack mitigating compounds 130a-c of the laminates 100a-c effectively confine cracks originating in one of the compounds 130a-c and the glass-based substrate 120 from propagating into the other of the compounds and the substrate. These behaviors, alone or together, can be characterized as crack deflection. As a result, cracks are deflected from bridging between the film 110 and the glass-based substrate 120, or between the crack mitigating composites 130a-c and the glass-based substrate 120. In one or more embodiments, the crack mitigating composites 130a-c can provide a low-toughness layer or interface exhibiting low fracture toughness and / or a low critical strain energy release rate, which can promote crack deflection into the crack mitigating composites 130a-c rather than through the crack mitigating composites into the film 110 and / or the glass-based substrate 120. As used herein, "facilitate" includes creating favorable conditions for cracks to deflect into the crack mitigating composites 130a-c rather than propagate into the glass-based substrate 120 or film 110. The term "facilitate" can also include providing a less tortuous path for crack propagation into and / or through the crack mitigating composites 130a-c rather than into the glass-based substrate 120 or film 110.

[0172] According to one or more embodiments of the laminates 100a-c, the average strain at break of the crack mitigating composites 130a-c can be greater than the average strain at break of the hard film 110. In one or more embodiments of the laminates 100a-c, the average strain at break of the crack mitigating composites 130a-c can be equal to or greater than about 0.5%, 0.7%, 1%, 1.5%, 2%, or even 4%. The average strain at break of the crack mitigating composites 130a-c can be 0.6%, 0.8%, 0.9%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 5%, or 6%, or more, and all ranges and subranges therebetween. In one or more embodiments, the average fracture strain (crack initiation strain) of the hard film 110 can be 1.5%, 1.0%, 0.7%, 0.5%, or even 0.4% or less, and all ranges and subranges therebetween. The average fracture strain of the film 110 can be 1.4%, 1.3%, 1.2%, 1.1%, 0.9%, 0.8%, 0.6%, 0.3%, 0.2%, 0.1%, or less, and all ranges and subranges therebetween. For the laminates 100a-c, the average fracture strain of the glass-based substrate can be greater than the average fracture strain of the hard film 110, and in some embodiments, greater than the average fracture strain of the crack mitigating composite 130a-c. In other specific embodiments of the laminates 100a-c, the crack mitigating composite 130a-c can have a higher average fracture strain than the glass-based substrate 120 to minimize any adverse mechanical effects of the crack mitigating composite on the glass-based substrate.

[0173] According to one or more embodiments, the critical strain energy release rate (G IC =K IC 2 / E) may be greater than the critical strain energy release rate of the hard film 110. In other examples, the crack mitigation composites 130a-c may exhibit a critical strain energy release rate that is 0.25 times or 0.5 times less than the critical strain energy release rate of the glass-based substrate. In a specific embodiment, the critical strain energy release rate of the crack mitigation composites 130a-c may be about 0.1 kJ / m 2 or less, about 0.09 kJ / m 2 or less, about 0.08kJ / m 2 or less, about 0.07 kJ / m 2 or less, about 0.06kJ / m 2or less, about 0.05kJ / m 2 or less, about 0.04 kJ / m 2 or less, about 0.03kJ / m 2 or less, about 0.02kJ / m 2 or less, about 0.01 kJ / m 2 or less, about 0.005kJ / m 2 or less, about 0.003kJ / m 2 or less, about 0.002kJ / m 2 or less, about 0.001 kJ / m 2 or less; but in some embodiments, the critical strain energy release rate of the crack mitigation composite 130a-c is greater than about 0.0001 kJ / m 2 (i.e. greater than about 0.1 J / m 2 ), and all ranges and subranges between the aforementioned values.

[0174] The crack mitigating compounds 130a-c used in the laminates 100a-c can have a refractive index greater than that of the glass-based substrate 120. In one or more embodiments, the refractive index of the crack mitigating compounds 130a-c can be less than that of the hardcoat 110. In some embodiments, the refractive index of the crack mitigating compounds 130a-c can be between the refractive indices of the glass-based substrate 120 and the film 110. For example, the refractive index of the crack mitigating compounds 130a-c can be in the range of about 1.45 to about 1.95, about 1.5 to about 1.8, about 1.6 to about 1.75, and all ranges and subranges therebetween. Alternatively, the refractive index of the crack mitigating compounds 130a-c can be substantially equal to the refractive index of the glass-based substrate over a substantial portion of the visible wavelength range (e.g., 450-650 nm), or no greater or lesser than that of the glass-based substrate by more than 0.05 refractive index units. In certain embodiments, the crack mitigating composites 130a-c are configured such that the optical transmittance of the substrate and crack mitigating composite differs by 1% or less from the optical transmittance of the substrate alone. In other words, the crack mitigating composites 130a-c can be configured such that the optical properties of the substrate (e.g., optical reflectivity and transmittance) are preserved.

[0175] In one or more embodiments, the crack mitigating compositions 130a-c of the laminates 100a, 100b, 100c are capable of withstanding high temperature processes. These processes may include vacuum deposition processes such as chemical vapor deposition (e.g., plasma-enhanced chemical vapor deposition), physical vapor deposition (e.g., reactive or non-reactive sputtering or laser ablation), thermal evaporation or electron beam evaporation, and / or atomic layer deposition. In one or more specific embodiments, the crack mitigating compositions 130a-c are capable of withstanding a vacuum deposition process in which the hardcoat 110 and / or other films disposed on the glass-based substrate 120 are deposited onto the crack mitigating compositions 130a-c by vacuum deposition. As used herein, the term "withstand" includes the crack mitigating compositions 130a-c withstanding temperatures exceeding 100° C., 200° C., 300° C., 400° C., 500° C., 600° C., and potentially even higher, such that no more than 10% weight loss and / or no more than 2% optical transmittance loss is observed in the crack mitigating compositions. In some embodiments, the crack mitigating composites 130a-c may be considered to withstand vacuum deposition or temperature treatment processes if, after film 110 and / or other films are deposited on a glass-based substrate (and deposited on crack mitigating composites 130a-c), the crack mitigating composites 130a-c experience a weight loss of less than or equal to 10%, less than or equal to 8%, less than or equal to 6%, less than or equal to 4%, less than or equal to 2%, or less than or equal to 1%. The deposition process (or testing after the deposition process) in which the crack mitigating composites 130a-c experience weight loss may include: temperatures of approximately 100° C. or greater, 200° C. or greater, 300° C. or greater, 400° C. or greater; an environment rich in a particular gas (e.g., oxygen, nitrogen, argon, etc.); and / or may be subjected to a high vacuum (e.g., 10 -6 The crack mitigation composite 130a or stack 130b may be formed in an environment where the crack mitigation composite 130a or stack 130b is deposited at a pressure between 100 torr (100 torr), at atmospheric conditions, and / or at pressures between high vacuum and atmospheric conditions. As will be discussed herein, the materials used to form the crack mitigation composite 130a or stack 130b may be specifically selected for their high temperature tolerance (i.e., ability to withstand high temperature processes, such as vacuum deposition processes) and / or their environmental tolerance (i.e., ability to withstand environments rich in specific gases or at specific pressures). These tolerances may include high temperature tolerance, high vacuum tolerance, low vacuum outgassing, high tolerance to plasma or ionized gases, high tolerance to ozone, high tolerance to UV, high tolerance to solvents, or high tolerance to acids or bases. In some cases, the crack mitigation composites 130a-c may be selected to pass the outgassing test of ASTM E595.

[0176] Various processes can be used to deposit, coat, or otherwise form the inorganic and polymeric components 33 and 35 of the crack mitigating composites 130a-c. For example, wet coating methods such as spin coating, spray coating, and dip coating can be utilized with various organic solvents, at least to form the polymeric component 35. Preferably, however, various vacuum-based deposition methods, such as thermal evaporation, electron beam evaporation, sputtering, and CVD methods, can be employed to facilitate the fabrication of both the inorganic and polymeric components 33 and 35. Vacuum deposition methods are advantageous because they do not rely on the use of any organic solvents (which can be toxic). Furthermore, vacuum deposition methods can provide greater control over thickness, layer uniformity, and adhesion between the various layers of the crack mitigating composites 130a-c and between the various layers of the composites and the hardcoat 110 or glass-based substrate 120, relative to other deposition and forming methods.

[0177] For example, these processing techniques can be Figure 7 , which is a cross-section of a laminate comprising a glass-based substrate 720, a hardcoat 710, and a crack mitigation composite 730 comprising two inorganic layers 733 and two polymeric layers 735, according to some embodiments of the present disclosure. Figure 7 In the laminated product, the organic layer (PMDA-ODA) 735 is co-evaporated by thermal evaporation, while the inorganic layer 733 (Al2O3) is deposited on the glass-based substrate 720 by electron beam evaporation. These steps are repeated to complete the crack mitigation composite 730, which contains two layers of polyimide and two layers of Al2O3. In addition, PMDA and ODA are polyimide precursors (e.g., polyimide precursors of the polymer layer 735), and when they are deposited onto the surface of the glass-based substrate 720 or the subsequent layer of the inorganic layer 733 and then thermally cured at 200°C, they undergo gradual polymerization to complete the formation of the polyimide layer. Using these vacuum-based deposition processes, for example, a laminated product as produced according to the aforementioned Figure 7 As depicted in the image of , both the inorganic layer 733 and the polymeric layer 735 of the crack mitigation composite 730 can be deposited in a single chamber capable of introducing multiple precursor sources. In a preferred embodiment, an additional ion cleaning step is performed between the deposition of the various layers comprising the inorganic layer 733 and the polymeric layer 735 to improve adhesion of subsequent layers and / or the hard film 710. In addition, the laminated articles 100a-100c (including Figure 7 The crack mitigation composites 130a-c of the article shown are then deposited using plasma enhanced chemical vapor deposition techniques to form a layer comprising silicon nitride (SiN xAt 200°C, SiNx scratch-resistant films (such as 100nm) were deposited using silane precursor gas and nitrogen in a high-density plasma-enhanced vapor deposition (HDPCVD) Versaline system from Plasma-Therm. Figure 7 membrane 710) shown.

[0178] Furthermore, the laminates 100a-c ( Figures 1A-1C ) can exhibit higher temperature tolerance, robustness to UV ozone or plasma treatment, UV transparency, robustness to environmental aging, low outgassing in a vacuum environment, etc. In the case where the hard film 110 is also formed by vacuum deposition, both the crack mitigating compounds 130a-c and the film 110 can be formed in the same or similar vacuum deposition chamber, or formed using the same or similar coating equipment.

[0179] According to some embodiments, the laminated articles 100a-c comprising the crack mitigation composites 130a-c are characterized in that the hard film 110 does not peel or does not substantially peel from the article when the film 110 is exposed to a garnet scratch test. As used herein, the "garnet scratch test" is performed by attaching a circular piece of 150 grit garnet sandpaper, about 6 mm in diameter, to the head of a Taber Abraser unit using double-sided tape. A total load of 1 kg is applied to the abrasive head (an additional load of about 650 g plus a mandrel load of about 350 g). Alternatively, a total load of 4 kg can be applied. The abrasive head is then swept across the surface of the sample for a length of about 30 mm in a single scratch, and the scratch is then inspected. While some scratches or damage marks were visible on the samples, the "substantially no peeling" standard as used herein is defined as the absence of visible areas of complete separation of the scratch-resistant film 110 from the substrate greater than approximately 100 microns in any spatial dimension within the central region of a ~30 mm garnet scratch path when inspected using an optical display microscope. In other words, "peeling" or "peel-related failure" is defined as the complete removal of the scratch-resistant film after undergoing the garnet scratch test. According to this standard, aspects of the present disclosure exhibited substantially no peeling when subjected to the garnet scratch test using both a total load of 1 kg and a total load of 4 kg.

[0180] Crack mitigation compounds 130a-c (see Figures 1A-1C) can be substantially optically clear and free of light scattering, for example, having an optical transmission haze of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, and all ranges and sub-ranges therebetween. As described herein, the transmission haze of the layer can be controlled by controlling the average size of the pores in the crack mitigating composites 130a-c. Exemplary average pore sizes in the layer can include 200 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, 10 nm or less, 5 nm or less, and all ranges and sub-ranges therebetween. These pore sizes can be estimated from light scattering measurements or directly analyzed using transmission electron microscopy (TEM) and other known methods.

[0181] In some embodiments, the crack mitigating compounds 130a-c can exhibit a refractive index similar to that of either the glass-based substrate 120 and / or the hardcoat 110 to minimize optical interference effects. Thus, the crack mitigating compounds 130a-c can exhibit a refractive index slightly higher than, equal to, or slightly lower than that of the substrate 120 and / or the hardcoat 110. Additionally or alternatively, the crack mitigating compounds 130a-c can exhibit a refractive index that can be adjusted to achieve an anti-reflective interference effect. The refractive index of the crack mitigating compounds 130a-c can be slightly adjusted by controlling the relative amounts and compositions of the inorganic element 33 and the polymeric element 35, as well as the thickness of any layers comprising the elements 33, 35 (e.g., as described above). Figure 1B and 1C The crack mitigating composites 130b, 130c shown are identical).

[0182] The thickness 13a-c of the crack mitigating composite 130a-c for the laminates 100a-c (which includes an average thickness in the case of variations in the crack mitigating composite) can be in the following ranges: about 0.001 μm to about 10 μm (1 nm to 10,000 nm), about 0.01 μm to about 1 μm (10 nm to about 1000 nm), about 0.05 μm to about 0.75 μm (50 nm to about 750 nm), about 0.01 μm to about 0.5 μm (10 nm to about 500 nm), about 0.02 μm to about 0.2 μm (20 nm to about 200 nm). In one or more embodiments, the thickness 13a-c of the crack mitigation composites 130a-c is in the range of about 0.02 μm to about 10 μm, about 0.03 μm to about 10 μm, about 0.04 μm to about 10 μm, about 0.05 μm to about 10 μm, about 0.06 μm to about 10 μm, about 0.07 μm to about 10 μm, about 0.08 μm to about 10 μm, about 0.09 μm to about 10 μm, about 0.1 μm to about 10 μm, about 0.01 μm to about 9 μm, about 0.01 μm to about 10 μm. about 8 μm, about 0.01 μm to about 7 μm, about 0.01 μm to about 6 μm, about 0.01 μm to about 5 μm, about 0.01 μm to about 4 μm, about 0.01 μm to about 3 μm, about 0.01 μm to about 2 μm, about 0.01 μm to about 1 micron, about 0.02 μm to about 1 micron, about 0.03 to about 1 μm, about 0.04 μm to about 0.5 μm, about 0.05 μm to about 0.25 μm, or about 0.05 μm to about 0.15 μm, and all ranges and subranges between the foregoing values.

[0183] In one or more embodiments, the thicknesses of the glass-based substrate 120, the hardcoat 110, and / or the crack mitigation composites 130a-c (e.g., thicknesses 12, 11, and 13a-c, respectively) may be specified relative to one another (see Figures 1A-1C ). For example, the thickness 13a-c of the crack mitigating composites 130a-c can be less than or equal to 10 times the thickness 11 of the hard film 110. In another example, if the thickness 11 of the hard film 110 is approximately 85 nm, the thickness 13a-c of the crack mitigating composites 130a-c can be approximately 850 nm or less. In another example, the thickness 13a-c of the crack mitigating composites 130a-c can be in the range of approximately 35 nm to approximately 80 nm, and the thickness 11 of the film 110 can be in the range of approximately 30 nm to approximately 300 nm. In another example, the thickness 13a-c of the crack mitigating composites 130a-c can be in the range of approximately 150 nm to approximately 450 nm, and the thickness 11 of the film 110 can be in the range of approximately 1 micron to approximately 3 microns.

[0184] In one variation, the thickness 13a-c of the crack mitigating composites 130a-c may be less than or equal to about 9, 8, 7, 6, 5, 4, 3, or twice the thickness 11 of the film 110, and all ranges and sub-ranges therebetween. In another variation, the thickness 11 of the film 110 and the thickness 13a-c of the crack mitigating composites 130a-c are each less than about 10 μm, less than about 5 μm, less than about 2 μm, less than about 1 μm, less than about 0.5 μm, or less than about 0.2 μm, and all ranges and sub-ranges therebetween. In some embodiments, the ratio of the thickness 13a-c of the crack mitigating compounds 130a-c to the thickness 11 of the film 110 can be in the range of about 1:1 to about 1:20, in the range of about 1:2 to about 1:6, in the range of about 1:3 to about 1:5, or in the range of about 1:3 to about 1:4, and all ranges and sub-ranges therebetween. In another variation, the thickness 13a, 13b of the crack mitigating compounds 130a-c is less than about 0.4 μm, and the thickness 11 of the film 110 is greater than the crack mitigating compounds 130a-c.

[0185] Additionally or alternatively, an indium tin oxide layer, a scratch resistant layer (e.g., AlO x N y, AlN, and combinations thereof), and an antireflective layer; and the crack mitigation composites 130a-c form a stacked element having a low total optical reflectivity. For example, in the visible wavelength range of 450-650 nm, 420-680 nm, or even 400-700 nm, the stacked element may have an overall (or total) reflectivity of 15% or less, 10% or less, 8% or less, 7% or less, 6.5% or less, 6% or less, 5.5% or less, and all ranges and subranges therebetween. The above reflectivity values ​​may exist in some embodiments, which include the reflectivity of a blank (or uncoated) glass interface (e.g., glass-based substrate 120) (wherein the reflectivity from the uncoated glass interface itself is about 4%), or can be characterized as the reflectivity from the first major surface of the glass-based substrate and the stack element (and associated interfaces) disposed on the first major surface (excluding the 4% reflectivity from the uncoated second major surface of the glass-based substrate). When one or more major surfaces of the glass-based substrate 220 are covered by a typical encapsulant (i.e., an additional film or layer) and the encapsulant has a refractive index of about 1.45-1.65, the average reflectivity from only the stack element structure and the coated interface of the stack element-glass (minus the reflectivity of the uncoated glass interface) in the visible wavelength range of 450-650 nm, 420-680 nm, or even 400-700 nm can be less than about 5%, 4%, 3%, 2%, or even less than about 1.5%, and all ranges and sub-ranges therebetween. In addition, the stack element can exhibit high optical transmittance, according to the following general relationship, this surface has both low reflectivity and low absorptivity. In the visible wavelength range of 450-650nm, 420-680nm, or even 400-700nm, the stack element's base transmittance value (when ignoring the reflectivity and absorptivity associated with the separate glass-based substrate 120 or encapsulation layer) can be greater than about 75%, 80%, 85%, 90%, 95%, or even 98%, and all ranges and sub-ranges therebetween.

[0186] The laminates 100a-c can be tailored by varying one or more properties of the hardcoat 110, the crack mitigating composites 130a-c, and / or the glass-based substrate 120 (see Figures 1A-1C) optical properties. For example, in the visible wavelength range of about 400 nm to about 700 nm, the articles 100a-c can exhibit a total reflectivity of 15% or less, 10% or less, 8% or less, 7% or less, 6.9% or less, 6.8% or less, 6.7% or less, 6.6% or less, 6.5% or less, 6.4% or less, 6.3% or less, 6.2% or less, 6.1% or less, and / or 6% or less, and all ranges and subranges therebetween. The ranges can be further varied as specified above, and the ranges for the stack element (i.e., such as a stack element comprising the hardcoat 110 and the crack mitigating composite 130a-c) / coated glass interface itself are listed above. In more specific embodiments, the articles 100a-c described herein can exhibit a lower average reflectivity and a greater average flexural strength than articles without the crack mitigating composite 130a-c. In one or more alternative embodiments, at least two of the optical, electrical, or mechanical properties of the articles 100a-c can be adjusted by varying the thickness of the glass-based substrate 120, the film 110, and / or the crack mitigation composites 130a-c. Additionally or alternatively, the average flexural strength of the articles 100a-c can be adjusted or improved by varying the thickness of the glass-based substrate 120, the film 110, and / or the crack mitigation composites 130a-c.

[0187] Furthermore, the reflectivity of the glass-based substrate 120 coated with the crack mitigating composite 130a-c can be within 2% or within 1% of the refractive index of the glass-based substrate itself. The refractive index of the crack mitigating composite can be less than 1.55 higher, 1.35 to 1.55 higher, or no higher than 0.05 higher than the refractive index of the substrate. The crack mitigating composite can have a total absorption and scattering value of less than 5% of the incident optical energy in the visible wavelength range of 400-800 nm.

[0188] Articles 100a-c (see Figures 1A-1C) may include one or more additional films (not shown) disposed on the glass-based substrate 120. In one or more embodiments of the articles 100a-c, the one or more additional films may be disposed on the hardcoat 110, or more generally, on a major surface opposite the film 110. Some of the additional films may be disposed in direct contact with the film 110. In one or more embodiments, the additional films may be positioned: 1) between the glass-based substrate 120 and the crack mitigating composite 130a-c (e.g., in the laminated articles 100a-c); or 2) between the crack mitigating composite 130a-c and the film 110. In one or more embodiments, both the crack mitigating composite 130a-c and the film 110 may be positioned between the glass-based substrate 120 and the additional films. Additional films may include protective layers, adhesive layers, planarization layers, anti-splintering layers, optical bonding layers, display layers, polarizing layers, light absorbing layers, reflection-modifying interference layers, scratch-resistant layers, barrier layers, passivation layers, hermetic layers, diffusion barriers, and combinations thereof, as well as other layers known in the art, to perform these or related functions. Examples of suitable protective or barrier layers include SiO-containing x 、SiN y 、SiO x N y or other similar materials and combinations thereof. These layers can also be modified to match or complement the optical properties of the hardcoat 110, the crack mitigating composites 130a-c, and / or the glass-based substrate 120. For example, the protective layer can be selected to have a similar refractive index as the crack mitigating composites 130a-c, the film 110, or the glass-based substrate 120.

[0189] In one or more embodiments, the articles 100a-c may be used in information display devices and / or touch sensing devices. In one or more alternative embodiments, the articles 100a-c may be part of a laminated structure, for example, as a glass-polymer-glass laminated safety glass for automotive or aircraft windows. An exemplary polymer material for use as an interlayer in these laminates is PVB (polyvinyl butyral), and many other interlayer materials are known in the art. Furthermore, there are a variety of options for the structure of the laminated glass, and there are no particular limitations. In the final application, for example, as an automotive windshield, sunroof, or side window, the articles 100a-c may be curved or shaped. The thickness 100a-c of the articles 100a-c may vary for design or mechanical reasons; for example, the articles 100a-c may be thicker at the edges than at the center of the article. The articles 100a-c may be acid polished or otherwise treated to remove or reduce the effects of surface imperfections.

[0190] Some embodiments of the present disclosure relate to cover glass applications utilizing the articles 100a-c described herein. In one or more embodiments, the cover glass may include a laminate having a glass-based substrate 120 (which may be strengthened or unstrengthened), a hard film 110 (e.g., AlO x N y 、AlN、SiO x N y 、SiAl v O x N y , Si3N4) and crack mitigation composites 130a-c comprising inorganic and polymeric components. Laminated articles 100a-c may include one or more additional films to reduce reflections and / or provide an easy-to-clean or anti-fingerprint surface on the laminate. Specifically, a silane or fluorinated silane layer of approximately 1-10 nm thick may be applied to the surface of the hardcoat to reduce friction, improve cleanability, or help reduce scratches on the user surface of the article.

[0191] Some embodiments of the present disclosure relate to touch sensing devices comprising articles described herein. In one or more embodiments, the touch sensor device may include a glass-based substrate 120 (which may be strengthened or unstrengthened), a hard film 110 (e.g., such as a hard film comprising a transparent conductive oxide and a scratch-resistant material such as AlO), and a substrate 120 having a plurality of surfaces. x N y 、AlN、SiO x N y 、SiAl v O x N y, Si3N4, and combinations thereof) and crack mitigation composites 130a-c. The transparent conductive oxide may comprise indium tin oxide, aluminum zinc oxide, fluorinated tin oxide, or other substances known in the art. In one or more embodiments, the conductive oxide portion of the hard film 110 is disposed discontinuously on the glass-based substrate 120. In other words, the conductive portion of the hard film 110 may be disposed on discrete areas of the glass-based substrate 120 (having the crack mitigation composites 130a-c). The discrete areas having the film form patterned or coated areas (not shown), while the discrete areas without the film form unpatterned or uncoated areas (not shown). In one or more embodiments, the patterned or coated areas and the unpatterned or uncoated areas are formed by continuously disposing the film 110 on the surface of the crack mitigation composites 130a-c, which in turn are located on the surface of the glass-based substrate 120, and then selectively etching away the film 110 in discrete areas to leave no film 110 in these discrete areas. The film 110 can be etched away using an etchant, such as an aqueous solution of HCl or FeCl3, such as TE-100 etchant commercially available from Transene Co. In one or more embodiments, the crack mitigation composites 130a-c are not significantly degraded or removed by the etchant. Alternatively, the film 110 can be selectively deposited onto discrete areas of the surface of the crack mitigation composites 130a-c, which in turn are on the surface of the glass-based substrate 120, thereby forming patterned or coated areas and unpatterned or uncoated areas.

[0192] In one or more embodiments of laminates 100a-c having a hard film 110 comprising conductive oxide portions and discrete regions, the total reflectivity of the uncoated regions is similar to the total reflectivity of the coated regions. In one or more embodiments, the total reflectivity of the unpatterned or uncoated regions differs from the total reflectivity of the patterned or coated regions by about 5% or less, 4.5% or less, 4% or less, 3.5% or less, 3% or less, 2.5% or less, 2.0% or less, 1.5% or less, or even 1% or less, and all ranges and subranges therebetween, within the visible wavelength range of about 400 nm to about 800 nm, about 450 nm to about 650 nm, about 420 nm to about 680 nm, or even about 400 nm to about 700 nm, and all ranges and subranges therebetween.

[0193] In some embodiments of the present disclosure, articles 100a-c comprising crack mitigation composites 130a-c and hard film 110 (which may comprise indium tin oxide or other transparent conductive oxides) exhibit a resistivity acceptable for use in touch sensing devices. In one or more embodiments, when film 110 is present in an article disclosed herein, the film 110 exhibits a sheet resistance of about 100 ohms / square or less, 80 ohms / square or less, 50 ohms or less, or even 30 ohms / square or less. In such embodiments, the film may have a thickness of about 200 nm or less, 150 nm or less, 100 nm or less, 80 nm or less, 50 nm or less, or even 35 nm or less, and all ranges and sub-ranges therebetween. In one or more specific embodiments, when the film is present in articles 100a-c, the film exhibits a resistivity of 10 x 10 -4 Ω-cm or less, 8x 10 -4 Ω-cm or less, 5x 10 -4 Ω-cm or less, or even 3x 10 -4 Ω-cm or less, and all ranges and sub-ranges therebetween. Thus, when hard film 110 is present in the articles 100a-c described herein having a conductive oxide portion, the hard film 110 can advantageously maintain the electrical and optical properties expected of transparent conductive oxide films and other such films used in touch sensing applications, including projected capacitive touch sensing devices.

[0194] The disclosure herein may also be applied to articles 100a-c and may also be applied to non-interactive or non-display articles 100a-c; for example, such articles may be used in situations where a device has a glass front side that is interactive and used for display and a back side that may be referred to in a very broad sense as "decorative," meaning that the back side may be "painted" with a certain color, with artwork or information about the manufacturer, model and serial number, texture, or other features.

[0195] For laminates 100a-c (see Figures 1A-1C ) optical properties, the hard film 110 may include scratch-resistant materials such as AlN, Si3N4, AlO x N y and SiO x N y, which possesses a relatively high refractive index of about 1.7 to about 2.1. The glass-based substrate 120 used in the laminated articles 100a-c typically has a refractive index of about 1.45 to about 1.65. In addition, the refractive index of the crack mitigating composite 130a-c used in the articles 100a-c is typically close to or somewhere between the refractive index range common to the substrate 120 and the film 110 (when present). Differences in these index values ​​(e.g., differences between the substrate 120 and the crack mitigating composite 130a-c) can result in undesirable optical interference effects. Specifically, at the interfaces 150 and / or 160 (see Figures 1A-1C ) can result in spectral reflectance oscillations that produce the apparent color observed in the articles 100a-c. Because the spectral reflectance oscillations shift with incident illumination angle, the color in the reflection also shifts with viewing angle. Ultimately, the observed color and color shift that vary with incident illumination angle is often distracting or objectionable to the user of the device, particularly under illumination with sharp spectral features, such as fluorescent illumination and some LED illumination. Additionally or alternatively, the crack mitigating composites 130a-c and / or the hardcoat 110 can have various layers or sublayers having alternating high and low refractive indices, thereby providing an optical impedance modulation effect that can be used to reduce reflectivity, control reflectivity to match a target value, reduce color, or reduce color shift in the coated article, as further described in the Examples below.

[0196] According to aspects of the present disclosure, by making the interface 150 and / or the interface 160 (see Figures 1A-1C ) can reduce observed tint and color shift, thereby reducing reflectance oscillations and reflectance color shifts throughout the article. In some aspects, the density, thickness, composition, and / or porosity of the crack mitigation composites 130a-c can be adjusted to minimize such reflectance at interfaces 150 and 160. For example, constructing layers 130a-c according to the aforementioned aspects can reduce the amplitude and / or oscillations of reflectance within the visible spectrum.

[0197] As used herein, the term "amplitude" includes the peak-to-valley variation in reflectivity or transmittance. Also as used herein, the term "transmittance" is defined as the percentage of incident light power within a given wavelength range that is transmitted through the articles 100a-c. The term "average transmittance" refers to the spectral average of the light transmittance multiplied by the optical efficiency function, as described by the CIE standard observer. The term "reflectivity" is defined as the percentage of incident light power within a given wavelength range that is reflected from the articles 100a-c. Generally, transmittance and reflectance are measured using a specific linewidth. In addition, the term "average amplitude" includes the peak-to-valley variation in reflectivity or transmittance averaged over every possible 100nm wavelength range within the optical wavelength region. As used herein, "optical wavelength region" includes the range of about 400nm to about 800nm.

[0198] According to one or more embodiments, the laminated articles 100a-c exhibit an average transmittance of 85% or greater across the visible spectrum. In some embodiments, the laminated articles 100a-c may exhibit an average transmittance of 80% or greater, 82% or greater, 85% or greater, 90% or greater, 91% or greater, 92% or greater, 93% or greater, 94% or greater, or 95% or greater, and all ranges and subranges therebetween.

[0199] In some aspects, the articles 100a-c exhibit an average total reflectance across the visible spectrum of 20% or less. For example, certain embodiments of the articles 100a-c exhibit a total reflectance of 20% or less, 15% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, or 5% or less, 4% or less, 3% or less, 2% or less, and all ranges and subranges therebetween.

[0200] According to one or more embodiments, the total reflectivity of the articles 100a-c is equal to or less than the total reflectivity of the glass-based substrate 120. In one or more embodiments, the articles 100a-c exhibit a relatively flat transmission spectrum, reflection spectrum, or transmission and reflection spectrum over the optical wavelength regime. In some embodiments, the relatively flat transmission and / or reflection spectrum comprises an average amplitude of about 5 percentage points or less along the entire optical wavelength regime or within some wavelength range segment within the optical wavelength regime. The wavelength range segment can be about 50 nm, about 100 nm, about 200 nm, or about 300 nm, and all ranges and sub-ranges therebetween. In some embodiments, the average oscillation amplitude can be about 4.5 percentage points or less, about 4 percentage points or less, about 3.5 percentage points or less, about 3 percentage points or less, about 2.5 percentage points or less, about 2 percentage points or less, about 1.75 percentage points or less, about 1.5 percentage points or less, about 1.25 percentage points or less, about 1 percentage point or less, about 0.75 percentage points or less, about 0.5 percentage points or less, about 0.25 percentage points or less, or about 0 percentage points, and all ranges and subranges therebetween. In one or more specific embodiments, articles 100 and 100a have a transmittance within a selected wavelength range segment of about 100 nm or 200 nm in the optical wavelength regime, wherein the maximum peak of the oscillation from the spectrum is about 80%, about 82%, about 84%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94% or about 95%, and all ranges and sub-ranges therebetween.

[0201] In some embodiments, the relatively stable average transmittance and / or average reflectance includes a maximum amplitude along a specific wavelength range segment in the optical wavelength regime, expressed as a percentage of the average transmittance or average reflectance. The average transmittance or average reflectance of the laminates 100a-c is also measured along the same specific wavelength range segment in the optical wavelength regime. The wavelength range segment can be about 50 nm, about 100 nm, or about 200 nm. In one or more embodiments, the articles 100 and 100a have an average oscillation amplitude of average transmittance and / or average reflectance of about 10% or less, about 5% or less, about 4.5% or less, about 4% or less, about 3.5% or less, about 3% or less, about 2.5% or less, about 2% or less, about 1.75% or less, about 1.5% or less, about 1.25% or less, about 1% or less, about 0.75% or less, about 0.5% or less, about 0.25% or less, or about 0.1% or less, and all ranges and sub-ranges therebetween. Within the optical wavelength regime, the articles have such percentage-based average oscillation amplitudes along wavelength range segments of about 50 nm, about 100 nm, about 200 nm, or about 300 nm. For example, within the optical wavelength regime, the article of the present disclosure may have an average transmittance of about 85% along a wavelength range of about 500 nm to about 600 nm, which is an approximately 100 nm wavelength segment. The article may also have a percentage-based oscillation amplitude of about 3% along the same wavelength range (500 nm to about 600 nm), meaning that the absolute (non-percentage-based) oscillation amplitude along the wavelength range of 500 nm to 600 nm is about 2.55 percentage points.

[0202] Some embodiments relate to electronic devices (not shown) comprising the articles 100a-c disclosed herein. These electronic devices may include any device or article having a display [e.g., consumer electronics, including cell phones, tablets, computers, wearable devices (e.g., watches), navigation systems, etc.], architectural products, transportation products (e.g., cars, trains, aircraft, ships, etc.), electrical products, or any article requiring a certain degree of transparency, scratch resistance, abrasion resistance, or a combination of the above properties. The cell phone may include a housing; electronic components at least partially or completely located within the housing, including at least a controller, memory, and a display, the display being at or near the front surface of the housing; and a laminated article 100a-c at or above the front surface of the housing so that it is above the display. Additional applications of the articles of the present disclosure need not necessarily include electronic devices, such as eyeglasses, sunglasses, windows, windshields of cars or aircraft, or glass-based screen protectors laminated to electronic devices using adhesives.

[0203] In one or more embodiments, the method includes applying the hard film 110 and / or the crack mitigation compounds 130a-c via a vacuum deposition process. In specific embodiments, the vacuum deposition process may employ temperatures of approximately 25°C, 50°C, 75°C, 100°C, 200°C, 300°C, 400°C, and all ranges and sub-ranges therebetween. In some embodiments, the crack mitigation compounds 130a-c may be formed via a wet process.

[0204] In one or more specific embodiments, the method includes controlling the thickness of the crack mitigating composites 130a-c and / or the hard film 110. Controlling the thickness of the crack mitigating composites 130a-c and / or films (e.g., the hard film 110) disclosed herein can be performed by controlling one or more processes for forming the crack mitigating composites, stacks, and / or films, such that the crack mitigating composites, stacks, and / or films are applied with a desired or defined thickness. In some embodiments, the method includes controlling the thickness of the crack mitigating layers 130a-c and / or the hard film 110 to maintain (or, in some cases, enhance) the average flexural strength of the glass-based substrate 120, the functional properties of the glass-based substrate 120, and / or the functional properties of the film 110.

[0205] In one or more alternative embodiments, the method includes controlling the continuity of the crack mitigating compounds 130a-c and / or the hard film 110. Controlling the continuity of the crack mitigating compounds 130a-c or the stack 130b may include forming a cracked crack mitigating compound and removing selected portions of the crack mitigating compound or stack to produce a discontinuous crack mitigating compound. In other embodiments, controlling the continuity of the crack mitigating compound or stack may include selectively forming the crack mitigating compound or stack to form a discontinuous crack mitigating compound or stack. Such embodiments may use masks, etchants, and combinations thereof to control the continuity of the crack mitigating compounds 130a-c.

[0206] In one or more embodiments, the method may include creating a controlled elastic modulus in the crack mitigating composites 130a-c. The method may also include controlling the inherent film stress of the crack mitigating composite 130a, stack 130b, and / or film 110 by controlling the deposition and fabrication process of the crack mitigating composite or stack.

[0207] As described herein, the method may include disposing an additional film on the glass-based substrate 120. In one or more embodiments, the method may include depositing the additional film on the glass-based substrate such that the additional film is disposed between the glass-based substrate 120 and the crack mitigation composite 130a-c, between the crack mitigation composite 130a-c and the hard film 110, or such that the film 110 is located between the crack mitigation composite 130a-c and the additional film. Alternatively, the method may include disposing the additional film on a major surface of the glass-based substrate 120 opposite the surface on which the film is disposed.

[0208] In one or more embodiments, the method includes strengthening the glass-based substrate 120 before or after the crack mitigating composites 130a-c, the hard film 110, and / or the additional film are disposed on the glass-based substrate. The glass-based substrate 120 may be strengthened by chemical strengthening or other means. The glass-based substrate 120 may be strengthened after the crack mitigating composites 130a-c are disposed on the glass-based substrate 120 but before the film 110 is disposed on the glass-based substrate. The glass-based substrate 120 may be strengthened after the crack mitigating composites 130a-c and the film 110 are disposed on the glass-based substrate 120 but before the additional film, if any, is disposed on the glass-based substrate. If no additional film is used, the glass-based substrate 120 may be strengthened after the crack mitigating composites 130a-c and the film 110 are disposed on the glass-based substrate.

[0209] The following examples represent certain non-limiting embodiments of the present disclosure.

[0210] Example 1: Strength of laminates with five layers of Al2O3 / polyimide crack mitigation composite and silicon nitride hard film.

[0211] By providing 2320Gorilla Laminate samples designated Examples 1A-1C ("Ex. 1A, Ex. 1B, Ex. 1A1, Ex. 1B1, and Ex. 1C") were formed using glass-based substrates having a composition of about 67 mol% SiO2, about 4 mol% B2O3, about 13 mol% Al2O3, about 14 mol% Na2O, and about 2.5 mol% MgO. The glass-based substrates had a thickness of 1 mm (Ex. 1A, Ex. 1B) or 0.7 mm (Ex. 1A1, Ex. 1B1, and Ex. 1C). The glass-based substrates were strengthened by ion exchange to provide a surface CS of about 800 MPa and a DOC of about 40 μm. The ion exchange process was performed by immersing the glass-based substrates in a bath of molten potassium nitrate (KNO3) heated to a temperature of about 350°C to 450°C. The glass-based substrate was immersed in the bath for 3-8 hours to obtain the surface CS and DOC. After the ion exchange process was completed, the glass-based substrates of Examples 1A-1C were cleaned in a KOH detergent solution provided by Semiclean KG at a temperature of about 50°C and a concentration of 2%. In Example 1, the Ex. 1C sample represents a control because it contains only a glass-based substrate. Similarly, the Ex. 1A and Ex. 1A1 samples were also used as controls because they have SiN with a thickness of about 440 nm. x In the samples Ex.1A and Ex.1A1, SiN was deposited at 200°C using silane precursor gas and nitrogen in a Versaline HDPCVD system from Plasma-Therm. x Dura mater.

[0212] In Example 1, samples designated as Ex. 1B and Ex. 1B1 were also prepared. For the Ex. 1B and Ex. 1B1 samples, the SiN x Strengthened glass-based substrates and hard films were prepared using a 0.7 mm or 1 mm thick film and a glass-based substrate. In addition, Ex. 1B and Ex. 1B1 each had a crack mitigation composite comprising a sequence of five Al2O3 and polyimide ("PI") layers, each having the following thickness: 10 nm Al2O3 (on the substrate) / 75 nm PI / 75 nm Al2O3 / 75 nm PI / 75 nm Al2O3 (directly below the hard film).

[0213] A ring-on-ring (ROR) load-to-failure test was used to demonstrate the retention of the average flexural strength of Ex. 1A-1C. For the ring-on-ring load-to-failure test, the side with the film and / or crack mitigation composite was placed in tension. Ring-on-ring load-to-failure test parameters included a contact radius of 1.6 mm (0.063 in), a crosshead speed of 1.2 mm / min (0.047 in / min), a load ring diameter of 1.27 mm (0.5 in), and a support ring diameter of 2.54 cm (1 in). Prior to testing, adhesive films were placed on both sides of the sample to be tested to contain broken glass fragments.

[0214] like Figure 8 As shown, a crack mitigation composite (such as one comprising a five-layer Al2O3 / PI layer sequence) is added to a substrate having SiN x Laminates of hardcoat and glass-based substrates [Ex. 1B (1 mm thick substrate) and Ex. 1B1 (0.7 mm thick substrate)] resulted in laminate failure loads that were approximately 36% and 42% higher (1 mm thick and 0.7 mm thick substrates) relative to laminates of similar construction but without the crack mitigating composite (i.e., Ex. 1A-1B and Ex. 1A1-1B1). Figure 8 As shown, the inclusion of a scratch-resistant film having a thickness of 440 nm (Ex. 1B and Ex. 1B1) but without a crack mitigating compound significantly reduced the average flexural strength of the glass-based substrate (see Ex. 1C). Given the relatively small difference in average flexural strength observed between the two groups of samples having different thicknesses of the glass-based substrate (i.e., 36% and 42%, respectively), it is clear that the thickness of the glass-based substrate does not have a significant impact on the significant effect of the crack mitigating compound.

[0215] Example 2: Scratch resistance of laminates with five layers of Al2O3 / polyimide crack mitigation composite and silicon nitride hard film.

[0216] Now refer to Figures 9A-9D , which are optical micrographs from respective laminates comprising a glass-based substrate having a hardcoat comprising a 2 micron thick silicon nitride layer and a fluorosilane layer, and respective laminates having no crack mitigating composite ( Figure 9A ), having a crack mitigation composite comprising three thick aluminum oxide layers and two thin polyimide layers ( Figure 9B ), having a crack mitigation composite comprising three thin aluminum oxide layers and two thick polyimide layers ( Figure 9C ), or with a crack mitigating compound comprising only polyimide ( Figure 9D ).make Figures 9A-9D Each sample shown was subjected to a garnet scratch test with a 4 kg load. More specifically, Figure 9AThe laminate shown is constructed with a fluorosilane and silicon nitride multilayer hard film directly over a glass-based substrate. Figure 9B and 9C The laminate shown is constructed with a multilayer hardcoat of fluorosilane and silicon nitride followed by five layers of crack mitigating composite directly over a glass-based substrate. Figure 9B and 9C The five-layer crack mitigation composite of the laminate comprises: Al2O3 / PI / Al2O3 / PI / Al2O3, with thicknesses of: 100 / 50 / 100 / 50 / 20 nm ( Figure 9B ) and 25 / 125 / 25 / 125 / 20nm( Figure 9C ) and having a 20 nm Al2O3 layer, which was found to act as an adhesion promoting layer when placed adjacent to a glass substrate. In contrast, it was found that placing a polyimide layer or SiO2 layer in close proximity to a glass substrate having a crack mitigating composite structure resulted in poor adhesion and scratch resistance in these laminates. Finally, Figure 9D The laminate shown is constructed with a multilayer hard film of fluorosilane and silicon nitride, and a polyimide (PI) layer with a thickness of 450 nm disposed directly on top of a glass-based substrate. Figure 9D A laminate of was used as a comparative example with a crack mitigation layer having only a polymer (non-composite). Figures 9A-9D It is evident from the optical microscopic images of the laminate having a five-layer crack mitigation composite structure consistent with aspects of the present disclosure ( Figure 9B and 9C ) demonstrates that compared to the control sample without crack mitigating compound ( Figure 9A ) has comparable scratch resistance. In contrast, the laminate having a single-layer crack mitigation layer and comprising only polyimide ( Figure 9D ) was prone to delamination during the garnet scratch test.

[0217] Example 3: Optical properties of laminates with seven layers of Al2O3 / polyimide crack mitigation composite and silicon nitride hard film.

[0218] exist Figure 10In

[15] , transmission spectra are provided for a designated laminate without a crack mitigating compound and a hardcoat (Ex. 2C, a glass-based substrate control), as well as three sets of samples with different crack mitigating compounds (Ex. 2A, 2B1, and 2B2). More specifically, the laminate designated Ex. 2A includes a crack mitigating compound on a glass-based substrate having the following structure and thicknesses: SiO2 (on substrate) / Al2O3 / PI / Al2O3 / PI / Al2O3 / PI / Al2O3 and 80 / 10 / 50 / 10 / 80 / 10 / 50 / 20 nm. Furthermore, the laminates designated Ex. 2B1 and Ex. 2B2 include polyimide layers derived from PMDA-ODA and ODPA-ODA, respectively, with thicknesses of 450 nm and 150 nm. Because the hardcoat disposed over the crack mitigating composite will dominate the optical properties of the disclosed laminates, the samples lacking such hardcoat were judged representative to demonstrate that the crack mitigating composite had relatively no effect on the overall optical properties of the disclosed laminates.

[0219] like Figure 10 As shown, the samples with polyimide crack mitigating compound layers (Ex. 2B1 and Ex. 2B2, traces 1002 and 1004, respectively) have relatively similar optical transmission levels in the visible wavelength range compared to the baseline laminate without crack mitigating compound (Ex. 2C, trace 1006), indicating that the PI layer has high optical transmittance. Although the laminate with seven layers of crack mitigating compound (Ex. 2, trace 1000) exhibits slightly more oscillations in the visible spectrum compared to the other samples, it still demonstrates high optical transmittance across the entire visible spectrum. Without being bound by theory, it is also believed that the thickness and composition of the various layers in the crack mitigating compound can be designed to eliminate or otherwise minimize the optical transmittance in the visible spectrum compared to the laminate of Ex. 2A. Figure 10 The optical interference effect is observed in the results of Ex. 2A. For example, Example 6 below describes in detail a laminate having a crack mitigation composite with a more optimized optical layer structure in accordance with the principles of the present disclosure.

[0220] Example 4: Surface roughness of laminates with Al2O3 / polyimide crack mitigation composite and silicon nitride hard film.

[0221] Now refer to Figure 11A and 11B , which provides atomic force microscopy (AFM) images of laminates comprising a glass-based substrate, a silicon nitride hard film having a thickness of 440 nm, and a crack mitigation composite comprising aluminum oxide and polyimide layers according to some embodiments of the present disclosure ( Figure 11A), and without crack mitigating compound ( Figure 11B ).exist Figure 11A and 11B The whiter areas correspond to peaks and other surface features that indicate the overall surface roughness of these samples. Figure 11A and 11B As shown, the root mean square (RMS) roughness of these samples was measured within a 2 μm×2 μm window on the outer surface of each silicon nitride film of these samples using atomic force microscopy (AFM) technology. Specifically, Figure 11A The sample shown has a crack mitigation composite and a silicon nitride hard film, and its surface roughness (on the silicon nitride film) is 1.68nm. In comparison, Figure 11B The sample shown has a silicon nitride hard film but no crack mitigation compound, and its surface roughness (on the silicon nitride film) is 1.55 nm. Therefore, the use of the crack mitigation compound only results in a nominal increase in surface roughness (i.e., from 1.55 nm to 1.68 nm), which is not observed when Figure 11A and 11B Since the outer surface roughness of laminated articles used for the intended uses of the present disclosure can contribute to scratch resistance, wear resistance, and low friction performance, the laminated articles and crack mitigating compositions and layers of the present disclosure are particularly advantageous in that they provide other improved properties (i.e., strength retention) without significantly reducing the outer surface roughness of the article.

[0222] Example 5: Scratch resistance of laminates with five layers of Al2O3 / polyimide and BaF crack mitigation composite and silicon nitride hard film.

[0223] Now refer to Figure 12A and 12B , which depicts optical microscope images of articles comprising a glass-based substrate, a silicon nitride hard film, and a barium fluoride crack mitigation composite subjected to a Brinell ramp load scratch test (0 to 150 mN) ( Figure 12A ); and optical microscope images of articles comprising a glass-based substrate, a silicon nitride hard film, and a crack mitigation composite comprising aluminum oxide and polyimide layers subjected to a Brinell ramp load scratch test ( Figure 12B ).exist Figure 12A and 12B In the figure, the scratch surface of the sample is shown, and the scratch test is performed from left to right, with the load level increasing as the stylus moves from left to right across the sample. The load level increases linearly with the distance traveled across the sample. Therefore, the distance the stylus travels until delamination occurs can be used to measure the load level associated with delamination.

[0224] Figure 12AThe laminate shown comprises a 300 nm thick barium fluoride crack mitigation composite and a 2 μm thick silicon nitride hard film. Figure 12A As can be clearly seen from the results of the Brinell ramp load test of the laminate shown, delamination was observed at approximately 100 mN during the test. Figure 12A The wear marks observed in the sample shown are scratches with a narrow width that widen significantly as the delamination occurs in the last third of the wear mark on the right side of the sample. Figure 12B The laminate shown has a five-layer structure of Al2O3 / PI / Al2O3 / PI / Al2O3 with a crack mitigation composite having a thickness of 20nm / 50nm / 100nm / 50nm / 100nm and a silicon nitride hard film having a thickness of 2μm, and the laminate does not experience any delamination under a scratch load of no more than 150nM. That is, the stylus moves from left to right in Figure 12B The sample shown was moved above and the load was increased up to 150 mN without any observed signs of delamination.

[0225] Example 6: Five layers of Al2O3 / polyimide crack mitigation composite and SiO2 / AlO x N y Optical properties of laminates of scratch-resistant films.

[0226] As detailed in Table 1 below, according to embodiments of the present disclosure, a laminate having a crack mitigation composite and a hardcoat structure was prepared that was configured to optimize optical properties. Specifically, a crack mitigation composite comprising alternating polyimide and Al2O3 layers was formed over a major surface of a glass substrate. Also as shown in Table 1 below, a crack mitigation composite comprising alternating SiO2 and AlO3 layers was formed over the major surface of the glass substrate. x N y The scratch-resistant film is made by thermal evaporation and electron beam evaporation of polyimide and Al2O3 layers, and SiO2 and AlO x N y The reactive sputtering is performed to produce the individual layer materials. x N y layers such that each such layer contains about 10 mol % oxygen.

[0227] The optical properties of the individual layers of the laminate were characterized by spectroscopic ellipsometry and then placed into a thin film optical model to form the structures listed in Table 1 below. Specifically, optical modeling was performed to optimize the layer thicknesses, thereby demonstrating that the laminate comprising five layers of the crack mitigating composite exhibits optimized optical performance. As listed in Table 1 below, the refractive index values ​​for the various layers associated with the crack mitigating composite and the scratch-resistant film are reported by optical measurements at a reference wavelength of 550 nm.

[0228] Table 1

[0229] layer Material Refractive index Thickness (nm) N / A Air 1 N / A 1 <![CDATA[SiO2]]> 1.4685 102.9 2 <![CDATA[AlO x N y ]]> 1.9540 32.7 3 <![CDATA[SiO2]]> 1.4685 14.6 4 <![CDATA[AlO x N y ]]> 1.9540 2000 5 <![CDATA[SiO2]]> 1.4685 8.1 6 <![CDATA[AlO x N y ]]> 1.9540 39.2 7 <![CDATA[SiO2]]> 1.4685 16.7 8 <![CDATA[AlO x N y ]]> 1.9540 14.0 9 <![CDATA[Al2O3]]> 1.6629 6.53 10 PMDA-ODA polyimide 1.6862 41.3 11 <![CDATA[Al2O3]]> 1.6629 67.3 12 PMDA-ODA polyimide 1.6862 114.0 13 <![CDATA[Al2O3]]> 1.6629 24.8 substrate Glass 1.5063

[0230] Now refer to Figure 13A and 13B , which presents modeled data on dual-surface transmittance (i.e., including both sides of the coated laminate) and first-surface reflectance (i.e., considering only the coated side of the laminate) obtained from laminates constructed as listed in Table 1. The dual-surface transmittance is for a 1 mm substrate based on the assumption that absorption in the glass can be safely ignored. Therefore, under the same assumptions, the results will not be different for a 0.7 mm thickness (or other thickness), and therefore, specific thicknesses are not shown in Table 1. Figure 13A As shown in FIG, within the wavelength range of 420 to 700 nm, the transmittance at 6, 20, and 40 degree angles of incidence (AOI) is greater than 90%. In addition, within the same wavelength range, the transmittance at an angle of incidence (AOI) of 60 degrees is greater than 84%. Figure 13B As shown in Figure 2, the reflectivity at 6, 20, and 40 degrees AOI is less than 5% in the wavelength range of 420 to 700 nm. In addition, the reflectivity at 60 degrees AOI is less than 10% in the same wavelength range.

[0231] Now refer to Figure 14A and 14B , which shows modeled data for dual-surface transmitted color and first-surface reflected color obtained from laminates constructed as listed in Table 1. Figure 14A and 14B The color data is shown such that for a*, positive values ​​are red and negative values ​​are green, and for b*, positive values ​​are yellow and negative values ​​are blue. More specifically, as will be understood by one of ordinary skill in the art, the D65 and F2 standard illuminants are used at all incident angles between 0 and 90 degrees. Figure 14A and 14B The estimated measurements shown in . Figure 14A , for all angles of incidence, the transmitted color lies between 0 and -1 in the a* coordinate and between 0 and +4 in the b* coordinate. Figure 14B , for all angles of incidence, the reflected color lies between -2 and +2 in the a* coordinate and between -5 and +2 in the b* coordinate.

[0232] Now refer to Figure 15 , which shows modeled optical data for first surface illumination reflectance obtained from laminates constructed as listed in Table 1. The data were taken for all incident angles between 0 and 90 degrees for D65 and F2 standard illuminants. Figure 15 Estimated measurements shown. Figure 15, for incident angles between 0 and 40 degrees, the reflectivity is less than 2%, and for incident angles between 0 and 60 degrees, the reflectivity is less than 6%.

[0233] Although the present invention has been described with a limited number of embodiments for illustrative purposes, those skilled in the art, having benefit of the present disclosure, will appreciate that other embodiments can be designed without departing from the scope of the present disclosure as disclosed herein. Accordingly, those skilled in the art may make various modifications, alterations, and alternatives without departing from the spirit and scope of the present disclosure.

Claims

1. A product comprising: a glass-based substrate comprising opposing major surfaces; a crack mitigating composite on one major surface thereof, the crack mitigating composite comprising an inorganic component and a polymeric component, wherein the polymeric component comprises polyurethane; and a hard film disposed on the crack mitigating composite, the hard film comprising an elastic modulus greater than or equal to the elastic modulus of the glass-based substrate, and The hard film comprises at least one of the following: metal-containing oxides, metal-containing oxynitrides, metal-containing nitrides, metal-containing carbides, silicon-containing polymers, carbon, and combinations thereof.

2. The article of claim 1, wherein The hard film includes a semiconductor.

3. The article of claim 1, wherein The article has an average flexural strength greater than or equal to 50% of the average flexural strength of the substrate when measured by the ROR test using an average of five or more samples.

4. The article according to any one of claims 1 to 3, wherein The crack mitigating composite is characterized by a ratio of elastic moduli between the inorganic component and the polymeric component greater than 10:

1.

5. The article according to any one of claims 1 to 3, wherein The hard film has an indentation hardness greater than or equal to 8 GPa.

6. The article according to any one of claims 1 to 3, wherein Inorganic components include oxides, nitrides, or oxynitrides.

7. The article according to any one of claims 1 to 3, wherein The article has a light transmittance greater than or equal to 50% in the visible spectrum from 400 nm to 800 nm.

8. The article of any one of claims 1 to 3, wherein The article has a pencil hardness of 9H or higher.

9. The article of any one of claims 1 to 3, wherein When the hard film is tested using the Brinell ramp load scratch test, the article has a delamination threshold of 150 mN or greater.

10. The article of any one of claims 1 to 3, wherein The hardcoat comprises a multi-layer antireflective coating, and wherein the crack mitigating composite and the hardcoat together comprise an average single-sided illumination reflectivity of less than 2%.

11. The article of any one of claims 1 to 3, wherein During cube corner indentation testing, any cracking, damage, or delamination associated with at least one of the hard film and the crack mitigating composite is less than 15 microns in length after the hard film is subjected to indentation from a diamond indenter at a load level of 250 mN.

12. A consumer electronic product comprising: a housing having a front surface, a rear surface, and side surfaces; electronic components at least partially located within the housing, the electronic components including at least a controller, a memory, and a display, the display being located at or near a front surface of the housing; as well as a cover glass disposed above the display, Wherein, at least one of a portion of the housing or the cover glass comprises the product according to any one of claims 1 to 3.

13. An article comprising: a glass-based substrate comprising opposing major surfaces; a crack mitigating composite on one major surface thereof, the crack mitigating composite comprising at least one inorganic layer and at least one polymeric layer; and a hard film disposed on the crack mitigating composite, the hard film comprising an elastic modulus greater than or equal to the elastic modulus of the glass-based substrate, wherein the inorganic layer comprises an oxide, a nitride or an oxynitride, and the polymeric layer comprises at least one of polyimide, polycarbonate, polyurethane, polyester and a fluoropolymer, and The hard film comprises at least one of the following: metal-containing oxides, metal-containing oxynitrides, metal-containing nitrides, metal-containing carbides, silicon-containing polymers, carbon, and combinations thereof.

14. The article of claim 13, wherein The hard film includes a semiconductor.

15. The article of claim 13, wherein The article has an average flexural strength greater than or equal to 50% of the average flexural strength of the substrate when measured by the ROR test using an average of five or more samples.

16. The article of any one of claims 13 to 15, wherein The product has at least one of the following: In the visible spectrum from 400 nm to 800 nm, the light transmittance is greater than or equal to 50%; When the hard film is tested using the Brinell ramp load scratch test, the delamination threshold is 150 mN or greater.

17. The article of any one of claims 13-15, wherein: The hard film has an indentation hardness greater than or equal to 8 GPa; or The article has a pencil hardness of 9H or greater.

18. The article of any one of claims 13-15, wherein: The at least one polymeric layer is a polyimide comprising PMDA-ODA, ODPA-ODA, BPDA-ODA, or a fluorinated polyimide; and The at least one inorganic layer comprises: SiO2, Al2O3, ZrO2, CaO, CaCO3, SnO, ZnO, SiN x 、AlN x 、AlO x N y 、Si u Al v O x N y , or SiO x N y .

19. The article of any one of claims 13 to 15, wherein The crack mitigating composite comprises two or more inorganic layers and at least one polymeric layer, wherein one of the two or more inorganic layers is in contact with a substrate and another of the two or more inorganic layers is in contact with a hardcoat.

20. The article of any one of claims 13-15, wherein Each of the at least one inorganic layer comprises an inorganic layer thickness, and each of the at least one polymeric layer comprises a polymeric layer thickness, and wherein a ratio of the polymeric layer thickness to the inorganic layer thickness is from 0.1:1 to 5:

1.

21. The article of any one of claims 13 to 15, wherein The hardcoat comprises a multi-layer antireflective coating, and wherein the crack mitigating composite and the hardcoat together comprise an average single-sided illumination reflectivity of less than 2%.

22. The article of any one of claims 13-15, wherein During cube corner indentation testing, any cracking, damage, or delamination associated with at least one of the hard film and the crack mitigating composite is less than 15 microns in length after the hard film is subjected to indentation from a diamond indenter at a load level of 250 mN.

23. The article of any one of claims 13-15, wherein The polymeric layer comprises polyurethane.

24. A consumer electronic product comprising: a housing having a front surface, a rear surface, and side surfaces; electronic components at least partially located within the housing, the electronic components including at least a controller, a memory, and a display, the display being located at or near a front surface of the housing; as well as a cover glass disposed above the display, Wherein, at least one of a portion of the housing or the cover glass comprises the product according to any one of claims 13 to 15.

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